**Meet the editor**

Dr. Viduranga Waisundara obtained her PhD degree in Food Science and Technology from the Department of Chemistry, National University of Singapore, in 2010. She was a lecturer at Temasek Polytechnic, Singapore, from July 2009 to March 2013. Following this, she relocated to her motherland of Sri Lanka and spearheaded the Functional Food Product Development Project at

the National Institute of Fundamental Studies from April 2013 to October 2016. She is currently a senior lecturer on a temporary basis at the Department of Food Technology, Faculty of Technology, Rajarata University of Sri Lanka. She is a prolific writer with many research publications and articles in newspapers and magazines. She is also the current Global Harmonization Initiative (GHI) Ambassador to Sri Lanka.

Contents

**Preface VII**

**Palm Oil 3**

Chapter 1 **Introductory Chapter: Multifaceted Perspectives of**

**Section 2 Impact of the Palm Oil Industry on the Environment 11**

Chapter 2 **Palm Oil Mill Effluent as an Environmental Pollutant 13**

**Section 3 Applications of Palm Oil and its Industrial Wastes 29**

Karliati, Ichsan Suwandhi and Ihak Sumardi

Hesam Kamyab, Shreeshivadasan Chelliapan, Mohd Fadhil Md Din,

Rudi Dungani, Pingkan Aditiawati, Sri Aprilia, Karnita Yuniarti, Tati

Aminu Aliyu Safana, Nurhayati Abdullah and Fauziah Sulaiman

Paridah Md. Tahir, Folahan Abdulwahab Taiwo Owolabi, Abdul Khalil H.P. Shawkataly, Abbas F. Mubarak Alkarkhi, Elemo Gloria Nwakaego, Oyedeko K.F. Kamilu, Igwe Chartheny Chima, Samsul

Shahabaldin Rezania, Tayebeh Khademi and Ashok Kumar

Chapter 3 **Biomaterial from Oil Palm Waste: Properties, Characterization**

Chapter 4 **Potential Application of Oil Palm Wastes Charcoal Briquettes**

Chapter 5 **Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial Application 75**

Viduranga Yashasvi Waisundara

**and Applications 31**

**for Coal Replacement 53**

Rizal and Arniza Ghazali

**Section 1 Introduction 1**

## Contents

**Preface XI**


Rizal and Arniza Ghazali


Preface

Palm oil production is one of the most important industries in the world, where countries such as Malaysia, Indonesia, and Nigeria have invested heavily in its plantation and production. Indonesia is the world's largest producer of palm oil, contributing to approximately 44% of the global supply in the years 2006–2009, which is followed by Malaysia with 43%. When taking palm oil production as a whole, approximately 10% goes to oil palm produce, while the re‐ maining 90% are considered as waste biomass. With these outcomes, there are several applica‐

This book primarily focuses on four aspects: (1) Introduction (2) impact of the palm oil in‐ dustry on the environment, (3) applications of palm oil and its industrial wastes, and (4) dietary applications of palm oil. Many food products and other types of resources are de‐ rived from palm oil, making it one of the most economically important agricultural crops. On the other hand, a declining supply of raw materials from natural resources has motivat‐ ed scientists worldwide to find alternatives to produce new materials from sustainable re‐ sources such as palm oil. It is with these aspects in mind that this book project was launched, and contributions were gathered from renowned experts who have rendered their

I would like to extend my gratitude to the authors who have generously supported this book project by submitting their chapters; this publication would not have been a success without their hard work. Also, my heartfelt appreciation is extended to the InTech Publish‐ ing team with whom I have worked with for many book projects; this is my fourth publica‐ tion with them. It has been a pleasure and heartening experience to see their growth as a leading open-access publisher. Last but not least, my appreciation goes to Mr. Julian Virag, the Publishing Process Manager assigned to this book, who has rendered his utmost support

In conclusion, it is hoped that this book will be of value to all those who are interested and involved in the palm oil industry. It is without a doubt that the significance of this book and its contents will increase with the rising importance of the commercial value of palm oil and

> **Dr. Viduranga Waisundara** Department of Food Technology

Rajarata University of Sri Lanka

Faculty of Technology

Mihintale, Sri Lanka

tions of the palm oil industry, which have led to commercialized by-products.

thoughts and views in putting the publication together.

in putting the material together.

its by-products themselves.


## Preface

Chapter 6 **Oleochemicals from Palm Oil for the Petroleum Industry 91** Ademola Rabiu, Samya Elias and Oluwaseun Oyekola

Chapter 7 **The Inclusion of Palm Oil Ash Biomass Waste in Concrete: A**

Chapter 8 **Mixture Proportioning for Oil Palm Kernel Shell 133**

Chapter 10 **Effects of Dietary Palm Oil on the Whole-Body Mineral**

Otchoumou, Jean Noel Yapi and Laurent Alla Yao

Hanizam Bt. Awang and Mohammed Zuhear Al-Mulali

Mohamed Gibigaye and Gildas Fructueux Godonou

Chapter 9 **Chemical Characteristics and Nutritional Properties of Hybrid**

Massimo Mozzon, Roberta Foligni and Urszula Tylewicz

**Composition of African Catfish, Heterobranchus longifilis**

Célestin Mélécony Ble, Olivier Assoi Etchian, Athanase Kraidy

**Literature Review 117**

**VI** Contents

**Section 4 Dietary Applications of Palm Oil 147**

**(Teleostei, Clariidae) 171**

**Palm Oils 149**

Palm oil production is one of the most important industries in the world, where countries such as Malaysia, Indonesia, and Nigeria have invested heavily in its plantation and production. Indonesia is the world's largest producer of palm oil, contributing to approximately 44% of the global supply in the years 2006–2009, which is followed by Malaysia with 43%. When taking palm oil production as a whole, approximately 10% goes to oil palm produce, while the re‐ maining 90% are considered as waste biomass. With these outcomes, there are several applica‐ tions of the palm oil industry, which have led to commercialized by-products.

This book primarily focuses on four aspects: (1) Introduction (2) impact of the palm oil in‐ dustry on the environment, (3) applications of palm oil and its industrial wastes, and (4) dietary applications of palm oil. Many food products and other types of resources are de‐ rived from palm oil, making it one of the most economically important agricultural crops. On the other hand, a declining supply of raw materials from natural resources has motivat‐ ed scientists worldwide to find alternatives to produce new materials from sustainable re‐ sources such as palm oil. It is with these aspects in mind that this book project was launched, and contributions were gathered from renowned experts who have rendered their thoughts and views in putting the publication together.

I would like to extend my gratitude to the authors who have generously supported this book project by submitting their chapters; this publication would not have been a success without their hard work. Also, my heartfelt appreciation is extended to the InTech Publish‐ ing team with whom I have worked with for many book projects; this is my fourth publica‐ tion with them. It has been a pleasure and heartening experience to see their growth as a leading open-access publisher. Last but not least, my appreciation goes to Mr. Julian Virag, the Publishing Process Manager assigned to this book, who has rendered his utmost support in putting the material together.

In conclusion, it is hoped that this book will be of value to all those who are interested and involved in the palm oil industry. It is without a doubt that the significance of this book and its contents will increase with the rising importance of the commercial value of palm oil and its by-products themselves.

> **Dr. Viduranga Waisundara** Department of Food Technology Faculty of Technology Rajarata University of Sri Lanka Mihintale, Sri Lanka

**Section 1**

**Introduction**

**Section 1**

## **Introduction**

**Chapter 1**

**Provisional chapter**

**Introductory Chapter: Multifaceted Perspectives of**

**Introductory Chapter: Multifaceted Perspectives of** 

Palm oil is extracted from the ripened mesocarp of the fruits of the oil palm tree *Elaeis guineensis*. The oil palm can produce two types of oil: (1) palm oil from the fibrous mesocarp (which has a brilliant, deep red-orange pulp) and (2) palm kernel oil (which resembles coconut oil) from the kernel [1–3]. Crude palm oil (CPO) can be processed into various downstream products; however, most of the phytonutrients are partially removed during the processing steps involved. The major processed product of CPO is deodorised palm oil which involves refining and bleaching. It is during this refining process that the carotenes which give CPO its characteristic red-orange colour become decomposed, resulting in refined, bleached, and

The five leading producers of palm oil around the world are Indonesia, Malaysia, Thailand, Colombia and Nigeria [4]. According to Mba et al. [4], the oil palm tree gives the highest yield of oil per unit area of cultivated land, at an estimated 58.431 million metric tons per year. It is estimated that 1 ha of oil palm plantation is able to produce up to 10 times more oil than other types of leading oilseed crops [4]. The refining process of CPO through chemical and physical

Bearing these in mind, this book primarily focuses on various aspects of the palm oil industry, principally its impact on the current consumer market as a crop of agricultural and industrial value and effects on the environment. The sections which follow in this introductory chapter give brief overviews on other aspects which may or may not be covered in the rest of the content chapters, so that the voids and gaps are ideally filled. It is of importance to see the food technological and health aspects of palm oil as well, and thus, this chapter covers a certain

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

DOI: 10.5772/intechopen.78771

**Palm Oil**

**1. Introduction**

**Palm Oil**

Viduranga Yashasvi Waisundara

Viduranga Yashasvi Waisundara

http://dx.doi.org/10.5772/intechopen.78771

Additional information is available at the end of the chapter

deodorised palm oil, which has a slight yellow colour [1].

refining is shown in the schematics as per **Figures 1** and **2**.

amount of content on the food value of this product too.

Additional information is available at the end of the chapter

#### **Introductory Chapter: Multifaceted Perspectives of Palm Oil Introductory Chapter: Multifaceted Perspectives of Palm Oil**

DOI: 10.5772/intechopen.78771

Viduranga Yashasvi Waisundara Viduranga Yashasvi Waisundara

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.78771

## **1. Introduction**

Palm oil is extracted from the ripened mesocarp of the fruits of the oil palm tree *Elaeis guineensis*. The oil palm can produce two types of oil: (1) palm oil from the fibrous mesocarp (which has a brilliant, deep red-orange pulp) and (2) palm kernel oil (which resembles coconut oil) from the kernel [1–3]. Crude palm oil (CPO) can be processed into various downstream products; however, most of the phytonutrients are partially removed during the processing steps involved. The major processed product of CPO is deodorised palm oil which involves refining and bleaching. It is during this refining process that the carotenes which give CPO its characteristic red-orange colour become decomposed, resulting in refined, bleached, and deodorised palm oil, which has a slight yellow colour [1].

The five leading producers of palm oil around the world are Indonesia, Malaysia, Thailand, Colombia and Nigeria [4]. According to Mba et al. [4], the oil palm tree gives the highest yield of oil per unit area of cultivated land, at an estimated 58.431 million metric tons per year. It is estimated that 1 ha of oil palm plantation is able to produce up to 10 times more oil than other types of leading oilseed crops [4]. The refining process of CPO through chemical and physical refining is shown in the schematics as per **Figures 1** and **2**.

Bearing these in mind, this book primarily focuses on various aspects of the palm oil industry, principally its impact on the current consumer market as a crop of agricultural and industrial value and effects on the environment. The sections which follow in this introductory chapter give brief overviews on other aspects which may or may not be covered in the rest of the content chapters, so that the voids and gaps are ideally filled. It is of importance to see the food technological and health aspects of palm oil as well, and thus, this chapter covers a certain amount of content on the food value of this product too.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**Figure 1.** Refining process of CPO through physical processes.

## **2. Applications in the food industry**

Palm oil has a very unique fatty acid (FA) and triacylglycerol (TAG) profile which makes it ideal for numerous food applications. It is the only vegetable oil presently available in the consumer market with an almost 1:1 composition of saturated and unsaturated FAs. CPO is primarily used in household and food retail outlets for cooking, frying and as a source of vitamins. Fractionation of CPO yields mainly palm olein as the liquid fraction and palm stearin as the solid fraction [4]. These fractions have distinct physico-chemical features. CPO, palm olein and palm stearin are important constituents of several food and industrial products such as shortenings and ice cream [4].

composition, it has a high smoke point of about 230°C [4, 6]. The process of frying heats the food right through to the middle, cooking its interior and creating a 'crust' on the surface of the food plus a characteristic fried food flavour, which has resulted in the popularity of such food products among consumers in both household as well as fast-food applications [7]. The hot oil serves as a medium of heat and mass transfer, while some of the oil is absorbed by the product and moisture in the form of vapour is given off [4]. Thus, frying could be considered as a processing method which combines cooking and drying. Given the importance of frying, palm oil has become an essential component in many food preparations, resulting in a high

Introductory Chapter: Multifaceted Perspectives of Palm Oil

http://dx.doi.org/10.5772/intechopen.78771

5

It is a well-known fact that there is a rapid depletion of crude oil reserves, increasing oil prices along with growing concerns about emission of greenhouse gases. This phenomenon

placement of value in the modern consumer market.

**Figure 2.** Refining processes of CPO through chemical processes.

**3. Palm oil-based biodiesel**

Palm oil is top prime among frying oils. Refined, bleached and deodorised palm oil is a versatile oil widely used in more than 150 countries worldwide [5]. In addition to its unique FA Introductory Chapter: Multifaceted Perspectives of Palm Oil http://dx.doi.org/10.5772/intechopen.78771 5

**Figure 2.** Refining processes of CPO through chemical processes.

composition, it has a high smoke point of about 230°C [4, 6]. The process of frying heats the food right through to the middle, cooking its interior and creating a 'crust' on the surface of the food plus a characteristic fried food flavour, which has resulted in the popularity of such food products among consumers in both household as well as fast-food applications [7]. The hot oil serves as a medium of heat and mass transfer, while some of the oil is absorbed by the product and moisture in the form of vapour is given off [4]. Thus, frying could be considered as a processing method which combines cooking and drying. Given the importance of frying, palm oil has become an essential component in many food preparations, resulting in a high placement of value in the modern consumer market.

#### **3. Palm oil-based biodiesel**

**2. Applications in the food industry**

**Figure 1.** Refining process of CPO through physical processes.

shortenings and ice cream [4].

4 Palm Oil

Palm oil has a very unique fatty acid (FA) and triacylglycerol (TAG) profile which makes it ideal for numerous food applications. It is the only vegetable oil presently available in the consumer market with an almost 1:1 composition of saturated and unsaturated FAs. CPO is primarily used in household and food retail outlets for cooking, frying and as a source of vitamins. Fractionation of CPO yields mainly palm olein as the liquid fraction and palm stearin as the solid fraction [4]. These fractions have distinct physico-chemical features. CPO, palm olein and palm stearin are important constituents of several food and industrial products such as

Palm oil is top prime among frying oils. Refined, bleached and deodorised palm oil is a versatile oil widely used in more than 150 countries worldwide [5]. In addition to its unique FA It is a well-known fact that there is a rapid depletion of crude oil reserves, increasing oil prices along with growing concerns about emission of greenhouse gases. This phenomenon has resulted in an increasing need for the adoption a global energy economy based on renewables. The usage of renewable energy technologies (RETs) are set to increase in future, directly influencing public opinion and the energy policies of governments around the world [8].

or mortality of CVD. Furthermore, Ismail et al. [19] observed that the effect seen between association of palm oil consumption and risk of coronary heart disease were not unique to only palm oil, especially since other food items were also included in the analysis, therefore

Introductory Chapter: Multifaceted Perspectives of Palm Oil

http://dx.doi.org/10.5772/intechopen.78771

7

According to Shahputra and Zen [22], conversion of forests and peat lands for oil palm cultivation is considered by many to be the largest source of greenhouse gas emissions. According to Agus et al. [23], oil palm plantations are estimated to be responsible for substantial and increasing of total carbon emissions in Indonesia, Malaysia and Papua New Guinea. Recent statistics indicate that while some provinces with large expansions in oil palm plantations have had an increase in deforestation, others have not [24]. For where the instance of deforestation has not taken place, this indicates that plantation land previously used for food crops including rice, is being converted into oil palm plantations, since the previous crops may have become less attractive due to poor irrigation infrastructure and

Shahputra and Zen [22] recommend that given the environmental impacts of destroying intact forest and peat lands, a key development strategy which could be adopted to support rural communities is to implement sustainable land use planning, involving expanding oil palm into degraded land mostly covered by grass such as *Imperata cylindrica* which is commonly found in countries such as Indonesia. Additionally, Shahputra and Zen state that a largescale oil palm expansion programme driven by estate companies needs to be accompanied by a well thought and effective smallholder development programme. Overall, if land issues could be resolved and local landowners included, oil palm acreage could be increased up to two-fold, without having to convert additional new forest land and peat lands, thus saving

The palm oil industry remains vital to many countries where it is grown in bulk, since its cultivation has led to socio-economic advancements and growth in gross domestic product. From the perspective of consumers, the palm oil is a good source of nutrients, functional bioactives, cooking media as well as a product to be consumed for health benefits. It has to be borne in mind though that there are environmental impacts in the mass cultivation of oil palm, and thus, the effects on farming practices resulting in deforestation and climate change need to be taken into account. Also, development of biofuel products and technologies based on the palm oil industry is heartening from the point of future sustainability. From this perspective, support should be rendered towards usage of different feedstocks and enhancing

rendering the association to be insignificant.

falling terms of trade.

**6. Conclusions**

**5. Impact of oil palm on forests and climate change**

the environment from having to undergo negative effects.

the efficiency of the production line to shift from petroleum to palm oil.

Biodiesel is an amber-yellow, liquid-based mono alkyl ester which is derived primarily from plant and animal oils [8]. The properties of biodiesel are nevertheless similar to petroleumbased diesel, although biodiesel is biodegradable, non-explosive and non-toxic which significantly reduces toxic emissions when burned [8–11]. Currently biodiesel is produced primarily from edible oils such as rapeseed oil, sunflower oil, soybean oil, tallow and palm oil [12, 13]. However, the fraction of palm oil which is being used for biodiesel production has increased from 3.2 to 8.3 million tonnes from 2009 to 2014, while Malaysia accounts for 40% of total global demand for strategically positioning the nation as a significant player in the global dynamics of biodiesel production [14]. CPO has the highest average oil yield of any oil-extracting crop, hence, its utilisation for biodiesel production offers many advantages over other crops used for the same purpose [15, 16].

## **4. Health benefits and safety of palm oil consumption**

The current demand for functional foods is attracting a wide range of customers around the world. In response, supermarkets and producers are adapting their products and have identified the growth potential of products which bear a 'free from' claim in their packaging [17]. Despite various statements against the consumption of palm oil, up to now there is no substantiated indication that consumption of palm oil in a balanced diet is related to any specific health concern. In fact, it has been shown that replacing palm oil in food products or diets with fats higher in saturated FAs or with added sugar to compensate for the palatability and taste, will not provide a health benefit [17].

The safety of both CPO and refined, bleached and deodorised palm oil has been studied extensively in mutagenicity, nutritional and toxicological studies, with no adverse effects reported [1]. In general, fats are subjected to heat, thermal oxidation occurs and mutagens are formed; this is a common occurrence to all fats and oils, and heating can also lead to deterioration of the nutritional quality of the oil. Repeatedly, heated CPO and refined palm oil have been tested for mutagenicity to determine the safety of edibility, and no adverse effects have been identified to date [1].

Cardiovascular diseases (CVD) are responsible for 31% of global deaths [18]. This disease is a group of diseases of the heart and blood vessels including coronary heart disease (CHD), cerebrovascular disease, peripheral arterial disease, rheumatic heart disease, congenital heart disease, deep vein thrombosis and also pulmonary embolism [19]. The high proportion of saturated FAs, especially palmitic acid, in palm oil has been linked to the increased risk of atherosclerosis [20, 21]. However, findings of the systematic review by Ismail et al. [19] indicated that there is no evidence of a clear association between palm oil consumption and risk or mortality of CVD. Furthermore, Ismail et al. [19] observed that the effect seen between association of palm oil consumption and risk of coronary heart disease were not unique to only palm oil, especially since other food items were also included in the analysis, therefore rendering the association to be insignificant.

## **5. Impact of oil palm on forests and climate change**

According to Shahputra and Zen [22], conversion of forests and peat lands for oil palm cultivation is considered by many to be the largest source of greenhouse gas emissions. According to Agus et al. [23], oil palm plantations are estimated to be responsible for substantial and increasing of total carbon emissions in Indonesia, Malaysia and Papua New Guinea. Recent statistics indicate that while some provinces with large expansions in oil palm plantations have had an increase in deforestation, others have not [24]. For where the instance of deforestation has not taken place, this indicates that plantation land previously used for food crops including rice, is being converted into oil palm plantations, since the previous crops may have become less attractive due to poor irrigation infrastructure and falling terms of trade.

Shahputra and Zen [22] recommend that given the environmental impacts of destroying intact forest and peat lands, a key development strategy which could be adopted to support rural communities is to implement sustainable land use planning, involving expanding oil palm into degraded land mostly covered by grass such as *Imperata cylindrica* which is commonly found in countries such as Indonesia. Additionally, Shahputra and Zen state that a largescale oil palm expansion programme driven by estate companies needs to be accompanied by a well thought and effective smallholder development programme. Overall, if land issues could be resolved and local landowners included, oil palm acreage could be increased up to two-fold, without having to convert additional new forest land and peat lands, thus saving the environment from having to undergo negative effects.

## **6. Conclusions**

has resulted in an increasing need for the adoption a global energy economy based on renewables. The usage of renewable energy technologies (RETs) are set to increase in future, directly influencing public opinion and the energy policies of governments around the

Biodiesel is an amber-yellow, liquid-based mono alkyl ester which is derived primarily from plant and animal oils [8]. The properties of biodiesel are nevertheless similar to petroleumbased diesel, although biodiesel is biodegradable, non-explosive and non-toxic which significantly reduces toxic emissions when burned [8–11]. Currently biodiesel is produced primarily from edible oils such as rapeseed oil, sunflower oil, soybean oil, tallow and palm oil [12, 13]. However, the fraction of palm oil which is being used for biodiesel production has increased from 3.2 to 8.3 million tonnes from 2009 to 2014, while Malaysia accounts for 40% of total global demand for strategically positioning the nation as a significant player in the global dynamics of biodiesel production [14]. CPO has the highest average oil yield of any oil-extracting crop, hence, its utilisation for biodiesel production offers many advantages over

The current demand for functional foods is attracting a wide range of customers around the world. In response, supermarkets and producers are adapting their products and have identified the growth potential of products which bear a 'free from' claim in their packaging [17]. Despite various statements against the consumption of palm oil, up to now there is no substantiated indication that consumption of palm oil in a balanced diet is related to any specific health concern. In fact, it has been shown that replacing palm oil in food products or diets with fats higher in saturated FAs or with added sugar to compensate for the palatability and

The safety of both CPO and refined, bleached and deodorised palm oil has been studied extensively in mutagenicity, nutritional and toxicological studies, with no adverse effects reported [1]. In general, fats are subjected to heat, thermal oxidation occurs and mutagens are formed; this is a common occurrence to all fats and oils, and heating can also lead to deterioration of the nutritional quality of the oil. Repeatedly, heated CPO and refined palm oil have been tested for mutagenicity to determine the safety of edibility, and no adverse effects have

Cardiovascular diseases (CVD) are responsible for 31% of global deaths [18]. This disease is a group of diseases of the heart and blood vessels including coronary heart disease (CHD), cerebrovascular disease, peripheral arterial disease, rheumatic heart disease, congenital heart disease, deep vein thrombosis and also pulmonary embolism [19]. The high proportion of saturated FAs, especially palmitic acid, in palm oil has been linked to the increased risk of atherosclerosis [20, 21]. However, findings of the systematic review by Ismail et al. [19] indicated that there is no evidence of a clear association between palm oil consumption and risk

world [8].

6 Palm Oil

other crops used for the same purpose [15, 16].

taste, will not provide a health benefit [17].

been identified to date [1].

**4. Health benefits and safety of palm oil consumption**

The palm oil industry remains vital to many countries where it is grown in bulk, since its cultivation has led to socio-economic advancements and growth in gross domestic product. From the perspective of consumers, the palm oil is a good source of nutrients, functional bioactives, cooking media as well as a product to be consumed for health benefits. It has to be borne in mind though that there are environmental impacts in the mass cultivation of oil palm, and thus, the effects on farming practices resulting in deforestation and climate change need to be taken into account. Also, development of biofuel products and technologies based on the palm oil industry is heartening from the point of future sustainability. From this perspective, support should be rendered towards usage of different feedstocks and enhancing the efficiency of the production line to shift from petroleum to palm oil.

## **Author details**

Viduranga Yashasvi Waisundara

Address all correspondence to: viduranga@gmail.com

Department of Food Technology, Faculty of Technology, Rajarata University of Sri Lanka, Mihintale, Sri Lanka

[13] Borugadda VB, Goud VV. Biodiesel production from renewable feedstocks: Status and opportunities. Renewable & Sustainable Energy Reviews. 2012;**16**(7):4763-4784

Introductory Chapter: Multifaceted Perspectives of Palm Oil

http://dx.doi.org/10.5772/intechopen.78771

9

[14] CIMB Regional Sector Navigator. Plantations: Refuelling Biodiesel Demand. 2014. Available

[15] Yee KF, Tan KT, Abdullah AZ, Lee KT. Life cycle assessment of palm biodiesel: Revealing

[16] Ramli A, Roslan A, Ayatollah K. Impact of palm oil-based biodiesel demand on palm oil

[17] Gambelli L, Logman M. Why palm oil intake is of no health concern. Agro FOOD

[18] Holub BJ. Clinical nutrition: 4. Omega-3 fatty acids in cardiovascular care. Canadian

[19] Ismail SR, Maarof SK, Ali SS, Ali A. Systematic review of palm oil consumption and the risk of cardiovascular disease. PLoS ONE. 2018;**13**(2):e0193533. DOI: 10.1371/journal.

[20] Brown W, Jacobson MF. Cruel Oil: How Palm Oil Harms Health, Rainforest & Wildlife.

[21] Edmond K, Kabagambe AB, Alberto A, Hannia C. The type of oil used for cooking is associated with the risk of nonfatal acute myocardial infarction in Costa Rica. The

[22] Shahputra MA, Zen Z. IOP Conference Series: Earth and Environmental Science. Vol.

[23] Agus F, Gunarso P, Sahardjo BH, Harris N, van Noorrdwijk M, Killeen TJ. Historical CO2 emission from land use and land use change from the oil palm industry in Indonesia, Malaysia and Papua New Guinea. In: Report from the Technical Panels of the 2nd Green

[24] Carlson KM, Curran LM, Ratnasari D, Pittman AM, Soares-Filho BS, Asner GP, Trigg SN, Gaveau DA, Lawrence D, Rodrigues HO. Committed carbon emission, deforestation, and community land conversion from oil palm plantation expansion in West Kalimantan, Indonesia. Proceedings of the National Academy of Sciences. 2012;**109**(19):7559-7564

facts and benefits for sustainability. Applied Energy. 2009;**86**(1):S189-S196

from: http://bit.ly/1yKRCo4 [Accessed: 17 May 2018]

price. Oil Palm Industry Economic Journal. 2007;**7**(2):19-27

Medical Association Journal. 2002;**166**(5):608-615

Centre for Science in the Public Interest. 2005. pp 1-31

Journal of Nutrition. 2005;**135**:2674-2679

House Gas Working Group of the RSPO. 2013

Industry Hi-Tech. 2015;**26**(6):24-28

pone.0193533

122. 2018. p. 012008

## **References**


[13] Borugadda VB, Goud VV. Biodiesel production from renewable feedstocks: Status and opportunities. Renewable & Sustainable Energy Reviews. 2012;**16**(7):4763-4784

**Author details**

8 Palm Oil

Mihintale, Sri Lanka

**References**

Viduranga Yashasvi Waisundara

Reviews. 2017;**75**(2):98-113

2015;**81**(2015):255-261

Technology. 2007;**109**(4):440-444

as biodiesel feedstock. Energy. 2008;**33**:1646-1653

Address all correspondence to: viduranga@gmail.com

Pacific Journal of Clinical Nutrition. 2003;**12**:355-362

of Lipid Science and Technology. 2014;**116**:1301-1315

Notes Series. Rome: MAFAP, FAO; 2013

Department of Food Technology, Faculty of Technology, Rajarata University of Sri Lanka,

[1] Loganathan R, Subramaniam KM, Radhakrishnan AM, Choo YM, Teng KT. Healthpromoting effects of red palm oil: Evidence from animal and human studies. Nutrition

[2] Sundram K, Sambanthamurthi R, Tan YA. Palm fruit chemistry and nutrition. Asia

[3] Gourichon H. Analysis of Incentives and Disincentives for Palm Oil in Nigeria. Technical

[4] Mba OI, Dumont MJ, Ngadi M. Palm oil: Processing, characterization and utilization in

[5] May CY, Nesaretnam K. Research advancements in palm oil nutrition. European Journal

[6] Gupta MK. Selection of frying oil. In: Gupta MK, Warner K, White PJ, editors. Frying Technology and Practices. Champaign, Illinois, USA: AOCS Press; 2004. pp. 29-36

[7] Marrikar JMN, Ghazali HM, Long K, Lai OM. Lard uptake and its detection in selected food products deep-fried in lard. Food Resource International. 2003;**36**:1047-1060

[8] Johari A, Nyakuma BB, Nor SHM, Mat R, Hashim H, Ahmad A, Zakaria ZY, Abdullah TAT. The challenges and prospects of palm oil based biodiesel in Malaysia. Energy.

[9] Liang YC, May CY, Foon CS, Ngan MA, Hock CC, Basiron Y. The effect of natural and synthetic antioxidants on the oxidative stability of palm diesel. Fuel. 2006;**85**(5-6):867-870

[10] Sern CH, May CY, Zakaria Z, Daik R, Foon CS. The effect of polymers and surfactants on the pour point of palm oil methyl esters. European Journal of Lipid Science and

[11] Sarin A, Arora R, Singh NP, Sarin R, Malhotra RK, Kundu K. Effect of blends of Palm-Jatropha Pongamia biodiesel on cloud point and pour point. Energy. 2009;**34**(11):2016-2021

[12] Gui MM, Lee KT, Bhatia S. Feasibility of edible oil vs. non-edible oil vs. waste edible oil

the food industry—A review. Food Bioscience. 2015;**10**(2015):26-41


**Section 2**

**Impact of the Palm Oil Industry on the**

**Environment**

**Impact of the Palm Oil Industry on the Environment**

**Chapter 2**

**Provisional chapter**

**Palm Oil Mill Effluent as an Environmental Pollutant**

In recent decades, Malaysia has been known as one of the world's leading producers and exporters of palm oil products. Every year, the number of palm oil mills increases rapidly, thus increasing the capacity of fresh fruit bunch waste or effluent discharge. Based on the data from the Malaysian Palm Oil Board in 2012, Malaysia produced 99.85 million tons of fresh fruit bunch (FFB) per year. However, about 5–5.7 tons of water was required in order to sterilize the palm fruit bunches and clarify the extracted oil to produce 1 ton of crude palm oil resulting in 50% of the water turning into palm oil mill effluent (POME). POME is one of the major environmental pollutants in Malaysia. The characteristics of POME and its behavior, if discharged directly, in water are described in this chapter. The suspended solid and nutrient content in POME could be able to support the growth of algae. This chapter aims to demonstrate that POME could be used as a main source for algae production, and this effluent is one of the main environmental problems in the

**Keywords:** POME, Malaysia, wastewater, environmental pollution,industry

These days, palm oil enterprise is developing quickly and turning into a noteworthy agriculture-based industry in Malaysia. The quantity of palm oil mills has elevated relatively, at beginning with 10 mills in 1960 moved to 410 operated mills in 2008. At least 44 million tons of POME was produced and are increasing every year in Malaysia [1], particularly because of the initiative of the government to promote palm oil industry. While the palm oil industry has been recognized strongly for its contribution toward economic growth and rapid

**Palm Oil Mill Effluent as an Environmental Pollutant**

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

DOI: 10.5772/intechopen.75811

Hesam Kamyab, Shreeshivadasan Chelliapan, Mohd Fadhil Md Din, Shahabaldin Rezania,

Hesam Kamyab, Shreeshivadasan Chelliapan, Mohd Fadhil Md Din, Shahabaldin Rezania,

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

Tayebeh Khademi and Ashok Kumar

Tayebeh Khademi and Ashok Kumar

http://dx.doi.org/10.5772/intechopen.75811

tropical region especially in Malaysia.

**Abstract**

**1. Introduction**

#### **Palm Oil Mill Effluent as an Environmental Pollutant Palm Oil Mill Effluent as an Environmental Pollutant**

DOI: 10.5772/intechopen.75811

Hesam Kamyab, Shreeshivadasan Chelliapan, Mohd Fadhil Md Din, Shahabaldin Rezania, Tayebeh Khademi and Ashok Kumar Hesam Kamyab, Shreeshivadasan Chelliapan, Mohd Fadhil Md Din, Shahabaldin Rezania, Tayebeh Khademi and Ashok Kumar

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.75811

#### **Abstract**

In recent decades, Malaysia has been known as one of the world's leading producers and exporters of palm oil products. Every year, the number of palm oil mills increases rapidly, thus increasing the capacity of fresh fruit bunch waste or effluent discharge. Based on the data from the Malaysian Palm Oil Board in 2012, Malaysia produced 99.85 million tons of fresh fruit bunch (FFB) per year. However, about 5–5.7 tons of water was required in order to sterilize the palm fruit bunches and clarify the extracted oil to produce 1 ton of crude palm oil resulting in 50% of the water turning into palm oil mill effluent (POME). POME is one of the major environmental pollutants in Malaysia. The characteristics of POME and its behavior, if discharged directly, in water are described in this chapter. The suspended solid and nutrient content in POME could be able to support the growth of algae. This chapter aims to demonstrate that POME could be used as a main source for algae production, and this effluent is one of the main environmental problems in the tropical region especially in Malaysia.

**Keywords:** POME, Malaysia, wastewater, environmental pollution,industry

## **1. Introduction**

These days, palm oil enterprise is developing quickly and turning into a noteworthy agriculture-based industry in Malaysia. The quantity of palm oil mills has elevated relatively, at beginning with 10 mills in 1960 moved to 410 operated mills in 2008. At least 44 million tons of POME was produced and are increasing every year in Malaysia [1], particularly because of the initiative of the government to promote palm oil industry. While the palm oil industry has been recognized strongly for its contribution toward economic growth and rapid

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

development, it has also contributed to environmental pollution due to the production of large quantities of by-products during the process of oil extraction [2, 3]. Furthermore, it is necessary to properly address the POME treatment so as not to contribute to human health hazards and environmental pollution.

solids. POME in its untreated shape is a high quality waste, relying upon the operation of the procedure. POME is generated mainly from oil extraction, washing and cleaning processes in the mill, and these contain cellulosic material, fat, oil and grease, and so on [15]. POME also contains substantial quantities of solids; both suspended solids and total dissolved solids in

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811 15

Oil palm is the most productive oil producing plant in the world, with 1 ha of oil palm producing between 10 and 35 tons of fresh fruit bunch (FFB) per year [15]. During processing of oil palm, more than 70% by weight of the fresh fruit brunch was left over as waste [16]. Usually, the harvested part is the fruit whereby oil is obtained from the fleshy mesocarp of the fruit. Despite the importance of the edible oil and fats extracted from the palm fruits, the POME contains residual oil which affects the environment cannot be ignored. Treatment and disposal of oily wastewater such as POME is presently one of the serious environmental problems. Palm oil mill wastes have existed for years but their effects on environment are at present more noticeable [15]. The oily waste has to be removed to prevent problems which are considered as hazardous pollutants particularly in the aquatic environments because they are highly toxic to the aquatic organisms. Discharging the effluents or by-products on the lands or release to the river may lead to pollution and might deteriorate the surrounding environment. In order to conserve the environment, an efficient management system in the treatment of these byproducts is needed [17]. Treatment of POME is essential to avoid environmental pollution [18]. POME wastes are the fiber free non-oil components obtained from the clarification zone of an oil mills. The significant contamination comes out of the fresh fruit brunch (FFB). In fact, every ton of FFB is composed of 230–250 kg of empty fruit bunches (EFB), 130–150 kg of fibers, 60–65 kg of shell and 55–60 kg of kernels and 160–200 kg of unrefined oil [19]. POME contains high amounts of oil and grease (4000 mg/L) and COD (50,000 mg/L). Although the effluent is nontoxic, it has a very high concentration of biochemical oxygen demand (BOD) (i.e., 25,000 mg/L) which becomes a serious threat to aquatic life when discharged in relatively large quantities into watercourses. The high amount of total solids (40,500 mg/L) contributes to the large amount of nutrients available in the wastewater, hence possible algae bloom.

Most palm oil mills in Malaysia have adopted the ponding system for the treatment of POME [20]. In general, there are four types of treatment systems adopted by the palm oil industry,

The most proper secondary treatment for POME is natural assimilation with the blend of anaerobic and aerobic ponds. Right now, the management of POME has developed from treatment of waste for transfer to gainful use of assets. POME contains generous amounts of significant plant supplement that shift as indicated by the level of treatment to which it is subjected. The potential utilization of recovery of water and natural issues from POME has been applied for different applications [21]. Commercial trials and applications of these

the range of 18,000 and 40,500 mg/L, respectively.

which are as follows:

**a.** Waste stabilization ponds, **b.** Activated sludge system,

**d.** Land application system.

**c.** Closed anaerobic digester and

POME is the wastewater produced by processing oil palm and comprises of different suspended materials. POME is 100 times more polluted than the municipal sewage which has a high biochemical oxygen demand (BOD) and chemical oxygen demand (COD). The effluent also contains higher concentration of organic nitrogen, phosphorus and different supplement substance [4]. POME is a non-harmful waste; however, it will pose environmental issue because of vast oxygen draining capacity to oceanic framework because of natural and supplement substance. It is also known to be a good source of nutrients [5]. The waste products generated during palm oil processing consist of oil palm trunks (OPT), oil palm fronds (OPF), empty fruit bunches (EFB), palm pressed fibers (PPF) and palm kernel shells, less fibrous material such as palm kernel cake and liquid discharge POME [2]. The wastes are in the form of high organic matter concentration such as cellulosic wastes with a mixture of carbohydrates and oils. The discharge of untreated POME creates adverse impact to the environment [6].

Nowadays, biological process is the most common practice way for the treatment of POME based on anaerobic and aerobic ponding system [2]. While the emerging technologies for the treatment of POME, the notion of nurturing POME and its derivatives as valuable resources should not be dismissed. Furthermore, it is necessary to properly address the POME treatment so as not to contribute to human health hazards and environmental pollution. At the point when contrasted with those routine wastewater treatment processes which introduce activated sludge and living floc to degrade natural carbonaceous issue to CO2 , and microalgae may acclimatize natural toxins into cell constituents, for example, lipid and carbohydrate, therefore attaining pollutant decrease in a more ecological friendly way [7]. Actually, microalgae have turned into the consideration for both wastewater treatment and biomass production as early as 1950s [8]. Small scale and economically viable technologies that combine wastewater treatment and energy production can treat the industrial effluents and enhance the availability of the energy simultaneously [9]. The feasible way that is more attentions in the present time is the use of microalgae, which is known to have the potential to treat wastewater [10] such as removal of CO2 and NOx [11] and high capacity of nutrient uptake [12]. The idea of using microalgae in wastewater treatment has been investigated since 1950s by Oswald and Gotaas [8]. There are several important aspects to be considered during the current study. POME is the major source of water pollutant in Malaysia [13]. For example, in a conventional palm oil mill, 600–700 kg of POME is generated for every 1000 kg of processed fresh fruit bunches (FFB) [14]. By utilizing the ingredients present in POME, this study will play a major role to solve the pollution problem resulting from the POME as it will pollute the environment if it is improperly discharged into the environment.

#### **2. Palm oil mill effluent**

In particular, POME is a basic expression referring to the effluent from the last phases of palm oil manufacture in the mill. It incorporates different fluids, dirt, leftover oil and suspended solids. POME in its untreated shape is a high quality waste, relying upon the operation of the procedure. POME is generated mainly from oil extraction, washing and cleaning processes in the mill, and these contain cellulosic material, fat, oil and grease, and so on [15]. POME also contains substantial quantities of solids; both suspended solids and total dissolved solids in the range of 18,000 and 40,500 mg/L, respectively.

Oil palm is the most productive oil producing plant in the world, with 1 ha of oil palm producing between 10 and 35 tons of fresh fruit bunch (FFB) per year [15]. During processing of oil palm, more than 70% by weight of the fresh fruit brunch was left over as waste [16]. Usually, the harvested part is the fruit whereby oil is obtained from the fleshy mesocarp of the fruit. Despite the importance of the edible oil and fats extracted from the palm fruits, the POME contains residual oil which affects the environment cannot be ignored. Treatment and disposal of oily wastewater such as POME is presently one of the serious environmental problems. Palm oil mill wastes have existed for years but their effects on environment are at present more noticeable [15]. The oily waste has to be removed to prevent problems which are considered as hazardous pollutants particularly in the aquatic environments because they are highly toxic to the aquatic organisms. Discharging the effluents or by-products on the lands or release to the river may lead to pollution and might deteriorate the surrounding environment. In order to conserve the environment, an efficient management system in the treatment of these byproducts is needed [17]. Treatment of POME is essential to avoid environmental pollution [18].

POME wastes are the fiber free non-oil components obtained from the clarification zone of an oil mills. The significant contamination comes out of the fresh fruit brunch (FFB). In fact, every ton of FFB is composed of 230–250 kg of empty fruit bunches (EFB), 130–150 kg of fibers, 60–65 kg of shell and 55–60 kg of kernels and 160–200 kg of unrefined oil [19]. POME contains high amounts of oil and grease (4000 mg/L) and COD (50,000 mg/L). Although the effluent is nontoxic, it has a very high concentration of biochemical oxygen demand (BOD) (i.e., 25,000 mg/L) which becomes a serious threat to aquatic life when discharged in relatively large quantities into watercourses. The high amount of total solids (40,500 mg/L) contributes to the large amount of nutrients available in the wastewater, hence possible algae bloom.

Most palm oil mills in Malaysia have adopted the ponding system for the treatment of POME [20]. In general, there are four types of treatment systems adopted by the palm oil industry, which are as follows:

**a.** Waste stabilization ponds,

development, it has also contributed to environmental pollution due to the production of large quantities of by-products during the process of oil extraction [2, 3]. Furthermore, it is necessary to properly address the POME treatment so as not to contribute to human health

POME is the wastewater produced by processing oil palm and comprises of different suspended materials. POME is 100 times more polluted than the municipal sewage which has a high biochemical oxygen demand (BOD) and chemical oxygen demand (COD). The effluent also contains higher concentration of organic nitrogen, phosphorus and different supplement substance [4]. POME is a non-harmful waste; however, it will pose environmental issue because of vast oxygen draining capacity to oceanic framework because of natural and supplement substance. It is also known to be a good source of nutrients [5]. The waste products generated during palm oil processing consist of oil palm trunks (OPT), oil palm fronds (OPF), empty fruit bunches (EFB), palm pressed fibers (PPF) and palm kernel shells, less fibrous material such as palm kernel cake and liquid discharge POME [2]. The wastes are in the form of high organic matter concentration such as cellulosic wastes with a mixture of carbohydrates and oils. The discharge of untreated POME creates adverse impact to the environment [6].

Nowadays, biological process is the most common practice way for the treatment of POME based on anaerobic and aerobic ponding system [2]. While the emerging technologies for the treatment of POME, the notion of nurturing POME and its derivatives as valuable resources should not be dismissed. Furthermore, it is necessary to properly address the POME treatment so as not to contribute to human health hazards and environmental pollution. At the point when contrasted with those routine wastewater treatment processes which introduce activated sludge and living floc to degrade natural carbonaceous issue to CO2

and microalgae may acclimatize natural toxins into cell constituents, for example, lipid and carbohydrate, therefore attaining pollutant decrease in a more ecological friendly way [7]. Actually, microalgae have turned into the consideration for both wastewater treatment and biomass production as early as 1950s [8]. Small scale and economically viable technologies that combine wastewater treatment and energy production can treat the industrial effluents and enhance the availability of the energy simultaneously [9]. The feasible way that is more attentions in the present time is the use of microalgae, which is known to have the potential

uptake [12]. The idea of using microalgae in wastewater treatment has been investigated since 1950s by Oswald and Gotaas [8]. There are several important aspects to be considered during the current study. POME is the major source of water pollutant in Malaysia [13]. For example, in a conventional palm oil mill, 600–700 kg of POME is generated for every 1000 kg of processed fresh fruit bunches (FFB) [14]. By utilizing the ingredients present in POME, this study will play a major role to solve the pollution problem resulting from the POME as

In particular, POME is a basic expression referring to the effluent from the last phases of palm oil manufacture in the mill. It incorporates different fluids, dirt, leftover oil and suspended

it will pollute the environment if it is improperly discharged into the environment.

,

and NOx [11] and high capacity of nutrient

hazards and environmental pollution.

14 Palm Oil

to treat wastewater [10] such as removal of CO2

**2. Palm oil mill effluent**


The most proper secondary treatment for POME is natural assimilation with the blend of anaerobic and aerobic ponds. Right now, the management of POME has developed from treatment of waste for transfer to gainful use of assets. POME contains generous amounts of significant plant supplement that shift as indicated by the level of treatment to which it is subjected. The potential utilization of recovery of water and natural issues from POME has been applied for different applications [21]. Commercial trials and applications of these technologies are currently underway, especially conversion of the solid residual materials into saleable value-added products.

prosperous with regular assets. Oil palm as of now involves the biggest real acreage of cultivated land in Malaysia [30, 31]. The total oil palm acreage from 1970 to 2000 has expanded from 320 to 3338 ha. In the year 2003, there were more than 3.79 million ha of land under palm oil cultivation, occupying more than 33% of the total developed area and 11% of the total land area of Malaysia [32]. Palm oil, edible oil, is derived from the meaty mesocarp of the fruit of oil palm (*Elaeis guineensis*). One hectare of oil palm produces 10–35 tons of fresh fruit bunches (FFB) per year [2, 33]. Malaysia produces about 41% of the world's supply of palm oil as shown in **Figure 1**. Malaysia also accounts for the highest percentage of global vegetable oils

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811 17

The oil palm has the expectancy of over 200 years, whereas the economic life is about 20–25 years. The nursery period is 11–15 months for plants, and first harvest is done after 32–38 months of planting. It takes 5–10 years for palm oil plant to reach the highest yield. The yield is approximately 45–56% of FFB, and the fleshy mesocarp of the fruit is used to get oil. The yield of oil from the kernel is about 40–50% [35]. Both mesocarp and kernel of fruit produce about 17 t ha−1 yr−1 of oil [6]. Starting with 5.8 ton of FFB about 1 ton of crude palm oil

While the oil palm industry has been recognized for its contribution toward economic growth and rapid development, it has also contributed to environmental pollution due to the produc-

POME contains high content of degradable organic matter, which is due in part to the presence of uncovered palm oil [36]. The discharge of improperly treated POME creates adverse impact to the environment (**Table 2**). However, the substances in POME are able to support the growth of microalgae. Microalgae naturally exist in many palm oil mill processes, phenomena known as "algae bloom," hence declining the water quality. Because POME consists of large amount of organic compounds and inorganic compounds which is hazardous to environmental health, microalgae have been suggested as a potential candidate to remove these

(CPO) is produced [2]. The world palm oil production is shown in **Table 1**.

tion of huge quantities of by-products from the oil extraction process [2].

pollutants and able to breakdown the organic compounds present in it [37, 38].

**2.4. Characteristic of POME and utilization by microalgae**

and fats trade in the year 2005 [34].

**Figure 1.** Palm oil production in 2007 [6].

#### **2.1. Malaysian palm oil industry**

In 2011, Malaysia was the second biggest oil palm producer in the world, with an aggregate of 16.6 million tons, a sum lesser than 1% from the total world's supply behind Indonesia. Since the oil palm industry is tremendous, with 67% of agricultural land secured with oil palm tree, biomass from oil palm contributes the most. As of now, 85.5% of the biomass residues are originating from the oil palm industry. Palm oil has a very good potential in producing alternative energy due to its calorific content. With 50% efficiency, biomass from oil palm can generate 8 Mton of energy and can save RM 7.5 billion per year of crude oil [14, 19]. More than 85% of palm oil mills in Malaysia have adopted ponding system for treating POME [20], while the rest have opted for open digesting tank [22]. These methods are regarded as conventional POME treatment method, whereby longer retention time and large treatment areas are required [23]. The effluent that comes out from palm oil mill is hazardous to the ecosystem due to its high-volume composition and nutrient. The discharge can lead to land and aquatic pollution if it is left untreated [24].

In view of the measurement estimation of aggregate unrefined palm oil generation in May 2001, the production of 985,063 ton of crude palm oil means, a total of 1,477,595 m<sup>3</sup> of water is being used, and likewise, 738,797 m<sup>3</sup> POME is discharged for a month. Without appropriate treatment, this wastewater will contaminate the encompassing surrounding. The present treatment technology of POME normally comprises of natural aerobic and anaerobic digestion. Biologically treated effluent is disposed via land provision system, hence providing vital supplements for growing plants. This system might be a decent decision for the disposal of treated effluent. However, acknowledging those rates of daily wastewater generation, for instance, around 26 m<sup>3</sup> /d for an average palm oil mill with an operating limit of 35 t/d FFB, it is doubtful that the surrounding plantations receiving it might effectively absorb all the treated effluent [25].

#### **2.2. Palm oil management**

Around 44 million m<sup>3</sup> of POME were produced in year 2013 to yield 19.66 million tons of total crude palm oil [14]. Around 85% of palm oil mills have treated raw POME using biological treatment [26]. The biological treatment of POME is a series of pond systems, including anaerobic, facultative and aerobic pond systems [19, 27]. However, the final treatment by aerobic pond system is struggling to achieve the discharge standards because of inefficient operational design [3]. The final effluent of the treated POME must comply with the discharge standards set by the Department of Environment (DOE), Malaysia. There is a requirement for a sound and effective management system in the treatment of these by-products in such a way that will assist to protect the environment and check the deterioration of air and river water quality. Treatment of POME is vital to avoid environmental contamination [28].

#### **2.3. Current state of POME treatment**

Indonesia and Malaysia are the two biggest oil palm manufacturing nations and is rich in various endemic and forest dwelling species [29]. Malaysia has a tropical atmosphere and is prosperous with regular assets. Oil palm as of now involves the biggest real acreage of cultivated land in Malaysia [30, 31]. The total oil palm acreage from 1970 to 2000 has expanded from 320 to 3338 ha. In the year 2003, there were more than 3.79 million ha of land under palm oil cultivation, occupying more than 33% of the total developed area and 11% of the total land area of Malaysia [32]. Palm oil, edible oil, is derived from the meaty mesocarp of the fruit of oil palm (*Elaeis guineensis*). One hectare of oil palm produces 10–35 tons of fresh fruit bunches (FFB) per year [2, 33]. Malaysia produces about 41% of the world's supply of palm oil as shown in **Figure 1**. Malaysia also accounts for the highest percentage of global vegetable oils and fats trade in the year 2005 [34].

The oil palm has the expectancy of over 200 years, whereas the economic life is about 20–25 years. The nursery period is 11–15 months for plants, and first harvest is done after 32–38 months of planting. It takes 5–10 years for palm oil plant to reach the highest yield. The yield is approximately 45–56% of FFB, and the fleshy mesocarp of the fruit is used to get oil. The yield of oil from the kernel is about 40–50% [35]. Both mesocarp and kernel of fruit produce about 17 t ha−1 yr−1 of oil [6]. Starting with 5.8 ton of FFB about 1 ton of crude palm oil (CPO) is produced [2]. The world palm oil production is shown in **Table 1**.

While the oil palm industry has been recognized for its contribution toward economic growth and rapid development, it has also contributed to environmental pollution due to the production of huge quantities of by-products from the oil extraction process [2].

#### **2.4. Characteristic of POME and utilization by microalgae**

technologies are currently underway, especially conversion of the solid residual materials

In 2011, Malaysia was the second biggest oil palm producer in the world, with an aggregate of 16.6 million tons, a sum lesser than 1% from the total world's supply behind Indonesia. Since the oil palm industry is tremendous, with 67% of agricultural land secured with oil palm tree, biomass from oil palm contributes the most. As of now, 85.5% of the biomass residues are originating from the oil palm industry. Palm oil has a very good potential in producing alternative energy due to its calorific content. With 50% efficiency, biomass from oil palm can generate 8 Mton of energy and can save RM 7.5 billion per year of crude oil [14, 19]. More than 85% of palm oil mills in Malaysia have adopted ponding system for treating POME [20], while the rest have opted for open digesting tank [22]. These methods are regarded as conventional POME treatment method, whereby longer retention time and large treatment areas are required [23]. The effluent that comes out from palm oil mill is hazardous to the ecosystem due to its high-volume composition and nutrient. The discharge can lead to land and aquatic

In view of the measurement estimation of aggregate unrefined palm oil generation in May 2001,

this wastewater will contaminate the encompassing surrounding. The present treatment technology of POME normally comprises of natural aerobic and anaerobic digestion. Biologically treated effluent is disposed via land provision system, hence providing vital supplements for growing plants. This system might be a decent decision for the disposal of treated effluent. However, acknowledging those rates of daily wastewater generation, for instance, around

/d for an average palm oil mill with an operating limit of 35 t/d FFB, it is doubtful that the

surrounding plantations receiving it might effectively absorb all the treated effluent [25].

quality. Treatment of POME is vital to avoid environmental contamination [28].

total crude palm oil [14]. Around 85% of palm oil mills have treated raw POME using biological treatment [26]. The biological treatment of POME is a series of pond systems, including anaerobic, facultative and aerobic pond systems [19, 27]. However, the final treatment by aerobic pond system is struggling to achieve the discharge standards because of inefficient operational design [3]. The final effluent of the treated POME must comply with the discharge standards set by the Department of Environment (DOE), Malaysia. There is a requirement for a sound and effective management system in the treatment of these by-products in such a way that will assist to protect the environment and check the deterioration of air and river water

Indonesia and Malaysia are the two biggest oil palm manufacturing nations and is rich in various endemic and forest dwelling species [29]. Malaysia has a tropical atmosphere and is

POME is discharged for a month. Without appropriate treatment,

of POME were produced in year 2013 to yield 19.66 million tons of

of water is being

the production of 985,063 ton of crude palm oil means, a total of 1,477,595 m<sup>3</sup>

into saleable value-added products.

**2.1. Malaysian palm oil industry**

16 Palm Oil

pollution if it is left untreated [24].

used, and likewise, 738,797 m<sup>3</sup>

**2.2. Palm oil management**

**2.3. Current state of POME treatment**

Around 44 million m<sup>3</sup>

26 m<sup>3</sup>

POME contains high content of degradable organic matter, which is due in part to the presence of uncovered palm oil [36]. The discharge of improperly treated POME creates adverse impact to the environment (**Table 2**). However, the substances in POME are able to support the growth of microalgae. Microalgae naturally exist in many palm oil mill processes, phenomena known as "algae bloom," hence declining the water quality. Because POME consists of large amount of organic compounds and inorganic compounds which is hazardous to environmental health, microalgae have been suggested as a potential candidate to remove these pollutants and able to breakdown the organic compounds present in it [37, 38].

**Figure 1.** Palm oil production in 2007 [6].


of 18,000–47,000 mg/L. POME also has very high BOD and COD contents which are in the range 25,000–54,000 mg/L and 50,000–100,000 mg/L, respectively [45]. POME while fresh is hot acidic and pH range between 4 and 5, brownish colloidal suspension containing high concentrations of natural matter, high quantities of total solids (40,500 mg/L), oil and grease (4000 mg/L) COD (50,000 mg/L) and BOD (25,000 mg/L) [15]. However, it also contains appreciable amounts of N, P, K, Mg and Ca which are the vital nutrient elements for plant growth [46]. The characteristic of POME based on Malaysian Palm Oil Board is shown in **Table 3**.

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811 19

According to Kamyab et al. [46], the raw or partially treated POME has an extremely high content of degradable organic matter. However, it has nontoxic nature and has fertilizing properties, POME can be used as fertilizer or animal feed substitute, in terms of providing sufficient mineral requirements. The Malaysian government provides an effort to reduce the effluent of palm oil through licensing system, which mainly consists of effluent standards and effluent charges. According to POME characteristic and standard discharge limit in Environmental Quality Act (EQA) 1974, the palm oil industry faces the challenge of balancing the environmental protection, its economic viability and sustainable development. The year 1978 witnessed the enactment of the Environmental Quality Regulations detailing POME discharge standards. **Table 4** shows the palm oil mill effluent discharge standard that

Normally, the characteristics of POME may vary considerably for different batches, days and factories, depending on the processing techniques and the age or type of fruit as well as the discharge limit of the factory, climate and condition of the palm oil processing [19]. Occasional oil palm cropping and activities of the palm oil will also impact those quality and quantity of the discharged POME, thus influence the ecological treatment procedure of POME [27]. Hence, the variation of the characteristics of POME, in terms of its quality and quantity, is the main reason that causes selection in the treatment of POME in the palm oil

**Parameter Mean Range** pH 4.2 3.4–5.2 Biological oxygen demand 25,000 10,250–43,750 Chemical oxygen demand 51,000 15,000–100,000 Total solids 40,000 11,500–79,000 Suspended solids 18,000 5000–54,000 Volatile solids 34,000 9000–72,000 Oil and grease 6000 130–18,000 Ammoniacal nitrogen 35 4–80 Total nitrogen 750 180–1400

must be followed.

industries [1, 47].

\*Units in mg/L except pH.

**Table 3.** Characteristics of POME [14].

**Table 1.** World palm oil production [2].


**Table 2.** Characteristics of POME and its respective standard discharge limit by the Malaysian Department of Environment [19, 20].

Alternatively, culturing microalgae in wastewater offers an economy, which is alternative to the traditional types of wastewater treatment [39, 40]. In the meantime, microalgae can apply the nitrogen and phosphorus compound in wastewater to produce microalgae biomass for various kinds of lipid generation, which can serve as a substrate for biofuel production [38, 41].

POME is a colloidal suspension, starting from the blend of sterilizer condensate, separator sludge and hydrocyclone wastewater in a proportion of 9:15:1, respectively [1]. In total, about 2.5–3.0 tons of POME for huge amounts of produced crude palm oil is obtained in the extraction procedure [42]. Fresh POME is a thick brownish colloidal blend of water, oil and fine-suspended solids. It is hot (80–900°C) and has a high BOD, which is 100 times as contaminating as domestic sewage [1]. The effluent is not hazardous, as no chemicals are added to the extraction procedure [43], and also acidic with a pH around 4.5 as it contains organic acids in complex forms that are suitable to be used as carbon sources [44]. Palm oil mill effluent is a high-strength pollutant with low pH due to the organic and free fatty acids arising from partial degradation of palm fruits before processing. The characteristics of POME depend on the quality of the raw material and the production processes [24]. It typically contains large amounts of total solids (40,500–75,000 mg/L) and oil and grease (2000–8300 mg/L). Its total nitrogen in the range of 400–800 mg/L and suspended solids contents in the range of 18,000–47,000 mg/L. POME also has very high BOD and COD contents which are in the range 25,000–54,000 mg/L and 50,000–100,000 mg/L, respectively [45]. POME while fresh is hot acidic and pH range between 4 and 5, brownish colloidal suspension containing high concentrations of natural matter, high quantities of total solids (40,500 mg/L), oil and grease (4000 mg/L) COD (50,000 mg/L) and BOD (25,000 mg/L) [15]. However, it also contains appreciable amounts of N, P, K, Mg and Ca which are the vital nutrient elements for plant growth [46]. The characteristic of POME based on Malaysian Palm Oil Board is shown in **Table 3**.

According to Kamyab et al. [46], the raw or partially treated POME has an extremely high content of degradable organic matter. However, it has nontoxic nature and has fertilizing properties, POME can be used as fertilizer or animal feed substitute, in terms of providing sufficient mineral requirements. The Malaysian government provides an effort to reduce the effluent of palm oil through licensing system, which mainly consists of effluent standards and effluent charges. According to POME characteristic and standard discharge limit in Environmental Quality Act (EQA) 1974, the palm oil industry faces the challenge of balancing the environmental protection, its economic viability and sustainable development. The year 1978 witnessed the enactment of the Environmental Quality Regulations detailing POME discharge standards. **Table 4** shows the palm oil mill effluent discharge standard that must be followed.

Normally, the characteristics of POME may vary considerably for different batches, days and factories, depending on the processing techniques and the age or type of fruit as well as the discharge limit of the factory, climate and condition of the palm oil processing [19]. Occasional oil palm cropping and activities of the palm oil will also impact those quality and quantity of the discharged POME, thus influence the ecological treatment procedure of POME [27]. Hence, the variation of the characteristics of POME, in terms of its quality and quantity, is the main reason that causes selection in the treatment of POME in the palm oil industries [1, 47].


**Table 3.** Characteristics of POME [14].

Alternatively, culturing microalgae in wastewater offers an economy, which is alternative to the traditional types of wastewater treatment [39, 40]. In the meantime, microalgae can apply the nitrogen and phosphorus compound in wastewater to produce microalgae biomass for various kinds of lipid generation, which can serve as a substrate for biofuel production [38, 41]. POME is a colloidal suspension, starting from the blend of sterilizer condensate, separator sludge and hydrocyclone wastewater in a proportion of 9:15:1, respectively [1]. In total, about 2.5–3.0 tons of POME for huge amounts of produced crude palm oil is obtained in the extraction procedure [42]. Fresh POME is a thick brownish colloidal blend of water, oil and fine-suspended solids. It is hot (80–900°C) and has a high BOD, which is 100 times as contaminating as domestic sewage [1]. The effluent is not hazardous, as no chemicals are added to the extraction procedure [43], and also acidic with a pH around 4.5 as it contains organic acids in complex forms that are suitable to be used as carbon sources [44]. Palm oil mill effluent is a high-strength pollutant with low pH due to the organic and free fatty acids arising from partial degradation of palm fruits before processing. The characteristics of POME depend on the quality of the raw material and the production processes [24]. It typically contains large amounts of total solids (40,500–75,000 mg/L) and oil and grease (2000–8300 mg/L). Its total nitrogen in the range of 400–800 mg/L and suspended solids contents in the range

**Table 2.** Characteristics of POME and its respective standard discharge limit by the Malaysian Department of

**Parameters Concentration (mg/L) Standard limit (mg/L)**

pH 4.7 5–9 Oil and grease 4000 50 BOD 25,000 100 COD 50,000 — Total solids 40,500 — Suspended solids 18,000 400 Total nitrogen 750 150

**Country Share (%) Amount (tons)**

Indonesia 44 19,000 Malaysia 41 17,350 Thailand 3 1123 Nigeria 2 850 Colombia 2 832 Others 8 832

Environment [19, 20].

**Table 1.** World palm oil production [2].

18 Palm Oil


Utilizing POME as supplements source to culture microalgae is not an another scenario in Malaysia. Most palm oil millers favor the culture of microalgae as a tertiary treatment before POME is released because of practically low cost and high impact. Consequently, vast majority of the nutrients such as nitrate and ortho-phosphates that are not detached during anaerobic digestion will be additionally treated in a microalgae pond. Thus, the cultured microalgae will be used as a food nutrition for live feed culture [50] Meanwhile, nitrogen source (usually

Temperature: 24–26°C

Light intensity 3000 lx

Light intensity of 150 μmol m−2 s−1

*Chlorella* sp. 1 L glass flask disk [4]

Mixing using aeration aquarium air pump

Mixing using aeration aquarium air pump

Light intensity, 4000–6000 lx

1 L glass flask disk [57]

Room temperature [58] Light intensity-continuous illumination at intensity of

5 L HPBR reactor with turbine impeller [46]

250 mL Erlenmeyer flask [38]

Light intensity, illuminated by four 32 W white fluorescence light continuous lighting (24 h) (Philip,

Mixing 60 rpm Lighting 8 h:16 h L:D

pH 6.5–7.5

pH 6.8–7.2, Temperature 28°C

pH 9–10.5

±15 μmol m−2 s−1

Temperature, 30°C

OLR, 36 kg COD m−3 d−1

OLR, 36 kg COD m−3 d−1

Light intensity, 15 μmol m−2 s−1

Temperature, 30°C

Germany) C:N, 100:6

C:N, 100:7

**Microalgae Growth condition References**

3 L PBR system [56]

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811 21

**Source of POME/ concentration**

with no dilution

POME collected from pond

Fresh POME with dilution 50% + 1 g/L urea

POME from anaerobic pond

POME collected from pond with concentration 250 mg

POME collected from pond with concentration 250 mg

POME collected from pond with concentration 250 mg

with 40% dilution

COD/L

COD/L

COD/L

*Chlorella pyrenoidosa*

*Spirulina platensis*

*Chlorella sorokiniana*

*Chlorella pyrenoidosa*

*Chlamydomonas incerta*

**Table 4.** Environmental quality [14, 42].

#### **2.5. Wastewater treatment technology**

The wastewater treatment technologies are expensive, dependent on skilled personnel and hard to carry out, as the volume of contaminated wastewater is huge [38]. Furthermore, the common conventional treatment is unable to meet the regulations set by the Department of Environment (DOE) with the level of BOD at 100 mg/L. According to Ahmad et al. [19], large quantities of water are used during the extraction of crude palm oil from the fresh fruit bunch, and about 50% of the water results in POME. The disposal of this very contaminating effluent is turning into a noteworthy issue assuming that it may be not continuously treated appropriately as well as a severe standard boundary obligatory set by the Malaysian Department of Environment for the discharge of effluent. A POME treatment system based on membrane technology shows high potential for decreasing the ecological issue, and also, this alternative treatment system offers water reusing [19].

The utilization of wastewater for the microalgal growth is considered beneficial for limiting the utilization of freshwater, dropping the cost of supplement option, expelling nitrogen and phosphorus from wastewater and generating microalgal biomass as bioresources for biofuel or value-added by-products. Three primary sources of wastewater are municipal (domestic), agricultural and industrial wastewater which included a variety of elements. Some elements in the wastewater, such as nitrogen and phosphorus, are valuable components for microalgal cultures [48].

#### **2.6. POME as nutrients source to culture microalgae**

A life cycle assessment on microalgae cultivation has underlined that 50% of energy use and greenhouse gas emissions are associated with fertilizer (nutrients) [49]. In general, culturing of microalgae on a large scale required high nitrogen and other related chemical fertilizers, which driven the process toward non-environmental friendly. On the other hand, culturing microalgae can actually play an important role as a self-purification process of natural wastewaters [50].

Utilizing POME as supplements source to culture microalgae is not an another scenario in Malaysia. Most palm oil millers favor the culture of microalgae as a tertiary treatment before POME is released because of practically low cost and high impact. Consequently, vast majority of the nutrients such as nitrate and ortho-phosphates that are not detached during anaerobic digestion will be additionally treated in a microalgae pond. Thus, the cultured microalgae will be used as a food nutrition for live feed culture [50] Meanwhile, nitrogen source (usually


**2.5. Wastewater treatment technology**

\*Units in mg/L except pH and temperature.

**Table 4.** Environmental quality [14, 42].

**Palm oil mill effluent discharge standards**

20 Palm Oil

**1/7/78– 30/6/79** **1/7/79– 30/6/80**

pH 5–9 5–9 5–9 5–9 5–9 5–9 BOD 5000 2000 1000 500 250 100 COD 10,000 4000 2000 1000 — — Total solids 4000 2500 2000 1500 — — Suspended solids 1200 800 600 400 400 400 Oil and grease 150 100 75 50 50 50 Ammoniacal nitrogen 25 15 15 10 150 100 Total nitrogen 200 100 75 50 — — Temperature °C 45 45 45 45 45 45

**1/7/80– 30/6/81** **1/7/81– 30/6/82** **1/7/82– 31/12/83** **1/1/84–there after**

treatment system offers water reusing [19].

**2.6. POME as nutrients source to culture microalgae**

cultures [48].

The wastewater treatment technologies are expensive, dependent on skilled personnel and hard to carry out, as the volume of contaminated wastewater is huge [38]. Furthermore, the common conventional treatment is unable to meet the regulations set by the Department of Environment (DOE) with the level of BOD at 100 mg/L. According to Ahmad et al. [19], large quantities of water are used during the extraction of crude palm oil from the fresh fruit bunch, and about 50% of the water results in POME. The disposal of this very contaminating effluent is turning into a noteworthy issue assuming that it may be not continuously treated appropriately as well as a severe standard boundary obligatory set by the Malaysian Department of Environment for the discharge of effluent. A POME treatment system based on membrane technology shows high potential for decreasing the ecological issue, and also, this alternative

The utilization of wastewater for the microalgal growth is considered beneficial for limiting the utilization of freshwater, dropping the cost of supplement option, expelling nitrogen and phosphorus from wastewater and generating microalgal biomass as bioresources for biofuel or value-added by-products. Three primary sources of wastewater are municipal (domestic), agricultural and industrial wastewater which included a variety of elements. Some elements in the wastewater, such as nitrogen and phosphorus, are valuable components for microalgal

A life cycle assessment on microalgae cultivation has underlined that 50% of energy use and greenhouse gas emissions are associated with fertilizer (nutrients) [49]. In general, culturing of microalgae on a large scale required high nitrogen and other related chemical fertilizers, which driven the process toward non-environmental friendly. On the other hand, culturing microalgae can actually play an important role as a self-purification process of natural wastewaters [50].


**Table 5.** Growth conditions for microalgae using POME.

appears in nitrate form) plays an important role in promoting microalgae growth. In order to grow microalgae effectively, the basic nitrate concentration required is in the range of 200– 400 mg/L [51]. Others minerals such as Fe, Zn, P, Mg, Ca and K that are required for microalgae growth are also present in POME. Thus, POME emerged to be an alternative option as a chemical remediation to grow microalgae for biomass production and simultaneously act as a part of wastewater treatment process [50].

Numerous species of microalgae exist in freshwater, seawater or brackish make them appropriate to be grown in great scale reactor on unfertile lands. The usage of macroalgae and micro-

**Growth rate (d−1)**

*C. pyrenoidosa* — 42 — 2.19 18 [56] *Chlorella* sp. — — 0.066 0.058 15 [57] *S. platensis* — — — 9.8 13 [57] *C. sorokiniana* — 28.27 0.099 8.0 20 [58] *C. pyrenoidosa* COD, 71.16% 68 1.8 0.13 10 [28] *Chlorella* sp. — — — 1.562 7 [59] *A. platensis* — — — 0.211 7 [60]

**Biomass** 

**productivity (g/L/d)**

resources, lagoons and ponds is called as phycoremediation [55]. This biological remediative treatment was introduced about 40 years ago when it was usually used in tertiary wastewater treatment [61]. The performance of microalgae growth cultivated in POME is shown in **Table 6**. As seen from **Table 6**, Kamyab et al. [28] have done their studies by focusing on the nutrients reduction in POME, lipid production and microalgae growth. Meanwhile, it can be found that other researchers have not focused much on nutrient reduction, which is to be considered

Malaysia is the biggest generator and exporter of palm oil. Palm oil processing is achieved in palm oil mills where oil is removed from a palm oil fruit bunch. Expansive amounts of water are utilized throughout the extraction of crude palm oil from the fresh fruit bunch, and around half of the water consequences in POME, which is a highly polluting wastewater that pollutes the environment if discharged directly due to its high COD and BOD concentration. In conclusion, the research was carried out mainly to investigate the influence of discharging POME from the treatment plant especially in tropical region like Malaysia and the effect on microalgae growth efficiency in POME. In other words, a combination of wastewater treatment and renewable bioenergies production would be an added advantage to the palm oil industry.

The authors would like to acknowledge IPASA, RAZAK School and MJIT in Universiti Teknologi Malaysia (UTM) for providing adequate facilities to conduct this research. The first author is a researcher of Universiti Teknologi Malaysia (UTM) under the Post-Doctoral

present in natural water

**Duration (d)**

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811

**Ref.**

23

algae in the utilization or remediation of the excess nutrients and CO2

**Lipid production (%)**

more important in relation to the growth of microalgae.

**3. Conclusion**

**Microalgae Nutrient** 

**Table 6.** Microalgae growth in POME.

**reduction (%)**

**Acknowledgements**

These days, there is an incredible and nonstop increment in industrialization, foundation and urban expansion in Asia, which has added to the critical wastes demand and water deficiency because of water contamination [52]. Industry in particular agro-based industry is one of the significant divisions releasing extensive amount of wastewater yearly influencing the other water sources and human life. The palm oil industry in Malaysia is generating the biggest amount of natural contamination loads into rivers [30, 33]. POME is a highly polluted waste having unpleasant odor. There is a greater need to find alternative way to utilize these organic pollutants for the good benefit of both human beings and the environment [21]. Microalgae cultivation in POME offers an alternative to conventional forms of tertiary wastewater treatments and spontaneously utilizes organic compounds present in POME to generate microalgae biomass for algae oil production [50]. There are several environmental and operational factors, which can affect the microalgae growth in order to make the cultivation fruitful. The natural effluent discarded from palm oil mill might be colloidal, dark and viscous, which should be considered prior media preparation for culturing the microalgae [53]. Vairappan and Yen [54] had found that for the marine *Isochrysis* sp., the concentration of POME at 5% dilution is the best concentration for culture media due to properties of POME. This dilution procedure will then enhance the light penetration into media for the algal growth in wastewater [55]. As described in **Table 5**, limited growth conditions are required for the growth of microalgae using palm oil mill effluent.

The concentrated nutrients (i.e., C, N, P, carbohydrate, lipid, protein and minerals) in POME are highly applied in biotechnology studies for growing microalgae [46]. The concentration extend about POME in various accepting water body may give high effect on the aquatic environments if the release surpasses the limit of standards set by Malaysia Environmental Quality Act.


**Table 6.** Microalgae growth in POME.

Numerous species of microalgae exist in freshwater, seawater or brackish make them appropriate to be grown in great scale reactor on unfertile lands. The usage of macroalgae and microalgae in the utilization or remediation of the excess nutrients and CO2 present in natural water resources, lagoons and ponds is called as phycoremediation [55]. This biological remediative treatment was introduced about 40 years ago when it was usually used in tertiary wastewater treatment [61]. The performance of microalgae growth cultivated in POME is shown in **Table 6**.

As seen from **Table 6**, Kamyab et al. [28] have done their studies by focusing on the nutrients reduction in POME, lipid production and microalgae growth. Meanwhile, it can be found that other researchers have not focused much on nutrient reduction, which is to be considered more important in relation to the growth of microalgae.

## **3. Conclusion**

appears in nitrate form) plays an important role in promoting microalgae growth. In order to grow microalgae effectively, the basic nitrate concentration required is in the range of 200– 400 mg/L [51]. Others minerals such as Fe, Zn, P, Mg, Ca and K that are required for microalgae growth are also present in POME. Thus, POME emerged to be an alternative option as a chemical remediation to grow microalgae for biomass production and simultaneously act as

CO2

CO2

Outdoor

*Arthrospira platensis*

**Microalgae Growth condition References**

Pressure regulators bring down the pressure of both

 and compressed air to 2 bars before entering their flow meters. The sparging tube of a flask culture

10 L of culture media in 20 L tank [60]

*Chlorella* sp. 1 L conical flask [59]

was placed at the bottom of the flask

 concentration (% v/v), 16% Sparging rate (vvm), 0.8 vvm

Light intensity, 10,000 lx

These days, there is an incredible and nonstop increment in industrialization, foundation and urban expansion in Asia, which has added to the critical wastes demand and water deficiency because of water contamination [52]. Industry in particular agro-based industry is one of the significant divisions releasing extensive amount of wastewater yearly influencing the other water sources and human life. The palm oil industry in Malaysia is generating the biggest amount of natural contamination loads into rivers [30, 33]. POME is a highly polluted waste having unpleasant odor. There is a greater need to find alternative way to utilize these organic pollutants for the good benefit of both human beings and the environment [21]. Microalgae cultivation in POME offers an alternative to conventional forms of tertiary wastewater treatments and spontaneously utilizes organic compounds present in POME to generate microalgae biomass for algae oil production [50]. There are several environmental and operational factors, which can affect the microalgae growth in order to make the cultivation fruitful. The natural effluent discarded from palm oil mill might be colloidal, dark and viscous, which should be considered prior media preparation for culturing the microalgae [53]. Vairappan and Yen [54] had found that for the marine *Isochrysis* sp., the concentration of POME at 5% dilution is the best concentration for culture media due to properties of POME. This dilution procedure will then enhance the light penetration into media for the algal growth in wastewater [55]. As described in **Table 5**, limited growth conditions are required for the growth of microalgae using palm oil mill effluent.

The concentrated nutrients (i.e., C, N, P, carbohydrate, lipid, protein and minerals) in POME are highly applied in biotechnology studies for growing microalgae [46]. The concentration extend about POME in various accepting water body may give high effect on the aquatic environments if the release surpasses the limit of standards set by Malaysia Environmental Quality Act.

a part of wastewater treatment process [50].

**Table 5.** Growth conditions for microalgae using POME.

**Source of POME/ concentration**

22 Palm Oil

deionized water

Fresh POME with dilution of 500 mL of POME in 400 mL

Fresh POME with dilution

of 1%

Malaysia is the biggest generator and exporter of palm oil. Palm oil processing is achieved in palm oil mills where oil is removed from a palm oil fruit bunch. Expansive amounts of water are utilized throughout the extraction of crude palm oil from the fresh fruit bunch, and around half of the water consequences in POME, which is a highly polluting wastewater that pollutes the environment if discharged directly due to its high COD and BOD concentration. In conclusion, the research was carried out mainly to investigate the influence of discharging POME from the treatment plant especially in tropical region like Malaysia and the effect on microalgae growth efficiency in POME. In other words, a combination of wastewater treatment and renewable bioenergies production would be an added advantage to the palm oil industry.

## **Acknowledgements**

The authors would like to acknowledge IPASA, RAZAK School and MJIT in Universiti Teknologi Malaysia (UTM) for providing adequate facilities to conduct this research. The first author is a researcher of Universiti Teknologi Malaysia (UTM) under the Post-Doctoral Fellowship Scheme (PDRU Grant) for the project: "Enhancing the Lipid Growth in Algae Cultivation for Biodiesel Production" (Vot No. Q.J130000.21A2.03E95).

[5] Kamyab H, Tin Lee C, Md Din MF, Ponraj M, Mohamad SE, Sohrabi M. Effects of nitrogen source on enhancing growth conditions of green algae to produce higher lipid.

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811 25

[6] Abdul Aziz H. Reactive extraction of sugars from oil palm empty fruit bunch hydrolysate using Naphthalene-2-Boronic acid [Doctoral dissertation]. Universiti Sains

[7] de Andrade GA, Berenguel M, Guzmán JL, Pagano DJ, Acién FG. Optimization of biomass production in outdoor tubular photobioreactors. Journal of Process Control.

[8] Oswald WJ, Gotaas HB. Photosynthesis in sewage treatment. Transactions of the

[9] Lansing S, Botero RB, Martin JF. Waste treatment and biogas quality in small-scale agri-

[10] Tarlan E, Dilek FB, Yetis U. Effectiveness of algae in the treatment of a wood-based pulp

[11] Jin HF, Santiago DE, Park J, Lee K. Enhancement of nitric oxide solubility using Fe (II) EDTA and its removal by green algae Scenedesmus sp. Biotechnology and Bioprocess

[12] Park KC, Whitney CGE, Kozera C, O'Leary SJB, McGinn PJ. Seasonal isolation of microalgae from municipal wastewater for remediation and biofuel applications. Journal of

[13] Kamarudin KF, Tao DG, Yaakob Z, Takriff MS, Rahaman MSA, Salihon J. A review on wastewater treatment and microalgal by-product production with a prospect of palm oil

mill effluent (POME) utilization for algae. Der Pharma Chemica. 2015;**7**(7):73-89

[15] Bala JD, Lalung J, Ismail N. Palm oil mill effluent (POME) treatment "microbial communities in an anaerobic digester": A review. International Journal of Scientific and

[16] Chavalparit O, Rulkens WH, Mol APJ, Khaodhair S. Options for environmental sustainability of the crude palm oil industry in Thailand through enhancement of industrial

[17] Kamyab H, Fadhil M, Lee C, Ponraj M, Soltani M, Eva S. Micro-macro algal mixture as a promising agent for treating POME discharge and its potential use as animal feed stock

[18] Kamyab H, Md Din MF, Ponraj M, Keyvanfar A, Rezania S, Taib SM, Abd Majid MZ. Isolation and screening of microalgae from agro-industrial wastewater (POME) for biomass and biodiesel sources. Desalination and Water Treatment. 2016;**57**(60):

ecosystems. Environment, Development and Sustainability. 2006;**8**(2):271-287

[14] Malaysian Palm Oil Board (MPOB). 2012. http://www.mpob.gov.my/

Desalination and Water Treatment. 2014;**52**(19-21):3579-3584

American Society of Civil Engineers. 1957;**122**:73-75

cultural digesters. Bioresource Technology. 2008;**99**:5881-5890

and paper industry wastewater. Bioresource Technology. 2002;**84**:1-5

Malaysia; 2007

2016;**37**:58-69

Engineering. 2008;**13**(1):48-52

Applied Microbiology.2015;**119**(1):76-87

Research Publications. 2014;**4**:1-23

enhancer. Jurnal Teknologi. 2014;**5**:1-4

29118-29125

## **Conflict of interest**

The authors declare that there is no conflict of interest.

## **Author details**

Hesam Kamyab1,2\*, Shreeshivadasan Chelliapan1 , Mohd Fadhil Md Din<sup>3</sup> , Shahabaldin Rezania<sup>1</sup> , Tayebeh Khademi<sup>4</sup> and Ashok Kumar5

\*Address all correspondence to: hesam\_kamyab@yahoo.com

1 Department of Engineering, UTM Razak School of Engineering and Advanced Technology, Universiti Teknologi Malaysia, Kuala Lumpur, Malaysia

2 Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, IL, USA

3 Centre for Environmental Sustainability and Water (IPASA), Department of Environmental Engineering, Faculty of Civil Engineering, Universiti Teknologi Malaysia, Johor, Malaysia

4 Faculty of Management, Universiti Teknologi Malaysia, Johor, Malaysia

5 Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan, India

## **References**


[5] Kamyab H, Tin Lee C, Md Din MF, Ponraj M, Mohamad SE, Sohrabi M. Effects of nitrogen source on enhancing growth conditions of green algae to produce higher lipid. Desalination and Water Treatment. 2014;**52**(19-21):3579-3584

Fellowship Scheme (PDRU Grant) for the project: "Enhancing the Lipid Growth in Algae

, Mohd Fadhil Md Din<sup>3</sup>

and Ashok Kumar5

1 Department of Engineering, UTM Razak School of Engineering and Advanced Technology,

2 Department of Mechanical and Industrial Engineering, University of Illinois at Chicago,

5 Department of Biotechnology and Bioinformatics, Jaypee University of Information

4 Faculty of Management, Universiti Teknologi Malaysia, Johor, Malaysia

3 Centre for Environmental Sustainability and Water (IPASA), Department of Environmental Engineering, Faculty of Civil Engineering, Universiti Teknologi Malaysia, Johor, Malaysia

[1] Wu TY, Mohammad AW, Jahim JM, Anuar N. A holistic approach to managing palm oil mill effluent (POME): Biotechnological advances in the sustainable reuse of POME.

[2] Singh RP, Ibrahim MH, Esa N, Iliyana MS. Composting of waste from palm oil mill: A sustainable waste management practice. Reviews in Environmental Science and Bio/

[3] Parthasarathy S, Mohammed RR, Fong CM, Gomes RL, Manickam S. A novel hybrid approach of activated carbon and ultrasound cavitation for the intensification of palm oil mill effluent (POME) polishing. Journal of Cleaner Production. 2016;**112**:1218-1226 [4] Hadiyanto MC, Soetrisnanto D. Phytoremecliations of palm oil mill effluent (POME) by using aquatic plants and microalge for biomass production. Journal of Environmental

,

Cultivation for Biodiesel Production" (Vot No. Q.J130000.21A2.03E95).

The authors declare that there is no conflict of interest.

Hesam Kamyab1,2\*, Shreeshivadasan Chelliapan1

, Tayebeh Khademi<sup>4</sup>

\*Address all correspondence to: hesam\_kamyab@yahoo.com

Universiti Teknologi Malaysia, Kuala Lumpur, Malaysia

**Conflict of interest**

24 Palm Oil

**Author details**

Shahabaldin Rezania<sup>1</sup>

Chicago, IL, USA

**References**

Technology, Waknaghat, Solan, India

Biotechnology Advances. 2009;**27**(1):40-52

Science and Technology. 2013;**6**(2):79-90

Technology. 2010;**9**(4):331-344


[19] Ahmad AL, Ismail S, Bhatia S. Water recycling from palm oil mill effluent (POME) using membrane technology. Desalination. 2003;**157**(1):87-95

[33] Abdullah AZ, Salamatinia B, Mootabadi H, Bhatia S. Current status and policies on biodiesel industry in Malaysia as the world's leading producer of palm oil. Energy Policy.

Palm Oil Mill Effluent as an Environmental Pollutant http://dx.doi.org/10.5772/intechopen.75811 27

[34] Sumathi S, Chai SP, Mohamed AR. Utilization of oil palm as a source of renewable energy in Malaysia. Renewable and Sustainable Energy Reviews. 2008;**12**(9):2404-2421

[35] Kittikun AH, Prasertsan P, Srisuwan G, Krause A. Environmental management of palm oil mill. In: Internet Conference on Material Flow Analysis of Integrated Bio-Systems;

[36] Ahmad S, Ab Kadir MZA, Shafie S. Current perspective of the renewable energy development in Malaysia. Renewable and Sustainable Energy Reviews. 2011;**15**(2):897-904 [37] kaMunoz, R., & Guieysse, B. Algal–bacterial processes for the treatment of hazardous

[38] Kamyab H, Din MFM, Ghoshal SK, Lee CT, Keyvanfar A, Bavafa AA, et al. Chlorella pyrenoidosa mediated lipid production using Malaysian agricultural wastewater:

[39] Hoh D, Watson S, Kan E. Algal biofilm reactors for integrated wastewater treatment and biofuel production: A review. Chemical Engineering Journal. 2016;**287**:466-473

[40] Ge S, Champagne P. Nutrient removal, microalgal biomass growth, harvesting and lipid yield in response to centrate wastewater loadings. Water Research. 2016;**88**:604-612 [41] Huang G, Chen F, Wei D, Zhang X, Chen G. Biodiesel production by microalgal biotech-

[42] Ma AN. Environmental management for the oil palm industry. Palm Oil Development.

[43] Khalid R, Wan Mustafa WA. External benefits of environmental regulation: Resource recovery and the utilisation of effluents. The Environmentalist. 1992;**12**:277-285

[44] Din MM, Ujang Z, Van Loosdrecht MCM, Ahmad A, Sairan MF. Optimization of nitrogen and phosphorus limitation for better biodegradable plastic production and organic removal using single fed-batch mixed cultures and renewable resources. Water Science

[45] Iwuagwu JO, Ugwuanyi JO. Treatment and valorization of palm oil mill effluent through production of food grade yeast biomass. Journal of Waste Management. 2014. http://

[46] Kamyab H, Din MFM, Hosseini SE, Ghoshal SK, Ashokkumar V, Keyvanfar A, et al. Optimum lipid production using agro-industrial wastewater treated microalgae as biofuel substrate. Clean Technologies and Environmental Policy. 2016;**18**(8):2513-2523 [47] Wong YS, Kadir MOA, Teng TT. Biological kinetics evaluation of anaerobic stabilization pond treatment of palm oil mill effluent. Bioresource Technology. 2009;**100**(21):4969-4975

Effects of photon and carbon. Waste and Biomass Valorization. 2016;**7**(4):779-788

contaminants: A review. Water Research. 2006;**40**(15):2799-2815

nology. Applied Energy. 2010;**87**:38-46

and Technology. 2006;**53**(6):15-20

dx.doi.org/10.1155/2014/439071

2000;**30**:1-10

2009;**37**(12):5440-5448

2000


[33] Abdullah AZ, Salamatinia B, Mootabadi H, Bhatia S. Current status and policies on biodiesel industry in Malaysia as the world's leading producer of palm oil. Energy Policy. 2009;**37**(12):5440-5448

[19] Ahmad AL, Ismail S, Bhatia S. Water recycling from palm oil mill effluent (POME) using

[20] Ma AN, Cheah SC, Chow MC, Yeoh BG.Current status of palm oil processing wastes management. In: Waste Management in Malaysia: Current Status and Prospects for Bioremediation.

[21] Kamyab H, Din MFM, Keyvanfar A, Majid MZA, Talaiekhozani A, Shafaghat A, et al. Efficiency of microalgae Chlamydomonas on the removal of pollutants from palm oil

[22] Yacob S, Hassan MA, Shirai Y, Wakisaka M, Subash S. Baseline study of methane emission from open digesting tanks of palm oil mill effluent treatment. Chemosphere. 2005;

[23] Poh PE, Chong MF. Development of anaerobic digestion methods for palm oil mill efflu-

[24] Aliyu S. Palm oil mill effluent: A waste or a raw material?. Journal of Applied Sciences

[25] Wah WP, Sulaiman NM, Nachiappan M, Varadaraj B. Pre-treatment and membrane ultrafiltration using treated palm oil mill effluent (POME). Songklanakarin Journal of

[26] Tong SL, Jaafar AB. POME Biogas capture, upgrading and utilization. Palm Oil Engi-

[27] Yacob S, Shirai Y, Hassan MA, Wakisaka M, Subash S. Start-up operation of semi- commercial closed anaerobic digester for palm oil mill effluent treatment. Process Bio-

[28] Kamyab H, Soltani M, Ponraj M, Din MF, Putri EV. A review on microalgae as potential lipid container with wastewater treating functions. Journal of Environmental Treatment

[29] Shafiqah N, Nasir M. Development of membrane anaerobic system (MAS) for palm oil

[30] Arif S, Tengku Mohd Ariff TA. The case study on the Malaysian palm oil. In: UNCTAD/ ESCAP Regional Workshop on Commodity Export Diversification and Poverty Reduction

[31] Hansen S. Feasibility study of performing an life cycle assessment on crude palm oil production in Malaysia (9 pp). The International Journal of Life Cycle Assessment.

[32] Yusoff S, Hansen SB. Feasibility study of performing of life cycle assessment on crude palm oil production in Malaysia. The International Jounal of Life Cycle Assessment.

mill effluent (POME) treatment. Universiti Malaysia Pahang; 2013

in South and Southe-East Asia, Bangkok; 2001

Malaysia: Ministry of Science Technology and the Environment; 1993. pp. 111-136

membrane technology. Desalination. 2003;**157**(1):87-95

mill effluent (POME). Energy Procedia. 2015;**75**:2400-2408

ent (POME) treatment. Bioresource Technology. 2009;**100**(1):1-9

Research. (January) 2012:466-473. ISSN: 1819-544X

Science and Technology. 2002;**24**:891-898

neering Bulletin. 2006;**78**(7)

chemistry. 2006;**41**(4):962-964

Techniques. 2013;**1**(2):76-80

2007;**12**(1):50-58

2007;**12**(1):50-58

**59**(11):1575-1581

26 Palm Oil


[48] Chiu SY, Kao CY, Chen TY, Chang YB, Kuo CM, Lin CS. Cultivation of microalgal *Chlorella* for biomass and lipid production using wastewater as nutrient resource. Bioresource Technology. 2015;**184**:179-189

**Section 3**

**Applications of Palm Oil and its Industrial**

**Wastes**


**Applications of Palm Oil and its Industrial Wastes**

[48] Chiu SY, Kao CY, Chen TY, Chang YB, Kuo CM, Lin CS. Cultivation of microalgal *Chlorella* for biomass and lipid production using wastewater as nutrient resource. Bio-

[49] Clarens AF, Resurreccion EP, White MA, Colosi LM. Environmental life cycle comparison of algae to other bioenergy feedstocks. Environmental Science & Technology.

[50] Lam MK, Lee KT, Mohamed AR. Life cycle assessment for the production of biodiesel: A case study in Malaysia for palm oil versus jatropha oil. Biofuels, Bioproducts and

[51] Li Y, Horsman M, Wu N, Lan CQ, Dubois-Calero N. Biofuels from microalgae. Bio-

[52] Prinz D, Juliani A, Brontowiyono W. Future water management problems in Asian

[53] Bello MM, Nourouzi MM, Abdullah LC, Choong TS, Koay YS, Keshani S. POME is treated for removal of color from biologically treated POME in fixed bed column: Applying wavelet neural network (WNN). Journal of Hazardous Materials. 2013;**262**:106-113 [54] Vairappan CS, Yen AM. Palm oil mill effluent (POME) cultured marine microalgae as supplementary diet for rotifer culture. Journal of Applied Phycology. 2008;**20**(5):603-608

[55] Olguín EJ, Galicia S, Mercado G, Pérez T. Annual productivity of Spirulina (Arthrospira) and nutrient removal in a pig wastewater recycling process under tropical conditions.

[56] Ponraj M, Din MFM. Effect of light/dark cycle on biomass and lipid productivity by Chlorella pyrenoidosa using palm oil mill effluent (POME). Journal of Scientific and

[57] Hadiyanto MMAN, Hartanto GD Enhancement of biomass production from Spirulina sp cultivated in POME medium. In: Proceedings of the International Conference on

[58] Putri EV, Din MFM, Ahmed Z, Jamaluddin H, Chelliapan S. Investigation of microalgae for high lipid content using palm oil mill effluent (Pome) as carbon source. In: International Conference on Environment and Industrial Innovation. IPCBEE; 2011

palm oil mill effluent (POME) medium. Advanced Materials Research. 2015;**1113**:311-316

[60] Sukumaran P, Nulit R, Zulkifly S, Halimoon N, Omar H, Ismail A. Potential of fresh POME as a growth medium in mass production of Arthrospira platensis. International

[61] Rawat I, Kumar RR, Mutanda T, Bux F. Dual role of microalgae: Phycoremediation of domestic wastewater and biomass production for sustainable biofuels production.

Journal of Current Microbiology and Applied Sciences. 2014;**3**(4):235-250

sequestration by microalgae culture in

megacities. Jurnal Sains & Teknologi Lingkungan. 2009;**1**(1):01-16

resource Technology. 2015;**184**:179-189

technology Progress. 2008a;**24**(4):815-820

Journal of Applied Phycology. 2003;**15**(2-3):249-257

Chemical and Material Engineering; 2012. pp. 1-6

[59] Ahmad AD, Salihon J, Tao DG. Evaluation of CO2

Applied Energy. 2011;**88**(10):3411-3424

Industrial Research. 2013;**72**(11):703-706

2010;**44**(5):1813-1819

28 Palm Oil

Biorefining. 2009;**3**(6):601-612

**Chapter 3**

**Provisional chapter**

**Biomaterial from Oil Palm Waste: Properties,**

**Biomaterial from Oil Palm Waste: Properties,** 

DOI: 10.5772/intechopen.76412

Oil palm are among the best known and most extensively cultivated plant families, especially Indonesia and Malaysia. Many common products and foods are derived from oil palm, its making them one of the most economically important plants. On the other hand, declining supply of raw materials from natural resources has motivated researchers to find alternatives to produce new materials from sustainable resources like oil palm. Oil palm waste is possibly an ideal source for cellulose-based natural fibers and particles. Generally, oil palm waste such as oil palm empty fruit bunches, oil palm trunk, oil palm shell and oil palm ash are good source of biomaterials. Lack of sufficient documentation of existing scientific information about the utilization of oil palm waste raw materials for biomaterial production is the driving force behind the this chapter. Incorporation of various types of biomaterial derived from oil palm waste resources as reinforcement in polymer matrices lead to the development of biocomposites products and this can be used in wide range of potential applications. Properties and characterization of biomaterial from oil palm waste will not only help to promote further study on nanomaterials derived from non-wood materials but also emphasize

the importance of commercially exploit oil palm waste for sustainable products.

**Keywords:** waste as green potential, cellulose fiber, oil palm particle, nanocellulose,

Sensitivity and concern for ecology and technology have sparked a new tendency towards the use of environmentally friendly materials in the world. Environmental-friendly

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

**Characterization and Applications**

**Characterization and Applications**

Rudi Dungani, Pingkan Aditiawati, Sri Aprilia,

Rudi Dungani, Pingkan Aditiawati, Sri Aprilia,

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76412

Ihak Sumardi

Ihak Sumardi

**Abstract**

biocomposites

**1. Introduction**

Karnita Yuniarti, Tati Karliati, Ichsan Suwandhi and

Karnita Yuniarti, Tati Karliati, Ichsan Suwandhi and

#### **Chapter 3 Provisional chapter**

#### **Biomaterial from Oil Palm Waste: Properties, Characterization and Applications Biomaterial from Oil Palm Waste: Properties, Characterization and Applications**

DOI: 10.5772/intechopen.76412

Rudi Dungani, Pingkan Aditiawati, Sri Aprilia, Karnita Yuniarti, Tati Karliati, Ichsan Suwandhi and Ihak Sumardi Rudi Dungani, Pingkan Aditiawati, Sri Aprilia, Karnita Yuniarti, Tati Karliati, Ichsan Suwandhi and Ihak Sumardi

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76412

#### **Abstract**

Oil palm are among the best known and most extensively cultivated plant families, especially Indonesia and Malaysia. Many common products and foods are derived from oil palm, its making them one of the most economically important plants. On the other hand, declining supply of raw materials from natural resources has motivated researchers to find alternatives to produce new materials from sustainable resources like oil palm. Oil palm waste is possibly an ideal source for cellulose-based natural fibers and particles. Generally, oil palm waste such as oil palm empty fruit bunches, oil palm trunk, oil palm shell and oil palm ash are good source of biomaterials. Lack of sufficient documentation of existing scientific information about the utilization of oil palm waste raw materials for biomaterial production is the driving force behind the this chapter. Incorporation of various types of biomaterial derived from oil palm waste resources as reinforcement in polymer matrices lead to the development of biocomposites products and this can be used in wide range of potential applications. Properties and characterization of biomaterial from oil palm waste will not only help to promote further study on nanomaterials derived from non-wood materials but also emphasize the importance of commercially exploit oil palm waste for sustainable products.

**Keywords:** waste as green potential, cellulose fiber, oil palm particle, nanocellulose, biocomposites

#### **1. Introduction**

Sensitivity and concern for ecology and technology have sparked a new tendency towards the use of environmentally friendly materials in the world. Environmental-friendly

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

"waste to wealth" programs are becoming increasingly important as a step to exploit and use biomass materials as raw material for biocomposite products for added value and new products. Biomass fibers (natural fibers, agricultural waste fibers, industrial timber waste etc.) have many techno-economic advantages over synthetic fibers such as glass fibers, carbon fiber and so on. Even in 1938, history has shown how Henry Ford uses soybean residues as a major raw material for the production of car interior frames components.

**2. Oil palm waste as green potential**

oil and lignocellulosic materials, is 231.5 kg dry weight/year.

143 million tonnes of the oil palm biomass annually [8, 9].

An oil palm tree reaches an average volume of 1.638 m3

therefore, more than 20 and 18.5 million m3

increase in palm oil mill effluents.

felled [10].

Palm oil is one commodity which demand is growing very rapidly in world and provide an important contribution to economic development. Increased demand for palm oil in the form of vegetable oils encourage the countries to spur the development of oil palm plantations. Consequently, with the increasing development of the palm oil industry will cause the

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

33

Despite this enormous production, the oil consists of only a minor fraction of the total biomass produced in the plantation. The remainder consists of a huge amount of lignocellulosic materials in the form of fronds (OPF), trunk (OPT), empty fruit bunches (EFB), pressed fruit fiber (PFF), pruning oil palm frond (POPF), and oil palm ash (OPA). Fortunately, all of the wastes are categorized as organic wastes that are environmentally degradable. However, owing to the large quantities generated, these wastes have the potential to pollute the environment. Sumanthi et al. [6] reported that the amount of biomass produced by an oil palm tree, include

Globally, oil palm biomass is produced and utilized in million metric tonnes annually. With the anticipated higher fresh fruit bunch yields and increase in planted areas in the world expected to produce more than 295 million tonnes of wastes annually. In Malaysia, the oil palm waste are produced of 135 million tonnes annually [7]. Meanwhile, Indonesia produced

Solid wastes of EFB and OPT has higher potential for commercial exploitation than the other types of biomass waste [8]. Consequently, EFB and OPT, which collectively comprise the bulk of lignocellulosic waste are available for commercial exploitation. However, producer countries of oil palm in the world such Malaysia and Indonesia, the zero-waste strategy must applicated to maintain the competitive edge of oil palm industry [9]. Other potential biomass wastes were OPF from the plantation fields. Fronds are obtained during regular pruning on FFB harvesting, when trees exceeding the economical age are

Malaysia and Indonesia, respectively. Bakar et al. [11] also reported that, the high OPT that can be used only 2/3 parts and recovery of oil palm lumber (outer part) generated an average

The oil palm wastes can be utilized to produce various types value added products which mean the resources of the substitute's material on wood-based industry. Many studies have investigated the utilization of solid oil palm wastes, utilization of EFB as alternative of fertilizer using EFB waste and liquid waste of oil palm factory as filler in biocomposites have been done for particleboard or fiberboard using cement as adhesive or thermosetting adhesive such as an urea formaldehyde have been conducted [3]. EFB can also be used as a major component of specialized construction materials [12, 13]. Previous studies and the latest on oil

of several patterns is tested is 30% [11], it can be generated about 5 million m3

after its commercial life span [11];

.

of biomass from OPT are available annually in

In general, there is continuous attempts to produce more high-value products from biomass. For example, biomass fibers from palm oil (OPBF) can be found continuously from oil palm fractures during pruning activities, when processing from oil palm stems during replanting (after 25 years) and periodic processing. Until this day, palm oil processing activities yield only 10% palm oil and palm kernel oil while the remaining 90% remain in the form of biomass or waste is still not used for the industry.

The oil palm industry has been producing a lot of oil palm biomass wastes in field and oil palm mills. The waste from mill consist of pressed fruit fibers (PFF), empty fruit bunch (EFB), oil palm shell (OPS), palm oil mill effluent (POME), whilst the other wastes from the plantation comprises of oil palm trunks (OPT) and oil palm fronds (OPF) during replanting after achieving its economic life spans [1]. The increase in oil palm plantation has been producing the waste in large quantities during the replanting; especially oil palm fronds (OPF) and oil palm trunk (OPT). Generally, 24% of OPF obtained from each oil palm trees in a year during harvesting at fresh fruit bunches (FFB) in the field. Meanwhile, OPT accounted for 70% of the replanting activities [2]. This means the potentiality of OPT availability would increase continuously as plantation is increasing and replanting is done throughout the year. Along with these two wastes, there are also other wastes like empty fruit bunch (EFB), oil palm shell (OPS) and waste (effluent) palm oil mill effluent (POME) [3].

These renewable biomass sources can be used for the development of biocomposites, power generation, paper production, construction board fillers, solid wood, mulching and soil conditioning as well as many other uses. Availability, price, performance, and biodegradable nature are among the factors that act as catalysts to promote the use of lignocellulose fiber of oil palm wastes as a value-added product. The oil palm sector generates a large number of biomass categorized as agricultural wastes which up to now only 10% are used as alternative raw materials for biocomposite-based industries, industrial raw materials, fertilizers, animal feeds, chemical derivatives and others. Much of this residual waste is not used but contributes to severe environmental problems when left in processing factories and farms just like that. Previous research on biomass and other agricultural waste has shown potential in its use for the production of various types of value-added products such as medium-density panel, chip board, thermoset composite and thermoplastic, nano biocomposite, pulp and paper manufacture [4, 5].

Through intensive research and development attempts, the world's oil palm biomass has been commercialized in a variety of biomass-based products. The use of lignocellulosic material from oil palm biomass for various types of value-added products through chemical processing, physical and biological innovation is now evolving.

## **2. Oil palm waste as green potential**

"waste to wealth" programs are becoming increasingly important as a step to exploit and use biomass materials as raw material for biocomposite products for added value and new products. Biomass fibers (natural fibers, agricultural waste fibers, industrial timber waste etc.) have many techno-economic advantages over synthetic fibers such as glass fibers, carbon fiber and so on. Even in 1938, history has shown how Henry Ford uses soybean residues as a major raw material for the production of car interior frames

In general, there is continuous attempts to produce more high-value products from biomass. For example, biomass fibers from palm oil (OPBF) can be found continuously from oil palm fractures during pruning activities, when processing from oil palm stems during replanting (after 25 years) and periodic processing. Until this day, palm oil processing activities yield only 10% palm oil and palm kernel oil while the remaining 90% remain in the form of biomass

The oil palm industry has been producing a lot of oil palm biomass wastes in field and oil palm mills. The waste from mill consist of pressed fruit fibers (PFF), empty fruit bunch (EFB), oil palm shell (OPS), palm oil mill effluent (POME), whilst the other wastes from the plantation comprises of oil palm trunks (OPT) and oil palm fronds (OPF) during replanting after achieving its economic life spans [1]. The increase in oil palm plantation has been producing the waste in large quantities during the replanting; especially oil palm fronds (OPF) and oil palm trunk (OPT). Generally, 24% of OPF obtained from each oil palm trees in a year during harvesting at fresh fruit bunches (FFB) in the field. Meanwhile, OPT accounted for 70% of the replanting activities [2]. This means the potentiality of OPT availability would increase continuously as plantation is increasing and replanting is done throughout the year. Along with these two wastes, there are also other wastes like empty fruit bunch (EFB), oil palm shell

These renewable biomass sources can be used for the development of biocomposites, power generation, paper production, construction board fillers, solid wood, mulching and soil conditioning as well as many other uses. Availability, price, performance, and biodegradable nature are among the factors that act as catalysts to promote the use of lignocellulose fiber of oil palm wastes as a value-added product. The oil palm sector generates a large number of biomass categorized as agricultural wastes which up to now only 10% are used as alternative raw materials for biocomposite-based industries, industrial raw materials, fertilizers, animal feeds, chemical derivatives and others. Much of this residual waste is not used but contributes to severe environmental problems when left in processing factories and farms just like that. Previous research on biomass and other agricultural waste has shown potential in its use for the production of various types of value-added products such as medium-density panel, chip board, thermoset composite and thermoplastic, nano biocomposite, pulp and paper manufacture [4, 5].

Through intensive research and development attempts, the world's oil palm biomass has been commercialized in a variety of biomass-based products. The use of lignocellulosic material from oil palm biomass for various types of value-added products through chemical pro-

components.

32 Palm Oil

or waste is still not used for the industry.

(OPS) and waste (effluent) palm oil mill effluent (POME) [3].

cessing, physical and biological innovation is now evolving.

Palm oil is one commodity which demand is growing very rapidly in world and provide an important contribution to economic development. Increased demand for palm oil in the form of vegetable oils encourage the countries to spur the development of oil palm plantations. Consequently, with the increasing development of the palm oil industry will cause the increase in palm oil mill effluents.

Despite this enormous production, the oil consists of only a minor fraction of the total biomass produced in the plantation. The remainder consists of a huge amount of lignocellulosic materials in the form of fronds (OPF), trunk (OPT), empty fruit bunches (EFB), pressed fruit fiber (PFF), pruning oil palm frond (POPF), and oil palm ash (OPA). Fortunately, all of the wastes are categorized as organic wastes that are environmentally degradable. However, owing to the large quantities generated, these wastes have the potential to pollute the environment. Sumanthi et al. [6] reported that the amount of biomass produced by an oil palm tree, include oil and lignocellulosic materials, is 231.5 kg dry weight/year.

Globally, oil palm biomass is produced and utilized in million metric tonnes annually. With the anticipated higher fresh fruit bunch yields and increase in planted areas in the world expected to produce more than 295 million tonnes of wastes annually. In Malaysia, the oil palm waste are produced of 135 million tonnes annually [7]. Meanwhile, Indonesia produced 143 million tonnes of the oil palm biomass annually [8, 9].

Solid wastes of EFB and OPT has higher potential for commercial exploitation than the other types of biomass waste [8]. Consequently, EFB and OPT, which collectively comprise the bulk of lignocellulosic waste are available for commercial exploitation. However, producer countries of oil palm in the world such Malaysia and Indonesia, the zero-waste strategy must applicated to maintain the competitive edge of oil palm industry [9]. Other potential biomass wastes were OPF from the plantation fields. Fronds are obtained during regular pruning on FFB harvesting, when trees exceeding the economical age are felled [10].

An oil palm tree reaches an average volume of 1.638 m3 after its commercial life span [11]; therefore, more than 20 and 18.5 million m3 of biomass from OPT are available annually in Malaysia and Indonesia, respectively. Bakar et al. [11] also reported that, the high OPT that can be used only 2/3 parts and recovery of oil palm lumber (outer part) generated an average of several patterns is tested is 30% [11], it can be generated about 5 million m3 .

The oil palm wastes can be utilized to produce various types value added products which mean the resources of the substitute's material on wood-based industry. Many studies have investigated the utilization of solid oil palm wastes, utilization of EFB as alternative of fertilizer using EFB waste and liquid waste of oil palm factory as filler in biocomposites have been done for particleboard or fiberboard using cement as adhesive or thermosetting adhesive such as an urea formaldehyde have been conducted [3]. EFB can also be used as a major component of specialized construction materials [12, 13]. Previous studies and the latest on oil palm biomass waste have shown the potentiality in its use for the production of various types of value-added products such as medium density panels, block board, laminated veneer lumber (LVL), mineral-bonded particleboard, plywood, chipboard, thermoset and thermoplastic composites, nanobiocomposite, pulp and paper manufacturing [14]. Islam et al. [15] used OPS as activated carbon. Abdul Khalil et al. [16] investigated the conversion of OPT and oil palm EFB into new plywood. Other researchers such as Zaidon et al. [17] and Deraman et al. [18] worked on making particleboard by mixing EFB and rubber wood. Oil palm biomass wastes in field and oil palm mills is illustrated in **Figure 1**.

**3. Properties and characterization of various oil palm waste and their** 

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

35

The cell wall structure of oil palm fibers consists of primary layer (P) and secondary layer (S1, S2 and S3). In general, oil palm fibers have varied variations in size, shape and structure of cell walls. Almost all the fiber structures are round. The layers of S1, S2 and S3 are strongly bonded and form structures such as sandwiches where microfibrils S1 and S3 corners are parallel to S2 layers. This sandwich structure provides additional strength to fiber for resistance to water strain, curve resistance to compressive strength, and bending stiffness to bending force. The primary walls of all oil palm fibers look like a thin layer. Some primary walls are

Studies show that the S2 layer is the majority layer of cell wall. This layer affects the strength of a single fiber. OPT fibers are found to have the most thick S2 layers of 3.43 μm. According to the S2 layer thickness, the OPT is estimated to have the highest strength as the fiber strength is dependent on the cellulose microfibrils that are in line with the fiber axis of the

EFB fibers are hard and strong multicellular fibers that have a central part called lacuna. Its porous surface morphology is important to provide better mechanical links with matrix resin for composite fabrication [22]. The fiber cross section is a polygon with a bundle or a vascular packet that is compact and surrounded by thickened layers of cells. Vascular fibers in monocytes are usually surrounded by several layers of thick cell walls that serve to provide tensile strength to side compression power [23]. OPF fibers consist of various sizes of vascular bundles. Vascular files are widely found in thin-walled parenchyma tissues. Each bundle consists of round gloves, vessels, fibers, phloem, and parenchyma tissue. The xylem and phloem tissues are clearly distinguishable where the phloem is divided into two separate parts in each

Different chemical compositions according to plant species and parts in the plant itself. It also varies by location, geographical condition, age, climate and soil conditions [24]. **Table 1** shows the differences in chemical composition between various types of oil palm biomass

In order for many applications, oil palm solid waste has physical and mechanical properties. **Table 2** shows the properties include physical and mechanical of different part of oil palm solid waste. These properties are very important in reinforcement of biomass in polymer composites. Dungani et al. [34] investigated that physical, mechanical and chemical properties of

various oil palm waste were examined to assess for many applications.

**products**

S2 layer [13, 20, 21].

bundle [12].

waste.

**3.2. Properties of various oil palm wastes**

**3.1. Structure and morphology of oil palm tree**

clearly distinguishable between the middle lamella to each other.

The motivation for using OPT as plywood was initially due to the difficulty in obtaining good quality timber, as well as the abundance of OPT in developing countries like Malaysia and Indonesia [3]. However, oil palm-based plywood mills only utilize about 40% of the OPT and the other 60% is discarded as waste due to its insufficient properties [19]. Only the outer part of OPT can be used for plywood, while the inner part of OPT, which is not strong enough to use as lumber, is discarded in large amounts. It is highly susceptible to degradation agents due to its high moisture content (around 80%) [19]. Abdul Khalil et al. [16] investigated the development of hybrid plywood by utilizing OPT and oil palm EFB. The results showed that hybridization of EFB with OPT improves some of the properties like bending strength, screw withdrawal, and shear strength of the plywood.

**Figure 1.** Various oil palm waste form and its derivative.

## **3. Properties and characterization of various oil palm waste and their products**

#### **3.1. Structure and morphology of oil palm tree**

palm biomass waste have shown the potentiality in its use for the production of various types of value-added products such as medium density panels, block board, laminated veneer lumber (LVL), mineral-bonded particleboard, plywood, chipboard, thermoset and thermoplastic composites, nanobiocomposite, pulp and paper manufacturing [14]. Islam et al. [15] used OPS as activated carbon. Abdul Khalil et al. [16] investigated the conversion of OPT and oil palm EFB into new plywood. Other researchers such as Zaidon et al. [17] and Deraman et al. [18] worked on making particleboard by mixing EFB and rubber wood. Oil palm biomass wastes

The motivation for using OPT as plywood was initially due to the difficulty in obtaining good quality timber, as well as the abundance of OPT in developing countries like Malaysia and Indonesia [3]. However, oil palm-based plywood mills only utilize about 40% of the OPT and the other 60% is discarded as waste due to its insufficient properties [19]. Only the outer part of OPT can be used for plywood, while the inner part of OPT, which is not strong enough to use as lumber, is discarded in large amounts. It is highly susceptible to degradation agents due to its high moisture content (around 80%) [19]. Abdul Khalil et al. [16] investigated the development of hybrid plywood by utilizing OPT and oil palm EFB. The results showed that hybridization of EFB with OPT improves some of the properties like bending strength, screw

in field and oil palm mills is illustrated in **Figure 1**.

34 Palm Oil

withdrawal, and shear strength of the plywood.

**Figure 1.** Various oil palm waste form and its derivative.

The cell wall structure of oil palm fibers consists of primary layer (P) and secondary layer (S1, S2 and S3). In general, oil palm fibers have varied variations in size, shape and structure of cell walls. Almost all the fiber structures are round. The layers of S1, S2 and S3 are strongly bonded and form structures such as sandwiches where microfibrils S1 and S3 corners are parallel to S2 layers. This sandwich structure provides additional strength to fiber for resistance to water strain, curve resistance to compressive strength, and bending stiffness to bending force. The primary walls of all oil palm fibers look like a thin layer. Some primary walls are clearly distinguishable between the middle lamella to each other.

Studies show that the S2 layer is the majority layer of cell wall. This layer affects the strength of a single fiber. OPT fibers are found to have the most thick S2 layers of 3.43 μm. According to the S2 layer thickness, the OPT is estimated to have the highest strength as the fiber strength is dependent on the cellulose microfibrils that are in line with the fiber axis of the S2 layer [13, 20, 21].

#### **3.2. Properties of various oil palm wastes**

EFB fibers are hard and strong multicellular fibers that have a central part called lacuna. Its porous surface morphology is important to provide better mechanical links with matrix resin for composite fabrication [22]. The fiber cross section is a polygon with a bundle or a vascular packet that is compact and surrounded by thickened layers of cells. Vascular fibers in monocytes are usually surrounded by several layers of thick cell walls that serve to provide tensile strength to side compression power [23]. OPF fibers consist of various sizes of vascular bundles. Vascular files are widely found in thin-walled parenchyma tissues. Each bundle consists of round gloves, vessels, fibers, phloem, and parenchyma tissue. The xylem and phloem tissues are clearly distinguishable where the phloem is divided into two separate parts in each bundle [12].

Different chemical compositions according to plant species and parts in the plant itself. It also varies by location, geographical condition, age, climate and soil conditions [24]. **Table 1** shows the differences in chemical composition between various types of oil palm biomass waste.

In order for many applications, oil palm solid waste has physical and mechanical properties. **Table 2** shows the properties include physical and mechanical of different part of oil palm solid waste. These properties are very important in reinforcement of biomass in polymer composites. Dungani et al. [34] investigated that physical, mechanical and chemical properties of various oil palm waste were examined to assess for many applications.


from OPF is suitable for many application such as tissue engineering, medical implants, drug delivery, wound dressing and cardiac devices due to their excellent properties. Nazir et al. [39] produced cellulose from EFB with formic acid and hydrogen peroxide. Owolabi et al. [40] studied isolation of cellulose from OPF rachis vascular bundle using sodium hydroxide and hydro-

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Shanmugarajah et al. [41] studied isolation of nanocellulose from EFB and investigated with sulfuric acid. Indarti et al. [42] produced cellulose nanocrystal from EFB by TEMPO mediated process follow with ultrasonication. They studied the effect of drying and solvent exchange

Several methods has been implied by researcher to produce nanoparticle such as mechanical process, supercritical fluid extraction and solvent extraction [43]. These methods are intended for removing the residual impurities from sources including mechanical pressing. Nanoparticles as one form of nanomaterials like nanotubes and nanolayer, depend on the numbers of dimensions in nano range. Nano particles are small size, narrow size distribution, high dispersion tendency and lower aggregation form [44]. Producing nanomaterials could be preparing by different methods, such as mechanical treatments, chemical treatments, elec-

Abdul Khalil et al. [43] investigated that OPS as nanoparticles for reinforcement in polymer composites. In prepared the nanoparticles, they used solvent extraction method. From analysis, the shape and surface of defatted OPS particles were angular, crushed shapes and irregular. Liauw et al. [45] stated that the bioresources when used extraction with supercritical fluid,

Many researchers also concerned to produce oil palm nanoparticles in the form of activated carbon and oil palm ash. Ruiz et al. [46] produced and characterized the activated carbon particle from OPS. Sukiran et al. [47] studied biochar particles from EFB by pyrolysis process by using fluidized bed reactor. Biochar particles can be used as fuel in form of briquettes, reinforcement in polymer composites, as antifouling in polymer membranes, biocatalyst and ink. Abdul Khalil et al. [48] investigated nanoparticles from oil palm ash (OPA) which is rich siliceous material. They successful reduce the size with ball mill process for 30 hours. Saba et al. [44] investigated nanoparticles from EFB with physical treatment and chemical treatment. To reduce macromolecular size to nano-size used high energy ball mill. Nasir et al. [49] succeeded to produce reduced rapheme oxide from rapheme oxide using OPL, PKS and EFB.

Over the past few decades, the polymer science have been development in a wide spectrum since emergence natural fiber-reinforced polymer composite materials. Its natural fiber composites have used in various applications such as automotive components, package trays, door pan-

**4. Potential application of oil palm waste-based composites**

els, headliners, dashboards and interior parts [50].

**3.4. Production and characterization of particles from oil palm waste**

gen peroxide.

process on thermal stability.

trospinning method and so on.

the high purity of oil could produced.

**Table 1.** Chemical composition of oil palm biomass waste.


**Table 2.** Physical and mechanical properties oil palm solid waste.

#### **3.3. Isolation and characterization of cellulose fibers from oil palm waste**

Many researcher investigated the isolation and characterization cellulose fibers from oil palm waste. They studied about isolation of cellulose from many part of oil palm waste, which are chemical treatment and mechanical treatment. There are several ways to isolate cellulose from oil palm solid waste, such as homogenization, ultrasonication, electrospinning, acid hydrolysis, and steam explosion [33]. The main purpose of extracting cellulose is to remove existing non-cellulose components such as hemicellulose, lignin, extractive compounds to obtain cellulosic nano fiber [35].

The following are the results of several researchers who conducted their research on oil palm solid waste. Nasution et al. [36] report their research has isolated cellulose from EFB with hydrochloric acid. The result show that the microcrystalline cellulose (MCC) was found in the form of alpha cellulose. From SEM analysis this treatment affected the structural of morphological of resulting of microfibrillated cellulose. Chieng et al. [37] investigated extraction nanocellulose from OPMF by acid hydrolysis. They used sulfuric acid to remove amorphous region of cellulose to found nanocellulose crystalline. The result show that increased crystallinity of cellulose after removing hemicellulose and lignin. After analysis process the fiber surface to be smoother and reduction in diameter and size. The diameter of nanocellulose about 1–6 nm and rod-like shape.

Nordin et al. [38] also isolated cellulose with sulfuric acid from OPF. The result show that nanocrystalline cellulose improved. From TEM analysis showed good dispersion of individual fiber resulted from chemo-mechanical treatment. They were subjected that the nanocellulose derived from OPF is suitable for many application such as tissue engineering, medical implants, drug delivery, wound dressing and cardiac devices due to their excellent properties. Nazir et al. [39] produced cellulose from EFB with formic acid and hydrogen peroxide. Owolabi et al. [40] studied isolation of cellulose from OPF rachis vascular bundle using sodium hydroxide and hydrogen peroxide.

Shanmugarajah et al. [41] studied isolation of nanocellulose from EFB and investigated with sulfuric acid. Indarti et al. [42] produced cellulose nanocrystal from EFB by TEMPO mediated process follow with ultrasonication. They studied the effect of drying and solvent exchange process on thermal stability.

#### **3.4. Production and characterization of particles from oil palm waste**

**3.3. Isolation and characterization of cellulose fibers from oil palm waste**

**Table 2.** Physical and mechanical properties oil palm solid waste.

**Table 1.** Chemical composition of oil palm biomass waste.

**Properties EFB EFB EFB OPT**

Tensile strength (MPa) 0.1–0.4 71 51.73–82.40 300–600 Young modulus (GPa) 1–9 1.7 0.95–1.86 15–32 Elongation et break (%) 8–18 11 9.5–12.15 —

) 0.7–1.55 — — 1.1

**Fibers Extractive (%) Holocellulose (%) Cellulose (%) Hemicellulose (%) Lignin (%) Ash (%)** EFB 2–4 68–86 43–65 17–33 13–37 1–6 OPF 2–5 80–83 40–50 34–38 20–21 2–3 OPT 4–7 42–45 29–37 12–17 18–23 2–3 OPS 0.9–2 40–47 27–35 15–19 48–55 1–4

lulosic nano fiber [35].

Density (gr/cm3

Sources: [25–29].

36 Palm Oil

Sources: [30–33].

about 1–6 nm and rod-like shape.

Many researcher investigated the isolation and characterization cellulose fibers from oil palm waste. They studied about isolation of cellulose from many part of oil palm waste, which are chemical treatment and mechanical treatment. There are several ways to isolate cellulose from oil palm solid waste, such as homogenization, ultrasonication, electrospinning, acid hydrolysis, and steam explosion [33]. The main purpose of extracting cellulose is to remove existing non-cellulose components such as hemicellulose, lignin, extractive compounds to obtain cel-

The following are the results of several researchers who conducted their research on oil palm solid waste. Nasution et al. [36] report their research has isolated cellulose from EFB with hydrochloric acid. The result show that the microcrystalline cellulose (MCC) was found in the form of alpha cellulose. From SEM analysis this treatment affected the structural of morphological of resulting of microfibrillated cellulose. Chieng et al. [37] investigated extraction nanocellulose from OPMF by acid hydrolysis. They used sulfuric acid to remove amorphous region of cellulose to found nanocellulose crystalline. The result show that increased crystallinity of cellulose after removing hemicellulose and lignin. After analysis process the fiber surface to be smoother and reduction in diameter and size. The diameter of nanocellulose

Nordin et al. [38] also isolated cellulose with sulfuric acid from OPF. The result show that nanocrystalline cellulose improved. From TEM analysis showed good dispersion of individual fiber resulted from chemo-mechanical treatment. They were subjected that the nanocellulose derived Several methods has been implied by researcher to produce nanoparticle such as mechanical process, supercritical fluid extraction and solvent extraction [43]. These methods are intended for removing the residual impurities from sources including mechanical pressing. Nanoparticles as one form of nanomaterials like nanotubes and nanolayer, depend on the numbers of dimensions in nano range. Nano particles are small size, narrow size distribution, high dispersion tendency and lower aggregation form [44]. Producing nanomaterials could be preparing by different methods, such as mechanical treatments, chemical treatments, electrospinning method and so on.

Abdul Khalil et al. [43] investigated that OPS as nanoparticles for reinforcement in polymer composites. In prepared the nanoparticles, they used solvent extraction method. From analysis, the shape and surface of defatted OPS particles were angular, crushed shapes and irregular. Liauw et al. [45] stated that the bioresources when used extraction with supercritical fluid, the high purity of oil could produced.

Many researchers also concerned to produce oil palm nanoparticles in the form of activated carbon and oil palm ash. Ruiz et al. [46] produced and characterized the activated carbon particle from OPS. Sukiran et al. [47] studied biochar particles from EFB by pyrolysis process by using fluidized bed reactor. Biochar particles can be used as fuel in form of briquettes, reinforcement in polymer composites, as antifouling in polymer membranes, biocatalyst and ink. Abdul Khalil et al. [48] investigated nanoparticles from oil palm ash (OPA) which is rich siliceous material. They successful reduce the size with ball mill process for 30 hours. Saba et al. [44] investigated nanoparticles from EFB with physical treatment and chemical treatment. To reduce macromolecular size to nano-size used high energy ball mill. Nasir et al. [49] succeeded to produce reduced rapheme oxide from rapheme oxide using OPL, PKS and EFB.

## **4. Potential application of oil palm waste-based composites**

Over the past few decades, the polymer science have been development in a wide spectrum since emergence natural fiber-reinforced polymer composite materials. Its natural fiber composites have used in various applications such as automotive components, package trays, door panels, headliners, dashboards and interior parts [50].


**4.1. Oil palm waste-based conventional composite**

**4.2. Oil palm waste-based polymer composites**

**Table 5.** Thermoplastic-based biocomposites polymer.

**Table 6.** Oil palm fiber-based hybrid composites.

can be manufactured from oil palm waste is presented in **Table 3**.

**Biocomposite References**

**Hybrid composites References**

EFB-glass fiber/polypropylene Rozman et al. [85] EFB-glass fiber/polyester Abdul Khalil et al. [26] EFB bio-composites hybridized-kaolinite Amin and Khairiah [86] Oil palm fibers-glass fiber/polyester Kumar et al. [87] EFB-glass fiber/phenol formaldehyde Sreekala et al. [64] Sisal-oil palm fibers/natural rubber Khanam et al. [88] EFB-glass fiber/vinylester Abdul Khalil et al. [89] EFB-jute/epoxy Jawaid et al. [90]

Oil palm fiber-glass fiber/epoxy Jawaid and Abdul Khalil [84]

Polypropylene/EFB Rozman et al. [78] High-density polyethylene composites/EFB Mohd Ishak et al. [79] High-density polyethylene composites/OPF/EFB Rozman et al. [80] Poly(vinyl chloride)/EFB Bakar et al. [81] Polyurethane/EFB Rozman et al. [82] Polypropylene/EFB-oil palm derived cellulose Khalid et al. [83]

Polyethylene/tapioca starch/EFB biofilm Roshafima and Wan Aizan [77]

The biomass wastes include trunk, empty fruit bunch, leaf, mesocarp fiber, etc. are convertible into various biocomposite products. The type of conventional composite performance can be tailored to the end use of the product with each category classification is simple low and high density. Conventional composites are used in some structural and non-structural product applications, including panels for internal closure purposes to panels for outdoor use in furniture and multi-building support structures. Review on each potential biocomposite products

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This section provides an overview of use of oil palm waste fiber in the field of composite material. Bio-based polymers such as polylactic acid (PLA), polyhydroxybutyrate (PHB), cellulose ester, soy-based plastic, starch plastic, polymer trimethylene terephthalate (PTT), functional

**Table 3.** Conventional composite based on oil palm waste.


**Table 4.** Thermoset based on biocomposite polymer and elastomer.

Utilization of natural fiber like oil palm empty fruit bunch (EFB) in polymer composites have some advantages such as low density, low cost, renewability, and biodegradability [51, 52]. The use of biomass from oil palm wastes has been demonstrated at the laboratory and preproduction levels as alternative raw wood materials for biocomposite production, for example particleboard, medium density fiberboard (MDF) and others [53]. These are the essential features and properties of fibers that are important and enable integration of oil palm biomass waste into existing industries for the purpose of product production.

#### **4.1. Oil palm waste-based conventional composite**

The biomass wastes include trunk, empty fruit bunch, leaf, mesocarp fiber, etc. are convertible into various biocomposite products. The type of conventional composite performance can be tailored to the end use of the product with each category classification is simple low and high density. Conventional composites are used in some structural and non-structural product applications, including panels for internal closure purposes to panels for outdoor use in furniture and multi-building support structures. Review on each potential biocomposite products can be manufactured from oil palm waste is presented in **Table 3**.

#### **4.2. Oil palm waste-based polymer composites**

This section provides an overview of use of oil palm waste fiber in the field of composite material. Bio-based polymers such as polylactic acid (PLA), polyhydroxybutyrate (PHB), cellulose ester, soy-based plastic, starch plastic, polymer trimethylene terephthalate (PTT), functional


**Table 5.** Thermoplastic-based biocomposites polymer.


**Table 6.** Oil palm fiber-based hybrid composites.

Utilization of natural fiber like oil palm empty fruit bunch (EFB) in polymer composites have some advantages such as low density, low cost, renewability, and biodegradability [51, 52]. The use of biomass from oil palm wastes has been demonstrated at the laboratory and preproduction levels as alternative raw wood materials for biocomposite production, for example particleboard, medium density fiberboard (MDF) and others [53]. These are the essential features and properties of fibers that are important and enable integration of oil palm biomass

waste into existing industries for the purpose of product production.

**Table 4.** Thermoset based on biocomposite polymer and elastomer.

**Biocomposites References**

Veneer and plywood Mokhtar et al. [54] and Rosli et al. [55]

Sandwich panel Srivaro et al. [58] and Srivaro [59] Fiberboards Onuorah [60] and Ramli et al. [53] Particleboards Sudin and Shaari [61] and Haslett [62]

Compressed lumber Choowang and Hiziroglu [56] and Choowang [57]

**Type of conventional composite References**

38 Palm Oil

**Table 3.** Conventional composite based on oil palm waste.

EFB/polyester Abdul Khalil et al. [63] OPF/phenol formaldehyde Sreekala et al. [64] OPF/glycidyl methacrylate Rozman et al. [65] Oil palm fibers/rubber Ismail et al. [66] Oil palm wood flour/natural rubber Ismail et al. [67] EFB (carbon black)/epoxy Abdul Khalil et al. [68] EFB/polycaprolactone Ibrahim et al. [69] EFB/phenol formaldehyde Chai et al. [70] Short palm tree fibers-polyester Kaddami et al. [71] Short palm tree fibers-epoxy Kaddami et al. [71] Polyethylene modified with crude palm oil Min et al. [72] EFB fiber/poly(butylene adipate-*co*-terephthalate) Siyamak et al. [73] EFB fiber/polyethylene Arif et al. [74]

EFB fiber/poly(vinyl chloride) Abdul Khalil et al. [75] OPT fiber/polypropylene Abdul Khalil et al. [76] vegetable oil-based resin and thermoset and elastomer biocomposites (**Table 4**) has revolutionized the plastic and petroleum world with biodegradable polymer.

Additionally, oil palm fiber can be used as a filler in thermoplastics and thermoset composites (**Table 5**). This composite has extensive applications in automotive furniture and components. In Malaysia, research and development in this area has finally reached commercialization levels to develop the thermoplastic composite, thermoset and elastomer composite for components used in the manufacture of proton cars [6]. In addition, hybrid composites also have lower modulus of storage than non-hybrid oil palm/PF composite composites. Research and production of various hybrid composites based on oil palm fiber are listed in **Table 6**.

## **5. Conversion of oil palm waste-based lignocellulosic to nanocellulose**

Lignocellulosic of oil palm fibers such as hemicellulose, lignin and especially cellulose are also potentially exploited in nanotechnology. The pulp fiber from the oil palm fiber to produce a network structure unit such as nano-sized mesh called cellulose microfibril, it are obtained through mechanical treatment of pulp fibers which include smoothing process and high-pressure homogenizer process. The degree of fiber fibrillation of the pulp will increase the flexural flexibility of the fiber [75, 84]. This increase is due to the complete fibrillation of most fibers. The use of pulp (cellulose) as a reinforced booster with additional high pressure homogenization, composite strength will increase linearly against water resistance values and other properties [91].

In general, related materials such as hydrolyzed microcrystalline cellulose will rapidly clot when it is drained [92]. This, will complicate the next process. Therefore, surface modification should be carried out so that cellulose has compatibility with the matrix. Examples of applications for surface-made nanofibrillar celluloses are high-performance films and materials of nanocomposites, materials with superb hydrophobic surfaces as well as optical properties, electrical conductivity, magnetic or unique adsorption, new wood-based fibers with nanoscans or modified surface textures [93]. Products include filters, textiles, films, packaging materials, casting and mold components.

been conducted over the years [97]. It has been reported that cellulose nanofibers from cellulosic oil palm fiber can used as a reinforcing agent in composites materials. Meanwhile, research in the use of oil palm waste nanofiller such as oil palm shell and oil palm ash for manufacturing of wood composites have been carried out by Dungani et al. [98] and Sasthiryar et al. [99]. In general, the results of these studies indicate that, the addition of nanofiller can improve the properties of composites. The research development of isolation of nanocellulose of oil palm biomass and its related methods in various treatment are shown in **Table 7**.

**Table 7.** Events in the exploration of isolation nanocellulose from oil palm biomass with various methods and their

**Event References**

Microfibrillated celluloses from OPEFB Goh et al. [100]

Nanofibrillated from EFB using ultrasound assisted hydrolysis Rosazley et al. [103]

Nanocellulose from OPF using alkaline processes Mohaiyiddin et al. [105] Production cellulose nanocrystals from OPF by hydrolysis treatment Saurabh et al. [106]

Production cellulose nanocrystals from OPF by chemo-mechanical treatment Nordin et al. [38]

Nanofillers obtained from OPA Abdul Khalil et al. [7]

Production defatted OPS nanoparticles Dungani et al. [101] and Rosamah et al.

Fahma et al. [39]

Rohaizu and Wanrosli [104]

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41

Adriana et al. [107]

Chieng et al. [108]

Surip et al. [110]

Lamaming et al. [111]

Bhat and Abdul Khalil [109]

[102]

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

Cellulose nanofibers were produced by hydrolyzing OPEFB with sulfuric

EFB nanocrystalline cellulose was isolated from OPEFB microcrystalline

Isolation of cellulose nanowhiskers from oil palm mesocarp fibers by acid

Oil palm mesocarp fiber as a source for the production of cellulose

The utilization of OPA as a nanofiller for the development of polymer

Nanocellulose was extracted from OPT fibers by a chemi-mechanical

Cellulose nanocrystals were isolated from OPT using acid hydrolysis

acid

cellulose

nanocrystals

nanocomposites

related applications.

technique

hydrolysis and microfluidization

method and total chlorine free method

The oil palm industry produces a high amount of waste during harvesting, replanting and processing at the plant. Generally, up to this day only 10% of the use of oil palm biomass residues is used as a biocomposite industrial raw material or as an alternative substitute material for wood raw materials. Oil palm waste that has lignocellulose content can be produce biomaterial

**6. Conclusion**

There are various methods had been reported for isolation of oil palm waste-based lignocellulosic to nanocellulose or nanoparticles, its can either in chemical treatment, mechanical treatment, and chemo-mechanical treatment processes [39, 94, 95] considered that alkali treatment seems to be effective in the removal of lignin and hemicelluloses components in palm oil EFB fiber. Mazlita et al. [96] suggested that chemical-sonication process were successfully generated from oil palm trunk (OPT) lignocellulosic biomass.

The characteristic of nanocellulose of oil palm wastes has great potential in applications such as strength enhancers polymer composites has been studied since the first half of the twentieth century. Nanocellulose extracted from oil palm biomass lignocellulosic can be classified in two main subcategories, nanofibrillated cellulose (NFC) and nanocrystalline cellulose (NCC). Research on the isolation nanofibres from oil palm biomass such as empty fruit bunch have


**Table 7.** Events in the exploration of isolation nanocellulose from oil palm biomass with various methods and their related applications.

been conducted over the years [97]. It has been reported that cellulose nanofibers from cellulosic oil palm fiber can used as a reinforcing agent in composites materials. Meanwhile, research in the use of oil palm waste nanofiller such as oil palm shell and oil palm ash for manufacturing of wood composites have been carried out by Dungani et al. [98] and Sasthiryar et al. [99]. In general, the results of these studies indicate that, the addition of nanofiller can improve the properties of composites. The research development of isolation of nanocellulose of oil palm biomass and its related methods in various treatment are shown in **Table 7**.

## **6. Conclusion**

vegetable oil-based resin and thermoset and elastomer biocomposites (**Table 4**) has revolu-

Additionally, oil palm fiber can be used as a filler in thermoplastics and thermoset composites (**Table 5**). This composite has extensive applications in automotive furniture and components. In Malaysia, research and development in this area has finally reached commercialization levels to develop the thermoplastic composite, thermoset and elastomer composite for components used in the manufacture of proton cars [6]. In addition, hybrid composites also have lower modulus of storage than non-hybrid oil palm/PF composite composites. Research and

Lignocellulosic of oil palm fibers such as hemicellulose, lignin and especially cellulose are also potentially exploited in nanotechnology. The pulp fiber from the oil palm fiber to produce a network structure unit such as nano-sized mesh called cellulose microfibril, it are obtained through mechanical treatment of pulp fibers which include smoothing process and high-pressure homogenizer process. The degree of fiber fibrillation of the pulp will increase the flexural flexibility of the fiber [75, 84]. This increase is due to the complete fibrillation of most fibers. The use of pulp (cellulose) as a reinforced booster with additional high pressure homogenization, composite strength will increase linearly against water resistance values and

In general, related materials such as hydrolyzed microcrystalline cellulose will rapidly clot when it is drained [92]. This, will complicate the next process. Therefore, surface modification should be carried out so that cellulose has compatibility with the matrix. Examples of applications for surface-made nanofibrillar celluloses are high-performance films and materials of nanocomposites, materials with superb hydrophobic surfaces as well as optical properties, electrical conductivity, magnetic or unique adsorption, new wood-based fibers with nanoscans or modified surface textures [93]. Products include filters, textiles, films, packaging

There are various methods had been reported for isolation of oil palm waste-based lignocellulosic to nanocellulose or nanoparticles, its can either in chemical treatment, mechanical treatment, and chemo-mechanical treatment processes [39, 94, 95] considered that alkali treatment seems to be effective in the removal of lignin and hemicelluloses components in palm oil EFB fiber. Mazlita et al. [96] suggested that chemical-sonication process were successfully gener-

The characteristic of nanocellulose of oil palm wastes has great potential in applications such as strength enhancers polymer composites has been studied since the first half of the twentieth century. Nanocellulose extracted from oil palm biomass lignocellulosic can be classified in two main subcategories, nanofibrillated cellulose (NFC) and nanocrystalline cellulose (NCC). Research on the isolation nanofibres from oil palm biomass such as empty fruit bunch have

production of various hybrid composites based on oil palm fiber are listed in **Table 6**.

tionized the plastic and petroleum world with biodegradable polymer.

**5. Conversion of oil palm waste-based lignocellulosic to** 

**nanocellulose**

40 Palm Oil

other properties [91].

materials, casting and mold components.

ated from oil palm trunk (OPT) lignocellulosic biomass.

The oil palm industry produces a high amount of waste during harvesting, replanting and processing at the plant. Generally, up to this day only 10% of the use of oil palm biomass residues is used as a biocomposite industrial raw material or as an alternative substitute material for wood raw materials. Oil palm waste that has lignocellulose content can be produce biomaterial as reinforcement in conventional biocomposite products (molded product panel, plywood, fiberboard, hybrid biocomposite, etc.) and advanced biocomposites (thermoplastics, thermosets and elastomers). Biomaterial can produce with or without treatment. That mean is the biomaterial from oil palm tree can be made from the fiber and isolated the cellulose content. Biomaterial from oil palm waste played an important role in the polymer composites and it can classified according to their origin. The types of biomaterial can be prepared from trunk, empty fruit bunch, frond, and shell. Reinforcement of biomaterials from different part of oil palm tree in thermoplastics and thermoset will give different characteristics. The different characteristic because of the physical and mechanical properties of oil palm fibers are mainly depended on their chemical content. The reinforcement oil palm waste into polymer composites have shown the sensitivity of certain mechanical and thermal properties to moisture absorption. These phenomena can be decreased by the employ fiber surface treatment.

**References**

10.1166/jbmb.2012.1212

10.1016/j.carbpol.2011.08.078

DOI: 10.1016/j.rser.2007.06.006

BioResources. 2012;**7**(4):5771-5780

Jakarta: BAW; 2010. pp. 125-143

Technology. 1998;**11**(1):1-11

10.1080/03602550701866840

2008

[1] Erwinsyah RC. Thermal insulation material from oil palm empty fruit bunch fibres.

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

43

[2] Abdul Khalil HPS, Amouzgar P, Jawaid M, Hassan A, Ahmad F, Hadiyane A, Dungani R. New approach to oil palm trunk core lumber material properties enhancement via resin impregnation. Journal of Biobased Materials and Bioenergy. 2012;**6**(3):1-10. DOI:

[3] Abdul Khalil HPS, Bhat AH, Jawaid M, Amouzgar P, Ridzuan R, Said MR. Agro-wastes: Mechanical and physical properties of resin impregnated oil palm trunk core lumber.

[4] Abdul Khalil HPS, Bakare IO, Khairul A, Issam AM, Bhat IUH. Effect of anhydride modification on the thermal stability of cultivated Acacia mangium. Journal of Wood

[6] Sumanthi S, Chai SP, Mohamed AR. Utilization of oil palm as a source of renewable energy in Malaysia. Renewable and Sustainable Energy Reviews. 2008;**12**(9):2404-2421.

[7] Abdul Khalil HPS, Rus Mahayuni AR, Bhat IH, Dungani R, Almulali MZ, Abdullah CK. Characterization of various organic waste nanofillers obtained from oil palm ash.

[8] Yuliansyah AT, Hirajima T, Rochmadi R. Development of the Indonesian palm oil industry and utilization of solid waste. Journal of Mining and Materials Processing Institute of

[9] Hambali E, Thahar E, Komarudin A. The potential of oil palm and rice biomass as bioenergy feedstock. In: I7th Biomass Asia Workshop; 2-3 July 2010, Jakarta-Indonesia.

[10] Erwinsyah. Improvement of oil palm wood properties using bioresin [thesis]. Dresden: Fakultät für Forst-, Geo- und Hydrowissenschaften, Technische Universität Dresden;

[11] Bakar ES, Rachman O, Hermawan D, Karlinasari L, Rosdiana N. Utilization of oil palm trunk (*Elaeis guineensis* Jacq) as conctruction materials and furniture (I): Physical, chemical and natural durability properties of oil palm wood. Journal of Forest Products

[12] Abdul Khalil HPS, Alwani MS, Ridzuan R, Kamarudin H, Khariul A. Chemical composition, morphological characteristics, and cell wall structure of Malaysian oil palm fibers. Journal of Polymer Plastics Technology and Engineering. 2008;**47**(3):273-280. DOI:

Japan. 2009;**125**(12):583-589. DOI: 10.2473/journalofmmij.125.583

Chemistry and Technology. 2011;**31**:154-171. DOI: 10.1080/02773813.2010.510586 [5] Abdul Khalil HPS, Bhat AH, Ireana Yusra AF. Green composites from sustainable cellulose nanofibrils: A review. Journal Carbohydrate Polymers. 2011;**87**:963-979. DOI:

Journal of Biotropia. 2007;**14**(1):32-50. DOI: 10.11598/btb.2007.14.1.23

Polymer Composites. 2010;**3**(4):638-644. DOI: 10.1002/pc.20841

In additions, biomaterial from oil palm waste reinforce in polymer composites could increase biodegradability, decrease environmental pollution, reduces cost and hazards. The waste disposal issue has directed most scientific research into eco-composite materials that can be readily degraded and assimilated by biological agent. The characterization of biomaterial reinforce in polymer matrix give some performance like, physical properties, chemical properties, mechanical composition, and also interaction between fiber as nanomaterial and matrix.

## **Acknowledgements**

The authors would like to thank Institut Teknologi Bandung (ITB) for providing Research University Grants (P3MI-ITB) and Ministry of Research, Technology and High Education for the Fundamental Research Grant Scheme (FRGS-115/RISTEKDIKTI/2016).

## **Conflict of interest**

The authors have declared that no competing interest exists.

## **Author details**

Rudi Dungani1 \*, Pingkan Aditiawati1 , Sri Aprilia2 , Karnita Yuniarti3 , Tati Karliati1 , Ichsan Suwandhi1 and Ihak Sumardi1

\*Address all correspondence to: rudi@sith.itb.ac.id

1 School of Life Sciences and Technology, Institut Teknologi Bandung, Bandung, Indonesia

2 Faculty of Engineering, Syiah Kuala University, Banda Aceh, Indonesia

3 Forestry Products Research and Development Center, Ministry of Environment and Forestry Indonesia, Bogor, Indonesia

## **References**

as reinforcement in conventional biocomposite products (molded product panel, plywood, fiberboard, hybrid biocomposite, etc.) and advanced biocomposites (thermoplastics, thermosets and elastomers). Biomaterial can produce with or without treatment. That mean is the biomaterial from oil palm tree can be made from the fiber and isolated the cellulose content. Biomaterial from oil palm waste played an important role in the polymer composites and it can classified according to their origin. The types of biomaterial can be prepared from trunk, empty fruit bunch, frond, and shell. Reinforcement of biomaterials from different part of oil palm tree in thermoplastics and thermoset will give different characteristics. The different characteristic because of the physical and mechanical properties of oil palm fibers are mainly depended on their chemical content. The reinforcement oil palm waste into polymer composites have shown the sensitivity of certain mechanical and thermal properties to moisture absorption. These phenomena can be decreased by the employ fiber surface treatment.

In additions, biomaterial from oil palm waste reinforce in polymer composites could increase biodegradability, decrease environmental pollution, reduces cost and hazards. The waste disposal issue has directed most scientific research into eco-composite materials that can be readily degraded and assimilated by biological agent. The characterization of biomaterial reinforce in polymer matrix give some performance like, physical properties, chemical properties, mechanical composition, and also interaction between fiber as nanomaterial and matrix.

The authors would like to thank Institut Teknologi Bandung (ITB) for providing Research University Grants (P3MI-ITB) and Ministry of Research, Technology and High Education for

, Sri Aprilia2

1 School of Life Sciences and Technology, Institut Teknologi Bandung, Bandung, Indonesia

3 Forestry Products Research and Development Center, Ministry of Environment and

2 Faculty of Engineering, Syiah Kuala University, Banda Aceh, Indonesia

, Karnita Yuniarti3

, Tati Karliati1

,

the Fundamental Research Grant Scheme (FRGS-115/RISTEKDIKTI/2016).

The authors have declared that no competing interest exists.

\*, Pingkan Aditiawati1

\*Address all correspondence to: rudi@sith.itb.ac.id

Forestry Indonesia, Bogor, Indonesia

and Ihak Sumardi1

**Acknowledgements**

42 Palm Oil

**Conflict of interest**

**Author details**

Rudi Dungani1

Ichsan Suwandhi1


[13] Abdul Khalil HPS, Bhat IH, Khairul A. Preliminary study on enhanced properties and biological resistance of chemically modified *Acacia* spp. BioResources. 2010;**5**(4):2720-2737

[27] Punsuvon P, Anpanurak W, Vaithanomsat P, Tungkananuruk N. Fractionation of chemical components of oil palm trunk by steam explosion. In: Proceedings of 31st Congress on Science and Technology of Thailand; 14-17 December 2005. Thailand: Suranaree

[28] Shinoj S, Visvanathan R, Panigrahi S, Kochubabu M. Oil palm fiber (OPF) and its composites: A review. Industrial Crops and Products. 2011;**33**(1):7-22. DOI: 10.1016/j.

[29] Arami-Niya A, Wan Daud WMA, Mjalli FS. Using granular activated prepared from oil

[30] Khanam PN, Abdul Khalil HPS, Jawaid M, Reddy GR, Narayana CS, Naidu SV. Sisal/ carbon fiber reinforced hybrid composites: Tensile, flexural and chemical resistance properties. Journal of Polymers and the Environment. 2010;**18**:727-733. DOI: 10.1007/

[31] Jawaid M, Abdul Khalil HPS, Abu Bakar A. Mechanical performance of oil palm empty fruit bunches/jute fibres reinforced epoxy hybrid composites. Materials Science and

[32] Khalid M, Ratnam CT, Luqman CA, Salmiaton A, Choong TSY, Jalaludin H. Thermal and dynamic mechanical behavior of cellulose- and oil palm empty fruit bunch (OPEFB) filled polypropylene biocomposites. Polymer-Plastics Technology and Engineering.

[33] Nafu YR, Tendo JF, Njeugna E, Oliver G, Cooke KO. Extraction and characterization of fibres from the stalk and spikelets of empty fruit bunch. Journal of Applied Chemistry.

[34] Dungani R, Karina M, Subyakto AS, Hermawan D, Hadiyane A. Agricultural waste fibers towards sustainability and advanced utilization: A review. Asian Journal Plant

[35] Ahmad Z, Saman HM, Tahir PM. Oil palm trunk fiber as bio-waste resources for concrete reinforcement. International Journal of Mechanical and Materials Engineering.

[36] Nasution H, Yurnaliza Y, Veronicha V, Irmadani I, Sitompul S. Preparation and characterization of cellulose microcrystalline (MCC) from fiber of empty fruit bunch palm oil. In: Proceedings of IOP Conference Series: Materials Science and Engineering; 14-15

[37] Chieng BCW, Lee SH, Ibrahim NA, Then YY, Loo YY. Isolation and characterization of cellulose nanocrystals from oil palm mesocarp fiber. Polymer. 2017;**9**(8):1-11. DOI:

[38] Nordin NA, Sulaiman O, Hashim R, Kassim MHM. Oil palm frond waste for the production of cellulose nanocrystals. Journal of Physical Science. 2017;**28**(2):115-126. DOI:

and Applied Pyrolysis. 2010;**89**(2):197-203. DOI: 10.1016/j.jaap.2010.08.006

Engineering: A. 2010;**527**(29):7944-7949. DOI: 10.1016/j.msea.2010.09.005

2009;**48**(12):1244-1251. DOI: 10.1080/03602550903282986

2015;**2015**:1-10. DOI: 10.1155/2015/750818

Science. 2016;**15**(1-2):42-55. DOI: 10.3923/ajps.2016

December 2017. Indonesia: IOP Publishing Ltd; 2017. pp. 1-8

and physical activation for methane adsoption. Journal of Analytical

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

45

University of Technology; 2005. pp. 166-189

indcrop.2010.09.009

palm shell by ZnCl2

s10924-010-0210-3

2010;**5**(2):199-207

10.3390/polym9080355

10.21315/jps2017.28.2.8


[27] Punsuvon P, Anpanurak W, Vaithanomsat P, Tungkananuruk N. Fractionation of chemical components of oil palm trunk by steam explosion. In: Proceedings of 31st Congress on Science and Technology of Thailand; 14-17 December 2005. Thailand: Suranaree University of Technology; 2005. pp. 166-189

[13] Abdul Khalil HPS, Bhat IH, Khairul A. Preliminary study on enhanced properties and biological resistance of chemically modified *Acacia* spp. BioResources. 2010;**5**(4):2720-2737

[14] Abdul Khalil HPS, Bhat AH. Oil Palm Biomass: Fiber Cultivation, Production and its

[15] Islam MN, Zailani R, Ani FN. Pyrolytic oil from fluidized bed pyrolysis of oil palm shell and its characterization. Renewable Energy. 1999;**17**(1):73-84. DOI: 10.1016/

[16] Abdul Khalil HPS, Fazita N, Bhat AH, Nik Fuad NA. Development and material properties of new hybrid plywood from oil palm biomass. Materials and Design. 2010;**31**:417-427.

[17] Zaidon A, Nizam AMN, Noor MYM, Abood F, Paridah MT, Yuziah MYN, Jalaludin H. Properties of particleboard made from pretreated particles of rubberwood, EFB and rubberwood-EFB blend. Journal of Applied Science. 2007;**7**(8):1145-1151. DOI: 10.3923/

[18] Deraman M, Zakaria S, Husin M, Aziz AA, Ramli R, Moktar A, Sahri MH. X-ray diffraction studies on fiber of oil palm empty fruit bunch and rubberwood for medium-density

[19] Rafidah J, Asma W, Puad E, Mahanim SMA, Shaharuddin H. Toward zero waste production of value added products from waste oil palm trunk (WOPT). In: Proceedings of 8th Biomass Asia Workshop; 2-3 July 2012, Hanoi-Vietnam. Hanoi: BAW; 2012. pp. 25-46

[20] Abdul Khalil HPS, Siti Alwani M, Mohd Omar AK. Cell wall structure of various tropical plant waste fibers. Journal of the Korean Wood Science and Technology. 2007;**35**:

[21] Bhat IUH, Abdullah CK, Abdul Khalil HPS, Ibrahim MH, Nurul Fazita MR. Properties enhancement of oil palm waste: Oil palm trunk lumber. Journal of Reinforced Plastics

[22] Sreekala MS, Kumaran MG, Thomas S. Oil palm fibers: Morphology, chemical composition, surface modification and mechanical properties. Journal of Applied Polymer

[23] Dickison W. Integrative Plant Anatomy. New York: Harcourt Academic Press; 2000. 205 p [24] Rowell RM, Han JS, Rowell JS. Characterization and factors effecting fiber properties. In: Frollini E, Leão AL, Mattoso LHC, editors. Handbook of Natural Polymers and Agrofibers Composites. 2nd ed. São Carlos: Embrapa Instrumentação Agropecuária; 2000. pp. 115-134

[25] Law KN, Wan Daud WR, Ghazali A. Morphological and chemical nature of fiber strands

[26] Abdul Khalil HPS, Hanida S, Kang CW, Nik Fuaad NA. Agro-hybrid composite: The effects on mechanical and physical properties of oil palm fiber (EFB)/glass hybrid reinforced polyester composites. Journal of Reinforced Plastics and Composites. 2007;

of oil palm empty-fruit-bunch (OPEFB). BioResources. 2007;**2**(3):352-362

**26**(2):203-218. DOI: 10.1177/0731684407070027

and Composites. 2010;**29**:3301-3308. DOI: 10.1177/0731684410372262

Science. 1997;**66**:821-835. DOI: 10.1002/(SICI)1097-4628(19971031)66:5

fiberboard. Journal of Materials Science Letters. 1999;**18**:249-253

Varied Applications. New York: Nova Science Publishers; 2010. 113 p

S0960-1481(98)00112-8

44 Palm Oil

jas.2007.1145.1151

9-15

DOI: 10.1016/j.matdes.2009.05.040


[39] Nazir MS, Wahjoedi BA, Yussof AW, Abdullah MA.Eco-friendly extraction and characterization of cellulose from oil palm empty fruit bunches. BioResources. 2013;**8**(2):2161-2172

[52] Ibrahim NA, Hashim N, Abdul Rahman MZ, Wan Yunus WMZ. Mechanical properties and morphology of oil palm empty fruit bunch-polypropylene composites: effect of adding ENGAGE 7467. Journal of Thermoplastic Composite Materials. 2011;**24**(5):713-732.

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

47

[53] Ridzuan R, Shaler S, Jamaludin MA. Properties of medium density fibreboard from oil palm empty fruit bunch fibre. Journal of Oil Palm Research. 2002;**14**(2):34-40

[54] Mokhtar A, Hassan K, Aziz AA, Wahid MB. Plywood from oil palm trunks. Journal of

[55] Rosli F, Ghazali CMR, Abdullah MMAB, Hussin K. A review: Characteristics of oil palm trunk (OPT) and quality improvement of palm trunk plywood by resin impregnation.

[56] Choowang R, Hiziroglu S. Properties of thermally-compressed oil palm trunks (*Elaeis* 

[57] Choowang R. Effects of hot pressing on resistance of compressed oil palm wood to subterranean termite (*Coptotermes gestroi* Wasmann) attack. BioResources. 2014;**9**(1):656-661

[58] Srivaro S, Matan N, Lam F. Stiffness and strength of oil palm wood core sandwich panel under center point bending. Materials & Design. 2015;**84**:154-162. DOI: 10.1016/j.

[59] Srivaro S. Utilization of bamboo as lightweight sandwich panels. Materials Science/

[60] Onuorah EO. Properties of fiberboards made from oil palm (*Elaeis guineensis*) stem and/or mixed tropical hardwood sawmill residues. Journal of Tropical Forest Science.

[61] Sudin R, Shaari K. Effect of wood/gypsum ratio and density on strength properties of gypsum-bonded particleboard from oil palm stems. Journal of Tropical Forest Science.

[62] Haslett AN. Suitability of oil palm trunk for timber uses. Journal of Tropical Forest

[63] Abdul Khalil HPS, AzuraMN, Issam AM, Said MR, Mohd Adawi TO. Oil palm empty fruit bunches (OPEFB) reinforced in new unsaturated polyester composites. Journal of Reinforced Plastics and Composites. 2008;**27**:1817-1826. DOI: 0.1177/0731684407087619 [64] Sreekala MS, George J, Kumaran MG, Thomas S. The mechanical performance of hybrid phenol-formaldehyde-based composites reinforced with glass and oil palm fibers. Composites Science and Technology. 2002;**62**:339-353. DOI: 10.1016/S0266-3538(01)00219-6 [65] Rozman HD, Kumar RN, Abdul Khalil HPS, Abusamah A, Lim PP. Preparation and properties of oil palm composite based on methacrylic silane and glycidyl methacrylate.

European Polymer Journal. 1997;**33**:225-230. DOI: 10.1016/S0014-3057(96)00220-0 [66] Ismail H, Rosnah N, Rozman HD. Effects of various bonding systems on oil palm fiber reinforced rubber composites. European Polymer Journal. 1997;**33**:1231-1238. DOI: 10.

*guinensis*). Journal of Tropical Forest Science. 2015;**27**(1):39-46

Medziagotyra. 2016;**22**(1):60-64. DOI: 10.5755/j01.ms.22.1.8887

DOI: 10.1177/0892705711401549

Oil Palm Research. 2011;**23**:1159-1165

BioResources. 2016;**11**(2):5565-5580

matdes.2015.06.097

2005;**17**(4):497-507

1991;**4**(1):80-86

Science. 1990;**2**(3):243-251

1016/S0014-3057(96)00254-6


[52] Ibrahim NA, Hashim N, Abdul Rahman MZ, Wan Yunus WMZ. Mechanical properties and morphology of oil palm empty fruit bunch-polypropylene composites: effect of adding ENGAGE 7467. Journal of Thermoplastic Composite Materials. 2011;**24**(5):713-732. DOI: 10.1177/0892705711401549

[39] Nazir MS, Wahjoedi BA, Yussof AW, Abdullah MA.Eco-friendly extraction and characterization of cellulose from oil palm empty fruit bunches. BioResources. 2013;**8**(2):2161-2172

[40] Owolabi FAWT, Arniza G, Wan Daun WR, Alkharkhi AFM. Effect of alkaline peroxide pre-treatment on microfibrillated cellulose from oil palm fronds rachis amenable for pulp and paper and bio-composite production. BioResources. 2016;**11**(2):3013-3026.

[41] Shanmugarajah B, Kiew PL, Chew IML, Choong TSY, Tan KW. Isolation of nanocrystalline cellulose (NCC) from palm oil empty fruit bunch (EFB): Preliminary result on FTIR and DLS analysis. Chemical Engineering Transactiions. 2015;**45**:1705-1710. DOI: 10.3303/

[42] Indarti E, Roslan R, Husin M, Wan Daud WS. Polylactic acid bionanocomposites filled with nanocrystalline cellulose from TEMPO-oxidized oil palm lignocellulosic biomass.

[43] Abdul Khalil HPS, Hossain MS, Amiranajwa N, Fazita ASN, Haafiz RMR, Suraya LNM, Dungani R, Fizree HM. Production and characterization of the defatted oil palm shell

[44] Saba N, Tahir PM, Abdan K, Ibrahim NA.Preparation and characterization of fire retardant nano-filler from oil palm empty fruit bunch fibers. BioResources. 2015;**10**(3):4530-4543

[45] Liauw MY, Natan FA, Widiyanti P, Ikasari D, Indraswati N, Soetaredjo FE. Extraction of neem oil (*Azadirachta indica* A. Juss) using n-hexane and ethanol: Studies of oil quality kinetic and thermodynamic. ARPN Journal of Engineering and Applied Sciences.

[46] Ruiz H, Zambtrano M, Giraldo L, Sierra R, Pirajan JCM. Production and characterization of activated carbon from oil-palm shell for carboxylic acid adsorption. Oriental Journal

[47] Sukiran MA, Abnisa F, Daud WMAW, Bakar MA, Loh SK. A review of torrefaction of oil palm solid wastes for biofuel production. Energy Conversion and Management.

[48] Abdul Khalil HPS, Fizree HM, Jawaid M, Alattas OS. Preparation and characterization of nano-structured materials from oil palm ash: A bio-agricultural waste from oil palm

[49] Nasir S, Hussein MZ, Yusof NA, Zainal Z. Oil palm waste-based precursors as a renewable and economical carbon sources for the preparation of reduced grapheme oxide from grapheme oxide. Nanomaterials. 2017;**7**(7):182-188. DOI: 10.3390/nano7070182 [50] Holbery J, Houston D. Natural-fiber-reinforced polymer composites in automotive applications. Journal of Minerals, Metals & Materials Society. 2006;**58**(11):80-86. DOI:

[51] Rozman HD, Ismail H, Jaffri RM, Aminullah A, Ishak ZAM. Mechanical properties of polyethylene-oil palm empty fruit bunch composites. Polymer-Plastics Technology and

Engineering. 1998;**37**(4):495-507. DOI: 10.1080/03602559808001376

DOI: 10.15376/biores.11.2.3013-3026

BioResources. 2016;**11**(4):8615-8626

nanoparticles. Sains Malaysiana. 2016;**45**(5):833-839

of Chemistry. 2015;**31**(2):753-762. DOI: 10.13005/ojc/310217

2017;**49**:101-120. DOI: 10.1016/j.enconman.2017.07.011

mill. BioResources. 2011;**6**(4):4537-4546

10.1007/s11837-006-0234-2

CET1545285

46 Palm Oil

2008;**3**(3):49-54


[67] Ismail H, Jaffri RM, Rozman HD. Oil palm wood flour filled natural rubber composites: Fatigue and hysteresis behaviour. Polymer International. 2000;**49**:618-622. DOI: 10.1002/1097-0126(200006)49:6

[79] Mohd Ishak ZA, Aminullah A, Ismail H, Rozman HD. Effect of silane-based coupling agents and acrylic acid based compatibilizers on mechanical properties of oil palm empty fruit bunch filled high-density polyethylene composites. Journal of Applied

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

49

[80] Rozman HD, Tay GS, Kumar RN, Abusamah A, Ismail H, Mohd Ishak ZA. The effect of oil extraction of the oil palm empty fruit bunch on the mechanical properties of polypropylene-oil palm empty fruit bunch-glass hybrid composites. Polymer Plastic Technology

[81] Bakar AA, Hassan A, Yusof AFM. Effect of oil palm empty fruit bunch and acrylic impact modifier on mechanical properties and processability of unplasticized poly(vinyl chloride) composites. Polymer-Plastics Technology and Engineering. 2005;**44**:1125-1137.

[82] Rozman HD, Ahmadhilmi KR, Abubakar A. Polyurethane (PU)-oil palm empty fruit bunch (EFB) composites: The effect of EFBG reinforcement in mat form and isocyanate treatment on the mechanical properties. Polymer Testing. 2004;**23**:559-565. DOI:

[83] Khalid M, Ratnam CT, Chuah TG, Ali S, Choong TSY. Comparative study of polypropylene composites reinforced with oil palm empty fruit bunch fiber and oil palm derived cellulose. Materials and Design. 2008;**29**:173-178. DOI: 10.1016/j.matdes.2006.

[84] Jawaid M, Abdul Khalil HPS. Cellulosic/synthetic fiber reinforced polymer hybrid composites: A review. Journal Carbohydrate Polymers. 2011;**86**:1-18. DOI: 10.1016/j.

[85] Rozman HD, Tay GS, Kumar RN, Abusamah A, Ismail H, Mohd Ishak ZA. The effect of oil extraction of the oil palm empty fruit bunch on the mechanical properties of polypropylene-oil palm empty fruit bunch-glass hybrid composites. Polymer Plastic Technology

[86] Amin KAM, Khairiah HB. Palm-based bio-composites hybridized with kaolinite. Journal

[87] Kumar RN, Wei LM, Rozman HD, Bakar AA. Fire resistant sheet moulding composites from hybrid reinforcements of oil palm fibers and glass fiber. International Journal of

[88] Khanam,PN, Abdul Khalil HPS, Reddy GR, Naidu SV. Tensile, flexural and chemical resistance properties of sisal fiber reinforced polymer composites: Effect of fiber surface treatment. Journal of Polymers and The Environment. 2011;**19**:115-119. DOI: 10.1007/

[89] Abdul Khalil HPS, Kang CW, Khairul A, Ridzuan R, Adawi TO.The effect of different laminations on mechanical and physical properties of hybrid composites. Journal of Reinforced

Plastics and Composites. 2009;**28**:1123-1137. DOI: abs/10.1177/0731684407087755

of Applied Polymer Science. 2007;**105**:2488-2496. DOI: 10.1002/app.25536

Engineering. 2001;**40**:103-115. DOI: abs/10.1081/PPT-100000058

Polymer Science. 1998;**68**:2189-2203. DOI: 10.1002/(SICI)1097-4628(19980627)68

Engineering. 2001;**40**:103-115. DOI: 10.1080/00914030500306446

DOI: 10.1081/PTE-200065237

11.002

carbpol.2011.04.043

s10924-010-0219-7

10.1016/j.polymertesting.2003.11.004

Polymeric Material. 1997;**37**:43-52


[79] Mohd Ishak ZA, Aminullah A, Ismail H, Rozman HD. Effect of silane-based coupling agents and acrylic acid based compatibilizers on mechanical properties of oil palm empty fruit bunch filled high-density polyethylene composites. Journal of Applied Polymer Science. 1998;**68**:2189-2203. DOI: 10.1002/(SICI)1097-4628(19980627)68

[67] Ismail H, Jaffri RM, Rozman HD. Oil palm wood flour filled natural rubber composites: Fatigue and hysteresis behaviour. Polymer International. 2000;**49**:618-622. DOI:

[68] Abdul Khalil HPS, Firoozian P, Bakare IO, Akil HM, Noor AM. Exploring biomass based carbon black as filler in epoxy composites: Flexural and thermal properties. Materials

[69] Ibrahim NA, Ahmad SNA, Yunus WMZW, Dahlan KZM. Effect of electron beam irradiation and poly(vinyl pyrrolidone) addition on mechanical properties of polycaprolactone with empty fruit bunch fiber (OPEFB) composite. Express Polymer Letters. 2009;**3**:

[70] Chai L, Zakaria S, Chia C, Nabihah S, Rasid R. Physico-mechanical properties of PF composite board from EFB fibers using liquefaction technique. Iranian Polymer Journal.

[71] Kaddami H, Dufresne A, Khelifi B, Bendahou A, Taourirte M, Raihane M, Issartel N, Sautereau H, Gerard JF, Sami N. Short palm tree fibers: Thermoset matrices composites.

[72] Min AM, Chuah TG, Chantara TR. Thermal and dynamic mechanical analysis of polyethylene modified with crude palm oil. Materials and Design. 2008;**29**:992-999. DOI:

[73] Siyamak S, Ibrahim NA, Abdolmohammadi S, Wan Yunus WZ, Rahman MZ. Effect of fiber esterification on fundamental properties of oil palm empty fruit bunch fiber/ poly(butylene adipate-*co*-terephthalate) biocomposites. International Journal of

[74] Arif MF, Yusoff PS, Ahmad MF. Effects of chemical treatment on oil palm empty fruit bunch reinforced high density polyethylene composites. Journal of Reinforced Plastics

[75] Abdul Khalil HPS, Tehrani MA, Davoudpour Y, Bhat AH, Jawaid M, Hasan A. Natural fiber reinforced poly(vinyl chloride) composites: A review. Journal of Reinforced Plastics

[76] Abdul Khalil HPS, Poh BT, Jawaid M. The effect of soil burial degradation of oil palm trunk fiber-filled recycled polypropylene composites. Journal of Reinforced Plastics and

[77] Roshafima RA, Wan Aizan WAR. Low density polyethylene/tapioca starch biofilm with palm oil as processing aid for food packaging. In: Proceeding of The International Conference on Advances Materials and Processing Technologies; 14-17 December 2008.

[78] Rozman HD, Peng GB, Mohd Ishak ZA. The effect of compounding techniques on the mechanical properties of oil palm empty fruit bunch-polypropylene composites. Journal of Applied Polymer Science. 1998;**70**:2647-2655. DOI: 10.1002/(SICI)1097-4628(19981226)70

Molecular Sciences. 2012;**13**:1327-1346. DOI: 10.3390/ijms13021327

and Composites. 2010;**29**:2105-2118. DOI: 10.1177/0731684409348976

and Composites. 2013;**32**:330-356. DOI: abs/10.1177/0731684412458553

Composites. 2010;**29**:1653-1663. DOI: 10.1177/0731684409102939

Kingdom of Bahrain: IEEE; 2008. pp. 156-169

Composites: Part A. 2006;**37**:1413-1422. DOI: 10.1016/j.compositesa.2005.06.020

and Design. 2010;**31**:3419-3425. DOI: 10.1016/j.matdes.2010.01.044

226-234. DOI: 10.3144/expresspolymlett.2009.29

10.1002/1097-0126(200006)49:6

2009;**18**:917-923

48 Palm Oil

10.1016/j.matdes.2007.03.023


[90] Jawaid M, Abdul Khalil HPS, Bakar AA, Khanam PN. Hybrid composite made from oil palm empty fruit bunches/jute fibers: Water absorption, thickness swelling and density behavior. Journal of Polymers and The Environment. 2011;**19**:106-109. DOI: 10.1007/ s10924-010-0203-2

[102] Rosamah E, Hossain MS, Abdul Khalil HPS, Nadira WOW, Dungani R, Nur Amiranajwa AS, Suraya LMN, Fizree HM, Mohd Omar AK. Properties enhancement using oil palm shell nanoparticles of fibers reinforced polyester hybrid composites. Advanced

Biomaterial from Oil Palm Waste: Properties, Characterization and Applications

http://dx.doi.org/10.5772/intechopen.76412

51

Composite Materials. 2017;**26**(3):259-272. DOI: 10.1080/09243046.2016.1145875

[103] Rosazley R, Shazana MZ, Izzati MA, Fareezal AW, Rushdan I, Ainun ZMA. Characterization of nanofibrillated cellulose produced from oil palm empty fruit bunch fibers (OPEFB) using ultrasound. Journal of Contemporary Issues and Thought. 2016;**6**:28-35

[104] Rohaizu R, Wanrosli WD. Sono-assisted TEMPO oxidation of oil palm lignocellulosic biomass for isolation of nanocrystalline cellulose. Ultrasonics Sonochemistry.

[105] Mohaiyiddin MS, Lin OH, Owi WT, Chan CH, Chia CH, Zakaria S, Villagracia AR, Md Akil H. Characterization of nanocellulose recovery from *Elaeis guineensis* frond for sustainable development. Clean Technologies and Environmental Policy. 2016;**18**:

[106] Saurabh CK, Dungani R, Owolabi AF, Atiqah NS, Zaidon A, Sri Aprilia NA, Sarker ZM, Abdul Khalil HPS. Effect of hydrolysis treatment on cellulose nanowhiskers from oil palm (*Elaeis guineesis*) fronds: morphology, chemical, crystallinity, and thermal charac-

[107] de Adriana C, de Sena NAR, Vanessa R, Vanessa KA, Carolina CA, Marcio TC, Luiz HMC, José MM. Production of cellulose nanowhiskers from oil palm mesocarp fibers by acid hydrolysis and microfluidization. Journal of Nanoscience and Nanotechnology.

[108] Chieng BW, Lee SH, Ibrahim NA, Then YY, Loo YY. Isolation and characterization of cellulose nanocrystals from oil palm mesocarp fiber. Polymer. 2017;**9**(355):1-11. DOI:

[109] Bhat AH, Abdul Khalil HPS. Exploring nano filler based on oil palm ash in polypropyl-

[110] Surip SN, Bonnia NN, Anuar H. Nanofibers from oil palm trunk (OPT): Preparation & chemical analysis. In: Proceedings of the IEEE Symposium on Business, Engineering and Industrial Applications; 23-26 September 2012. Indonesia: IEEE; 2012. pp. 809-812

[111] Lamaminga J, Hashim R, Sulaimana O, Leh CP, Sugimoto T, Nordin NA. Cellulose nanocrystals isolated from oil palm trunk. Carbohydrate Polymers. 2015;**127**:202-208.

2017;**34**:631-639. DOI: 10.1016/j.ultsonch.2016.06.040

2503-2512. DOI: 10.1007/s10098-016-1191-2

teristics. BioResources. 2016;**11**(3):6742-6755

10.3390/polym9080355

2017;**17**(7):4970-4976. DOI: 10.1166/jnn.2017.13451

ene composites. BioResources. 2011;**6**:1288-1297

DOI: 10.1016/j.carbpol.2015.03.043


[102] Rosamah E, Hossain MS, Abdul Khalil HPS, Nadira WOW, Dungani R, Nur Amiranajwa AS, Suraya LMN, Fizree HM, Mohd Omar AK. Properties enhancement using oil palm shell nanoparticles of fibers reinforced polyester hybrid composites. Advanced Composite Materials. 2017;**26**(3):259-272. DOI: 10.1080/09243046.2016.1145875

[90] Jawaid M, Abdul Khalil HPS, Bakar AA, Khanam PN. Hybrid composite made from oil palm empty fruit bunches/jute fibers: Water absorption, thickness swelling and density behavior. Journal of Polymers and The Environment. 2011;**19**:106-109. DOI: 10.1007/

[91] Kamel S. Nanotechnology and its applications in lignocellulosic composites: A mini review. Express Polymer Letters. 2007;**1**:546-575. DOI: 10.3144/expresspolymlett.2007.78

[92] Gabriel AS. Introduction to nanotechnology and its applications to medicine. Surgical

[93] Schmidt D, Shah D, Giannelis EP. New advances in polymer/layered silicate nanocomposites. Current Opinion in Solid State and Materials Science. 2002;**6**:205-212. DOI:

[94] Fahma F, Iwamoto S, Hori N, Iwata T, Takemura A. Isolation, preparation, and characterization of nanofibers from oil palm empty-fruit-bunch (opefb). Cellulose. 2010;**17**:977-985.

[95] Fahma F, Iwamoto S, Hori N, Iwata T, Takemura A. Effect of pre-acid-hydrolysis treatment on morphology and properties of cellulose nanowhiskers from coconut husk.

[96] Mazlita Y, Lee HV, Hamid SBA. Preparation of cellulose nanocrystals bio-polymer from agro-industrial wastes: Separation and characterization. Polymers & Polymer

[97] Ferrer A, Filpponen I, Rodríguez A, Laine J, Rojas OJ. Valorization ofresidual empty palm fruit bunch Fibers (EPFBF) by microfluidization: Produc-tion of nanofibrillated cellulose and EPFBF nanopaper. Bioresource Technology. 2012;**125**:249-255. DOI:

[98] Dungani R, Abdul Khalil HPS, Islam MN, Davoudpour Y, Rumidatul A. Modification of the inner part of the oil palm trunk lumber (OPTL) with oil palm shell (OPS) nanoparticles and phenol formaldehyde (PF) resin: Physical, mechanical and thermal proper-

[99] Sasthirya S, Abdul Khalil HPS, Ahmad ZA, Islam MN, Dungani R, Fizree HM. Carbon nanofiller-enhanced ceramic composites: Thermal and electrical studies. BioResources.

[100] Goh KY, Ching YC, Chuah CH, Abdullah LC, Liou NS. Individualization of microfibrillated celluloses from oil palm empty fruit bunch: Comparative studies between acid hydrolysis and ammonium persulfate oxidation. Cellulose. 2016;**23**:379-390. DOI:

[101] Dungani R, Islam MN, Abdul Khalil HPS, Hartati S, Abdullah CK, Dewi M, Hadiyane A. Termite resistance study of oil palm trunk lumber (OPTL) impregnated with oil palm

shell meal and phenol- formaldehyde resin. BioResources. 2013;**8**(4):4937-4950

Neurology. 2004;**61**:216-220. DOI: 10.1016/j.surneu.2003.09.036

Cellulose. 2011;**18**:443-450. DOI: 10.1007/s10570-010-9480-0

s10924-010-0203-2

50 Palm Oil

10.1016/S1359-0286(02)00049-9

DOI: 10.1007/s10570-010-9436-4

Composites. 2016;**24**(9):719-728

10.1016/j.biortech.2012.08.108

2014;**9**(2):3143-3151

10.1007/s10570-015-0812-y

ties. BioResources. 2013;**9**(1):455-471


**Chapter 4**

**Provisional chapter**

**Potential Application of Oil Palm Wastes Charcoal**

**Potential Application of Oil Palm Wastes Charcoal** 

DOI: 10.5772/intechopen.74863

This study is aimed at investigating the potentials of oil palm wastes as an alternative to fossil fuels (coal) for domestic heat generation via briquettes (solid fuels) production. In this study oil palm wastes such as empty fruit bunches (EFB), mesocarp fiber (MF) and palm kernel shell (PKS) were pyrolyzed at temperatures of 400°C for 120 min and a heating rate of 10°C min−1. The biochar and bio-oil obtained were blended in the ratio of 60:40 weight percentages and compressed at a constant pressure of 400 kg cm−2 for charcoal briquettes production. The combustion profiles, heat release of the charcoal briquettes and Malaysian sub-bituminous coal were analyzed and compared through thermogravimetric analysis (TGA). Comparably, MF and PKS charcoal briquettes had higher HHV of 26.15 and 25.99 MJ kg−1, individually than coal which has 24.21 MJ kg−1, while EFB charcoal briquette showed the lowest value 23.93 MJ kg−1. Therefore, it can be said that all the charcoal briquettes showed a positive sign to replace coal. The maximum and minimum heat released of 0.059 and 0.048 W were obtained from the combustion of EFB and MF charcoal briquettes. It was established that in each ton of raw (dry basis) of EFB, MF, and PKS, there is 0.177, 0.212 and 0.228 tons of charcoal briquettes which correspond to 1.866, 2.055 and 2.414 MW of heat. Therefore, the findings in this study could contribute toward achieving the targeted 500 MW of green energy initiated in 2005 by the Malaysian government. Furthermore, the production of charcoal briquettes could be one of the proper methods to minimize the agricultural disposal

**Keywords:** oil palm wastes, charcoal briquettes, coal replacement, heat generation

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

**Briquettes for Coal Replacement**

**Briquettes for Coal Replacement**

Aminu Aliyu Safana, Nurhayati Abdullah and

Aminu Aliyu Safana, Nurhayati Abdullah and

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.74863

Fauziah Sulaiman

Fauziah Sulaiman

**Abstract**

problem in Malaysia.

#### **Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement**

DOI: 10.5772/intechopen.74863

Aminu Aliyu Safana, Nurhayati Abdullah and Fauziah Sulaiman Aminu Aliyu Safana, Nurhayati Abdullah and Fauziah Sulaiman

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.74863

#### **Abstract**

This study is aimed at investigating the potentials of oil palm wastes as an alternative to fossil fuels (coal) for domestic heat generation via briquettes (solid fuels) production. In this study oil palm wastes such as empty fruit bunches (EFB), mesocarp fiber (MF) and palm kernel shell (PKS) were pyrolyzed at temperatures of 400°C for 120 min and a heating rate of 10°C min−1. The biochar and bio-oil obtained were blended in the ratio of 60:40 weight percentages and compressed at a constant pressure of 400 kg cm−2 for charcoal briquettes production. The combustion profiles, heat release of the charcoal briquettes and Malaysian sub-bituminous coal were analyzed and compared through thermogravimetric analysis (TGA). Comparably, MF and PKS charcoal briquettes had higher HHV of 26.15 and 25.99 MJ kg−1, individually than coal which has 24.21 MJ kg−1, while EFB charcoal briquette showed the lowest value 23.93 MJ kg−1. Therefore, it can be said that all the charcoal briquettes showed a positive sign to replace coal. The maximum and minimum heat released of 0.059 and 0.048 W were obtained from the combustion of EFB and MF charcoal briquettes. It was established that in each ton of raw (dry basis) of EFB, MF, and PKS, there is 0.177, 0.212 and 0.228 tons of charcoal briquettes which correspond to 1.866, 2.055 and 2.414 MW of heat. Therefore, the findings in this study could contribute toward achieving the targeted 500 MW of green energy initiated in 2005 by the Malaysian government. Furthermore, the production of charcoal briquettes could be one of the proper methods to minimize the agricultural disposal problem in Malaysia.

**Keywords:** oil palm wastes, charcoal briquettes, coal replacement, heat generation

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

## **1. Introduction**

#### **1.1. Energy demand**

International Energy Agency (IEA) in its new policy scenario stated that the world energy demand is anticipated to persistently rise yearly to about 1.2% from 2008 to 2035, with 70% of the demand imminent from the developing countries. However, the majority (87%) of this energy demand will be obtained mainly from fossil fuels. The rise of the entire global energy demand is associated with the increase in the world population and global economic growth [1, 2]. Furthermore, the energy uses in the main cities of developing countries is related to stages of greenhouse-gas (GHG) emissions and are anticipated to increase [3]. Global warming has been one of the fundamental environmental problems for many decades. However, the quantity of CO2 in the atmosphere will persistently increase, except key modifications are made in the manner fossil fuels are utilized in the energy production [4, 5]. Fossil fuels still control the world's energy market value of about 1.5 trillion United States Dollars (USD). For example, the World Energy Council (WEC) estimated in 2007 that recoverable coal mineral deposits would be about 850 billion tons in 2006 [6].

The burning of coal generates more CO2 emissions than combustion of both oil and natural gas by 1.5 and 2 separately [7]. Malaysia is not an exception in the use of fossil fuels for power generation. As at 2010, the coal generation in Malaysia is derived majorly from six mines in Sarawak. There are about 1724 million tons of coal resources of which 274 million tons are identified, 347 million tons indicated and the balance of 1102 million tons as inferred [2]. Presently, community and political sensitivities to environmental problems and energy security have focused on the promotion of non-fossil fuel energy sources instead of fossil fuels. Renewable energy sources such as small hydropower, solar, wind, geothermal and biomass have presently contributed 14% of total world energy consumption, of which 62% is biomass [8].

and solar energy (sunlight) with water are mixed via photosynthesis. However, burning of biomass results in the release of carbon dioxide into the atmosphere accompanied by the conversion of stored chemical energy in the biomass into thermal energy [11]. Biomass supplies a clean, renewable energy source that could considerably improve our environment, economy and energy security by reducing the burning of fossil fuels, emission of greenhouse gasses (GHG)

**Decades 2001 2010 2020 2030 2040** Total consumption (million tons oil equivalent) 10,038 10,549 11,425 12,352 13,310 Biomass 1080 1313 1791 2483 3271 Large hydro 22.70 266 309 341 358 Geothermal 43.20 86 186 333 493 Small hydro 9.50 19 49 106 189 Wind 4.70 44 266 542 688 Solar thermal 4.10 15 66 244 480 Photovoltaic 0.10 2.00 24 221 784 Solar thermal electricity 0.10 0.40 3.00 16 68 Marine (tidal/wave/ocean) 0.05 0.10 0.40 3.00 20 Total RES 1365.5 1745.5 2964.4 4289 6351 Contribution of RES in (%) 13.60 16.60 23.60 34.70 47.70

Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement

http://dx.doi.org/10.5772/intechopen.74863

55

Biomass can be used to generate heat and power for industry and domestic purposes. This particular value over wind power and solar energy via photovoltaic cells makes biomass a significant pillar in the energy contribution today and in the future. Biomass such as wood, energy crops, forest and agricultural residue, industrial and municipal wastes could be the prominent alternatives to coal [12, 13]. Moreover, according to statistics from the IEA, biomass contributed about 10% of primary global energy demand in the year 2005. Biomass can be converted into gas and liquid fuels (bio-oil, biodiesel, and bioethanol) through gasification and pyrolysis, transesterification and fermentation

Biomass is a lignocellulosic material obtained from living organic substances such as wood and agricultural wastes. However, non-lignocellulosic substances, like an animal and municipal solid wastes (MSW) are also regarded as biomass. The three major constituents of biomass [15, 16] are cellulose, hemicellulose, and lignin. It also contains water extractives and ash [16]. The constituents are highly associated and chemically bonded by noncovalent forces. They are cross-linked collectively, thus bearing composition and firmness of the plant [15].

)0.9–1.7]m for cellulose, hemicellulose, and lignin respectively,

H10O<sup>5</sup>

)m,

The basic structures of biomass lignocelluloses components can be written as (C<sup>6</sup>

and environmental pollution [12].

**Table 1.** Global renewable energy scenario by 2040.

respectively [14].

)m and [C<sup>9</sup>

H10O<sup>3</sup>

where m is a degree of polymerization [14].

·(OCH<sup>3</sup>

(C<sup>5</sup> H8 O4

#### **1.2. Renewable energy sources**

Renewable energy is an energy source which does not vanish. These types of energy sources have been in use since the beginning of human civilization. They are abundantly available because they exist naturally in our environment [9]. There are three sources of energy and these include; fossil fuels, renewable and nuclear power sources. However, among these energy sources, renewable energy is the only source that can be used to generate energy repeatedly. They can also be used easily to provide the domestic energy demand for local communities. **Table 1** presents the global renewable energy scenario as predicted by the year 2040. Sun is the largest source of all energies. Renewable energy sources (RES) have advantages for the alleviation of greenhouse gas emission, minimizing global warming by replacing conventional energy sources and reducing disposal of a lot of wastes. Renewable energy sources such as biomass, hydropower, geothermal, solar, the wind and marine energies provide about 14% of the total world energy demand. The percentage is predicted to improve extensively to about 30–80% by 2100 as shown in **Table 1** [10].

#### **1.3. Biomass energy**

Among the renewable energies, biomass is the largest and an essential one that has been employed in both developed and developing countries. Biomass is formed when carbon dioxide


**Table 1.** Global renewable energy scenario by 2040.

**1. Introduction**

54 Palm Oil

**1.1. Energy demand**

the quantity of CO2

deposits would be about 850 billion tons in 2006 [6].

The burning of coal generates more CO2

**1.2. Renewable energy sources**

**1.3. Biomass energy**

International Energy Agency (IEA) in its new policy scenario stated that the world energy demand is anticipated to persistently rise yearly to about 1.2% from 2008 to 2035, with 70% of the demand imminent from the developing countries. However, the majority (87%) of this energy demand will be obtained mainly from fossil fuels. The rise of the entire global energy demand is associated with the increase in the world population and global economic growth [1, 2]. Furthermore, the energy uses in the main cities of developing countries is related to stages of greenhouse-gas (GHG) emissions and are anticipated to increase [3]. Global warming has been one of the fundamental environmental problems for many decades. However,

made in the manner fossil fuels are utilized in the energy production [4, 5]. Fossil fuels still control the world's energy market value of about 1.5 trillion United States Dollars (USD). For example, the World Energy Council (WEC) estimated in 2007 that recoverable coal mineral

gas by 1.5 and 2 separately [7]. Malaysia is not an exception in the use of fossil fuels for power generation. As at 2010, the coal generation in Malaysia is derived majorly from six mines in Sarawak. There are about 1724 million tons of coal resources of which 274 million tons are identified, 347 million tons indicated and the balance of 1102 million tons as inferred [2]. Presently, community and political sensitivities to environmental problems and energy security have focused on the promotion of non-fossil fuel energy sources instead of fossil fuels. Renewable energy sources such as small hydropower, solar, wind, geothermal and biomass have presently contributed 14% of total world energy consumption, of which 62% is biomass [8].

Renewable energy is an energy source which does not vanish. These types of energy sources have been in use since the beginning of human civilization. They are abundantly available because they exist naturally in our environment [9]. There are three sources of energy and these include; fossil fuels, renewable and nuclear power sources. However, among these energy sources, renewable energy is the only source that can be used to generate energy repeatedly. They can also be used easily to provide the domestic energy demand for local communities. **Table 1** presents the global renewable energy scenario as predicted by the year 2040. Sun is the largest source of all energies. Renewable energy sources (RES) have advantages for the alleviation of greenhouse gas emission, minimizing global warming by replacing conventional energy sources and reducing disposal of a lot of wastes. Renewable energy sources such as biomass, hydropower, geothermal, solar, the wind and marine energies provide about 14% of the total world energy demand. The percentage

is predicted to improve extensively to about 30–80% by 2100 as shown in **Table 1** [10].

Among the renewable energies, biomass is the largest and an essential one that has been employed in both developed and developing countries. Biomass is formed when carbon dioxide

in the atmosphere will persistently increase, except key modifications are

emissions than combustion of both oil and natural

and solar energy (sunlight) with water are mixed via photosynthesis. However, burning of biomass results in the release of carbon dioxide into the atmosphere accompanied by the conversion of stored chemical energy in the biomass into thermal energy [11]. Biomass supplies a clean, renewable energy source that could considerably improve our environment, economy and energy security by reducing the burning of fossil fuels, emission of greenhouse gasses (GHG) and environmental pollution [12].

Biomass can be used to generate heat and power for industry and domestic purposes. This particular value over wind power and solar energy via photovoltaic cells makes biomass a significant pillar in the energy contribution today and in the future. Biomass such as wood, energy crops, forest and agricultural residue, industrial and municipal wastes could be the prominent alternatives to coal [12, 13]. Moreover, according to statistics from the IEA, biomass contributed about 10% of primary global energy demand in the year 2005. Biomass can be converted into gas and liquid fuels (bio-oil, biodiesel, and bioethanol) through gasification and pyrolysis, transesterification and fermentation respectively [14].

Biomass is a lignocellulosic material obtained from living organic substances such as wood and agricultural wastes. However, non-lignocellulosic substances, like an animal and municipal solid wastes (MSW) are also regarded as biomass. The three major constituents of biomass [15, 16] are cellulose, hemicellulose, and lignin. It also contains water extractives and ash [16]. The constituents are highly associated and chemically bonded by noncovalent forces. They are cross-linked collectively, thus bearing composition and firmness of the plant [15]. The basic structures of biomass lignocelluloses components can be written as (C<sup>6</sup> H10O<sup>5</sup> )m, (C<sup>5</sup> H8 O4 )m and [C<sup>9</sup> H10O<sup>3</sup> ·(OCH<sup>3</sup> )0.9–1.7]m for cellulose, hemicellulose, and lignin respectively, where m is a degree of polymerization [14].

#### **1.4. Oil palm biomass in Malaysia**

Palm oil has made significant and continued development in the worldwide market in the past few decades. Malaysia and Indonesia are the top producing countries of palm oil in the world, which together produced about 85% of the total world palm oil. Additional producing countries comprise Thailand, Columbia, Nigeria, Papua New Guinea and Ecuador [17]. Oil palm is the most important product that has changed the situation of the agricultural sector and economy in Malaysia. It is projected that in the period 2016–2020, the standard yearly production of palm oil in Malaysia will achieve 15.4 million tons. Lignocellulosic biomass which is produced from the oil palm industries incorporate oil palm trunks (OPT), oil palm fronds (OPF), empty fruit bunches (EFB) and palm pressed fibers (PPF), palm shells, and palm oil mill effluent (POME). The occurrence of these oil palm wastes has created a significant disposal crisis, but the primary objectives of waste management in Malaysia are to limit and reuse the waste and recuperate the energy. This principally applies to agro-industrial wastes, for example, palm oil residues as applied to municipal waste. One of the significant advantages of oil palm wastes is that the palm oil mill is independent in energy, utilizing PPF, EFB, and shell are used as fuel to generate steam in waste fuel boilers for handling, and power-generation with steam turbines [18].

these processes include dewatering and drying, pulverization or grinding, and densification process such as pellets. Besides the above-mentioned conventional pre-treatment, there is also another important and efficient method for upgrading biomass as a fuel known as torrefaction [11]. Torrefaction can be described as a thermochemical process carried out in the temperature range of 200–300°C under an oxygen-free condition with a purpose to upgrade the

Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement

http://dx.doi.org/10.5772/intechopen.74863

57

Pyrolysis conversion process is one of the prominent thermochemical methods through which biomass are converted into three major by-products namely; solid char, bio-oil, and gases [27, 28]. A pyrolysis procedure is divided into slow pyrolysis and fast pyrolysis. Slow pyrolysis yields more biochar yet less bio-oil with around 35% as biochar, 30% as bio-oil and 35% as syngas. However, fast pyrolysis gives a yield of around 15% biochar, 70% bio-oil, and 13% syngas [20]. The pyrolysis parameters such as temperature, retention time, heating rate, particle size, inert gas and reactor type give different pyrolysis product yields. Temperature and holding time are among the most significant operating parameters. As the temperature and residence time rise, the biochar yield is reduced because of gasification of the solid biochar. With increased temperature up to 500°C, the greatest bio-oil yield can be accomplished. However, the yield drops with further increment in temperature. Interestingly, gas products are favored at high temperature and long holding time not surprisingly because of the quantity of volatiles released with increasing temperature [20]. For woody biomass, the liquid product is typically maximized at a temperature around 500–520°C for fast pyrolysis. However, lower temperatures favor the production

Briquetting is a process of compressing materials into a small portable size with a diameter ranging from 30 to 100 mm and of any length depending on the technology applied, which could either be screw or piston compression [30]. The briquetting process is perhaps regarded as a way to improve the application of low-grade wastes materials. Briquetting is mainly used for compacting of biomass and none biomass sources such as plastic, many types of milled paper wastes and other combustible wastes [31]. Municipal solid waste (MSW), industrial waste and sludge are used to produce fuel briquettes in some countries [32]. It is well-known and believed that biomass residues could be utilized as a replacement to fuel for combustion at coal-fired power plants [33]. There are many processes for briquetting; they include pre-treatment and operational parameters (factors) that controlled the quality of fuel briquettes. Furthermore, physical properties such as a binder, moisture content, particle size and compressing forces (pressure) are among the factors that influence the quality of briquettes regarding durability and resistivity during transportation [34]. However, a briquette quality

In this research, the potential application of empty fruit bunches, mesocarp fiber and palm kernel shell for coal replacement was investigated. These biomasses were pyrolyzed and the bio-oil and biochar obtained were used to form charcoal briquettes (solid fuels). The viscosity

of bio-oil was improved by the addition of 10% starch and used as a binder.

quality standard of biomass [26].

of biochar [29].

**1.6. Biomass briquetting for solid fuels**

significantly depends on the drying process [35].

The oil extraction rate is just around 10% of the palm oil production with the larger part 90% remaining as biomass. For instance, in 1 kg of palm oil about 4 kg of dry biomass is generated [19, 20]. The oil palm wastes generated from palm oil industry in Malaysia is among the most excellent biomass residues. After being lignocellulosic biomass, they also show non-edible characteristic which makes them attractive globally [21]. Specifically, Malaysia produced around 9.9 million tons of palm oil wastes as a fundamental of biomass sources including EFB, shell, and fiber, which continues to expand at 5% yearly [22]. However, the proportions of agricultural residues generated from oil palm include mesocarp fiber (13.5%), palm kernel shell (5.5%) and empty fruit bunch (22%). Palm shell and palm fiber were utilized as fuel to power the steam boilers, whereas empty fruit bunch is used for mulching in the plantation area [23].

In 2009, the oil palm wastes rendered in Malaysia were 7.0 million tons of EFB, 11.6 million tons of PKS and MF, 44.8 million tons of fronds and 13.9 million tons of trunks. However, the eminent expected utility of these wastes is assumed to circumscribe [24]. Between the oil palm biomass, mesocarp fiber contains a high calorific value in comparison with palm shell and EFB [23]. These oil palm residues comprise various chemical composition and high heating value of about 18–19 MJ kg−1. They are better complement and ingredients for fuels in the form of pellets and briquettes [25]. It has been declared that in the year 2012 there were profitable oil palm wastes (dry weight) of about 83 million tons in Malaysia. Moreover, it will eventually ascend to 100 million tons in few years to come (2020) [24]. These wastes will continue to contribute to the agricultural wastes disposal problem in Malaysia except necessary action are taken.

#### **1.5. Thermochemical conversion of biomass**

The direct combustion of biomass is not the best way to use it as burning fuel. Some processes can be used to upgrade the standard of biomass for better and proper application. Some of these processes include dewatering and drying, pulverization or grinding, and densification process such as pellets. Besides the above-mentioned conventional pre-treatment, there is also another important and efficient method for upgrading biomass as a fuel known as torrefaction [11]. Torrefaction can be described as a thermochemical process carried out in the temperature range of 200–300°C under an oxygen-free condition with a purpose to upgrade the quality standard of biomass [26].

Pyrolysis conversion process is one of the prominent thermochemical methods through which biomass are converted into three major by-products namely; solid char, bio-oil, and gases [27, 28]. A pyrolysis procedure is divided into slow pyrolysis and fast pyrolysis. Slow pyrolysis yields more biochar yet less bio-oil with around 35% as biochar, 30% as bio-oil and 35% as syngas. However, fast pyrolysis gives a yield of around 15% biochar, 70% bio-oil, and 13% syngas [20]. The pyrolysis parameters such as temperature, retention time, heating rate, particle size, inert gas and reactor type give different pyrolysis product yields. Temperature and holding time are among the most significant operating parameters. As the temperature and residence time rise, the biochar yield is reduced because of gasification of the solid biochar. With increased temperature up to 500°C, the greatest bio-oil yield can be accomplished. However, the yield drops with further increment in temperature. Interestingly, gas products are favored at high temperature and long holding time not surprisingly because of the quantity of volatiles released with increasing temperature [20]. For woody biomass, the liquid product is typically maximized at a temperature around 500–520°C for fast pyrolysis. However, lower temperatures favor the production of biochar [29].

#### **1.6. Biomass briquetting for solid fuels**

**1.4. Oil palm biomass in Malaysia**

56 Palm Oil

power-generation with steam turbines [18].

**1.5. Thermochemical conversion of biomass**

Palm oil has made significant and continued development in the worldwide market in the past few decades. Malaysia and Indonesia are the top producing countries of palm oil in the world, which together produced about 85% of the total world palm oil. Additional producing countries comprise Thailand, Columbia, Nigeria, Papua New Guinea and Ecuador [17]. Oil palm is the most important product that has changed the situation of the agricultural sector and economy in Malaysia. It is projected that in the period 2016–2020, the standard yearly production of palm oil in Malaysia will achieve 15.4 million tons. Lignocellulosic biomass which is produced from the oil palm industries incorporate oil palm trunks (OPT), oil palm fronds (OPF), empty fruit bunches (EFB) and palm pressed fibers (PPF), palm shells, and palm oil mill effluent (POME). The occurrence of these oil palm wastes has created a significant disposal crisis, but the primary objectives of waste management in Malaysia are to limit and reuse the waste and recuperate the energy. This principally applies to agro-industrial wastes, for example, palm oil residues as applied to municipal waste. One of the significant advantages of oil palm wastes is that the palm oil mill is independent in energy, utilizing PPF, EFB, and shell are used as fuel to generate steam in waste fuel boilers for handling, and

The oil extraction rate is just around 10% of the palm oil production with the larger part 90% remaining as biomass. For instance, in 1 kg of palm oil about 4 kg of dry biomass is generated [19, 20]. The oil palm wastes generated from palm oil industry in Malaysia is among the most excellent biomass residues. After being lignocellulosic biomass, they also show non-edible characteristic which makes them attractive globally [21]. Specifically, Malaysia produced around 9.9 million tons of palm oil wastes as a fundamental of biomass sources including EFB, shell, and fiber, which continues to expand at 5% yearly [22]. However, the proportions of agricultural residues generated from oil palm include mesocarp fiber (13.5%), palm kernel shell (5.5%) and empty fruit bunch (22%). Palm shell and palm fiber were utilized as fuel to power the steam boilers, whereas empty fruit bunch is used for mulching in the plantation area [23]. In 2009, the oil palm wastes rendered in Malaysia were 7.0 million tons of EFB, 11.6 million tons of PKS and MF, 44.8 million tons of fronds and 13.9 million tons of trunks. However, the eminent expected utility of these wastes is assumed to circumscribe [24]. Between the oil palm biomass, mesocarp fiber contains a high calorific value in comparison with palm shell and EFB [23]. These oil palm residues comprise various chemical composition and high heating value of about 18–19 MJ kg−1. They are better complement and ingredients for fuels in the form of pellets and briquettes [25]. It has been declared that in the year 2012 there were profitable oil palm wastes (dry weight) of about 83 million tons in Malaysia. Moreover, it will eventually ascend to 100 million tons in few years to come (2020) [24]. These wastes will continue to contribute to the agricultural wastes disposal problem in Malaysia except necessary action are taken.

The direct combustion of biomass is not the best way to use it as burning fuel. Some processes can be used to upgrade the standard of biomass for better and proper application. Some of Briquetting is a process of compressing materials into a small portable size with a diameter ranging from 30 to 100 mm and of any length depending on the technology applied, which could either be screw or piston compression [30]. The briquetting process is perhaps regarded as a way to improve the application of low-grade wastes materials. Briquetting is mainly used for compacting of biomass and none biomass sources such as plastic, many types of milled paper wastes and other combustible wastes [31]. Municipal solid waste (MSW), industrial waste and sludge are used to produce fuel briquettes in some countries [32]. It is well-known and believed that biomass residues could be utilized as a replacement to fuel for combustion at coal-fired power plants [33]. There are many processes for briquetting; they include pre-treatment and operational parameters (factors) that controlled the quality of fuel briquettes. Furthermore, physical properties such as a binder, moisture content, particle size and compressing forces (pressure) are among the factors that influence the quality of briquettes regarding durability and resistivity during transportation [34]. However, a briquette quality significantly depends on the drying process [35].

In this research, the potential application of empty fruit bunches, mesocarp fiber and palm kernel shell for coal replacement was investigated. These biomasses were pyrolyzed and the bio-oil and biochar obtained were used to form charcoal briquettes (solid fuels). The viscosity of bio-oil was improved by the addition of 10% starch and used as a binder.

## **2. Materials and methods**

#### **2.1. Biomass sample collection and preparation**

The oil palm biomass used in this study include mesocarp fibers (MF), empty fruit bunch (EFB) and palm kernel shells (PKS) as shown in **Figures 1**–**3**. They were obtained freshly from a palm oil mill located in Nibong Tebal, Pulau Pinang, Malaysia. These biomass samples were the by-products from different procedures such as pressing and nut cracking in the milling process industries where crude palm oil is generated. The biomass samples were dried to a moisture content lower than 10 wt%, for 24 h at 105°C. EFB sample was cut into smaller sizes, and all the samples were stored into desiccators before experiments and analyses. The Sago starch was obtained from MYDIN shopping mall located at Bukit Jambul, Pulau Pinang, Malaysia. Sub-bituminous coal was supplied by a company based in Sarawak, Malaysia.

#### **2.2. Physiochemical characterization**

Proximate analysis was carried out by ASTM E871 for moisture content, ASTM E872 for volatile matter content, and ASTM E1755-01 for ash content, from which the difference was used to determine the amount of fixed carbon. Elemental analysis was conducted to analyze the percentages of carbon (C), hydrogen (H), nitrogen (N), sulfur (S), and oxygen (O). It was performed using a Perkin Elmer 2400 analyzer, and 2–2.8 mg of sample was used to measure the percentage weight of each element present. The higher heating value (HHV) was determined using bomb calorimeter system IKA C 200, and oxygen station C248 with an empty water hose. For each test run, 0.5–0.8 g of the sample was measured and placed in the crucible joined to the thread from the ignition wire, which was then closed, and oxygen gas was pumped in. The lignocellulosic compositions of the materials were measured according to the procedure prescribed by Sukiran [22].

#### **2.3. Pyrolysis experiment**

The pyrolysis experiment was conducted three times separately using a stainless-steel reactor of 150 mm length and 70 mm internal diameter; about 180 g of raw biomass was weighed and placed inside the electric furnace. The reactor was heated at a temperature of 400°C for 120 min and at a heating rate of 10°C min−1. During the pyrolysis, the reactor temperature was monitored using a K-type thermocouple, and nitrogen (N<sup>2</sup> ) was used as the reaction gas at a rate of 2 l/min as shown in **Figure 4**.

**2.4. Briquetting tools and methods**

**Figure 4.** A schematic of the pyrolysis system.

**Figure 3.** Oil palm kernel shell as received.

**Figure 2.** Oil palm fiber as received.

The cylindrical briquetting mold used was made from hardened steel with an inner diameter of 19.4 mm and a height of 50.2 mm. Other briquetting parts are press piston of 65.0 mm and stop piston of 10.0 mm. The manual hydraulic pressing machine (briquetting machine) used is purposely manufactured for experimental work. It has a maximum pressuring capacity of only 1000 kg cm−2 (98.07 MPa). For each bio-briquettes made, about 10–20 g of the mixture was

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**Figure 1.** Oil palm EFB as received.

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**Figure 2.** Oil palm fiber as received.

**2. Materials and methods**

58 Palm Oil

**2.2. Physiochemical characterization**

**2.3. Pyrolysis experiment**

rate of 2 l/min as shown in **Figure 4**.

**Figure 1.** Oil palm EFB as received.

**2.1. Biomass sample collection and preparation**

The oil palm biomass used in this study include mesocarp fibers (MF), empty fruit bunch (EFB) and palm kernel shells (PKS) as shown in **Figures 1**–**3**. They were obtained freshly from a palm oil mill located in Nibong Tebal, Pulau Pinang, Malaysia. These biomass samples were the by-products from different procedures such as pressing and nut cracking in the milling process industries where crude palm oil is generated. The biomass samples were dried to a moisture content lower than 10 wt%, for 24 h at 105°C. EFB sample was cut into smaller sizes, and all the samples were stored into desiccators before experiments and analyses. The Sago starch was obtained from MYDIN shopping mall located at Bukit Jambul, Pulau Pinang, Malaysia. Sub-bituminous coal was supplied by a company based in Sarawak, Malaysia.

Proximate analysis was carried out by ASTM E871 for moisture content, ASTM E872 for volatile matter content, and ASTM E1755-01 for ash content, from which the difference was used to determine the amount of fixed carbon. Elemental analysis was conducted to analyze the percentages of carbon (C), hydrogen (H), nitrogen (N), sulfur (S), and oxygen (O). It was performed using a Perkin Elmer 2400 analyzer, and 2–2.8 mg of sample was used to measure the percentage weight of each element present. The higher heating value (HHV) was determined using bomb calorimeter system IKA C 200, and oxygen station C248 with an empty water hose. For each test run, 0.5–0.8 g of the sample was measured and placed in the crucible joined to the thread from the ignition wire, which was then closed, and oxygen gas was pumped in. The lignocellulosic compositions of the materials were measured according to the procedure prescribed by Sukiran [22].

The pyrolysis experiment was conducted three times separately using a stainless-steel reactor of 150 mm length and 70 mm internal diameter; about 180 g of raw biomass was weighed and placed inside the electric furnace. The reactor was heated at a temperature of 400°C for 120 min and at a heating rate of 10°C min−1. During the pyrolysis, the reactor temperature was

) was used as the reaction gas at a

monitored using a K-type thermocouple, and nitrogen (N<sup>2</sup>

**Figure 3.** Oil palm kernel shell as received.

#### **2.4. Briquetting tools and methods**

The cylindrical briquetting mold used was made from hardened steel with an inner diameter of 19.4 mm and a height of 50.2 mm. Other briquetting parts are press piston of 65.0 mm and stop piston of 10.0 mm. The manual hydraulic pressing machine (briquetting machine) used is purposely manufactured for experimental work. It has a maximum pressuring capacity of only 1000 kg cm−2 (98.07 MPa). For each bio-briquettes made, about 10–20 g of the mixture was placed into a mold and compressed at a constant pressure of 400 kg cm−2 for 2–5 min until no more change occurred on load reading. This procedure was replicated for all the briquettes produced. The mold and piston, and schematic briquetting machine setup are displayed in **Figures 5** and **6**, respectively.

The starch was ground to powder and mix with the bio-oil of about 50 ml and warmed. The mixture was stirred vigorously until a uniform solution was observed (bio-oil binder). The biochar and bio-oil (binder) were mixed in the ratio of 60:40 weight percentages. The mixture was allowed to dry for 10 min at room temperature before feeding into mold and press. The weight of briquette produced was recorded instantly and placed under ambient conditions for about 7 days to dry. The briquette procedure is summarized in **Figure 7**.

#### **2.5. Thermogravimetric analysis (TGA)**

Thermogravimetric analysis (TGA) was performed on the sample using a Perkin Elmer STA 6000 thermogravimetric analyzer. Thermal analysis was used to examine the thermal performance of the samples by observing the weight alteration that happened as the samples were heated, concerning hemicellulose, cellulose, and lignin, and identifying their thermal degradation behavior. The analysis was carried out in the presence of nitrogen (N<sup>2</sup> ) gas flow under a 10°C min−1 heating rate, with a sample size of 250–355 μm and the samples were heated from ambient temperature to about 850°C.

After the charcoal briquettes had been manufactured and dried, they were ground and subjected to combustion together with coal via TGA from a temperature range of 30–850°C at a constant heating rate of 10°C min−1 under oxygen environment at a flow rate of 50 ml min−1. In the combustion analysis, the combustion profiles such as peak temperature, ignition temperature, and burnout temperature at each combustion zone were determined. Also, the amount of weight loss, briquettes burnt, combustion rate and heat release during combustion were analyzed. The graph of DTG %/min versus temperature was used to determine the combustion properties of the briquettes. The combustion rate and heat release were computed with the equations shown below [23].

$$\text{Combustion rate = total mass of burst brighter/burning time} \tag{1}$$

$$\text{Heat release} = \text{calorific value} \times \text{combustion rate} \tag{2}$$

**3. Results and discussion**

**Figure 7.** Briquetting processes.

**Figure 6.** A schematic briquetting machine.

**3.1. Lignocellulosic components of oil palm wastes**

hemicelluloses, and 25–30 and 5–20% lignin, respectively [36].

**3.2. Proximate and elemental analysis**

The composition of cellulose, hemicellulose, lignin, and extractive in the oil palm wastes was in the range of 20–39, 23–35, 20–49 and 3–10 wt%, respectively as shown in **Table 2**. Comparatively, empty fruit bunch has high cellulose and hemicellulose, and low lignin and extractives contents than others. Mesocarp fiber has a high content of extractive than PKS and EFB, which could be responsible for it higher heating value than others. The high lignin content in palm shell resulted in a high yield of biochar. The cellulose, hemicellulose, lignin, extractive and ash components of oil palm wastes were respectively found in other research to be 33.9, 26.1, 27.7, 6.9 and 3.5 (% dry wt.) for MF. While, 38.3, 35.3, 22.1, 2.7 and 1.6 (% dry wt.) for EFB, 20.8, 22.7, 50.7, 4.8 and 1.0 (% dry wt.) for PKS [20]. The percentage compositions of lignocellulosic play a vital role in the pyrolysis products yield. The lignocellulosic components of wood and Switchgrass were 35–50 and 30–50% cellulose, 20–30 and 10–40%

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The results from the proximate analysis of oil palm biomass are given in **Table 2**. The moisture, ash and fixed carbon contents were 7.30, 7.51 and 10.09 wt% for EFB, 6.2, 7.02 and 15.83 wt%

**Figure 5.** Briquette mold and piston.

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**Figure 6.** A schematic briquetting machine.

placed into a mold and compressed at a constant pressure of 400 kg cm−2 for 2–5 min until no more change occurred on load reading. This procedure was replicated for all the briquettes produced. The mold and piston, and schematic briquetting machine setup are displayed in

The starch was ground to powder and mix with the bio-oil of about 50 ml and warmed. The mixture was stirred vigorously until a uniform solution was observed (bio-oil binder). The biochar and bio-oil (binder) were mixed in the ratio of 60:40 weight percentages. The mixture was allowed to dry for 10 min at room temperature before feeding into mold and press. The weight of briquette produced was recorded instantly and placed under ambient conditions

Thermogravimetric analysis (TGA) was performed on the sample using a Perkin Elmer STA 6000 thermogravimetric analyzer. Thermal analysis was used to examine the thermal performance of the samples by observing the weight alteration that happened as the samples were heated, concerning hemicellulose, cellulose, and lignin, and identifying their thermal degra-

a 10°C min−1 heating rate, with a sample size of 250–355 μm and the samples were heated from

After the charcoal briquettes had been manufactured and dried, they were ground and subjected to combustion together with coal via TGA from a temperature range of 30–850°C at a constant heating rate of 10°C min−1 under oxygen environment at a flow rate of 50 ml min−1. In the combustion analysis, the combustion profiles such as peak temperature, ignition temperature, and burnout temperature at each combustion zone were determined. Also, the amount of weight loss, briquettes burnt, combustion rate and heat release during combustion were analyzed. The graph of DTG %/min versus temperature was used to determine the combustion properties of the briquettes. The combustion rate and heat release were computed with

Combustion rate = total mass of burnt briquette/burning time (1)

Heat release = calorific value × combustion rate (2)

) gas flow under

for about 7 days to dry. The briquette procedure is summarized in **Figure 7**.

dation behavior. The analysis was carried out in the presence of nitrogen (N<sup>2</sup>

**Figures 5** and **6**, respectively.

60 Palm Oil

**2.5. Thermogravimetric analysis (TGA)**

ambient temperature to about 850°C.

the equations shown below [23].

**Figure 5.** Briquette mold and piston.

**Figure 7.** Briquetting processes.

## **3. Results and discussion**

#### **3.1. Lignocellulosic components of oil palm wastes**

The composition of cellulose, hemicellulose, lignin, and extractive in the oil palm wastes was in the range of 20–39, 23–35, 20–49 and 3–10 wt%, respectively as shown in **Table 2**. Comparatively, empty fruit bunch has high cellulose and hemicellulose, and low lignin and extractives contents than others. Mesocarp fiber has a high content of extractive than PKS and EFB, which could be responsible for it higher heating value than others. The high lignin content in palm shell resulted in a high yield of biochar. The cellulose, hemicellulose, lignin, extractive and ash components of oil palm wastes were respectively found in other research to be 33.9, 26.1, 27.7, 6.9 and 3.5 (% dry wt.) for MF. While, 38.3, 35.3, 22.1, 2.7 and 1.6 (% dry wt.) for EFB, 20.8, 22.7, 50.7, 4.8 and 1.0 (% dry wt.) for PKS [20]. The percentage compositions of lignocellulosic play a vital role in the pyrolysis products yield. The lignocellulosic components of wood and Switchgrass were 35–50 and 30–50% cellulose, 20–30 and 10–40% hemicelluloses, and 25–30 and 5–20% lignin, respectively [36].

#### **3.2. Proximate and elemental analysis**

The results from the proximate analysis of oil palm biomass are given in **Table 2**. The moisture, ash and fixed carbon contents were 7.30, 7.51 and 10.09 wt% for EFB, 6.2, 7.02 and 15.83 wt%


wastes such as oil palm frond and oil palm trunk have high and low content of oxygen (50.88 and 53.12 wt%) and carbon (42.76 and 40.64 wt%), respectively [38, 39], than EFB, MF, and PKS. For rice husk and Sawdust, they have a carbon content of 47.80 and 46.90 wt% [37] above

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The calorific value is used to measure the energy content and thermal efficiency of materials. In this work, the higher and lower heating values (HHV and LHV) of oil palm wastes was determined and calculated, respectively. The results acquired disclosed that the HHV of EFB, MF and PKS were respectively found as 16.9, 19.06 and 19.5 MJ kg−1 as shown in **Table 2**. Other fuels such as Sub-bituminous Malaysian coal and Olive husk possess a high heating value of 24.6 MJ kg−1 [23] and 21.80 MJ kg−1 [37], respectively in relative to oil palm wastes studied in this work. The LHV was computed to be 15.5 MJ kg−1 for EFB, 17.9 MJ kg−1 for MF

**Figure 8** displays the TGA and differential thermogravimetry (DTG) curves of the sample. The samples showed similar behavior during pyrolysis. The first small peak corresponds to the evaporation of moisture and the early weight loss at a temperature lower than 150°C for all the palm biomass samples. The degradation of hemicelluloses commences at temperatures of around 270°C for EFB, 290°C for MF, and 300°C for the PKS. It is reported by Sulaiman and Abdullah that DTG curves for PKS and MF attain separate peaks for hemicellulose at around 300°C and cellulose above 300°C [40]. In this study, the peak at about 310°C and the two peaks at 360°C correspond to the degradation of cellulose for EFB, MF, and PKS, respectively. Though the breakdown of cellulose and hemicelluloses is a constant progression, the weight loss of these constituents was sustained throughout nearly the whole heating period. However, the maximum decline speeds of the celluloses are between 300 and 360°C, and for the hemicelluloses,

that of EFB and MF.

**3.3. Calorific heating value**

and 18.1 MJ kg−1 for PKS, respectively.

**Figure 8.** Thermal analysis (TGA and DTG curves).

**3.4. Thermogravimetric analysis**

b By difference.

**Table 2.** Physiochemical properties of oil palm wastes.

for MF, and 4.9, 8.7 and 15.9 wt% for PKS, respectively. The volatile matter content was between 75 and 82 wt%, whereby EFB has high volatile matter than MF and PKS. Relatively, similar results in (wt%) can be found in the other study [28]. Comparing with other biomass sources, EFB has similar volatile matter content with Sawdust (82.20 wt%) and lower than that of Rice husk (61.81 wt%). However, the cotton stalk has high fixed carbon and high ash content than all the oil palm wastes studied [37]. The percentage of volatile matter, fixed carbon, ash content, and moisture are reasonable parameters of pyrolysis product yields. Jahirul et al. reported that the percentages of volatile matter, fixed carbon, ash content, and moisture are suitable parameters of pyrolysis product yields. Biomass with high volatile matter generates large amounts of bio-oil and syngas, whereas fixed carbon enlarges the biochar generation. Moisture content in biomass influences the heat transfer system with primary outcomes on product distribution. Also, an increase in moisture content increases liquid product yield and reduces the yield of solid and gas product. Which could be associated with the huge amount of condensate water generates from the moisture in the liquid phase [36].

The chemical composition of oil palm wastes stipulates the elements present. The results of the analysis in **Table 2** above revealed that the PKS comprises a high carbon content of 50.29 wt% and low oxygen content of 42.82 wt% than the contents in MF and EFB, respectively. The hydrogen, sulfur, and nitrogen contents were found to be respectively 6.20, 0.09 and 0.47 wt% for EFB, 5.52, 0.12 and 0.59 wt% for MF, and 6.35, 0.08 and 0.48 wt% for PKS. Other oil palm wastes such as oil palm frond and oil palm trunk have high and low content of oxygen (50.88 and 53.12 wt%) and carbon (42.76 and 40.64 wt%), respectively [38, 39], than EFB, MF, and PKS. For rice husk and Sawdust, they have a carbon content of 47.80 and 46.90 wt% [37] above that of EFB and MF.

#### **3.3. Calorific heating value**

The calorific value is used to measure the energy content and thermal efficiency of materials. In this work, the higher and lower heating values (HHV and LHV) of oil palm wastes was determined and calculated, respectively. The results acquired disclosed that the HHV of EFB, MF and PKS were respectively found as 16.9, 19.06 and 19.5 MJ kg−1 as shown in **Table 2**. Other fuels such as Sub-bituminous Malaysian coal and Olive husk possess a high heating value of 24.6 MJ kg−1 [23] and 21.80 MJ kg−1 [37], respectively in relative to oil palm wastes studied in this work. The LHV was computed to be 15.5 MJ kg−1 for EFB, 17.9 MJ kg−1 for MF and 18.1 MJ kg−1 for PKS, respectively.

#### **3.4. Thermogravimetric analysis**

for MF, and 4.9, 8.7 and 15.9 wt% for PKS, respectively. The volatile matter content was between 75 and 82 wt%, whereby EFB has high volatile matter than MF and PKS. Relatively, similar results in (wt%) can be found in the other study [28]. Comparing with other biomass sources, EFB has similar volatile matter content with Sawdust (82.20 wt%) and lower than that of Rice husk (61.81 wt%). However, the cotton stalk has high fixed carbon and high ash content than all the oil palm wastes studied [37]. The percentage of volatile matter, fixed carbon, ash content, and moisture are reasonable parameters of pyrolysis product yields. Jahirul et al. reported that the percentages of volatile matter, fixed carbon, ash content, and moisture are suitable parameters of pyrolysis product yields. Biomass with high volatile matter generates large amounts of bio-oil and syngas, whereas fixed carbon enlarges the biochar generation. Moisture content in biomass influences the heat transfer system with primary outcomes on product distribution. Also, an increase in moisture content increases liquid product yield and reduces the yield of solid and gas product. Which could be associated with the huge amount

**Properties (wt%) EFB MF PKS** Cellulose 39.80 32.60 20.70 Hemicelluloseb 35.90 29.20 23.30 Lignin 20.40 27.90 49.50 Extractives 3.90 10.30 6.50 Moisture content 7.30 6.2 4.90 Volatile matter 82.40 77.15 75.40 Ash content 7.51 7.02 8.70 Fixed carbon<sup>b</sup> 10.09 15.83 15.90 Carbon 42.80 46.37 50.29 Hydrogen 6.20 5.52 6.35 Nitrogen 0.47 0.59 0.48 Sulfur 0.09 0.12 0.08 Oxygen<sup>b</sup> 50.44 47.47 42.82 HHV (MJ kg−1) 16.9 19.06 19.5 LHV (MJ kg−1) 15.5 17.9 18.1

The chemical composition of oil palm wastes stipulates the elements present. The results of the analysis in **Table 2** above revealed that the PKS comprises a high carbon content of 50.29 wt% and low oxygen content of 42.82 wt% than the contents in MF and EFB, respectively. The hydrogen, sulfur, and nitrogen contents were found to be respectively 6.20, 0.09 and 0.47 wt% for EFB, 5.52, 0.12 and 0.59 wt% for MF, and 6.35, 0.08 and 0.48 wt% for PKS. Other oil palm

of condensate water generates from the moisture in the liquid phase [36].

a

62 Palm Oil

b

By difference.

Weight percentage dry basis (wt%).

**Table 2.** Physiochemical properties of oil palm wastes.

**Figure 8** displays the TGA and differential thermogravimetry (DTG) curves of the sample. The samples showed similar behavior during pyrolysis. The first small peak corresponds to the evaporation of moisture and the early weight loss at a temperature lower than 150°C for all the palm biomass samples. The degradation of hemicelluloses commences at temperatures of around 270°C for EFB, 290°C for MF, and 300°C for the PKS. It is reported by Sulaiman and Abdullah that DTG curves for PKS and MF attain separate peaks for hemicellulose at around 300°C and cellulose above 300°C [40]. In this study, the peak at about 310°C and the two peaks at 360°C correspond to the degradation of cellulose for EFB, MF, and PKS, respectively. Though the breakdown of cellulose and hemicelluloses is a constant progression, the weight loss of these constituents was sustained throughout nearly the whole heating period. However, the maximum decline speeds of the celluloses are between 300 and 360°C, and for the hemicelluloses,

**Figure 8.** Thermal analysis (TGA and DTG curves).

they are between 270 and 300°C. The degradation of lignin is seen at 650°C, but PKS shows high resistance to temperature due to its high lignin content. The total weight losses between 100 and 450°C are 78.6, 75.71, and 98.5% for EFB, MF, and PKS, respectively.

has been reported that during the pyrolysis process cellulose, hemicelluloses and lignin were respectively found to demonstrate the highest to the lowest disintegration rate. At temperature more than 400°C the cellulose content was almost pyrolyzed with a little quantity of solid

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The bio-oil yields as seen in **Figure 9** indicated that the quantity of bio-oil produced was between 34 and 35%. However, EFB and PKS produced the maximum and minimum quantities of 35.97 and 35.20% of the bio-oils, respectively. The fact that the EFB and MF generated a high amount of bio-oil than PKS could be attributed to the high amount of cellulose and hemicelluloses as shown in **Table 2**. It has been [36] noted that cellulose is principally responsible for bio-oil production during the pyrolysis of biomass (around 500°C). However, best quality of bio-oil can be generated from biomass with high lignin content. Biomass with high volatile matter generates large amounts of bio-oil and syngas. Moisture content in biomass has an influence in the heat transfer process with significant effects on product distribution [36]. The bio-oil binder viscosity has improved to 40 cP with addition of 10% starch from the

The charcoal briquette samples produced, and its physical properties are displayed in **Figure 10** and **Table 3**, respectively. The physical and combustion properties of charcoal briquettes obtained in this work were compared with Malaysian sub-bituminous coal (Coal) for replace-

The proximate analysis and HHV of the charcoal briquettes are shown in **Table 3**. From the results, volatile matter, fixed carbon, ash, moisture content and HHV were respectively found to be between 41 to 49, 39 to 50, 6 to 11, 2 to 4 wt% and 23 to 26 MJ kg−1. The maximum volatile matter of 49.74 wt% was received from EFB solid fuel, while the minimum value of 41.92 wt% was acquired from PKS solid fuel. Coal had shown the highest fixed carbon followed by MF, PKS and EFB solid fuels, respectively. The sequence of the calorific values was MF first, followed by PKS, coal and then EFB at last. The sequence could be according to the volatile matter

**3.6. Combustion characteristics of charcoal briquettes and coal**

remnant [42].

*3.5.2. Bio-oil yield*

initial value of 3 cP.

ment purposes.

**Figure 10.** Charcoal briquettes samples.

#### **3.5. Pyrolysis products yield**

The biochar, bio-oil and gas yields obtained from the pyrolysis of oil palm wastes at a temperature of 400°C, a heating rate of 10°C min−1 and for 120 min holding time are shown in **Figure 9** for EFB, MF, and PKS. Jahirul et al. reported that the decomposition of lignocellulosic components relies on temperature, heating rate, and other contaminants because of their different molecular structures. Hemicellulose ordinary decomposes easily, followed by cellulose, while lignin decomposes at last. However, during pyrolysis lignin and hemicellulose do not affect each other but both can influence the pyrolysis of cellulose. They also reported that the percentages of volatile matter, fixed carbon, ash content, and moisture are suitable parameters of pyrolysis product yields. [36].

#### *3.5.1. Biochar yield*

As evident in **Figure 9**, PKS and MF were distinguished as the samples that yielded a huge quantity of biochar compared with EFB. The quantities of biochar yield were 42.11% for EFB, 45.12% for MF and 46.57% for PKS, respectively. The influence of lignin (fixed carbon) and cellulose on biochar yields were observed accordingly. It was shown in **Table 2** that PKS and MF comprehend eminent quantity of lignin and fixed carbon, and less amount of cellulose than did EFB and therefore, they give rise to a large amount of biochar compared to EFB. It is known that biochar is from lignin content. Thus, biochar elemental composition is near to that of lignin [36].

The yield of biochar could be associated with either primary or secondary decomposition of raw samples during pyrolysis which consequently influenced the pyrolysis conversion processes. Moreover, the disintegration of cellulose, hemicelluloses, and lignin during the pyrolysis plays a vital function in the yield of biochar [28, 41]. The high yield of biochar at low temperatures demonstrates that the material has been only partially pyrolyzed [41]. It

**Figure 9.** Pyrolysis products obtained from EFB, fiber and shell.

has been reported that during the pyrolysis process cellulose, hemicelluloses and lignin were respectively found to demonstrate the highest to the lowest disintegration rate. At temperature more than 400°C the cellulose content was almost pyrolyzed with a little quantity of solid remnant [42].

#### *3.5.2. Bio-oil yield*

The bio-oil yields as seen in **Figure 9** indicated that the quantity of bio-oil produced was between 34 and 35%. However, EFB and PKS produced the maximum and minimum quantities of 35.97 and 35.20% of the bio-oils, respectively. The fact that the EFB and MF generated a high amount of bio-oil than PKS could be attributed to the high amount of cellulose and hemicelluloses as shown in **Table 2**. It has been [36] noted that cellulose is principally responsible for bio-oil production during the pyrolysis of biomass (around 500°C). However, best quality of bio-oil can be generated from biomass with high lignin content. Biomass with high volatile matter generates large amounts of bio-oil and syngas. Moisture content in biomass has an influence in the heat transfer process with significant effects on product distribution [36]. The bio-oil binder viscosity has improved to 40 cP with addition of 10% starch from the initial value of 3 cP.

#### **3.6. Combustion characteristics of charcoal briquettes and coal**

The charcoal briquette samples produced, and its physical properties are displayed in **Figure 10** and **Table 3**, respectively. The physical and combustion properties of charcoal briquettes obtained in this work were compared with Malaysian sub-bituminous coal (Coal) for replacement purposes.

The proximate analysis and HHV of the charcoal briquettes are shown in **Table 3**. From the results, volatile matter, fixed carbon, ash, moisture content and HHV were respectively found to be between 41 to 49, 39 to 50, 6 to 11, 2 to 4 wt% and 23 to 26 MJ kg−1. The maximum volatile matter of 49.74 wt% was received from EFB solid fuel, while the minimum value of 41.92 wt% was acquired from PKS solid fuel. Coal had shown the highest fixed carbon followed by MF, PKS and EFB solid fuels, respectively. The sequence of the calorific values was MF first, followed by PKS, coal and then EFB at last. The sequence could be according to the volatile matter

**Figure 10.** Charcoal briquettes samples.

**Figure 9.** Pyrolysis products obtained from EFB, fiber and shell.

they are between 270 and 300°C. The degradation of lignin is seen at 650°C, but PKS shows high resistance to temperature due to its high lignin content. The total weight losses between 100 and

The biochar, bio-oil and gas yields obtained from the pyrolysis of oil palm wastes at a temperature of 400°C, a heating rate of 10°C min−1 and for 120 min holding time are shown in **Figure 9** for EFB, MF, and PKS. Jahirul et al. reported that the decomposition of lignocellulosic components relies on temperature, heating rate, and other contaminants because of their different molecular structures. Hemicellulose ordinary decomposes easily, followed by cellulose, while lignin decomposes at last. However, during pyrolysis lignin and hemicellulose do not affect each other but both can influence the pyrolysis of cellulose. They also reported that the percentages of volatile matter, fixed carbon, ash content, and moisture are suitable parameters of pyrolysis product yields. [36].

As evident in **Figure 9**, PKS and MF were distinguished as the samples that yielded a huge quantity of biochar compared with EFB. The quantities of biochar yield were 42.11% for EFB, 45.12% for MF and 46.57% for PKS, respectively. The influence of lignin (fixed carbon) and cellulose on biochar yields were observed accordingly. It was shown in **Table 2** that PKS and MF comprehend eminent quantity of lignin and fixed carbon, and less amount of cellulose than did EFB and therefore, they give rise to a large amount of biochar compared to EFB. It is known that biochar is from lignin content. Thus, biochar elemental composition is near to that of lignin [36]. The yield of biochar could be associated with either primary or secondary decomposition of raw samples during pyrolysis which consequently influenced the pyrolysis conversion processes. Moreover, the disintegration of cellulose, hemicelluloses, and lignin during the pyrolysis plays a vital function in the yield of biochar [28, 41]. The high yield of biochar at low temperatures demonstrates that the material has been only partially pyrolyzed [41]. It

450°C are 78.6, 75.71, and 98.5% for EFB, MF, and PKS, respectively.

**3.5. Pyrolysis products yield**

64 Palm Oil

*3.5.1. Biochar yield*


b By difference.

**Table 3.** Physiochemical properties charcoal briquettes and coal (solid fuels).

content and other factors present in the solid fuels that determine the quality of fuel. However, the low volatile matter and high ash content could make fuel difficult to ignite and thus, could not be recognized as good combustible fuel. Comparably, MF and PKS charcoal briquettes had higher HHV of 26.15 and 25.99 MJ kg−1, individually than coal which has 24.21 MJ kg−1, except EFB charcoal briquette which showed the lowest value 23.93 MJ kg−1. Therefore, it can be said that all the charcoal briquettes showed similar properties with coal. And, therefore regarded as the best choice to replace coal.

It was previously stated that for a solid fuel to ignite and burn easily, it must contain a moderate percentage of volatile matter. It was observed that high moisture and ash contents could lead to ignition and other combustion difficulties [37, 43]. The significant benefits that biomass has as a combustion fuel are the high volatility and high reactivity of the fuel and the resulting char [44]. Based on these reasons, and since all the charcoal briquettes obtained in this study had similar properties or even better than coal, the choice of the best fuel is established on volatile, ash and moisture contents, respectively because of their role during combustion. All the solid fuels were subjected to combustion at 10°C min−1, and the results of combustion profiles acquired using DTG is shown in **Figure 11**.

Before analysis, the combustion temperature starting from 30 to around 850°C is partitioned into zones as shown in **Table 4**. It is seen from the figure that all the solid fuels showed a comparable peak between the temperature of 30 and 200°C. This peak could be ascribed to dehydration of moisture during the combustion. However, inside the primary zone, coal showed the highest weight reduction of 8.825 wt% and a peak temperature of 77°C, while MF demonstrated the least weight reduction of 3.382 wt% and a peak temperature of 59°C as seen in **Tables 4** and **5** respectively.

The second zone began from 140 and lasted to around 560°C. This zone showed the greatest weight reduction and most astounding peak temperature, and ignition temperatures. As apparent from **Table 5**, EFB and coal showed the most elevated weight reduction of 30.728

and 29.603%, individually. The ignition temperature of the solid fuels in **Table 6** was 235°C for EFB, 254°C for MF, 265°C for PKS and 368°C for coal. Along these lines, peak temperature

**EFB MF PKS Coal**

**First zone Second zone Third zone**

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EFB 30–140 140–360 360–644 MF 30–140 140–356 356–780 PKS 30–140 140–351 351–739 Coal 30–200 200–557 557–780

I 3.539 3.382 4.461 8.825 II 30.728 12.00 18.868 29.603 III 14.408 20.247 21.62 10.278

took after ignition temperature and the value recorded was displayed in **Table 6**.

**Figure 11.** DTG curves for solid fuels combustion.

**Table 4.** Temperature intervals for different zones.

**Table 5.** Weight loss of solid fuels at different zones, % by weight.

**Zones Weight loss, wt%**

**Solid fuels Temperature intervals (°C)**

Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement http://dx.doi.org/10.5772/intechopen.74863 67

**Figure 11.** DTG curves for solid fuels combustion.

**Properties (wt%) EFB MF PKS Coal** Moisture content 4.23 3.87 2.91 2.65 Volatile matter 49.74 43.23 41.92 42.05 Ash content 11.20 6.61 8.15 7.44 Fixed carbon<sup>b</sup> 39.06 50.16 49.93 50.51 Carbon 58.11 62.93 65.07 64.66 Hydrogen 5.03 5.87 6.11 7.91 Nitrogen 0.97 0.98 0.93 1.16 Oxygen<sup>b</sup> 35.89 30.22 27.89 26.27 HHV (MJ kg−1) 23.93 26.15 25.99 24.21

content and other factors present in the solid fuels that determine the quality of fuel. However, the low volatile matter and high ash content could make fuel difficult to ignite and thus, could not be recognized as good combustible fuel. Comparably, MF and PKS charcoal briquettes had higher HHV of 26.15 and 25.99 MJ kg−1, individually than coal which has 24.21 MJ kg−1, except EFB charcoal briquette which showed the lowest value 23.93 MJ kg−1. Therefore, it can be said that all the charcoal briquettes showed similar properties with coal. And, therefore regarded

It was previously stated that for a solid fuel to ignite and burn easily, it must contain a moderate percentage of volatile matter. It was observed that high moisture and ash contents could lead to ignition and other combustion difficulties [37, 43]. The significant benefits that biomass has as a combustion fuel are the high volatility and high reactivity of the fuel and the resulting char [44]. Based on these reasons, and since all the charcoal briquettes obtained in this study had similar properties or even better than coal, the choice of the best fuel is established on volatile, ash and moisture contents, respectively because of their role during combustion. All the solid fuels were subjected to combustion at 10°C min−1, and the results of combustion

Before analysis, the combustion temperature starting from 30 to around 850°C is partitioned into zones as shown in **Table 4**. It is seen from the figure that all the solid fuels showed a comparable peak between the temperature of 30 and 200°C. This peak could be ascribed to dehydration of moisture during the combustion. However, inside the primary zone, coal showed the highest weight reduction of 8.825 wt% and a peak temperature of 77°C, while MF demonstrated the least weight reduction of 3.382 wt% and a peak temperature of 59°C as seen

The second zone began from 140 and lasted to around 560°C. This zone showed the greatest weight reduction and most astounding peak temperature, and ignition temperatures. As apparent from **Table 5**, EFB and coal showed the most elevated weight reduction of 30.728

a

66 Palm Oil

b

By difference.

Weight percentage dry basis (wt%).

as the best choice to replace coal.

in **Tables 4** and **5** respectively.

**Table 3.** Physiochemical properties charcoal briquettes and coal (solid fuels).

profiles acquired using DTG is shown in **Figure 11**.


**Table 4.** Temperature intervals for different zones.


**Table 5.** Weight loss of solid fuels at different zones, % by weight.

and 29.603%, individually. The ignition temperature of the solid fuels in **Table 6** was 235°C for EFB, 254°C for MF, 265°C for PKS and 368°C for coal. Along these lines, peak temperature took after ignition temperature and the value recorded was displayed in **Table 6**.

Temperature extends between 356 and 780°C is perceived as zone three. It can be seen from **Figure 11** that the rapid combustion of MF and PKS proceeded in this zone with a most extreme weight reduction of 20.247 and 21.62 wt%, individually as listed in **Table 6**. The recorded burnout temperature was 675, 788, 786 and 770°C for EFB, MF, PKS, and coal separately. The peak around 700°C for PKS could be because of the breakdown of calcium carbonate.

#### **3.7. Heat generated from the combustion of solid fuel**

The combustion period for solid fuels was around 45 min. The amount of fuel consumed, and time taken to reach burnout temperature for each fuel was ascertained. The time taken was evaluated and found to be 40, 44, 44 and 42 min for EFB, MF, PKS, and coal individually. Likewise, the burning rate and heat discharge from the initial temperature to burnout temperature was additionally determined as displayed in **Table 7**.

require higher temperature and longer burning time to finish the conversion. This might be because of the presence of a lot of inorganic material. It can, therefore, be presumed that MF

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69

It can be established from **Table 7** that in every 1 mg of EFB briquettes consumed; there is 0.0112 W of heat release. Therefore, based on these, the amount of heat that can be generated from 1 ton of EFB briquette is evaluated and shown in **Table 8**. It can be noticed that 1 ton of raw EFB can deliver 0.177 ton of briquettes which corresponds to 1.866 MW of heat. Furthermore, **Table 8** demonstrated that in every ton of raw MF, roughly 0.212 tons of briquettes could be obtained, which can give up to 2.055 MW of heat. For 1 ton of raw PKS, 0.228 tons of briquette can be delivered, and this connects to around 2.414 MW of heat.

During the combustion the primary zone, coal showed the highest weight reduction of 8.825 wt%. In the second zone, EFB showed the highest weight reduction of 30.728%. The rapid combustion of MF and PKS proceed in zone III with a most extreme weight reduction of 20.247 and 21.62 wt% individually. It was found that EFB is the easiest to ignite at 235°C due to high volatile matter content while MF attained the highest burnout temperature of 788°C. The maximum and minimum heat release of 0.059 and 0.048 W were obtained from the combustion of EFB and MF respectively. It was established that in each ton of raw (dry basis) of EFB, fiber, and PKS, there is 0.177, 0.212 and 0.228 tons of charcoal briquettes which corresponds to 1.866, 2.055 and 2.414 MW of heat respectively. Therefore, the findings in this study could contribute toward achieving the targeted 500 MW of green energy initiated in 2005 by the Malaysian government. It can also reduce dependence on fossil fuels for heat generation which in turn reduce the global warming, and minimize deforestation globally. Most importantly, the 100 million tons of oil palm wastes that will be generated in the year 2020 in Malaysia can easily be converted to useful products for heat generation. Also, application of various types of biomass for briquettes production can create job opportunities and enhance environmental sanitation in developing countries.

The authors wish to express their gratitude to the Universiti Sains Malaysia for financing this research through grants RUI [1001/PFIZIK/814250], [1001/PFIZIK/814228] and FRGS [203/

PFIZIK/6711410]. ORCID: Corresponding author: 0000-0003-2322-5467.

fuel could be viewed as steady since it might deliver heat for an extended period.

**Solid fuels Briquettes (ton) Power (MW)** EFB 0.177 1.866 MF 0.212 2.055 PKS 0.228 2.414

**Table 8.** Power generated per 1 ton of raw oil palm biomass.

**4. Conclusion**

**Acknowledgements**

As seen from **Figure 11**, the solid fuels showed diverse conduct amid combustion particularly inside zones II and III. In this manner, the amount of fuel consumed ought not to be equivalent because the time taken for each fuel to approach the burnout temperature is additionally not equivalent. As apparent from the figure and **Table 7**, EFB fuel indicated high reactivity and therefore brought about high burning rate and heat discharge. The most extreme fuel consumed and heat discharge for EFB were separately observed to be 5.248 × 10−6 kg and 0.059 W. MF fuel discharge less amount of heat since it is less reactive as shown in **Figure 9** which prompted moderate amount of fuel consumed.

Nonetheless, low heat discharged by MF (0.048 W) amid burning could be identified with the low amount of fuel burnt (1.443 × 10−9). Equivalently, combustion of MF, PKS, and coal may


**Table 6.** Peak and burnout temperatures of solid fuels.


**Table 7.** Combustion rate and heat release as at burnout temperature.


**Table 8.** Power generated per 1 ton of raw oil palm biomass.

require higher temperature and longer burning time to finish the conversion. This might be because of the presence of a lot of inorganic material. It can, therefore, be presumed that MF fuel could be viewed as steady since it might deliver heat for an extended period.

It can be established from **Table 7** that in every 1 mg of EFB briquettes consumed; there is 0.0112 W of heat release. Therefore, based on these, the amount of heat that can be generated from 1 ton of EFB briquette is evaluated and shown in **Table 8**. It can be noticed that 1 ton of raw EFB can deliver 0.177 ton of briquettes which corresponds to 1.866 MW of heat. Furthermore, **Table 8** demonstrated that in every ton of raw MF, roughly 0.212 tons of briquettes could be obtained, which can give up to 2.055 MW of heat. For 1 ton of raw PKS, 0.228 tons of briquette can be delivered, and this connects to around 2.414 MW of heat.

## **4. Conclusion**

Temperature extends between 356 and 780°C is perceived as zone three. It can be seen from **Figure 11** that the rapid combustion of MF and PKS proceeded in this zone with a most extreme weight reduction of 20.247 and 21.62 wt%, individually as listed in **Table 6**. The recorded burnout temperature was 675, 788, 786 and 770°C for EFB, MF, PKS, and coal separately. The peak around 700°C for PKS could be because of the breakdown of calcium

The combustion period for solid fuels was around 45 min. The amount of fuel consumed, and time taken to reach burnout temperature for each fuel was ascertained. The time taken was evaluated and found to be 40, 44, 44 and 42 min for EFB, MF, PKS, and coal individually. Likewise, the burning rate and heat discharge from the initial temperature to burnout tem-

As seen from **Figure 11**, the solid fuels showed diverse conduct amid combustion particularly inside zones II and III. In this manner, the amount of fuel consumed ought not to be equivalent because the time taken for each fuel to approach the burnout temperature is additionally not equivalent. As apparent from the figure and **Table 7**, EFB fuel indicated high reactivity and therefore brought about high burning rate and heat discharge. The most extreme fuel consumed and heat discharge for EFB were separately observed to be 5.248 × 10−6 kg and 0.059 W. MF fuel discharge less amount of heat since it is less reactive as shown in **Figure 9**

Nonetheless, low heat discharged by MF (0.048 W) amid burning could be identified with the low amount of fuel burnt (1.443 × 10−9). Equivalently, combustion of MF, PKS, and coal may

**Solid fuels Peak temperature (°C) Ignition temperature Burnout temperature**

**Solid fuels Fuel burnt (kg) CR (kg/s) Heat release (W)**

EFB 5.248 × 10−6 2.187 × 10−9 0.059 MF 3.810 × 10−6 1.443 × 10−9 0.048 PKS 4.830 × 10−6 1.830 × 10−9 0.051 Coal 5.001 × 10−6 1.985 × 10−9 0.052

**Table 7.** Combustion rate and heat release as at burnout temperature.

EFB 57 280 472 235 675 MF 59 287 513 254 788 PKS 67 303 473 265 786 Coal 77 440 671 368 770

**3.7. Heat generated from the combustion of solid fuel**

which prompted moderate amount of fuel consumed.

**I II III**

**Table 6.** Peak and burnout temperatures of solid fuels.

perature was additionally determined as displayed in **Table 7**.

carbonate.

68 Palm Oil

During the combustion the primary zone, coal showed the highest weight reduction of 8.825 wt%. In the second zone, EFB showed the highest weight reduction of 30.728%. The rapid combustion of MF and PKS proceed in zone III with a most extreme weight reduction of 20.247 and 21.62 wt% individually. It was found that EFB is the easiest to ignite at 235°C due to high volatile matter content while MF attained the highest burnout temperature of 788°C. The maximum and minimum heat release of 0.059 and 0.048 W were obtained from the combustion of EFB and MF respectively. It was established that in each ton of raw (dry basis) of EFB, fiber, and PKS, there is 0.177, 0.212 and 0.228 tons of charcoal briquettes which corresponds to 1.866, 2.055 and 2.414 MW of heat respectively. Therefore, the findings in this study could contribute toward achieving the targeted 500 MW of green energy initiated in 2005 by the Malaysian government. It can also reduce dependence on fossil fuels for heat generation which in turn reduce the global warming, and minimize deforestation globally. Most importantly, the 100 million tons of oil palm wastes that will be generated in the year 2020 in Malaysia can easily be converted to useful products for heat generation. Also, application of various types of biomass for briquettes production can create job opportunities and enhance environmental sanitation in developing countries.

## **Acknowledgements**

The authors wish to express their gratitude to the Universiti Sains Malaysia for financing this research through grants RUI [1001/PFIZIK/814250], [1001/PFIZIK/814228] and FRGS [203/ PFIZIK/6711410]. ORCID: Corresponding author: 0000-0003-2322-5467.

## **Conflict of interest**

The authors have declared no conflict of interest.

## **Author details**

Aminu Aliyu Safana1,2\*, Nurhayati Abdullah1 and Fauziah Sulaiman1

\*Address all correspondence to: basalihe2@gmail.com

1 School of Physics, Universiti Sains Malaysia, Pulau Pinang, Malaysia

2 Department of Physics, Federal University Dutse, Dutse, Nigeria

## **References**

[1] Umar MS, Jennings P, Urmee T. Generating renewable energy from oil palm biomass in Malaysia: The feed-in tariff policy framework. Biomass and Bioenergy. 2014;**62**:37-46. DOI: 10.1016/j.biombioe.2014.01.020

[10] Panwar N, Kaushik S, Kothari S. Role of renewable energy sources in environmental protection: A review. Renewable and Sustainable Energy Reviews. 2011;**15**(3):1513-1524.

Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement

http://dx.doi.org/10.5772/intechopen.74863

71

[11] Chen W-H, Huan-Chun H, Ke-Miao L, Wen-Jhy L, Ta-Chang L. Thermal pretreatment of wood (Lauan) block by torrefaction and its influence on the properties of the biomass.

[12] Gaetano C, D'Amicoa M, Rizzo M, Pecorino B. Analysis of biomass availability for energy use in Sicily. Renewable and Sustainable Energy Reviews. 2015;**52**:1025-1030.

[13] Basu P, Sadhukhan AK, Gupta P, Rao S, Dhungana A, Acharya B. An experimental and theoretical investigation on torrefaction of a large wet wood particle. Bioresource

[14] Chen W-H, Wen-Yi C, Ke-Miao L, Ying-Pin H. An evaluation on improvement of pulverized biomass property for solid fuel through torrefaction. Applied Energy.

[15] Kambo HS, Dutta A. A comparative review of biochar and hydrochar in terms of production, physico-chemical properties and applications. Renewable and Sustainable

[16] Lynam JG. Pretreatment of lignocellulosic biomass with acetic acid, salts, and ionic liquids [thesis]. Reno: Master of Science in Chemical Engineering, University of Nevada; 2011

[17] Abdullah N, Sulaiman F, Safana AA, Ibrahim AI. Potential application of oil palm wastes for coal replacement. In: Proceedings of International Conference on Advanced Science, Engineering and Technology (ICASET) 2015; 21-22 December 2015; Seberang

[18] Abdullah N, Sulaiman F. The oil palm wastes in Malaysia. In: Matovic MD, editor. Biomass Now—Sustainable Growth and Use. http://www.intechopen.com/books/2013.

[19] Sulaiman F, Abdullah N, Gerhauser H, Shariff A. A perspective of oil palm and its

[20] Kong S-H, Soh-Kheang L, Robert TB, Rahimd SA, Salimon J. Biochar from oil palm biomass: A review of its potential and challenges. Renewable and Sustainable Energy

[21] Uemura Y, Omar WN, Tsutsui T, Yusup SB. Torrefaction of oil palm wastes. Fuel.

[22] Sukiran MAB. Pyrolysis of empty oil palm fruit bunches using the quartz fluidised-fixed bed reactor [thesis]. Kuala Lumpur: Department of Chemistry, University of Malaya; 2008

[23] Idris SS, Rahman NA, Ismail K. Combustion characteristics of Malaysian oil palm biomass, sub-bituminous coal and their respective blends via thermogravimetric analysis (TGA). Bioresource Technology. 2012;**123**:581-591. DOI: 10.1016/j.biortech.2012.07.065

Jaya, Penang. Penang, Malaysia: AIP; 2016. p. 020004. DOI: 10.1063/1.4965052

Energy. 2011;**36**(5):3012-3021. DOI: 10.1016/j.energy.2011.02.045

Technology. 2014;**159**:215-222. DOI: 10.1016/j.biortech.2014.02.105

Energy Reviews. 2015;**45**(0):359-378. DOI: 10.1016/j.rser.2015.01.050

2011;**88**(11):3636-3644. DOI: 10.1016/j.apenergy.2011.03.040

wastes. Journal of Physical Science. 2010;**21**(1):67-77

2011;**90**(8):2585-2591. DOI: 10.1016/j.fuel.2011.03.021

Reviews. 2014;**39**:729-739. DOI: 10.1016/j.rser.2014.07.107

DOI: 10.1016/j.rser.2010.11.037

DOI: 10.1016/j.rser.2015.07.174

DOI: 10.5772/55302


[10] Panwar N, Kaushik S, Kothari S. Role of renewable energy sources in environmental protection: A review. Renewable and Sustainable Energy Reviews. 2011;**15**(3):1513-1524. DOI: 10.1016/j.rser.2010.11.037

**Conflict of interest**

70 Palm Oil

**Author details**

**References**

The authors have declared no conflict of interest.

Aminu Aliyu Safana1,2\*, Nurhayati Abdullah1

DOI: 10.1016/j.biombioe.2014.01.020

DOI: 10.1016/S0961-9534(02)00185-X

10.1111/j.1749-6632.2010.05890.x

\*Address all correspondence to: basalihe2@gmail.com

1 School of Physics, Universiti Sains Malaysia, Pulau Pinang, Malaysia

2 Department of Physics, Federal University Dutse, Dutse, Nigeria

2010;**14**(4):1241-1252. DOI: 10.1016/j.rser.2009.12.003

2009;**37**(1):181-189. DOI: 10.1016/j.enpol.2008.08.016

Reviews. 2016;**57**:186-191. DOI: 10.1016/j.rser.2015.12.118

Australia: University of New South Wales; 2007

Bogotá. Energy. 2015;**92**:612-621. DOI: 10.1016/j.energy.2015.02.003

and Fauziah Sulaiman1

[1] Umar MS, Jennings P, Urmee T. Generating renewable energy from oil palm biomass in Malaysia: The feed-in tariff policy framework. Biomass and Bioenergy. 2014;**62**:37-46.

[2] Tick HO, Pang SY, Chua SC. Energy policy and alternative energy in Malaysia: Issues and challenges for sustainable growth. Renewable and Sustainable Energy Reviews.

[3] Pardo Martínez CI. Energy and sustainable development in cities: A case study of

[4] Zhang X-P, Cheng X-M. Energy consumption, carbon emissions, and economic growth in China. Ecological Economics. 2009;**68**(10):2706-2712. DOI: 10.1016/j.ecolecon.2009.05.011 [5] Berndes G, Hoogwijk M, Van den Broek R. The contribution of biomass in the future global energy supply: A review of 17 studies. Biomass and Bioenergy. 2003;**25**(1):1-28.

[6] Shafiee S, Topal E. When will fossil fuel reserves be diminished? Energy Policy.

[7] Paul RE, Jonathan JB, Kevin E, Michael H, Benjamin MS III, Richard H, Richard WC, Beverly M, Nancy LR, Melissa MA, Samir KD, Leslie G. Full cost accounting for the life cycle of coal. Annals of the New York Academy of Sciences. 2011;**1219**:73-98. DOI:

[8] Nakomcic-Smaragdakis B, Cepic Z, Dragutinovic N. Analysis of solid biomass energy potential in Autonomous Province of Vojvodina. Renewable and Sustainable Energy

[9] Bahafun KA. Analysis of renewable energy potential in Malaysia. Postgraduate Coursework Student Faculty of Electrical Engineering and Telecommunications (Eet).


[24] Awalludin MF, Othman S, Rokiah H, Wan NA, Wan N. An overview of the oil palm industry in Malaysia and its waste utilization through thermochemical conversion, specifically via liquefaction. Renewable and Sustainable Energy Reviews. 2015;**50**:1469- 1484. DOI: 10.1016/j.rser.2015.05.085

[37] Saidura R, Abdelaziza EA, Demirbas A, Hossain MS, Mekhilef S. A review on biomass as a fuel for boilers. Renewable and Sustainable Energy Reviews. 2011;**15**(5):2262-2289.

Potential Application of Oil Palm Wastes Charcoal Briquettes for Coal Replacement

http://dx.doi.org/10.5772/intechopen.74863

73

[38] Abnisa F, Arami-Niya A, Daud WW, Sahu JN, Noor IM. Utilization of oil palm tree residues to produce bio-oil and bio-char via pyrolysis. Energy Conversion and Management.

[39] Wan Asma Ibrahim, Surya Prakash Chandak. Converting waste oil palm into a resource

[40] Sulaiman F, Abdullah N, Gerhauser H, Shariff A. An outlook of Malaysian energy, oil palm industry and its utilization of wastes as useful resources. Biomass and Bioenergy.

[41] Angın D. Effect of pyrolysis temperature and heating rate on biochar obtained from pyrolysis of safflower seed press cake. Bioresource Technology. 2013;**128**:593-597. DOI:

[42] Yang H, Yan R, Chen H, Lee DH, Liang DT, Zheng C. Mechanism of palm oil waste pyrolysis in a packed bed. Energy & Fuels. 2006;**20**:1321-1328. DOI: 10.1021/ef0600311

[43] Demirbas A. Potential applications of renewable energy sources, biomass combustion problems in boiler power systems and combustion related environmental issues. Progress in Energy and Combustion Science. 2005;**31**(2):171-192. DOI: 10.1016/j.pecs.2005.02.002

[44] Demirbas A. Combustion characteristics of different biomass fuels. Progress in Energy and Combustion Science. 2004;**30**(2):219-230. DOI: 10.1016/j.pecs.2003.10.004

2013;**76**:1073-1082. DOI: 10.1016/j.enconman.2013.08.038

2011;**35**(9):3775-3786. DOI: 10.1016/j.biombioe.2011.06.018

DOI: 10.1016/j.rser.2011.02.015

final report. UNEP; 2012

10.1016/j.biortech.2012.10.150


[37] Saidura R, Abdelaziza EA, Demirbas A, Hossain MS, Mekhilef S. A review on biomass as a fuel for boilers. Renewable and Sustainable Energy Reviews. 2011;**15**(5):2262-2289. DOI: 10.1016/j.rser.2011.02.015

[24] Awalludin MF, Othman S, Rokiah H, Wan NA, Wan N. An overview of the oil palm industry in Malaysia and its waste utilization through thermochemical conversion, specifically via liquefaction. Renewable and Sustainable Energy Reviews. 2015;**50**:1469-

[25] Sui LP, Lama PY, Sokhansanj S, Jim Lim C, Xiaotao TB, Stephen JD, Pribowo A, Mabee WE. Steam explosion of oil palm residues for the production of durable pellets. Applied

[26] Medic D, Darr M, Shah A, Potter B, Zimmerman J. Effects of torrefaction process parameters on biomass feedstock upgrading. Fuel. 2012;**91**(1):147-154. DOI: 10.1016/j.

[27] Sukiran MA, Chin CM, Bakar NK. Bio-oils from pyrolysis of oil palm empty fruit

[28] Abnisa F, Arami-Niya A, Daud WW, Sahu JN. Characterization of bio-oil and bio-char from pyrolysis of palm oil wastes. Bioenergy Research. 2013;**6**(2):830-840. DOI: 10.1007/

[29] Hugo Thormas J. Pyrolysis of sugarcane bagasse [thesis]. South Africa: Engineering (Chemical Engineering) Department of Process Engineering, University of Stellenbosch;

[30] Faizal HM, Latiff ZA, Mazlan A Wahid, Darus AN. Physical and combustion characteristics of biomass residues from palm oil mills. In: New Aspects of Fluid Mechanics, Heat Transfer and Environment: Proceedings of the 8 th International Conference on Heat

[31] Kersa J, Kulua P, Aruniita A, Laurmaaa V, Križanb P, Šoošb L, Kaskc Ü. Determination of physical, mechanical and burning characteristics of polymeric waste material briquettes. Estonian Journal of Engineering. 2010;**16**(4):307. DOI: 10.3176/eng.2010.4.06 [32] Bernice A, Nikiema J, Gebrezgabher S, Odonkor E, Njenga M. A Review on Production,

[33] Demirbas A, Sahin-Demirbas A. Briquetting properties of biomass waste materials.

[34] Kaliyan N, Vance Morey R. Factors affecting strength and durability of densified biomass products. Biomass and Bioenergy. 2008;**33**(3):337-359. DOI: 10.1016/j.biombioe.2008.08.005

[35] Shyamalee D, Amarasinghe A, Senanayaka N. Evaluation of different binding materials in forming biomass briquettes with saw dust. International Journal of Scientific and

[36] Jahirul MI, Rasul MG, Chowdhury AA, Ashwath N. Biofuels production through biomass pyrolysis: A technological review. Energies. 2012;**5**(12):4952-5001. DOI: 10.3390/

Energy. 2015;**141**:160-166. DOI: 10.1016/j.apenergy.2014.12.029

bunches. American Journal of Applied Sciences. 2009;**6**(5):869-875

Transfer, Thermal Engineering and Environment. 2010

Energy Sources. 2004;**26**(1):83-91

Research Publications. 2015;**5**(3):1-8

en5124952

Marketing and Use of Fuel Briquettes2016. DOI: 10.5337/2017.200

1484. DOI: 10.1016/j.rser.2015.05.085

fuel.2011.07.019

72 Palm Oil

s12155-013-9313-8

2010


**Chapter 5**

**Provisional chapter**

**Pulp and Paper Potentials of Alkaline Peroxide Pre-**

**Pulp and Paper Potentials of Alkaline Peroxide Pre-**

Paridah Md. Tahir,

Paridah Md. Tahir,

Arniza Ghazali

**Abstract**

Folahan Abdulwahab Taiwo Owolabi,

Folahan Abdulwahab Taiwo Owolabi,

Elemo Gloria Nwakaego, Oyedeko K.F. Kamilu,

Oyedeko K.F. Kamilu, Igwe Chartheny Chima,

Abbas F. MubarakAlkarkhi, Elemo GloriaNwakaego,

Igwe Chartheny Chima, Samsul Rizal and

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.74430

the natural biodiversity.

Abdul Khalil H.P. Shawkataly, Abbas F. Mubarak Alkarkhi,

Samsul Rizal and Arniza Ghazali

Abdul Khalil H.P. Shawkataly,

**Treated of Oil Palm Waste and Industrial Application**

This chapter explores the potentials of the alkaline peroxide pre-treated oil palm vascular bundle (oil palm waste) in the industrial production of pulp, paper and other cellulosic products like microcrystalline cellulose. Management of this escalating waste is a herculean task and creates environmental hazards hence urgent action is needed to create value out of these waste biomass. The pulp and paper industry being a large consumer of lignocellulose materials preferred the use of coniferous and deciduous trees for pulp production and papermaking because their cellulose fibres in the pulp make durable paper. In addition to this, the global population explosion and the economic development has resulted in the significant increase in demand for paper. With improvements in pulp processing technology through the use of environmental benign technology like alkaline peroxide pre-treatment it has been considered as suitable for paper pulp and other cellulose based products such as microcrystalline cellulose. Characterization of the alkaline peroxide pre-treated oil palm vascular bundles using the scanning electron microscope (SEM), Fourier transmission infra-red (FTIR) spectroscopy and X-Ray Diffraction (XRD) analyses confirm the micro-sized cellulose fibres. Use of these lignocellulosic materials can reduce the burden on the forest while supporting

**Keywords:** alkaline peroxide, FTIR, oil palm waste, pulp and paper, SEM, oil palm

vascular bundle, industrial production of pulp and paper

**Treated of Oil Palm Waste and Industrial Application**

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

DOI: 10.5772/intechopen.74430

#### **Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial Application Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial Application**

DOI: 10.5772/intechopen.74430

Paridah Md. Tahir, Folahan Abdulwahab Taiwo Owolabi, Abdul Khalil H.P. Shawkataly, Abbas F. Mubarak Alkarkhi, Elemo Gloria Nwakaego, Oyedeko K.F. Kamilu, Igwe Chartheny Chima, Samsul Rizal and Arniza Ghazali Paridah Md. Tahir, Folahan Abdulwahab Taiwo Owolabi, Abdul Khalil H.P. Shawkataly, Abbas F. MubarakAlkarkhi, Elemo GloriaNwakaego, Oyedeko K.F. Kamilu, Igwe Chartheny Chima, Samsul Rizal and Arniza Ghazali Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.74430

#### **Abstract**

This chapter explores the potentials of the alkaline peroxide pre-treated oil palm vascular bundle (oil palm waste) in the industrial production of pulp, paper and other cellulosic products like microcrystalline cellulose. Management of this escalating waste is a herculean task and creates environmental hazards hence urgent action is needed to create value out of these waste biomass. The pulp and paper industry being a large consumer of lignocellulose materials preferred the use of coniferous and deciduous trees for pulp production and papermaking because their cellulose fibres in the pulp make durable paper. In addition to this, the global population explosion and the economic development has resulted in the significant increase in demand for paper. With improvements in pulp processing technology through the use of environmental benign technology like alkaline peroxide pre-treatment it has been considered as suitable for paper pulp and other cellulose based products such as microcrystalline cellulose. Characterization of the alkaline peroxide pre-treated oil palm vascular bundles using the scanning electron microscope (SEM), Fourier transmission infra-red (FTIR) spectroscopy and X-Ray Diffraction (XRD) analyses confirm the micro-sized cellulose fibres. Use of these lignocellulosic materials can reduce the burden on the forest while supporting the natural biodiversity.

**Keywords:** alkaline peroxide, FTIR, oil palm waste, pulp and paper, SEM, oil palm vascular bundle, industrial production of pulp and paper

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

## **1. Introduction**

As the global demand for palm oil increases in the global markets, many tropical countries like Malaysia, Indonesia, Nigeria and others, have invested heavily in its plantation and production of Crude Palm Oil (CPO) and Palm Kernel Oil. Indonesia is the world's largest producer of palm oil contributing about 44% of the total world supply, which is followed by Malaysia, with 43% of the total world supply of palm oil (year 2006–2009) [1, 2]. The palm oil industry contributes \$7.3 billion annually to the Malaysian GDP through export [3]. In Malaysia, over 75% of oil palm plantation in Malaysia spread within four states, which include, Sabah, Johor, Pahang and Sarawak, each of which has over half a million hectares under cultivation. It was reported that about 4.3 million ha lands were utilized for oil palm plantations in 2007 which has increased to 4.49 million hectares in 2009 and it is predicted that the annual production will be increased to 50 million tons by the year 2030 [4, 5]. With the proposed increase in the oil palm plantation, there is expected increase in the oil palm waste generation. From the present estimated 83 million tonnes (dry weight) of oil palm waste generated, Awalludin and coworkers [5] reported that, it is expected to rise by 40% dry weight by 2020. From the oil palm production activities, 10% of the products goes to the oil palm produce while the remaining 90% are considered as waste biomass [6]. These waste biomass include, Oil Palm Trunk (OPT) generated after 25 years replanting scheme and Oil Palm Fronds (OPF) generated during monthly pruning during and replanting season. Although these are either used as main source of energy for power generation in oil palm mills or as organic fertilizers for natural decomposition. OPF which is the largest waste generated through the activities of the oil plantation is reported to generate about 15 tons per hectare of dried of OPF and are pruned and left to rot away at the plantation site [7]. This has been reported to constitute environmental menace to the dump sites [8]. Mushtaq and coworkers [8] reported that during oil-palm fruit harvesting, about 44 million tonnes of OPF dry weight are generated. The management of these enormous wastes has demanded the attention of researchers to proffer ways of value addition. Other oil palm waste generated is empty fruit bunches (EFB) from the oil mills, oil palm shells, kernel cake and mesocarp fibres [9]. Apart from palm oil mill effluent (POME), other oil palm wastes generated are lignocellulosic wastes which represents an extraordinarily large amount of renewable bio-resource available in the universe and has wide array of applications as raw material especially for cellulose based materials [10].

use of low cost pretreatment catalyst and should justify the cost of downstream processing steps [13]. Oil palm lignocellular wastes fibres have been proven to be suitable as ideal source for pulp and paper, cellulose based micro and nanofibres. It's a fast growing accumulation that has been considered as an advantage. Based on extensive studies on the use of cellulosic plant fibres for various industrial applications, oil palm wastes are reported as being sustainable, reusable, and eco-friendly. Research studies into the properties of the oil palm wastes show that the processing is cheap and low cost since they are considered as wastes. The polymer reinforced green composite obtained by their application has been characterize as having low energy consumption, light weight, low environmental hazard, and are renewable [14].

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Hydrogen peroxide is a mild oxidant [15]. Its highest efficiency in bleaching and delignification is observed when the reaction is conducted in alkaline medium. In the presence of sodium hydroxide, and absence of any stabilizing agents like diethylenetriamine penta- acetic acid (DTPA), or ethylene diamine tetraacetic acid (EDTA) etc. hydrogen peroxide is unstable [16]. Hydrogen peroxide readily decomposes (Eq. 1) to generate more active radicals such as perhydroxyl acid, hydroxide ions, superoxides, which play prominent role in dissolving lignin hence releasing the fibre for paper making [17]. The mechanism of alkaline peroxide delignification reaction of hydrogen peroxide revealed that it is strongly pH dependent [18] with an

H2 O2 ⇔ H+ + HOO<sup>−</sup> (1)

Under these conditions, the active species responsible for the elimination of chromophoric groups from lignin are hydroperoxide anion (HOO−) [19]. **Table 1** shows the list and characteristics of active radicals and anions from hydrogen peroxide decomposition in alkaline

bleaching of mechanical, thermomechanical, chemimechanical, and semichemical pulps [21].

**Reactants Name Type Nature Function pH range** HOO͞ Hydroperoxide anion Anion N Reductant Alkaline OH͞ Hydroxide ion Anion N Alkaline HOO• Hydroperoxyl Radical Radical E Oxidant Acidic HO• Hydroxyl radical Radical E Oxidant Acidic

O2̄ Superoxide anion radical Radical, Anion N Oxidant Alkaline/neutral

decomposition in alkaline medium.

O2

−

decomposition. The alkaline peroxide delignification procedure is a lignin-retaining

·, are the primary lignin oxidizing species.

from the reaction mixture indicat-

**1.1. System with alkaline peroxide pretreatment of lignocelluloses**

optimum at pH 11.5–11.6, pKa for the dissociation:

decomposition products such as ·OH and O2

The delignification reaction witnessed the evolution of O<sup>2</sup>

medium [20].

H2 O2

ing H2 O2

Source: [20].

**Table 1.** Active radicals and anions from H2

The quality of the cellulosic products from this cellulose depends on the source of the original cellulose, the type of treatment and the kinds of the extraction procedures [11]. The effective utilization of lignocellulosic is conversely, not totally devoid of challenges. Among the range of the challenges associated with the use of lignocellulosic biomass apart from byproducts generated during pretreatment are, resistance of the plant cell wall due to integral structural complexity of lignocellulosic fractions and strong hindrance from the inhibitors [12]. Similarly, the knowledge of suitable pretreatment method and extent of cell wall deconstruction for generation of value-added products are equally very important in the choice of the pretreatment methods. The pretreatment techniques for overcoming biomass resistance could be selected over an array of methods which include: avoidance of cellulose fibre size reduction, preservation of the hemicellulose, minimization of bye products, reduction in energy consumptions, use of low cost pretreatment catalyst and should justify the cost of downstream processing steps [13]. Oil palm lignocellular wastes fibres have been proven to be suitable as ideal source for pulp and paper, cellulose based micro and nanofibres. It's a fast growing accumulation that has been considered as an advantage. Based on extensive studies on the use of cellulosic plant fibres for various industrial applications, oil palm wastes are reported as being sustainable, reusable, and eco-friendly. Research studies into the properties of the oil palm wastes show that the processing is cheap and low cost since they are considered as wastes. The polymer reinforced green composite obtained by their application has been characterize as having low energy consumption, light weight, low environmental hazard, and are renewable [14].

#### **1.1. System with alkaline peroxide pretreatment of lignocelluloses**

**1. Introduction**

76 Palm Oil

As the global demand for palm oil increases in the global markets, many tropical countries like Malaysia, Indonesia, Nigeria and others, have invested heavily in its plantation and production of Crude Palm Oil (CPO) and Palm Kernel Oil. Indonesia is the world's largest producer of palm oil contributing about 44% of the total world supply, which is followed by Malaysia, with 43% of the total world supply of palm oil (year 2006–2009) [1, 2]. The palm oil industry contributes \$7.3 billion annually to the Malaysian GDP through export [3]. In Malaysia, over 75% of oil palm plantation in Malaysia spread within four states, which include, Sabah, Johor, Pahang and Sarawak, each of which has over half a million hectares under cultivation. It was reported that about 4.3 million ha lands were utilized for oil palm plantations in 2007 which has increased to 4.49 million hectares in 2009 and it is predicted that the annual production will be increased to 50 million tons by the year 2030 [4, 5]. With the proposed increase in the oil palm plantation, there is expected increase in the oil palm waste generation. From the present estimated 83 million tonnes (dry weight) of oil palm waste generated, Awalludin and coworkers [5] reported that, it is expected to rise by 40% dry weight by 2020. From the oil palm production activities, 10% of the products goes to the oil palm produce while the remaining 90% are considered as waste biomass [6]. These waste biomass include, Oil Palm Trunk (OPT) generated after 25 years replanting scheme and Oil Palm Fronds (OPF) generated during monthly pruning during and replanting season. Although these are either used as main source of energy for power generation in oil palm mills or as organic fertilizers for natural decomposition. OPF which is the largest waste generated through the activities of the oil plantation is reported to generate about 15 tons per hectare of dried of OPF and are pruned and left to rot away at the plantation site [7]. This has been reported to constitute environmental menace to the dump sites [8]. Mushtaq and coworkers [8] reported that during oil-palm fruit harvesting, about 44 million tonnes of OPF dry weight are generated. The management of these enormous wastes has demanded the attention of researchers to proffer ways of value addition. Other oil palm waste generated is empty fruit bunches (EFB) from the oil mills, oil palm shells, kernel cake and mesocarp fibres [9]. Apart from palm oil mill effluent (POME), other oil palm wastes generated are lignocellulosic wastes which represents an extraordinarily large amount of renewable bio-resource available in the universe and has wide array of

applications as raw material especially for cellulose based materials [10].

The quality of the cellulosic products from this cellulose depends on the source of the original cellulose, the type of treatment and the kinds of the extraction procedures [11]. The effective utilization of lignocellulosic is conversely, not totally devoid of challenges. Among the range of the challenges associated with the use of lignocellulosic biomass apart from byproducts generated during pretreatment are, resistance of the plant cell wall due to integral structural complexity of lignocellulosic fractions and strong hindrance from the inhibitors [12]. Similarly, the knowledge of suitable pretreatment method and extent of cell wall deconstruction for generation of value-added products are equally very important in the choice of the pretreatment methods. The pretreatment techniques for overcoming biomass resistance could be selected over an array of methods which include: avoidance of cellulose fibre size reduction, preservation of the hemicellulose, minimization of bye products, reduction in energy consumptions, Hydrogen peroxide is a mild oxidant [15]. Its highest efficiency in bleaching and delignification is observed when the reaction is conducted in alkaline medium. In the presence of sodium hydroxide, and absence of any stabilizing agents like diethylenetriamine penta- acetic acid (DTPA), or ethylene diamine tetraacetic acid (EDTA) etc. hydrogen peroxide is unstable [16]. Hydrogen peroxide readily decomposes (Eq. 1) to generate more active radicals such as perhydroxyl acid, hydroxide ions, superoxides, which play prominent role in dissolving lignin hence releasing the fibre for paper making [17]. The mechanism of alkaline peroxide delignification reaction of hydrogen peroxide revealed that it is strongly pH dependent [18] with an optimum at pH 11.5–11.6, pKa for the dissociation:

$$\rm H\_2O\_2 \quad \Leftrightarrow \rm H^\* + HOO^- \tag{1}$$

Under these conditions, the active species responsible for the elimination of chromophoric groups from lignin are hydroperoxide anion (HOO−) [19]. **Table 1** shows the list and characteristics of active radicals and anions from hydrogen peroxide decomposition in alkaline medium [20].

H2 O2 decomposition products such as ·OH and O2 − ·, are the primary lignin oxidizing species. The delignification reaction witnessed the evolution of O<sup>2</sup> from the reaction mixture indicating H2 O2 decomposition. The alkaline peroxide delignification procedure is a lignin-retaining bleaching of mechanical, thermomechanical, chemimechanical, and semichemical pulps [21].


**Table 1.** Active radicals and anions from H2 O2 decomposition in alkaline medium.

If the reaction contribution is not properly controlled, these radical materials are likely to redeposit on the biomass surface. Pulp brightness may be achieved by either lignin removal (delignification) or lignin decolonization [22]. This anion was found to be a strong nucleophile that is site specific, during bleaching, preferentially attacks ethylenic and carbonyl groups present in lignin. As a consequence, such chromophores as quinones, cinnamaldehyde, and ring-conjugated ketoses are converted to none chromophoric species [20]. On the other hand, radical species such as hydroxyl radicals (HO•) generated from the hydrogen peroxide alkaline decomposition, are responsible for delignification and solubilization of hemicelluloses [21]. Sequel to the mechanism of alkaline peroxide delignification, Gould [19] reported the use of alkaline peroxide in the delignification of agricultural residues to enhance enzymatic conversion of the cellulose-rich residue to glucose. According to the report, approximately one-half of the lignin is dissolved. Most of the hemicellulose present in agricultural residues such as wheat straw and corn stover was solubilized when the residue was treated at 25°C in an alkaline solution of hydrogen peroxide.

in the pretreatment study. The result shows that the time factor, the AP pretreated concentration factor and the interactive effect of the time and the AP treatment factors are statistically significant at 95% confidence level. This development led to the determination of the level of significant effect through post hoc test conducted on the AP pretreatment on the pulp and strength properties of the formed handsheet with the different alkaline peroxide dosage as displayed in **Table 2**. The significant differences in the AP concentration levels for the homogenous subset of all the independent variables namely: Screened yield, kappa number, Canadian freeness test (CFS), Tensile, Burst and Tear indexes and ISO brightness (**Table 2**) shows that the pulp and paper properties increased with an increase in the AP concentration. The result shows best pretreatment is obtained for papers prepared at a high concentration of AP pretreatment. The differences among the alkaline peroxide concentration pretreatment levels were tested, by using Duncan Multiple Range test and the significant distinctions are

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From the result obtained, there is generally increase in the pulp and paper properties investigated with the AP pretreatment of the oil palm vascular bundles, with the increase in the AP concentration. The increase in the pulp and paper properties as observed with increase in the AP concentrations is attributable to the dissolution of lignin fragment and the loss of some extractives from the OPF VB. This shows that an increase in the concentration of AP results in gradual reduction in lignin molecule and hemicellulose removal. A reverse trend, however, was obtained for high AP concentration in the screened yield. A general drop in the pulp screened yield between 50.44 and 57.70% was apparent at high AP concentration. This observation could be attributable to the gradual increase in the rate of lignin dissolution resulting in the lignin modification and hemicellulose loss as conspicuously shown on the result obtained from the TGA/DTG curves and FTIR spectra (**Figures 1**–**4**) respectively. The decline in the screened pulp yield obtained at high AP concentration is also attributable to the high rate of micro-to-nano scale cogenerated fibrils that escaped the P200 screen during screening stage, resulting in low screened pulp yield. This presence of these fines particles enhances the water retention of the pulp web resulting in the low value of the CSF as shown in **Table 2** at high AP concentrations. Conversely, an increase in alkaline peroxide level is attributable to better extent of lignin removal. As a result, an increased amount of delignification agents was available to access the more remote chromophoric groups within the OPF structure. This

**CSF (ml) Tensile** 

Low 13.45 40.21b 114.55a 780a 1.59c 2.87c 2.33b 28.528a Medium 13.70 42.67a 101.10b 550b 9.085b 5.95b 5.37a 27.806b High 14.00 38.07c 91.20c 241.67c 13.34a 7.90a 5.63a 24.183c

**Index (mN/g)** **Burst Index (kpa m2 /g)**

**Tear Index (mN m2 /g)**

**ISO Brightness**

denoted by letters a, b, and c (**Table 2**).

**Treatment PH Yield (%) Kappa** 

**Number**

Means within a column with different letters are significantly different at P < 0.05.

**Table 2.** DMRT for AP significantly different effects on pulp and paper properties.

NB: a = Highest significant; b = Lower significant; c = Least significant.

## **2. Characterization of alkaline peroxide pre-treated oil palm waste fibre**

Screening the effect of the alkaline peroxide pre-treated vascular bundle fibre particles was carried out with three different alkaline peroxide concentrated liquors: low (H<sup>2</sup> O2 : NaOH; 1.5:1.0), medium (H2 O2 : NaOH; 2.5:2.0) and high (H2 O2 :NaOH; 5.0:4.0) at alkaline peroxide pretreated oil palm frond vascular bundles (AP-OPF VB) reaction duration ranging from 10 to 60 min, with 0 min serving as control.

After the reaction period, the solid pulp was dried at 103°C and subjected to Fourier Transform Infrared (FTIR) spectroscopy to elucidate the changes in the functional groups predominating the samples before and after pulping. To further exploit the effect of the AP pretreatment, extracted cellulose fibre, crystallinity and the thermal analysis through the study of the thermogravimetry analysis TGA and derivative thermogravimetry (DTG) as reported by Lamaming and coworkers [22] were used to characterize the extracted cellulose fibres in terms of thermal stability, miscibility, and the reaction enthalpy that occur during the temperature-dependent phase transition. Also the TGA was used to characterize the thermal stability of materials through the study of the thermal degradation of the fibre at varying temperature. The knowledge of the X-ray diffraction pattern XRD of the cellulose fibres is used to estimate the purity of the AP treated biomass. This is based on the crystallinity values. The result and surface morphology of the produced OPF VB fibres and Handsheet were studied with the aid of the scanning electron microgram (SEM).

#### **2.1. Evaluation of the pulp fibres from AP pre-treated OPF vascular bundles**

Two-way ANOVA of the AP level and pretreatment duration as independent factors on the screened pulp properties (screen yield, kappa number and the CSF), the paper mechanical properties (Tensile, Burst and Tear indexes) and ISO brightness shows significant difference in the pretreatment study. The result shows that the time factor, the AP pretreated concentration factor and the interactive effect of the time and the AP treatment factors are statistically significant at 95% confidence level. This development led to the determination of the level of significant effect through post hoc test conducted on the AP pretreatment on the pulp and strength properties of the formed handsheet with the different alkaline peroxide dosage as displayed in **Table 2**. The significant differences in the AP concentration levels for the homogenous subset of all the independent variables namely: Screened yield, kappa number, Canadian freeness test (CFS), Tensile, Burst and Tear indexes and ISO brightness (**Table 2**) shows that the pulp and paper properties increased with an increase in the AP concentration. The result shows best pretreatment is obtained for papers prepared at a high concentration of AP pretreatment. The differences among the alkaline peroxide concentration pretreatment levels were tested, by using Duncan Multiple Range test and the significant distinctions are denoted by letters a, b, and c (**Table 2**).

If the reaction contribution is not properly controlled, these radical materials are likely to redeposit on the biomass surface. Pulp brightness may be achieved by either lignin removal (delignification) or lignin decolonization [22]. This anion was found to be a strong nucleophile that is site specific, during bleaching, preferentially attacks ethylenic and carbonyl groups present in lignin. As a consequence, such chromophores as quinones, cinnamaldehyde, and ring-conjugated ketoses are converted to none chromophoric species [20]. On the other hand, radical species such as hydroxyl radicals (HO•) generated from the hydrogen peroxide alkaline decomposition, are responsible for delignification and solubilization of hemicelluloses [21]. Sequel to the mechanism of alkaline peroxide delignification, Gould [19] reported the use of alkaline peroxide in the delignification of agricultural residues to enhance enzymatic conversion of the cellulose-rich residue to glucose. According to the report, approximately one-half of the lignin is dissolved. Most of the hemicellulose present in agricultural residues such as wheat straw and corn stover was solubilized when the residue was treated at 25°C in an alka-

**2. Characterization of alkaline peroxide pre-treated oil palm waste** 

carried out with three different alkaline peroxide concentrated liquors: low (H<sup>2</sup>

: NaOH; 2.5:2.0) and high (H2

**2.1. Evaluation of the pulp fibres from AP pre-treated OPF vascular bundles**

Two-way ANOVA of the AP level and pretreatment duration as independent factors on the screened pulp properties (screen yield, kappa number and the CSF), the paper mechanical properties (Tensile, Burst and Tear indexes) and ISO brightness shows significant difference

Screening the effect of the alkaline peroxide pre-treated vascular bundle fibre particles was

pretreated oil palm frond vascular bundles (AP-OPF VB) reaction duration ranging from 10

After the reaction period, the solid pulp was dried at 103°C and subjected to Fourier Transform Infrared (FTIR) spectroscopy to elucidate the changes in the functional groups predominating the samples before and after pulping. To further exploit the effect of the AP pretreatment, extracted cellulose fibre, crystallinity and the thermal analysis through the study of the thermogravimetry analysis TGA and derivative thermogravimetry (DTG) as reported by Lamaming and coworkers [22] were used to characterize the extracted cellulose fibres in terms of thermal stability, miscibility, and the reaction enthalpy that occur during the temperature-dependent phase transition. Also the TGA was used to characterize the thermal stability of materials through the study of the thermal degradation of the fibre at varying temperature. The knowledge of the X-ray diffraction pattern XRD of the cellulose fibres is used to estimate the purity of the AP treated biomass. This is based on the crystallinity values. The result and surface morphology of the produced OPF VB fibres and Handsheet were studied with the aid

O2

O2

:NaOH; 5.0:4.0) at alkaline peroxide

: NaOH;

line solution of hydrogen peroxide.

O2

to 60 min, with 0 min serving as control.

of the scanning electron microgram (SEM).

**fibre**

78 Palm Oil

1.5:1.0), medium (H2

From the result obtained, there is generally increase in the pulp and paper properties investigated with the AP pretreatment of the oil palm vascular bundles, with the increase in the AP concentration. The increase in the pulp and paper properties as observed with increase in the AP concentrations is attributable to the dissolution of lignin fragment and the loss of some extractives from the OPF VB. This shows that an increase in the concentration of AP results in gradual reduction in lignin molecule and hemicellulose removal. A reverse trend, however, was obtained for high AP concentration in the screened yield. A general drop in the pulp screened yield between 50.44 and 57.70% was apparent at high AP concentration. This observation could be attributable to the gradual increase in the rate of lignin dissolution resulting in the lignin modification and hemicellulose loss as conspicuously shown on the result obtained from the TGA/DTG curves and FTIR spectra (**Figures 1**–**4**) respectively. The decline in the screened pulp yield obtained at high AP concentration is also attributable to the high rate of micro-to-nano scale cogenerated fibrils that escaped the P200 screen during screening stage, resulting in low screened pulp yield. This presence of these fines particles enhances the water retention of the pulp web resulting in the low value of the CSF as shown in **Table 2** at high AP concentrations. Conversely, an increase in alkaline peroxide level is attributable to better extent of lignin removal. As a result, an increased amount of delignification agents was available to access the more remote chromophoric groups within the OPF structure. This


Means within a column with different letters are significantly different at P < 0.05. NB: a = Highest significant; b = Lower significant; c = Least significant.

**Table 2.** DMRT for AP significantly different effects on pulp and paper properties.

**Figure 1.** TGA curves for OPF vascular bundle fibres [7].

power of alkaline peroxide [23]. About 50% lignin was reportedly removed from a couple of lignocelluloses biomass (corn stover, oak shavings, kenaf, straw and wheat straw, which has been reported possessed similar morphological properties) treated with 2% (w/v) solution of alkaline peroxide [15]. Also, the same observation was reported when alkaline peroxide was optimized at 8.6% (w/v) [19]. With the treatment of alkaline peroxide for wheat straw, 60% reduction in lignin was recorded [23]. A similar result was reported by sun and coworkers [17] that treatment with the alkaline solution of hydrogen peroxide on rye straw resulted in 60% delignification. The overall result shows a reduction in the lignin by 25.56, 32.05 and 38.43% for pulp generated from the low, medium and high AP concentration pulping system. Since Kappa number is a measure of the total amount of residual lignin in the pulp that is

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**Figure 4.** FTIR spectra of OPF vascular bundle fibres at different AP pretreatment.

**Figure 3.** X-ray diffractometry patterns of APMP pulp from OPF vascular bundles [7].

**Figure 2.** DTG curves of the raw and extracted OPF vascular bundle fibres [7].

contributed to the low Kappa number obtained at high AP concentration **Table 2**. Despite the general decrease in the Kappa number with time with the increase in the concentration of chemical charge, the high Kappa number results (**Table 2**), is attributable to the weak oxidizing Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial… http://dx.doi.org/10.5772/intechopen.74430 81

**Figure 3.** X-ray diffractometry patterns of APMP pulp from OPF vascular bundles [7].

**Figure 4.** FTIR spectra of OPF vascular bundle fibres at different AP pretreatment.

contributed to the low Kappa number obtained at high AP concentration **Table 2**. Despite the general decrease in the Kappa number with time with the increase in the concentration of chemical charge, the high Kappa number results (**Table 2**), is attributable to the weak oxidizing

**Figure 2.** DTG curves of the raw and extracted OPF vascular bundle fibres [7].

**Figure 1.** TGA curves for OPF vascular bundle fibres [7].

80 Palm Oil

power of alkaline peroxide [23]. About 50% lignin was reportedly removed from a couple of lignocelluloses biomass (corn stover, oak shavings, kenaf, straw and wheat straw, which has been reported possessed similar morphological properties) treated with 2% (w/v) solution of alkaline peroxide [15]. Also, the same observation was reported when alkaline peroxide was optimized at 8.6% (w/v) [19]. With the treatment of alkaline peroxide for wheat straw, 60% reduction in lignin was recorded [23]. A similar result was reported by sun and coworkers [17] that treatment with the alkaline solution of hydrogen peroxide on rye straw resulted in 60% delignification. The overall result shows a reduction in the lignin by 25.56, 32.05 and 38.43% for pulp generated from the low, medium and high AP concentration pulping system. Since Kappa number is a measure of the total amount of residual lignin in the pulp that is oxidizable with KMnO4 , its value is used to determine the residual lignin content in the pulp. Result in **Table 2** also shows that the optical properties are significantly affected by the AP pre- treatment concentration. The decrease in brightness at high concentrations of the AP liquor is attributable to the redeposition of the alkaline leachate on the surface of the biomass hence resulting to the phenomenon of alkaline darkening. This is similar to the observation reported by Liu and co-workers [24].

decomposition graph, presents thermal degradation peaks of lignin compound as a result of the breakdown of ether and carbon–carbon linkages [30]. With further heating beyond 400°C, all the fibres at the specified AP concentrations, had residual weight of approximately 27.47, 12.71, 13.55 and 13.34% for untreated OPF fibre and cellulose fibres obtained at low, medium and high AP concentrations, respectively. The residual char obtained at the end of the heating exercise was ascribed to the combination of the residual lignin and ash in the samples. This is in line with the result of Rosa et al. [30], and Sonia and Dasan [26]. The amount of the residual char after the thermal decompositions reflects the amount of residual lignin and the ash. The result shows that the residual char reduces significantly compared to the raw OPF-VB biomass. This is attributable to the successful removal of the amorphous part of the

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83

The cellulose chain contains the crystalline (ordered) regions and the amorphous (disordered) regions [29]. **Table 3** shows the values of the fibre crystallinity of the OPF-VB fibres obtained from AP pretreatment systems. Crystallinity values are calculated by the formulae reported by Segal and team [31]. From **Table 3**, it is evident that there is an increase in the cellulose crystallinity as the alkaline peroxide concentrations increases from low AP concentrations to the medium AP concentrations. The percentage crystallinity dropped for fibres extracted at

The observed drop in the percentage crystallinity of the extracted fibre at high AP concentrations was as a result of a high amount of fines generated in the high AP concentration in the AP pretreatment system. This is in line with the observation reported by Segal and team [31] who similarly witnessed the loss of crystallinity upon excessive refining. Similarly, both Habibi and coworkers [32] and Lamaming and team [20] independently reported changes in crystallinity index of the respective substrate due to pretreatment. Trache and coworkers [33] reported that during refining, the intermolecular hydrogen bonds of cellulose are broken, causing the collapse of the crystal structure of the cellulose fibre. The x-ray diffraction patterns of the cellulosic fibres at different AP concentrations are shown in **Figure 3**, matching with the monoclinic sphenodic structure characteristic of cellulose 1 polymorph (which is unmodified form of natural cellulose) [34]. The similarity in the three X-ray diffraction patterns in **Figure 3** shows that the AP treatment at different concentrations maintains the natu-

extracted fibres [22].

**3.2. X-Ray diffraction**

high AP concentrations.

ral cellulose 1 polymorphs structure of the biomass.

**Table 3.** Crystallinity index of the OPF VB fibres.

**AP fibre Samples Crystallinity** Low-AP 28.1% Medium-AP 35.7% High-AP 27.4%

## **3. Characterization of alkaline peroxide pre-treated OPF fibres**

The extracted fibres were next characterized for their thermal properties and functional groups.

#### **3.1. Thermal characterization of OPF AP pulp**

Thermogravimetric analysis (TGA) was measured to access the thermal stability of the extracted fibres. It provides quantitative information on weight change during heating process [25]. From the result shown in **Figures 1** and **2**, the thermogravimetry analysis TGA and derivative thermogravimetry DTG curves obtained for both the raw and the extracted OPF fibres at different AP concentrations. Where (a) untreated represents fibre OPF-R, (b) Fibre pre-treated at 1.0% NaOH: 1.5% H2 O2 —OPF-LOW, (c) Fibre pre-treated at 2.0% NaOH: 2.5% H2 O2 —OPF-Medium, and (d) Fibre pre-treated at 4.0% NaOH: 5.0% H2 O2 ; OPF-High AP concentrations. From the graph, the initial weight loss was observed to occur between 50 and 106°C for the raw sample while the weight loss for the extracted samples were observed between 50 and 110; 50 and 118 and 50 and 119°C for cellulose from low; medium and high AP concentrations, respectively. This first stage of weight loss, which is not accompanied with samples thermal degradation, corresponds to loss in the volatile materials and vaporization of water because of the hydrophilic nature of the lignocellulose fibres in all the samples [26]. The second stage of weight loss, was observed between 230 and 282; 262 and 366; 254 and 366; and 270 and 366°C for raw and the extracted fibres at low, medium and high AP concentrations, respectively. This corresponds to hemicellulose, pectin and cellulose degradation as previously found by Eriksen and coworkers [27].

From DTG (**Figure 2**), the maximum thermal degradation peak corresponds to 342; 366; 374 and 382°C for untreated OPF fibre and cellulose fibres obtained at low, medium and high AP concentrations, respectively and this corresponds to the decomposition temperature of cellulose [28]. This weight loss was attributed to thermal depolymerization and cleavage of the glycosidic linkages of cellulose [29]. From the DTG curves (**Figure 2**), the lower temperature peak at around 290°C was observed from raw (untreated fibre) and AP extracted fibres at H<sup>2</sup> O2 : NaOH 1.5:1.0, corresponds to the decomposition of hemicellulose [25]. This temperature peak was found to shift to a higher temperature and remained as a shoulder for AP-treated fibres at H2 O2 : NaOH of 2.5:2.0 and H2 O2 : NaOH of 5.0:4.0, indicating partial removal of hemicellulose from the fibre. From the DTG result it could be deduced that, the extracted cellulose has higher thermal stability than the raw OPF fibre. The third decay stage of the thermal decomposition graph, presents thermal degradation peaks of lignin compound as a result of the breakdown of ether and carbon–carbon linkages [30]. With further heating beyond 400°C, all the fibres at the specified AP concentrations, had residual weight of approximately 27.47, 12.71, 13.55 and 13.34% for untreated OPF fibre and cellulose fibres obtained at low, medium and high AP concentrations, respectively. The residual char obtained at the end of the heating exercise was ascribed to the combination of the residual lignin and ash in the samples. This is in line with the result of Rosa et al. [30], and Sonia and Dasan [26]. The amount of the residual char after the thermal decompositions reflects the amount of residual lignin and the ash. The result shows that the residual char reduces significantly compared to the raw OPF-VB biomass. This is attributable to the successful removal of the amorphous part of the extracted fibres [22].

#### **3.2. X-Ray diffraction**

oxidizable with KMnO4

groups.

82 Palm Oil

2.5% H2

at H2 O2 O2

reported by Liu and co-workers [24].

**3.1. Thermal characterization of OPF AP pulp**

Fibre pre-treated at 1.0% NaOH: 1.5% H2

ously found by Eriksen and coworkers [27].

: NaOH of 2.5:2.0 and H2

, its value is used to determine the residual lignin content in the pulp.

—OPF-LOW, (c) Fibre pre-treated at 2.0% NaOH:

: NaOH of 5.0:4.0, indicating partial removal of hemicel-

O2

; OPF-High

O2 :

Result in **Table 2** also shows that the optical properties are significantly affected by the AP pre- treatment concentration. The decrease in brightness at high concentrations of the AP liquor is attributable to the redeposition of the alkaline leachate on the surface of the biomass hence resulting to the phenomenon of alkaline darkening. This is similar to the observation

The extracted fibres were next characterized for their thermal properties and functional

Thermogravimetric analysis (TGA) was measured to access the thermal stability of the extracted fibres. It provides quantitative information on weight change during heating process [25]. From the result shown in **Figures 1** and **2**, the thermogravimetry analysis TGA and derivative thermogravimetry DTG curves obtained for both the raw and the extracted OPF fibres at different AP concentrations. Where (a) untreated represents fibre OPF-R, (b)

O2

—OPF-Medium, and (d) Fibre pre-treated at 4.0% NaOH: 5.0% H2

AP concentrations. From the graph, the initial weight loss was observed to occur between 50 and 106°C for the raw sample while the weight loss for the extracted samples were observed between 50 and 110; 50 and 118 and 50 and 119°C for cellulose from low; medium and high AP concentrations, respectively. This first stage of weight loss, which is not accompanied with samples thermal degradation, corresponds to loss in the volatile materials and vaporization of water because of the hydrophilic nature of the lignocellulose fibres in all the samples [26]. The second stage of weight loss, was observed between 230 and 282; 262 and 366; 254 and 366; and 270 and 366°C for raw and the extracted fibres at low, medium and high AP concentrations, respectively. This corresponds to hemicellulose, pectin and cellulose degradation as previ-

From DTG (**Figure 2**), the maximum thermal degradation peak corresponds to 342; 366; 374 and 382°C for untreated OPF fibre and cellulose fibres obtained at low, medium and high AP concentrations, respectively and this corresponds to the decomposition temperature of cellulose [28]. This weight loss was attributed to thermal depolymerization and cleavage of the glycosidic linkages of cellulose [29]. From the DTG curves (**Figure 2**), the lower temperature peak at around 290°C was observed from raw (untreated fibre) and AP extracted fibres at H<sup>2</sup>

NaOH 1.5:1.0, corresponds to the decomposition of hemicellulose [25]. This temperature peak was found to shift to a higher temperature and remained as a shoulder for AP-treated fibres

lulose from the fibre. From the DTG result it could be deduced that, the extracted cellulose has higher thermal stability than the raw OPF fibre. The third decay stage of the thermal

O2

**3. Characterization of alkaline peroxide pre-treated OPF fibres**

The cellulose chain contains the crystalline (ordered) regions and the amorphous (disordered) regions [29]. **Table 3** shows the values of the fibre crystallinity of the OPF-VB fibres obtained from AP pretreatment systems. Crystallinity values are calculated by the formulae reported by Segal and team [31]. From **Table 3**, it is evident that there is an increase in the cellulose crystallinity as the alkaline peroxide concentrations increases from low AP concentrations to the medium AP concentrations. The percentage crystallinity dropped for fibres extracted at high AP concentrations.

The observed drop in the percentage crystallinity of the extracted fibre at high AP concentrations was as a result of a high amount of fines generated in the high AP concentration in the AP pretreatment system. This is in line with the observation reported by Segal and team [31] who similarly witnessed the loss of crystallinity upon excessive refining. Similarly, both Habibi and coworkers [32] and Lamaming and team [20] independently reported changes in crystallinity index of the respective substrate due to pretreatment. Trache and coworkers [33] reported that during refining, the intermolecular hydrogen bonds of cellulose are broken, causing the collapse of the crystal structure of the cellulose fibre. The x-ray diffraction patterns of the cellulosic fibres at different AP concentrations are shown in **Figure 3**, matching with the monoclinic sphenodic structure characteristic of cellulose 1 polymorph (which is unmodified form of natural cellulose) [34]. The similarity in the three X-ray diffraction patterns in **Figure 3** shows that the AP treatment at different concentrations maintains the natural cellulose 1 polymorphs structure of the biomass.


**Table 3.** Crystallinity index of the OPF VB fibres.

after APMP process. This is apparent from the result in **Figure 4**. From the result, among the common bands were the 3400–3300 cm−1 region, which is attributed to the stretching of O-H groups, whereas those around 2900–2800 cm−1 were due to the stretching of C-H [20]. The appearance weak band at 2362–2135 cm−1 for the AP pretreated pulp at different concentrations is attributed to the C-C stretching vibration. This peak could be the result having phenyl ethynyl group that was generated during lignin dissolution [35] suggesting also lignin dissolution with AP treatment. The peak located at 1734 cm−1 in the raw OPF was assigned to the C=O stretching of the acetyl group in hemicellulose [37] or ester linkage of the carboxylic group in the ferulic and p-coumaric acids of either lignin or hemicelluloses [36]. The FTIR spectra reveal (as shown in Section 4) a shoulder at 1733 cm−1 for fibres generated via AP pretreatment system employing the medium and high AP concentrations. This characterizes the significant dissolution of hemicelluloses with the medium and high AP systems, in agreement with the DTG result in **Figure 4**. This observation is in contrast with the report by Ghazali and co-workers [17] that an increase in alkaline solution of hydrogen peroxide concentration caused an increase of lignin oxidation through a reduction in the aromatic rings. The peak at 1247 cm−1 could also be associated to the C=O stretching of the aryl group in lignin [35]. The shift of this peak coupled with weak absorbance was believed to be due to the reduction of lignin after the chemical treatments, while the weak signal indicates the presence of residual lignin [22]. The absorbance between 1426 and 1427 cm−1 for the raw OPF and OPF

Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial…

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85

be observed as peaks around 1112–1114; 1054–1056 cm−1 and 897 cm−1 in all the pulp samples. It is characteristic of glycosidic linkage between sugar unit samples [33], which are not present in the spectra of the raw samples. The absorbance peak at 1160–1164 cm−1 in the OPF raw sample and pulp is due to the anti-symmetrical deformation of the C-O-C band [36]. However the vibration peak at 897 cm−1, which was absent in the raw sample, appear in the OPF pulp at the various concentrations. This was assigned to the glycosidic bonds, which are symmetric

Statistically, significant differences in the effects of AP concentration treatment level on the strength properties (tensile index, burst index and tear index) are also shown in **Table 1**. The ANOVA result shows that all the paper properties are significantly affected by the AP treatment except the burst index. The study showed that increase in the AP concentrations enhances the strength properties of the paper formed, which is in agreement with the trend already established with the paper apparent density. The impact of the high AP level on the fibrillation of OPF vascular bundle fibres become more apparently portrayed on the pulp web strength properties, and this stems from the higher probability of the lignin transformation to low molecular weight fragments and hence easily leached at high AP concentration treatment [17]. Furthermore high AP concentrations level produces higher fibrillation, which enhances fibre bonding and reduces fibre coarseness, thus leading to improved mechanical strength of the paper. Unlike the other strength properties, the ANOVA for AP treatment and time effect on AP strength properties (**Table 1**), the burst strength show no significant effect on the AP and time interaction effect. This observation is attributable to the fact that the bursting

**3.4. Effect of alkaline peroxide pretreatment concentration on paper properties**

symmetric bending [14]. The stretching of C=O and O-H can

pulps is associated to the CH2

in polysaccharides [35].

**Figure 5.** SEM images of (a) Raw OPF sample (b) AP treated fibre at low AP concentration (1.0 :1.5), (c) AP treated fibre at Medium AP concentration (2.0 : 2.5) and (d) AP treated fibre at high AP concentration (4.0 : 5.0) paper web at different AP concentrations.

It is evident from **Figure 5** that the peaks at 22.20°, 22.40°, and 22.10° corresponding to A, B, and C, respectively are characteristic of native cellulose I polymorph [20, 31]. The X-ray diffraction technique revealed that the extracted cellulose fibres could be easily hydrolysed into the crystalline sample. Due to the softening effect of the treated fibres at high AP concentrations, the high fibrillations, cell wall delaminations aid the production of fibrillar fines at high AP concentrations; expose the crystalline cellulosic materials in OPF in a more profound manner.

The observed drop in the fibre crystallinity observed at high AP concentration treatment is attributable to the presence of certain threshold of fines content in the pulp. In a separate reports, Segal and coworkers [31] reported that fibre crystallinity could be lost by refining while Rafiee and Keshavarz [34] reported that fibre crystallinity could be lost due to high chemical treatment. This trend in the fibre crystallinity is in agreement with the report in the literatures [34]. The X-ray diffraction technique revealed that the extracted cellulose fibres could be easily hydrolysed into the crystalline sample.

#### **3.3. Correlation between FTIR spectroscopy, DTG and XRD**

The FTIR spectra of the raw and pulped fibres are shown in **Figure 4**, which shows the FTIR spectra of OPF fibre (A) Raw OPF vascular bundle fibres (B) OPF isolated at 1.5%:1.0%; H2 O2 :NaOH AP concentrations (C) OPF isolated at 2.5%:2.0%; H2 O2 :NaOH AP concentrations (D) OPF isolated at 5.0%:4.0%; H2 O2 :NaOH AP concentrations. Analysis shows that despite the similarity, there are some shifts, disappearance and appearance of some signals of samples after APMP process. This is apparent from the result in **Figure 4**. From the result, among the common bands were the 3400–3300 cm−1 region, which is attributed to the stretching of O-H groups, whereas those around 2900–2800 cm−1 were due to the stretching of C-H [20]. The appearance weak band at 2362–2135 cm−1 for the AP pretreated pulp at different concentrations is attributed to the C-C stretching vibration. This peak could be the result having phenyl ethynyl group that was generated during lignin dissolution [35] suggesting also lignin dissolution with AP treatment. The peak located at 1734 cm−1 in the raw OPF was assigned to the C=O stretching of the acetyl group in hemicellulose [37] or ester linkage of the carboxylic group in the ferulic and p-coumaric acids of either lignin or hemicelluloses [36]. The FTIR spectra reveal (as shown in Section 4) a shoulder at 1733 cm−1 for fibres generated via AP pretreatment system employing the medium and high AP concentrations. This characterizes the significant dissolution of hemicelluloses with the medium and high AP systems, in agreement with the DTG result in **Figure 4**. This observation is in contrast with the report by Ghazali and co-workers [17] that an increase in alkaline solution of hydrogen peroxide concentration caused an increase of lignin oxidation through a reduction in the aromatic rings. The peak at 1247 cm−1 could also be associated to the C=O stretching of the aryl group in lignin [35]. The shift of this peak coupled with weak absorbance was believed to be due to the reduction of lignin after the chemical treatments, while the weak signal indicates the presence of residual lignin [22]. The absorbance between 1426 and 1427 cm−1 for the raw OPF and OPF pulps is associated to the CH2 symmetric bending [14]. The stretching of C=O and O-H can be observed as peaks around 1112–1114; 1054–1056 cm−1 and 897 cm−1 in all the pulp samples.

It is characteristic of glycosidic linkage between sugar unit samples [33], which are not present in the spectra of the raw samples. The absorbance peak at 1160–1164 cm−1 in the OPF raw sample and pulp is due to the anti-symmetrical deformation of the C-O-C band [36]. However the vibration peak at 897 cm−1, which was absent in the raw sample, appear in the OPF pulp at the various concentrations. This was assigned to the glycosidic bonds, which are symmetric in polysaccharides [35].

#### **3.4. Effect of alkaline peroxide pretreatment concentration on paper properties**

It is evident from **Figure 5** that the peaks at 22.20°, 22.40°, and 22.10° corresponding to A, B, and C, respectively are characteristic of native cellulose I polymorph [20, 31]. The X-ray diffraction technique revealed that the extracted cellulose fibres could be easily hydrolysed into the crystalline sample. Due to the softening effect of the treated fibres at high AP concentrations, the high fibrillations, cell wall delaminations aid the production of fibrillar fines at high AP concentrations; expose the crystalline cellulosic materials in OPF in a more profound manner. The observed drop in the fibre crystallinity observed at high AP concentration treatment is attributable to the presence of certain threshold of fines content in the pulp. In a separate reports, Segal and coworkers [31] reported that fibre crystallinity could be lost by refining while Rafiee and Keshavarz [34] reported that fibre crystallinity could be lost due to high chemical treatment. This trend in the fibre crystallinity is in agreement with the report in the literatures [34]. The X-ray diffraction technique revealed that the extracted cellulose fibres

**Figure 5.** SEM images of (a) Raw OPF sample (b) AP treated fibre at low AP concentration (1.0 :1.5), (c) AP treated fibre at Medium AP concentration (2.0 : 2.5) and (d) AP treated fibre at high AP concentration (4.0 : 5.0) paper web at different

The FTIR spectra of the raw and pulped fibres are shown in **Figure 4**, which shows the FTIR spectra of OPF fibre (A) Raw OPF vascular bundle fibres (B) OPF isolated at 1.5%:1.0%;

the similarity, there are some shifts, disappearance and appearance of some signals of samples

O2

:NaOH AP concentrations. Analysis shows that despite

:NaOH AP concentrations

could be easily hydrolysed into the crystalline sample.

(D) OPF isolated at 5.0%:4.0%; H2

H2 O2

AP concentrations.

84 Palm Oil

**3.3. Correlation between FTIR spectroscopy, DTG and XRD**

:NaOH AP concentrations (C) OPF isolated at 2.5%:2.0%; H2

O2

Statistically, significant differences in the effects of AP concentration treatment level on the strength properties (tensile index, burst index and tear index) are also shown in **Table 1**. The ANOVA result shows that all the paper properties are significantly affected by the AP treatment except the burst index. The study showed that increase in the AP concentrations enhances the strength properties of the paper formed, which is in agreement with the trend already established with the paper apparent density. The impact of the high AP level on the fibrillation of OPF vascular bundle fibres become more apparently portrayed on the pulp web strength properties, and this stems from the higher probability of the lignin transformation to low molecular weight fragments and hence easily leached at high AP concentration treatment [17]. Furthermore high AP concentrations level produces higher fibrillation, which enhances fibre bonding and reduces fibre coarseness, thus leading to improved mechanical strength of the paper. Unlike the other strength properties, the ANOVA for AP treatment and time effect on AP strength properties (**Table 1**), the burst strength show no significant effect on the AP and time interaction effect. This observation is attributable to the fact that the bursting strength of paper is a composite strength property that is affected by various other properties of the sheet, principally tensile strength and stretch [27]. The reason for the low burst index at low and medium AP concentrations is attributed to the presence of hemicellulose in the pulp fibre [27]. The extraordinary improvement in the burst index at high AP concentrations is attributed to the refining effect of well softened OPF biomass. The refining process is expected to increase the fibre swelling, hydration and extend of fibrillation degree, which result in an improved fibre flexibility and thus, bonding and strength of the paper. This enhances paper physical properties and burst index [22].

**Conflict of interest**

**Author details**

Paridah Md. Tahir1

Abbas F. Mubarak Alkarkhi4

Serdang, Selangor, Malaysia

Alor Gajah, Malacca, Malaysia

2009;**13**(6):1456-1464

BioResources. 2006;**1**(2):220-232

Waste Management: New Research; 2012:161-177

Universiti Sains Malaysia, Penang, Malaysia

Ikeja, Lagos, Nigeria

Lagos, Nigeria

**References**

Igwe Chartheny Chima2

The authors declare that there is no conflict of interests regarding the publication of this paper.

Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial…

and Arniza Ghazali7

\*, Abdul Khalil H.P. Shawkataly3

http://dx.doi.org/10.5772/intechopen.74430

,

, Oyedeko K.F. Kamilu5

,

87

, Folahan Abdulwahab Taiwo Owolabi2

, Samsul Rizal6

\*Address all correspondence to: fathok2375@gmail.com

, Elemo Gloria Nwakaego2

1 Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia,

2 Pulp and Paper Technology Division, Federal Institute of Industrial Research Oshodi,

3 Bioprocessing and Paper coating Division, Universiti Sains Malaysia, Penang, Malaysia

4 Universiti Kuala Lumpur Malaysian Institute of Chemical and Bioengineering Technology,

5 Department of Chemical Engineering, Faculty of Engineering Lagos State University Ojo,

6 Department of Mechanical Engineering, Syiah Kuala University, Banda Aceh, Indonesia

[1] Lam MK, Tan KT, Lee KT, Mohamed AR. Malaysian palm oil: Surviving the food versus fuel dispute for a sustainable future. Renewable and Sustainable Energy Reviews.

[2] Singh PS, Othman H, Rokiah P, Cheu L, Singh RP. Using biomass residues from oil palm industry as a raw material for pulp and paper industry: Potential benefits and threat to the environment. Environment, Development and Sustainability. 2013;**15**(2):367-383

[3] Shawkataly Abdul Khalil HP, Alwani MS, Omar AKM. Chemical Composition, Anatomy, Lignin Distribution, And Cell Wall Structure Of Malaysian Plant Waste Fibers.

[4] Singh RP, Rupam PF, Singh A, Embrandiri A, Ibrahims MH. Towards Sustainable Palm Oil Production: Minimizing the Environmental Damage from Oil Palm Processing.

7 Bioresource, Paper and Coatings Technology (BPC), School of Industrial Technology,

#### **3.5. Surface Morphological Transformation of Papers from OPF**

The paper samples obtained from the three AP pre-treatment concentrations (Low, Medium and High) were examined with Scanning Electron Microscope analysis (SEM) (**Figure 5**) to monitor the morphological transformation of the paper surface.

**Figure 5** shows SEM images of (a) raw OPF vascular bundle and (b–d) handsheet surface corresponding to AP of (b) low; (c) medium; (d) high AP concentrations.

Overall as apparent in SEM analysis, the alkaline peroxide pretreatment has two effects on the fibre: In synergy with refining it increases the uniformity of paper arising from better interlocking of fibre and because of the softening effect of the alkaline peroxide chemical treatment, the treated samples displaced a greater degree of fibre collapsibility at high concentration. It exposes more cellulose of the biomass by modifying the lignin and leaching out the fragmented lignin.

## **4. Conclusion(s)**

The study revealed that alkaline peroxide pretreatment of the OPF-VB at various AP concentrations produced a high quality pulp that could be attributed to easier fibre extraction from the biomass. Apart from the physical and mechanical properties, spectroscopic analyses confirm the ability of the pulping protocol to effectively remove non cellulosics such as hemicelluloses, reduce the lignin content while realizing pulp and paper of high ISO optical brightness. The thermal analysis showed that the AP pretreated cellulose fibres have higher thermal stability than the raw sample, which made them suitable as biodegradable raw material in the polymer composite. The FTIR spectra is consistent also with the crystallinity values of the extracted cellulose fibres, which increased with an increase in the AP concentrations but decreased at high AP concentrations due to an increasingly generated fines materials, forming as a result of disruption of fibrous cell walls. The study showed that these extracted fibres will be useful in paper production and with further processing could be used as raw material for biodegradable composites with improved qualities.

## **Acknowledgements**

The authors thankful to the Higher Institution Centre of Excellence (HICoE) Ministry of Higher Education Malaysia Grant No. 6369107, the School of Industrial Technology Universiti Sains Malaysia and also the Federal institute of Industrial Research Oshodi Nigeria for their role in the successful completion of this book chapter.

## **Conflict of interest**

strength of paper is a composite strength property that is affected by various other properties of the sheet, principally tensile strength and stretch [27]. The reason for the low burst index at low and medium AP concentrations is attributed to the presence of hemicellulose in the pulp fibre [27]. The extraordinary improvement in the burst index at high AP concentrations is attributed to the refining effect of well softened OPF biomass. The refining process is expected to increase the fibre swelling, hydration and extend of fibrillation degree, which result in an improved fibre flexibility and thus, bonding and strength of the paper. This enhances paper

The paper samples obtained from the three AP pre-treatment concentrations (Low, Medium and High) were examined with Scanning Electron Microscope analysis (SEM) (**Figure 5**) to

**Figure 5** shows SEM images of (a) raw OPF vascular bundle and (b–d) handsheet surface cor-

Overall as apparent in SEM analysis, the alkaline peroxide pretreatment has two effects on the fibre: In synergy with refining it increases the uniformity of paper arising from better interlocking of fibre and because of the softening effect of the alkaline peroxide chemical treatment, the treated samples displaced a greater degree of fibre collapsibility at high concentration. It exposes more cellulose of the biomass by modifying the lignin and leaching out the fragmented lignin.

The study revealed that alkaline peroxide pretreatment of the OPF-VB at various AP concentrations produced a high quality pulp that could be attributed to easier fibre extraction from the biomass. Apart from the physical and mechanical properties, spectroscopic analyses confirm the ability of the pulping protocol to effectively remove non cellulosics such as hemicelluloses, reduce the lignin content while realizing pulp and paper of high ISO optical brightness. The thermal analysis showed that the AP pretreated cellulose fibres have higher thermal stability than the raw sample, which made them suitable as biodegradable raw material in the polymer composite. The FTIR spectra is consistent also with the crystallinity values of the extracted cellulose fibres, which increased with an increase in the AP concentrations but decreased at high AP concentrations due to an increasingly generated fines materials, forming as a result of disruption of fibrous cell walls. The study showed that these extracted fibres will be useful in paper production and with further processing could be used as raw material for biodegradable composites with improved qualities.

The authors thankful to the Higher Institution Centre of Excellence (HICoE) Ministry of Higher Education Malaysia Grant No. 6369107, the School of Industrial Technology Universiti Sains Malaysia and also the Federal institute of Industrial Research Oshodi Nigeria for their

physical properties and burst index [22].

86 Palm Oil

**4. Conclusion(s)**

**Acknowledgements**

role in the successful completion of this book chapter.

**3.5. Surface Morphological Transformation of Papers from OPF**

monitor the morphological transformation of the paper surface.

responding to AP of (b) low; (c) medium; (d) high AP concentrations.

The authors declare that there is no conflict of interests regarding the publication of this paper.

## **Author details**

Paridah Md. Tahir1 , Folahan Abdulwahab Taiwo Owolabi2 \*, Abdul Khalil H.P. Shawkataly3 , Abbas F. Mubarak Alkarkhi4 , Elemo Gloria Nwakaego2 , Oyedeko K.F. Kamilu5 , Igwe Chartheny Chima2 , Samsul Rizal6 and Arniza Ghazali7

\*Address all correspondence to: fathok2375@gmail.com

1 Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, Serdang, Selangor, Malaysia

2 Pulp and Paper Technology Division, Federal Institute of Industrial Research Oshodi, Ikeja, Lagos, Nigeria

3 Bioprocessing and Paper coating Division, Universiti Sains Malaysia, Penang, Malaysia

4 Universiti Kuala Lumpur Malaysian Institute of Chemical and Bioengineering Technology, Alor Gajah, Malacca, Malaysia

5 Department of Chemical Engineering, Faculty of Engineering Lagos State University Ojo, Lagos, Nigeria

6 Department of Mechanical Engineering, Syiah Kuala University, Banda Aceh, Indonesia

7 Bioresource, Paper and Coatings Technology (BPC), School of Industrial Technology, Universiti Sains Malaysia, Penang, Malaysia

## **References**


[6] Wanrosli W, Zainuddin Z, Law K, Asro R. Pulp from oil palm fronds by chemical processes. Industrial Crops and Products. 2007;**25**(1):89-94

[19] Gould JM. Alkaline peroxide delignification of agricultural residues to enhance enzymatic saccharification. Biotechnology and Bioengineering. 1984;**26**(1):46-52. DOI: 10.1002/

Pulp and Paper Potentials of Alkaline Peroxide Pre-Treated of Oil Palm Waste and Industrial…

http://dx.doi.org/10.5772/intechopen.74430

89

[20] Lamaming J, Hashim R, Sulaiman O, Leh CP, Sugimoto T, Nordin NA. Cellulose nanocrystals isolated from oil palm trunk. Carbohydrate Polymers. 2015;**127**:202-208

[21] Agarwal UP, Reiner RR, Ralph SA. Estimation of cellulose crystallinity of lignocelluloses using near-IR FT-Raman spectroscopy and comparison of the Raman and Segal-WAXS

[22] Saba N, Paridah MT, Abdan K, Ibrahim NA. Effect of oil palm nano filler on mechanical and morphological properties of kenaf reinforced epoxy composites. Construction and

[23] Alemdar A, Sain M. Isolation and characterization of nanofibers from agricultural residues Wheat straw and soy hulls. Bioresource Technology. 2007;**9**(6):1664-1671. DOI:

[24] Liu W, Hou Q, Mao C, Yuan Z, Li K. Effect of Hemicellulose Pre-extraction on the Properties and Bleachability of Aspen (Populus tremuloides) Chemithermomechanical Pulp. Industrial & Engineering Chemistry Research. 2012;**51**(34):11122-11127. DOI:

[25] Wen J-L, Sun S-L, Xue B-L, Sun R-C. Quantitative structures and thermal properties of birch lignins after ionic liquid pretreatment. Journal of Agricultural and Food Chemistry.

[26] Sonia A, Priya Dasan K. Chemical, morphology and thermal evaluation of cellulose microfibers obtained from *Hibiscus sabdariffa*. Carbohydrate Polymers. 2013;**92**(1):668-674

[27] Eriksen Ø, Syverud K, Gregersen Ø. The use of microfibrillated cellulose produced from kraft pulp as strength enhancer in TMP paper. Nordic Pulp and Paper Research Journal.

[28] Alwani MS, Khalil HPSA, Sulaiman O, Islam MN, Dungani R. An approach to using agricultural waste fibres in biocomposites application: Thermogravimetric analysis and

[29] Moriana R, Vilaplana F, Karlsson S, Ribes A. Correlation of chemical, structural and thermal properties of natural fibres for their sustainable exploitation. Carbohydrate

[30] Rosa SML, Rehman N, de Miranda MIG, Nachtigall S, Bica CID. Chlorine-free extraction of cellulose from rice husk and whisker isolation. Carbohydrate Polymers.

[31] Segal L, Creely J, Martin A, Conrad C. An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Textile Research Journal.

methods. Journal of Agricultural and Food Chemistry. 2012;**61**(1):103-113

bit.260260110 PMid:18551585

Building Materials. 2016;**123**:15-26

10.1021/ie300265s

Polymers. 2014;**112**:422-431

2012;**87**(2):1131-1138

1959;**29**(10):786-794

10.1016/j.biortech.2007.04.029 PMid:17566731

2013;**61**(3):635-645. DOI: 10.1021/jf3051939 PMid:23265413

2008;**23**:299-304. DOI: 10.3183/NPPRJ-2008-23-03-p299-304

activation energy study. BioResources. 2014;**9**(1):218-230


[19] Gould JM. Alkaline peroxide delignification of agricultural residues to enhance enzymatic saccharification. Biotechnology and Bioengineering. 1984;**26**(1):46-52. DOI: 10.1002/ bit.260260110 PMid:18551585

[6] Wanrosli W, Zainuddin Z, Law K, Asro R. Pulp from oil palm fronds by chemical pro-

[7] Owolabi AWT, Ghazali A, Wanrosli WD, Abbas FMA. Effect of alkaline peroxide pretreatment on microfibrillated cellulose from oil palm fronds rachis amenable for pulp

[8] Mushtaq F, Abdullah TA, Mat TR, Ani FN. Optimization and characterization of bio-oil produced by microwave assisted pyrolysis of oil palm shell waste biomass with microwave absorber. Bioresource Technology. 2015;**190**:442-450. DOI: 10.1016/j.

[9] Schuchardt F, Wulfert K, Darnoko D, Herawan T. Effect of new palm oil mill processes on the EFB and POME utilization. Journal of Oil Palm Research (Special Issue). 2008:

[10] Shuit SH, Tan KT, Lee KT, Kamaruddin A. Oil palm biomass as a sustainable energy

[11] M.P.O. Board. Overview of the Malaysian Oil Palm Industry. Selangor: Economics &

[12] Abdul Khalil HPS, Siti Alwani M, Ridzuan R, Kamarudin H, Khairul A. Chemical Composition Morphological Characteristics, and Cell Wall Structure of Malaysian Oil

[13] Abdul Khalil HPS, Hossain MS, Rosamah E. High pressure enzymatic hydrolysis to reveal physicochemical and thermal properties of bamboo fiber using a supercritical

[14] Saurabh CK, Mustapha A, Masri MM, Owolabi FA,T Syakir MI, Dungani R, Paridah MT, Jawaid M, Abdul Khalil HPS. Isolation and characterization of cellulose nanofibers from Gigantochloa scortechinii as a reinforcement material. Journal of Nanomaterials.

[15] Gould JM. Studies on the mechanism of alkaline peroxide delignification of agricultural residues. Biotechnology and Bioengineering. 1985;**27**(3):225-231. DOI: 10.1002/

[16] Alvarez-Vasco C, Zhang X. Alkaline hydrogen peroxide (AHP) pretreatment of softwood: enhanced enzymatic hydrolysability at low peroxide loadings. Biomass and Bioenergy.

[17] Sun RC, Fang J, Tomkinson J. Delignification of rye straw using hydrogen peroxide.

[18] Palamae S, Palachum W, Chisti Y, Choorit W. Retention of hemicellulose during delignification of oil palm empty fruit bunch (EFB) fiber with peracetic acid and alkaline peroxide. Biomass and Bioenergy. 2014;**66**:240-248. DOI: 10.1016/j.biombioe.2014.03.045

Palm Fibers. Polymer-Plastics Technology and Engineering. 2008;**47**:273-280

source: A Malaysian case study. Energy. 2009;**34**(9):1225-1235

water fermenter. BioResources. 2014;**9**(4):7710-7720

Industrial Crops and Products. 2000;**12**(2):71-83

Industry Development Division; 2012

and paper and bio-composite production. BioResources. 2016;**11**(2):3013-3026

cesses. Industrial Crops and Products. 2007;**25**(1):89-94

biortech.2015.02.055

115-126

88 Palm Oil

2016;**3**:1-8

2017;**96**:96-102

bit.260270303 PMid:18553662


[32] Habibi Y, Lucia LA, Rojas OJ. Cellulose nanocrystals: Chemistry, self-assembly, and applications. Chemical Reviews. 2010;**110**(6):3479-3500

**Chapter 6**

**Provisional chapter**

**Oleochemicals from Palm Oil for the Petroleum**

**Oleochemicals from Palm Oil for the Petroleum** 

DOI: 10.5772/intechopen.76771

Waste vegetable oils as a sustainable, low-cost and low-toxicity feedstock are attracting more interests for the production of oleochemicals that are excellent substitutes for petroleum-based chemicals widely used in the petroleum industry. The compounds resulting from transesterification-epoxidation-sulfonation of waste vegetable oils have great potential as bio-based surface active agents with extensive application in the petroleum industry. The oleo-surfactant from vegetable oils is gaining increasing attention as alternative to the costlier and non-biodegradable petrochemical-based surfactants currently in use. This chapter reports on cost-effective processes to convert waste palm oil into high-grade surfactants aiming at its filed application in petroleum production to enhance recovery of crude oils from reservoir. The first section focused on the formulation of a high-performance bifunctional solid catalyst with basic and acidic sites that are able to mediate simultaneous esterification and transesterification reactions. In the second part, the methyl esters were epoxidized and then sulfonated to produce the anionic surfactant. The feedstock and the methyl ester produced were analyzed with gas chromatography-mass spectrophotometer (GC-MS) and the sulfonated functional group (S═O) was

detected using Fourier-transform infrared spectroscopy (FTIR) analysis.

**Keywords:** oleochemicals, waste palm oil, surfactants, bifunctional catalyst, esterification, transesterification, epoxidation, sulfonation, enhanced oil recovery

A cost-effective and sustainable supply of energy sources is of enormous importance to the economy and national security. Oleochemicals are chemicals derived from sustainable

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

**Industry**

**Industry**

Ademola Rabiu, Samya Elias and

Ademola Rabiu, Samya Elias and

http://dx.doi.org/10.5772/intechopen.76771

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

Oluwaseun Oyekola

Oluwaseun Oyekola

**Abstract**

**1. Introduction**


#### **Oleochemicals from Palm Oil for the Petroleum Industry Oleochemicals from Palm Oil for the Petroleum Industry**

DOI: 10.5772/intechopen.76771

Ademola Rabiu, Samya Elias and Oluwaseun Oyekola Ademola Rabiu, Samya Elias and Oluwaseun Oyekola

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76771

#### **Abstract**

[32] Habibi Y, Lucia LA, Rojas OJ. Cellulose nanocrystals: Chemistry, self-assembly, and

[33] Trache D, Donnot A, Khimeche K, Benelmir R, Brosse N. Physico-chemical properties and thermal stability of microcrystalline cellulose isolated from Alfa fibres. Carbohydrate

[34] Rafiee Z, Keshavarz V. Synthesis and characterization of polyurethane/microcrystalline cellulose bionanocomposites. Progress in Organic Coatings. 2015;**86**:190-193

[35] Trache D, Hussin MH, Hui Chuin CT, Sabar S, Fazita MRN, Taiwo OFA, Hassan TM, Haafiz MKM. Microcrystalline cellulose: Isolation, characterization and bio-composites application—A review. International Journal of Biological Macromolecules. 2016;**93**:

[36] Saba N, Paridah TM, Abdan K, Ibrahim NA. Preparation and Characterization of Fire Retardant Nano-Filler from Oil Palm Empty Fruit Bunch Fibers. BioResources.

applications. Chemical Reviews. 2010;**110**(6):3479-3500

Polymers. 2014;**104**:223-230

789-804

90 Palm Oil

2015;**10**(3):4530-4543

Waste vegetable oils as a sustainable, low-cost and low-toxicity feedstock are attracting more interests for the production of oleochemicals that are excellent substitutes for petroleum-based chemicals widely used in the petroleum industry. The compounds resulting from transesterification-epoxidation-sulfonation of waste vegetable oils have great potential as bio-based surface active agents with extensive application in the petroleum industry. The oleo-surfactant from vegetable oils is gaining increasing attention as alternative to the costlier and non-biodegradable petrochemical-based surfactants currently in use. This chapter reports on cost-effective processes to convert waste palm oil into high-grade surfactants aiming at its filed application in petroleum production to enhance recovery of crude oils from reservoir. The first section focused on the formulation of a high-performance bifunctional solid catalyst with basic and acidic sites that are able to mediate simultaneous esterification and transesterification reactions. In the second part, the methyl esters were epoxidized and then sulfonated to produce the anionic surfactant. The feedstock and the methyl ester produced were analyzed with gas chromatography-mass spectrophotometer (GC-MS) and the sulfonated functional group (S═O) was detected using Fourier-transform infrared spectroscopy (FTIR) analysis.

**Keywords:** oleochemicals, waste palm oil, surfactants, bifunctional catalyst, esterification, transesterification, epoxidation, sulfonation, enhanced oil recovery

#### **1. Introduction**

A cost-effective and sustainable supply of energy sources is of enormous importance to the economy and national security. Oleochemicals are chemicals derived from sustainable

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

resources that are majorly oils and fats of vegetable and animal origin [1]. These resources are widely available or can be easily cultivated (virgin vegetable oils) or cheaply sourced (waste vegetable oils and animal fat) in virtually all parts of the world. These ecological and economic advantages are responsible for the growing importance of oleochemicals as energy resources and intermediates for manufacturing of industrial chemicals [2, 3]. This is responsible for the renew research interest in oleochemicals as one of the most cost-effective and widely available substitutes for a number of industrial chemicals and fuels currently derived from fossil fuels [2, 4].

and amphoterics and cationics as corrosion inhibitors and biocides [13]. Surfactants are also essential additives in drilling process operations [14] to reduce water loss and as additives in drilling, completion and fracking fluids to enhance lubricity (for better flow) and pumpability (to control foaming) [15]. It is also put into effective use in the clean-up of crude oil spillages serving as oil slick dispersants or spreader [16] or as oil herder for easy burning [17]. The world production of synthetic surfactants reaches 13 million tons annually, making it an economi-

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 93

However, commercial surfactants used in these processes are usually expensive and required in large quantities which limit the economics of the process [19]. Most of these petroleumbased surfactants are also toxic raising concern of their environmental impact [20]. Thus, a less hazardous and cost-effective but high performance surfactant formulation for an efficient oil recovery is required. These have led to interest in green and cost-effective processes for the manufacturing of commercial surfactants from sustainable feedstock [21]. Bio-based surfactants, due to their biodegradability and lower critical micelle concentration [22] are therefore becoming more attractive for the application in the petroleum industry [12]. It was reported that the global biosurfactant market value is expected to grow to around \$25 billion

Surfactant is one of the oleochemicals that can be produced from epoxidized methyl esters from palm oil [1]. The sulfonation of the esters has been used to produce methyl ester sulfonate surfactants [15, 18]. The anionic surfactant possesses good surface-active properties [15], excellent detergency and is less sensitive to water hardness [24]. It is therefore projected that the global market for methyl ester sulfonates will experience significant growth as demand for biodegradable surfactants increases [18]. The first-generation feedstock employed to obtain the esters are coconut and soybean oils [25]. These edible oils still dominate the process accounting for more than 95% of biodiesel production [26]. Though easily cultivated and produced, these are relatively costly feedstock and have been the food materials that have ignited the food versus fuel issue [26]. Also, as the cost of edible oils rise due to growing demands, the

This led to the interest in employing waste vegetable and non-edible oils as the preferred feedstock for commercial production of alternative surfactants [28]. However, a wider utilization of waste vegetable oils for bio-based chemicals production is still limited by the cost of pretreatment [2]. The poor quality of the waste vegetable oils due to high content of free fatty acids and water poses some challenges. Of equal interest is the heterogeneity of these cheap feedstocks in terms of compositions that necessitate pretreatment steps which led to increased cost of production and lower the competitiveness of the bio-products against petroleum-derived alternatives. This chapter presents cost-effective processes to produce a sulfonated surfactant from waste palm oil using heterogeneous bi-functional

The goal is to synthesize a cheaper and less hazardous surfactant that will be both economical and effective for surface activity as well as reservoir rock wettability alteration to achieve a

cost of their derivative surfactants will increase as well [27].

cally important chemical [18].

by 2018–2020 [23].

solid catalysts.

significant improvement in oil recovery.

Basic oleochemicals include fatty acids, methyl esters, fatty alcohols of these fatty acids and glycerol [1, 5] as well as fatty amines [6]. With a better understanding of oleochemistry, researchers now variously functionalize triglycerides in vegetable oils to manufacture different useful products [7]. The structure of oleochemicals with the presence of long-chain methylene sequences facilitates a ready functionalization into a wide range of products [8]. The approaches include epoxidation, acrylation of epoxies, transesterification reactions [7, 8] and amidation and amination to generate esters, amides and amines [1]. The sustained interest in the chemistry and conversion of fats and oils and the industrial applications of the bio-based or oleochemicals produced therefrom is being spurred by many factors. Prominent among the drivers is the fast depletion of the world fossil resources, the concern over extreme climatic conditions [7] leading to more stringent environmental standards and regulations and the growing demands for green fuels and cleaner technology with significantly reduced carbon and environmental footprints.

Also there is a growing surplus of fats and waste vegetable oils worldwide resulting in disposal and management challenges. Chhetri et al. [9] citing several sources reported that in 2008, the US produced about 100 million gallons of waste vegetable oil every day. The figures are 135,000 tons/year in Canada, 900,000 tons/year in EU countries while UK produced over 200,000 tons per annum. This is in addition to millions of tons of chicken fats being produced globally every year. The use of waste vegetable oils and non-edible oils in the production processes in place of refined vegetable oils has led to a significant improvement in the economics of oleochemical processes [5]. The conversion of the hitherto waste materials into industrial fuels and chemicals also significantly reduce the environmental impact of the production processes [5].

These have led to the growing awareness of the potentials of waste vegetable oils as sustainable and cost-effective feedstock [10] for the production of industrial chemicals and as energy carriers. Methyl esters produced from the transesterification of triglycerides molecules in the vegetable oils and animal fats with an alcohol [11] are used directly as green fuels (due to its lower emissions of particulate matter and greenhouse gasses) and as chemical intermediates due to its high functionality. Also aiding the extensive uses is the fact that vegetable oils are inherently biodegradable as well as its low toxicity [7]. Epoxidized methyl esters from vegetable oils are used as chemical intermediate to manufacture a variety of industrial chemicals that are ready substitute for petrochemicals [7].

Surfactants are employed in all stages of petroleum production and processing. Usual applications include the use of non-ionic surfactants as demulsifying agents [12], anionics as defoamers and amphoterics and cationics as corrosion inhibitors and biocides [13]. Surfactants are also essential additives in drilling process operations [14] to reduce water loss and as additives in drilling, completion and fracking fluids to enhance lubricity (for better flow) and pumpability (to control foaming) [15]. It is also put into effective use in the clean-up of crude oil spillages serving as oil slick dispersants or spreader [16] or as oil herder for easy burning [17]. The world production of synthetic surfactants reaches 13 million tons annually, making it an economically important chemical [18].

resources that are majorly oils and fats of vegetable and animal origin [1]. These resources are widely available or can be easily cultivated (virgin vegetable oils) or cheaply sourced (waste vegetable oils and animal fat) in virtually all parts of the world. These ecological and economic advantages are responsible for the growing importance of oleochemicals as energy resources and intermediates for manufacturing of industrial chemicals [2, 3]. This is responsible for the renew research interest in oleochemicals as one of the most cost-effective and widely available substitutes for a number of industrial chemicals and fuels currently derived

Basic oleochemicals include fatty acids, methyl esters, fatty alcohols of these fatty acids and glycerol [1, 5] as well as fatty amines [6]. With a better understanding of oleochemistry, researchers now variously functionalize triglycerides in vegetable oils to manufacture different useful products [7]. The structure of oleochemicals with the presence of long-chain methylene sequences facilitates a ready functionalization into a wide range of products [8]. The approaches include epoxidation, acrylation of epoxies, transesterification reactions [7, 8] and amidation and amination to generate esters, amides and amines [1]. The sustained interest in the chemistry and conversion of fats and oils and the industrial applications of the bio-based or oleochemicals produced therefrom is being spurred by many factors. Prominent among the drivers is the fast depletion of the world fossil resources, the concern over extreme climatic conditions [7] leading to more stringent environmental standards and regulations and the growing demands for green fuels and cleaner technology with significantly reduced

Also there is a growing surplus of fats and waste vegetable oils worldwide resulting in disposal and management challenges. Chhetri et al. [9] citing several sources reported that in 2008, the US produced about 100 million gallons of waste vegetable oil every day. The figures are 135,000 tons/year in Canada, 900,000 tons/year in EU countries while UK produced over 200,000 tons per annum. This is in addition to millions of tons of chicken fats being produced globally every year. The use of waste vegetable oils and non-edible oils in the production processes in place of refined vegetable oils has led to a significant improvement in the economics of oleochemical processes [5]. The conversion of the hitherto waste materials into industrial fuels and chemicals

These have led to the growing awareness of the potentials of waste vegetable oils as sustainable and cost-effective feedstock [10] for the production of industrial chemicals and as energy carriers. Methyl esters produced from the transesterification of triglycerides molecules in the vegetable oils and animal fats with an alcohol [11] are used directly as green fuels (due to its lower emissions of particulate matter and greenhouse gasses) and as chemical intermediates due to its high functionality. Also aiding the extensive uses is the fact that vegetable oils are inherently biodegradable as well as its low toxicity [7]. Epoxidized methyl esters from vegetable oils are used as chemical intermediate to manufacture a variety of industrial chemicals

Surfactants are employed in all stages of petroleum production and processing. Usual applications include the use of non-ionic surfactants as demulsifying agents [12], anionics as defoamers

also significantly reduce the environmental impact of the production processes [5].

from fossil fuels [2, 4].

92 Palm Oil

carbon and environmental footprints.

that are ready substitute for petrochemicals [7].

However, commercial surfactants used in these processes are usually expensive and required in large quantities which limit the economics of the process [19]. Most of these petroleumbased surfactants are also toxic raising concern of their environmental impact [20]. Thus, a less hazardous and cost-effective but high performance surfactant formulation for an efficient oil recovery is required. These have led to interest in green and cost-effective processes for the manufacturing of commercial surfactants from sustainable feedstock [21]. Bio-based surfactants, due to their biodegradability and lower critical micelle concentration [22] are therefore becoming more attractive for the application in the petroleum industry [12]. It was reported that the global biosurfactant market value is expected to grow to around \$25 billion by 2018–2020 [23].

Surfactant is one of the oleochemicals that can be produced from epoxidized methyl esters from palm oil [1]. The sulfonation of the esters has been used to produce methyl ester sulfonate surfactants [15, 18]. The anionic surfactant possesses good surface-active properties [15], excellent detergency and is less sensitive to water hardness [24]. It is therefore projected that the global market for methyl ester sulfonates will experience significant growth as demand for biodegradable surfactants increases [18]. The first-generation feedstock employed to obtain the esters are coconut and soybean oils [25]. These edible oils still dominate the process accounting for more than 95% of biodiesel production [26]. Though easily cultivated and produced, these are relatively costly feedstock and have been the food materials that have ignited the food versus fuel issue [26]. Also, as the cost of edible oils rise due to growing demands, the cost of their derivative surfactants will increase as well [27].

This led to the interest in employing waste vegetable and non-edible oils as the preferred feedstock for commercial production of alternative surfactants [28]. However, a wider utilization of waste vegetable oils for bio-based chemicals production is still limited by the cost of pretreatment [2]. The poor quality of the waste vegetable oils due to high content of free fatty acids and water poses some challenges. Of equal interest is the heterogeneity of these cheap feedstocks in terms of compositions that necessitate pretreatment steps which led to increased cost of production and lower the competitiveness of the bio-products against petroleum-derived alternatives. This chapter presents cost-effective processes to produce a sulfonated surfactant from waste palm oil using heterogeneous bi-functional solid catalysts.

The goal is to synthesize a cheaper and less hazardous surfactant that will be both economical and effective for surface activity as well as reservoir rock wettability alteration to achieve a significant improvement in oil recovery.

## **2. Application of surfactants to enhance oil recovery**

Surfactants are surface active polymeric molecules that contain amphiphilic molecules with hydrophilic part (that is, water soluble or polar) and a hydrophobic or lipophilic part (that is, oil soluble or nonpolar) [29]. These moieties will therefore partition preferentially at the interface of a immiscible fluid system with different degrees of polarity [29]. When introduced into a water-oil system for instance, the surfactant hydrophilic head interacts with water molecules and the hydrophobic tail interacts with the trapped oil [30]. Hence, they dissolve in both aqueous phase (water) and oleic phase (or organic solvents) resulting into reduced interfacial tensions between the phases. They as well alter the wettability of the reservoir rock surface by adsorbing to the liquid-rock interface, thus making the rock surface have a strong attraction toward one of the immiscible fluids, preferably water [31].

A microemulsion of hydrocarbons and water dosed with a large amount of surfactants was found to significantly improve crude recovery [36]. Surfactant flooding is widely employed to manipulate the phase behavior of the reservoir fluids to counteract the high capillary force trapping oil in the pores of the reservoir during enhanced oil recovery process [21, 37, 38]. Surfactant improves the microscopic displacement efficiency by lowering the interfacial tension between oil and water to form a highly stable water-in-oil emulsion as well as between crude oil and rock thus increasing the capillary number, which combines to facilitate greater mobilization of the oil droplets trapped in the reservoir rock [35, 39, 40]. The surface active chemical promotes the formation of microemulsions at the crude oil and the displacing fluid (mostly water) interface [41, 42] thus causing a significant lowering of the fluids' interfacial tension. This is required to efficiently mobilize a substantial percentage of the residual oil toward the production wells to enhance overall crude recovery [43]. Behind the oil bank, the

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 95

In the 2000s, oil fields subjected to surfactant-polymer and ASP flooding yielded higher oil recovery compared with those in the late 1970s and 1980s [25]. Improvement in the chemical functionality as a result of better insight into the process schemes is the principal reason for this accomplishment [21]. Since then, surfactants have been considered as an excellent enhanced oil recovery agents due to their ability to considerably reduce the interfacial tension and modify reservoir wetting characteristics. Depending on the nature of the hydrophilic group (head group), the surfactants are classified as anionic, cationic, zwitterionic or amphoteric or nonionic [45]. Typically in this field, anionic surfactants are used in sandstone rock matrices while for carbonate rocks, cationic amphiphiles are surfactants that are more effective. Nonionic surfactants are ideal for high salinity reservoirs, but are most often used as

A major challenge with micellar flooding is the loss of surfactant through interaction with reservoir rock [46] and surfactant partitioning into the oil interface [47]. The high cost of production of surfactants makes this potential loss an issue. As previously mentioned, most of the commercial surfactants are petroleum-based and toxic raising concern of sustainability and environmental impact [20]. It is therefore imperative to find alternative, environmentally friendly, and cost-effective processes to produce surfactants on industrial scale from sustainable feedstock. Oleochemical surfactants aside from being biodegradable and less toxic possess other excellent properties suitable for several potential applications in the petroleum industry and a good substitute for the petroleum-based commercial surfactants. These

include functionality under extreme conditions and the inherent high specificity [48].

Fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) are produced from transesterification of glycerides with methanol and ethanol, respectively. The triglycerides which serve as the starting material for the alkyl esters production are found in all vegetable oils, and other edible oils [49] and animal fats. Conventional feedstocks for the alkyl esters production

surfactant prevents the mobilized oil from being re-trapped [44].

co-surfactants due to their lower surface activity ability [35, 45].

**3. Production of methyl esters from waste palm oil**

In petroleum production, crude recovery from matured fields are declining at a rate faster than the discovery and production of new fields needed to maintain or increase the production rate to meet the energy demand. Therefore, resources are being committed to maximize oil recovery from matured reservoirs and tight rock formations. More than half of the original oil in place (OOIP) remains trapped in the petroleum reservoirs, after conventional production operations. This is attributed to poor sweep efficiency and oil droplets trapped by capillary forces due to high interfacial tension (IFT) between oil and water. There is therefore the need to economically recover more of this residual (or tail end) crude in declining and abandoned wells [12].

More effective enhanced oil recovery (EOR) methods that ensure an economical production of the tail end (trapped oil) from these oil fields are being continuously researched. Such technologies include thermal flooding (steam injection, in-situ combustion), chemical (surfactants, polymers, solvents, alkali) flooding, miscible and immiscible gas displacement, and microbial EOR to produce the hard-to-recover oils in older fields [32–34]. Among these techniques, chemicals flooding techniques have emerged as one of the most effective techniques to improve crude oil recovery from maturing fields. Chemicals (also referred to as micellar) flooding is widely employed due to ease of application and availability of wide range of chemicals. It involves injections of surfactants, polymers and alkali, and their various combination into the reservoirs to mobilize the trapped oil and improve recovery [35].

The alkali-surfactant-polymer (ASP) flooding is the most cost-effective technique, so far having recorded as much as 68% improved recovery from abandoned and depleted oilfield, particularly field past its peak production stage. ASP flooding involves the injection of a mixture of alkali, surfactant, and polymer into the reservoir. It is an effective chemical EOR technique due to the fact that it employs the synergy of the three techniques [35]. It has been employed in the oil industry to, among others, allow for better sweeping of the reservoir by lowering the interfacial tension (IFT) between oil and water (by the surfactant), alter reservoir rock wettability from oil wet to water wet (using the alkali), and to increase the crude mobility ratio (with the polymer). The technique has resulted considerably to improve the recovery factors at additional cost estimated to be as low as US\$2.42 per additional barrel for an onshore field.

A microemulsion of hydrocarbons and water dosed with a large amount of surfactants was found to significantly improve crude recovery [36]. Surfactant flooding is widely employed to manipulate the phase behavior of the reservoir fluids to counteract the high capillary force trapping oil in the pores of the reservoir during enhanced oil recovery process [21, 37, 38]. Surfactant improves the microscopic displacement efficiency by lowering the interfacial tension between oil and water to form a highly stable water-in-oil emulsion as well as between crude oil and rock thus increasing the capillary number, which combines to facilitate greater mobilization of the oil droplets trapped in the reservoir rock [35, 39, 40]. The surface active chemical promotes the formation of microemulsions at the crude oil and the displacing fluid (mostly water) interface [41, 42] thus causing a significant lowering of the fluids' interfacial tension. This is required to efficiently mobilize a substantial percentage of the residual oil toward the production wells to enhance overall crude recovery [43]. Behind the oil bank, the surfactant prevents the mobilized oil from being re-trapped [44].

**2. Application of surfactants to enhance oil recovery**

toward one of the immiscible fluids, preferably water [31].

abandoned wells [12].

94 Palm Oil

Surfactants are surface active polymeric molecules that contain amphiphilic molecules with hydrophilic part (that is, water soluble or polar) and a hydrophobic or lipophilic part (that is, oil soluble or nonpolar) [29]. These moieties will therefore partition preferentially at the interface of a immiscible fluid system with different degrees of polarity [29]. When introduced into a water-oil system for instance, the surfactant hydrophilic head interacts with water molecules and the hydrophobic tail interacts with the trapped oil [30]. Hence, they dissolve in both aqueous phase (water) and oleic phase (or organic solvents) resulting into reduced interfacial tensions between the phases. They as well alter the wettability of the reservoir rock surface by adsorbing to the liquid-rock interface, thus making the rock surface have a strong attraction

In petroleum production, crude recovery from matured fields are declining at a rate faster than the discovery and production of new fields needed to maintain or increase the production rate to meet the energy demand. Therefore, resources are being committed to maximize oil recovery from matured reservoirs and tight rock formations. More than half of the original oil in place (OOIP) remains trapped in the petroleum reservoirs, after conventional production operations. This is attributed to poor sweep efficiency and oil droplets trapped by capillary forces due to high interfacial tension (IFT) between oil and water. There is therefore the need to economically recover more of this residual (or tail end) crude in declining and

More effective enhanced oil recovery (EOR) methods that ensure an economical production of the tail end (trapped oil) from these oil fields are being continuously researched. Such technologies include thermal flooding (steam injection, in-situ combustion), chemical (surfactants, polymers, solvents, alkali) flooding, miscible and immiscible gas displacement, and microbial EOR to produce the hard-to-recover oils in older fields [32–34]. Among these techniques, chemicals flooding techniques have emerged as one of the most effective techniques to improve crude oil recovery from maturing fields. Chemicals (also referred to as micellar) flooding is widely employed due to ease of application and availability of wide range of chemicals. It involves injections of surfactants, polymers and alkali, and their various combi-

The alkali-surfactant-polymer (ASP) flooding is the most cost-effective technique, so far having recorded as much as 68% improved recovery from abandoned and depleted oilfield, particularly field past its peak production stage. ASP flooding involves the injection of a mixture of alkali, surfactant, and polymer into the reservoir. It is an effective chemical EOR technique due to the fact that it employs the synergy of the three techniques [35]. It has been employed in the oil industry to, among others, allow for better sweeping of the reservoir by lowering the interfacial tension (IFT) between oil and water (by the surfactant), alter reservoir rock wettability from oil wet to water wet (using the alkali), and to increase the crude mobility ratio (with the polymer). The technique has resulted considerably to improve the recovery factors at additional cost estimated to be as low as US\$2.42 per additional barrel for an onshore field.

nation into the reservoirs to mobilize the trapped oil and improve recovery [35].

In the 2000s, oil fields subjected to surfactant-polymer and ASP flooding yielded higher oil recovery compared with those in the late 1970s and 1980s [25]. Improvement in the chemical functionality as a result of better insight into the process schemes is the principal reason for this accomplishment [21]. Since then, surfactants have been considered as an excellent enhanced oil recovery agents due to their ability to considerably reduce the interfacial tension and modify reservoir wetting characteristics. Depending on the nature of the hydrophilic group (head group), the surfactants are classified as anionic, cationic, zwitterionic or amphoteric or nonionic [45]. Typically in this field, anionic surfactants are used in sandstone rock matrices while for carbonate rocks, cationic amphiphiles are surfactants that are more effective. Nonionic surfactants are ideal for high salinity reservoirs, but are most often used as co-surfactants due to their lower surface activity ability [35, 45].

A major challenge with micellar flooding is the loss of surfactant through interaction with reservoir rock [46] and surfactant partitioning into the oil interface [47]. The high cost of production of surfactants makes this potential loss an issue. As previously mentioned, most of the commercial surfactants are petroleum-based and toxic raising concern of sustainability and environmental impact [20]. It is therefore imperative to find alternative, environmentally friendly, and cost-effective processes to produce surfactants on industrial scale from sustainable feedstock. Oleochemical surfactants aside from being biodegradable and less toxic possess other excellent properties suitable for several potential applications in the petroleum industry and a good substitute for the petroleum-based commercial surfactants. These include functionality under extreme conditions and the inherent high specificity [48].

## **3. Production of methyl esters from waste palm oil**

Fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) are produced from transesterification of glycerides with methanol and ethanol, respectively. The triglycerides which serve as the starting material for the alkyl esters production are found in all vegetable oils, and other edible oils [49] and animal fats. Conventional feedstocks for the alkyl esters production are vegetable oils from palm, sunflower, groundnut, soybean, cotton, coconut, rapeseed, palm kernel, olive and nonedible oils (for instance, oil from Jatropha, sesame, rubber seed, tobacco seed, rice bran, camelina, and karanja) [50]. Other renewable resources such as oils from plant carbohydrates, sucrose, glucose, sorbitol, starches, animal fats and so on, have also been reported for FAME production [51].

Triglycerides (also referred to as phospholipids or triacylglycerols) are triesters of fatty acids [52] comprising of three fatty acid units attached to a three-carbon backbone [53]. A fatty acid is a carboxylic acid containing a long unbranched aliphatic chain of an even number of carbon atoms, from 4 to 2, which can be either saturated or unsaturated [54]. If all carbon atoms of the fatty acid are attached to single bonds, they are considered saturated. Fatty acid molecules are further grouped as monosaturated if the fatty acid molecules have one double bond and polysaturated if it contains more than one double bond (as shown in **Figure 1**). The fatty acid composition of a specific oil sample has a major influence on its reactivity as well as on the physical and performance properties of the esters obtainable therefrom [54]. When the fatty acid molecule is attached to other fragments, it is referred to as free fatty acid (FFA).

a figure that is expected to increase rapidly as a result of growth in human population and increase in food consumption [61]. Some of waste vegetable oil is utilized in soap making, but the larger volumes are dumped into rivers and landfills with its attendant environmental pollution [62]. The use of waste cooking oil to produce oleochemicals will assist in the reduction of this environmental issue [9] and, at the same time, lower the cost of production. However, the high FFA contents, solids and water impurities in waste vegetable oils will impact on the yield, product quality, and the economic feasibility of the process [63]. A relatively high FFA content in the feedstock will promote saponification of triglycerides forming by-products such

**8 10 12 14 16 18 18:01 18:02 18:03 20:01 22:01**

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 97

Tallow 4 30 20 40 5 1

Soya 8 5 28 53 6

Coconut 8 7 48 17 9 1 7 2 1

Palm 2 42 5 41 10

Palm kernel 4 5 51 15 7 1 15 2

This has resulted in poor yield as well as need for products purification [63, 65]. Waste cooking oils also contain water, which if not removed will promote hydrolysis of triglyceride to form more FFA [66]. The choice of the catalyst is a key factor when producing biodiesel via catalytic transesterification, which is also dependent on the FFA existent in the oil [67]. For virgin vegetable and other oils with a lower FFAs content, base-catalyzed reaction gives a significant conversion in a reasonably short time whereas for oils containing higher FFAs stock, acid-catalyzed esterification followed by transesterification is the best option [68] to prevent

In this work, the goal is to use the fatty acid esters from waste vegetable oils to produce bio-based surfactants. The processes involved simultaneous esterification and transesterification of waste palm oil over bifunctional heterogeneous catalyst to produce alkyl esters (majorly methyl or ethyl esters) and glycerol. The catalyst esterified the FFA into methyl esters in a one-step process and hence eliminated the pretreatment step. The first section of this study focused on formulation of a high performance bifunctional solid catalyst, CaO/

, with basic and acidic sites that are able to mediate simultaneous esterification and

as soap and water as illustrated in **Figure 2** [64] .

**Table 1.** Fatty acids distribution of common oils and fat.

hydrolysis of the esters product.

**Figure 2.** Esterification of free fatty acid reaction.

**Fat/oil Carbon chain (%)**

Al2 O3

Palm oil is a triacylglycerol obtained from the oil palm *Elaeis guineensis* [6]. The fact that palm oil predominantly consist of short-chain (C8 -C10) and medium-chain (C12-C14) fatty acids (as shown in **Table 1**) therefore makes it a valuable feedstock for the manufacturing of oleochemicals [55]. In fact, close to 60% of the palm kernel oil and about 5% of the palm oil were used for the manufacture of oleochemicals [56]. The rapid increase in production in the last decade has made palm oil the most consumed vegetable oil in the world [57, 58]. Global consumption of vegetable oils in 2016 was reported to be around 184 million tons, of which palm oil accounted for 38.7% while soybean oil, rapeseed oil, and sunflower oil accounted for 28.9, 15, and 8.5%, respectively [59]. An estimated 58 million metric tons of palm oil was reportedly produced in 2016 [60].

Waste or used vegetable oils are cheap source of triglycerides and are widely available in large quantities worldwide. About 29 million tons of waste cooking oil are generated every year [29],


**Table 1.** Fatty acids distribution of common oils and fat.

are vegetable oils from palm, sunflower, groundnut, soybean, cotton, coconut, rapeseed, palm kernel, olive and nonedible oils (for instance, oil from Jatropha, sesame, rubber seed, tobacco seed, rice bran, camelina, and karanja) [50]. Other renewable resources such as oils from plant carbohydrates, sucrose, glucose, sorbitol, starches, animal fats and so on, have also been

Triglycerides (also referred to as phospholipids or triacylglycerols) are triesters of fatty acids [52] comprising of three fatty acid units attached to a three-carbon backbone [53]. A fatty acid is a carboxylic acid containing a long unbranched aliphatic chain of an even number of carbon atoms, from 4 to 2, which can be either saturated or unsaturated [54]. If all carbon atoms of the fatty acid are attached to single bonds, they are considered saturated. Fatty acid molecules are further grouped as monosaturated if the fatty acid molecules have one double bond and polysaturated if it contains more than one double bond (as shown in **Figure 1**). The fatty acid composition of a specific oil sample has a major influence on its reactivity as well as on the physical and performance properties of the esters obtainable therefrom [54]. When the fatty

acid molecule is attached to other fragments, it is referred to as free fatty acid (FFA).

Palm oil is a triacylglycerol obtained from the oil palm *Elaeis guineensis* [6]. The fact that palm

shown in **Table 1**) therefore makes it a valuable feedstock for the manufacturing of oleochemicals [55]. In fact, close to 60% of the palm kernel oil and about 5% of the palm oil were used for the manufacture of oleochemicals [56]. The rapid increase in production in the last decade has made palm oil the most consumed vegetable oil in the world [57, 58]. Global consumption of vegetable oils in 2016 was reported to be around 184 million tons, of which palm oil accounted for 38.7% while soybean oil, rapeseed oil, and sunflower oil accounted for 28.9, 15, and 8.5%, respectively [59]. An estimated 58 million metric tons of palm oil was reportedly

Waste or used vegetable oils are cheap source of triglycerides and are widely available in large quantities worldwide. About 29 million tons of waste cooking oil are generated every year [29],


reported for FAME production [51].

96 Palm Oil

oil predominantly consist of short-chain (C8

produced in 2016 [60].

**Figure 1.** Classification triglyceride molecules.

a figure that is expected to increase rapidly as a result of growth in human population and increase in food consumption [61]. Some of waste vegetable oil is utilized in soap making, but the larger volumes are dumped into rivers and landfills with its attendant environmental pollution [62]. The use of waste cooking oil to produce oleochemicals will assist in the reduction of this environmental issue [9] and, at the same time, lower the cost of production. However, the high FFA contents, solids and water impurities in waste vegetable oils will impact on the yield, product quality, and the economic feasibility of the process [63]. A relatively high FFA content in the feedstock will promote saponification of triglycerides forming by-products such as soap and water as illustrated in **Figure 2** [64] .

This has resulted in poor yield as well as need for products purification [63, 65]. Waste cooking oils also contain water, which if not removed will promote hydrolysis of triglyceride to form more FFA [66]. The choice of the catalyst is a key factor when producing biodiesel via catalytic transesterification, which is also dependent on the FFA existent in the oil [67]. For virgin vegetable and other oils with a lower FFAs content, base-catalyzed reaction gives a significant conversion in a reasonably short time whereas for oils containing higher FFAs stock, acid-catalyzed esterification followed by transesterification is the best option [68] to prevent hydrolysis of the esters product.

In this work, the goal is to use the fatty acid esters from waste vegetable oils to produce bio-based surfactants. The processes involved simultaneous esterification and transesterification of waste palm oil over bifunctional heterogeneous catalyst to produce alkyl esters (majorly methyl or ethyl esters) and glycerol. The catalyst esterified the FFA into methyl esters in a one-step process and hence eliminated the pretreatment step. The first section of this study focused on formulation of a high performance bifunctional solid catalyst, CaO/ Al2 O3 , with basic and acidic sites that are able to mediate simultaneous esterification and

transesterification reactions for the production of methyl esters from waste vegetable oils. This is necessitated by the high FFA content of waste palm oil. The acidic oxide eliminated the need for the removal of the FFA by converting it to esters via the esterification reaction. The esterification step faciliatted by the acidic oxide eliminate acid pretreatment step which is required to remove the FFA and hence costly and as well required disposal of the fatty acid (wastes). The reaction with methanol was investigated over the catalyst in a well stirred batch reactor at an optimum reaction condition.

CaO/Al2

O3

A 80% CaO/20% Al2

overhead stirrer.

(**Figure 3**).

oxides ratios, 70% CaO/30% Al2

from waste palm oil. Alumina (Al2

hydroxide was used as the precipitating agent.

tive metal nitrates. The required amount of Al(NO3

O3

catalysts with different oxide ratios were studied in the production of methyl esters

thermal and mechanical stability, large pore size and pore volume, and high specific surface area [83]. The catalyst was produced via the co-precipitation method and characterized using thermal gravimetric analysis (TGA), X-ray diffraction (XRD), Brunner-Emmett-Teller (BET) analysis, scanning electron microscopy with energy dispersive X-ray (SEM-EDX), and transmission electron microscopy (TEM) techniques. All chemicals utilized for the catalyst synthesis were of analytical reagent grade and were used without prior purification. Calcium and aluminum nitrates were used as the basic and acidic oxide precursor salts, while sodium

respective oxyhydroxides from a solution containing the calculated amount of the respec-

(Merck, 99%) were introduced into a 2 L flask. Just enough deionized water to dissolve the salts but to avoid splashing of the solutions during the vigorous stirring was added. The solution was heated to boiling over a Heidolph MR 3001 K hot plate fitted with a thermocouple (Heidolph EKT 3001). The flask and the hot plate are arranged under a Dragon Lab OS20-S overhead stirrer setup. The required amount of NaOH pellets (Merck, 98%) is dissolved in deionized water and brought to boiling as well and added to the boiling nitrate solutions. The solution is maintained at 90°C and stirred vigorously for about 15 min to promote the nucleation-dissolution processes. The stirrer speed was initially set at 1000 rpm, but increased gradually to 2200 rpm as the solution viscosity due to nucleation rises using the high power

The solution was allowed to cool for about 20 min and then filtered in a Buckner filter setup fitted with a vacuum pump. The precipitate was washed several times with warm distilled water until the filtrates were free of nitrate confirmed with the silver brown ring test. The precipitates were placed in a convective oven and dried overnight at a temperature of 120°C, to decompose the oxyhydroxides into the desired hydroxides (and possibly oxides). The above procedure was repeated to synthesize other test catalysts but with different basic to acidic

and 60% CaO/40% Al2

Prior to reaction, the catalyst powder was calcined to decomposes the hydroxides, activate and stabilize the crystalline structure. First, the calcination temperature required was determined using TGA. The dried precipitate was calcined in a well-defined pattern

This is done with an induction furnace (Kiln Contracts) fitted with Gefran P800 programmable temperature controller with ramping capacity, in flowing air set at the flow rate to fluidized the powder in a fluidized bed reactor. The calcination step involves thermal decomposition, crystallization, and recrystallization processes and some degree of sintering. This step will remove interstitial water in the sample and other volatiles from the solid catalyst precursor. It

oxide was used in all cases due to the prevalence of triglycerides in the waste oils.

O3

O3

also helps to convert and stabilize the particles in the crystallite form.

)3 ·9H2

) was chosen as the acidic oxide due to its exceptionally

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771

O (Kimix, 98%) and Ca(NO3

. A higher ratio of basic (CaO)

)2 ·4H2 O 99

(by weight) catalyst is prepared using NaOH to co-precipitate the

O3

#### **3.1. Catalysts preparation and characterization**

Due to difficulties encountered during homogeneous transesterification, attention was shifted to heterogeneous catalyzed transesterification for methyl ester production [69–74]. The most studied solid heterogeneous catalysts are metal oxides of alkaline earth metals (Mg, Ca, Be, Ba, Sr), mixed oxides, zeolites, γ-alumina as well as hydrotalcites [11, 75]. CaO is mostly utilized due to its cheap price, high activity (due to a relatively high basic strength), long catalyst life as well as moderate reaction conditions [76]. Presently, most of the industrial processes for the production of methyl esters involve the reaction between edible oils and methanol in the presence of an alkaline catalyst [11]. But as mentioned earlier, waste and other cheap oils contain high amounts of FFA and water and are therefore not suitable for the process using an alkali (or even acidic) catalyst owing to simultaneous saponification reaction which lowers yield of the esters.

Teng et al. [77] reported that the presence of water at 4 wt% in rapeseed oil lowered the conversion to 86% from 98%. This is attributed to hydrolysis of the triglycerides in the presence of water. This also causes serious separation and emulsification problems. Consequently, a two-stage process [78] where the feedstock is first pretreated to reduce the content of FFA was developed. It is achieved by the use of catalysts such as ferric sulfate or iron sulfate and sulfuric acid (to remove the FFA), followed by the use of a basic catalyst to produce methyl esters [79]. Patil et al. [80] also reported a two-step process to convert waste cooking oil to methyl esters. The process included esterification reaction for the conversion of FFA to esters using iron sulfate, followed by transesterification of the triglycerides using KOH. However, the two-stage process still faced the issue of catalyst removal in both steps. It was suggested that in the first step, the catalyst removal issue can be prevented by acid catalyst neutralization and by using high quantities of alkaline catalyst in the second step [81]. But the use of extra amount of catalyst will not only add additional costs to methyl ester production, the catalysts must still be removed from the product stream.

Bimetallic solid oxide catalysts with acidic and basic oxide sites are able to efficiently convert high FFA oils into esters due to their ability to facilitate simultaneous esterification and transesterification reactions. These catalysts are also more tolerant of the water in the feedstock while given better esters yield in shorter reaction time [82]. Processing cheap oils with these catalysts requires no neutralization step (to remove the FFA contents) and since they do not dissolve in the reaction mixture, simple products purification steps are required. The catalysts being recyclable give a more sustainable resource management as well.

CaO/Al2 O3 catalysts with different oxide ratios were studied in the production of methyl esters from waste palm oil. Alumina (Al2 O3 ) was chosen as the acidic oxide due to its exceptionally thermal and mechanical stability, large pore size and pore volume, and high specific surface area [83]. The catalyst was produced via the co-precipitation method and characterized using thermal gravimetric analysis (TGA), X-ray diffraction (XRD), Brunner-Emmett-Teller (BET) analysis, scanning electron microscopy with energy dispersive X-ray (SEM-EDX), and transmission electron microscopy (TEM) techniques. All chemicals utilized for the catalyst synthesis were of analytical reagent grade and were used without prior purification. Calcium and aluminum nitrates were used as the basic and acidic oxide precursor salts, while sodium hydroxide was used as the precipitating agent.

transesterification reactions for the production of methyl esters from waste vegetable oils. This is necessitated by the high FFA content of waste palm oil. The acidic oxide eliminated the need for the removal of the FFA by converting it to esters via the esterification reaction. The esterification step faciliatted by the acidic oxide eliminate acid pretreatment step which is required to remove the FFA and hence costly and as well required disposal of the fatty acid (wastes). The reaction with methanol was investigated over the catalyst in a well stirred batch

Due to difficulties encountered during homogeneous transesterification, attention was shifted to heterogeneous catalyzed transesterification for methyl ester production [69–74]. The most studied solid heterogeneous catalysts are metal oxides of alkaline earth metals (Mg, Ca, Be, Ba, Sr), mixed oxides, zeolites, γ-alumina as well as hydrotalcites [11, 75]. CaO is mostly utilized due to its cheap price, high activity (due to a relatively high basic strength), long catalyst life as well as moderate reaction conditions [76]. Presently, most of the industrial processes for the production of methyl esters involve the reaction between edible oils and methanol in the presence of an alkaline catalyst [11]. But as mentioned earlier, waste and other cheap oils contain high amounts of FFA and water and are therefore not suitable for the process using an alkali (or even acidic) catalyst owing to simultaneous saponification reaction which lowers

Teng et al. [77] reported that the presence of water at 4 wt% in rapeseed oil lowered the conversion to 86% from 98%. This is attributed to hydrolysis of the triglycerides in the presence of water. This also causes serious separation and emulsification problems. Consequently, a two-stage process [78] where the feedstock is first pretreated to reduce the content of FFA was developed. It is achieved by the use of catalysts such as ferric sulfate or iron sulfate and sulfuric acid (to remove the FFA), followed by the use of a basic catalyst to produce methyl esters [79]. Patil et al. [80] also reported a two-step process to convert waste cooking oil to methyl esters. The process included esterification reaction for the conversion of FFA to esters using iron sulfate, followed by transesterification of the triglycerides using KOH. However, the two-stage process still faced the issue of catalyst removal in both steps. It was suggested that in the first step, the catalyst removal issue can be prevented by acid catalyst neutralization and by using high quantities of alkaline catalyst in the second step [81]. But the use of extra amount of catalyst will not only add additional costs to methyl ester production, the catalysts

Bimetallic solid oxide catalysts with acidic and basic oxide sites are able to efficiently convert high FFA oils into esters due to their ability to facilitate simultaneous esterification and transesterification reactions. These catalysts are also more tolerant of the water in the feedstock while given better esters yield in shorter reaction time [82]. Processing cheap oils with these catalysts requires no neutralization step (to remove the FFA contents) and since they do not dissolve in the reaction mixture, simple products purification steps are required. The catalysts

being recyclable give a more sustainable resource management as well.

reactor at an optimum reaction condition.

yield of the esters.

98 Palm Oil

**3.1. Catalysts preparation and characterization**

must still be removed from the product stream.

A 80% CaO/20% Al2 O3 (by weight) catalyst is prepared using NaOH to co-precipitate the respective oxyhydroxides from a solution containing the calculated amount of the respective metal nitrates. The required amount of Al(NO3 )3 ·9H2 O (Kimix, 98%) and Ca(NO3 )2 ·4H2 O (Merck, 99%) were introduced into a 2 L flask. Just enough deionized water to dissolve the salts but to avoid splashing of the solutions during the vigorous stirring was added. The solution was heated to boiling over a Heidolph MR 3001 K hot plate fitted with a thermocouple (Heidolph EKT 3001). The flask and the hot plate are arranged under a Dragon Lab OS20-S overhead stirrer setup. The required amount of NaOH pellets (Merck, 98%) is dissolved in deionized water and brought to boiling as well and added to the boiling nitrate solutions. The solution is maintained at 90°C and stirred vigorously for about 15 min to promote the nucleation-dissolution processes. The stirrer speed was initially set at 1000 rpm, but increased gradually to 2200 rpm as the solution viscosity due to nucleation rises using the high power overhead stirrer.

The solution was allowed to cool for about 20 min and then filtered in a Buckner filter setup fitted with a vacuum pump. The precipitate was washed several times with warm distilled water until the filtrates were free of nitrate confirmed with the silver brown ring test. The precipitates were placed in a convective oven and dried overnight at a temperature of 120°C, to decompose the oxyhydroxides into the desired hydroxides (and possibly oxides). The above procedure was repeated to synthesize other test catalysts but with different basic to acidic oxides ratios, 70% CaO/30% Al2 O3 and 60% CaO/40% Al2 O3 . A higher ratio of basic (CaO) oxide was used in all cases due to the prevalence of triglycerides in the waste oils.

Prior to reaction, the catalyst powder was calcined to decomposes the hydroxides, activate and stabilize the crystalline structure. First, the calcination temperature required was determined using TGA. The dried precipitate was calcined in a well-defined pattern (**Figure 3**).

This is done with an induction furnace (Kiln Contracts) fitted with Gefran P800 programmable temperature controller with ramping capacity, in flowing air set at the flow rate to fluidized the powder in a fluidized bed reactor. The calcination step involves thermal decomposition, crystallization, and recrystallization processes and some degree of sintering. This step will remove interstitial water in the sample and other volatiles from the solid catalyst precursor. It also helps to convert and stabilize the particles in the crystallite form.

**Figure 3.** Catalyst calcination pattern.

Samples of the catalyst were characterized to determine among others the thermal behavior, the morphological properties, and elemental compositions. The BET, SEM-EDX, and TEM analyses were used to determine the surface area, particle size, particle size distribution, pore size, the pore volume distribution, elemental composition, and distribution. The bulk phases present were studied using XRD, whereas the reducibility and the maximum degree of reduction of the metal oxides were studied by means of the TGA method.

#### *3.1.1. Thermal stability*

Thermogravimetry analysis (TGA) continuously measures the mass and the rate of change in the weight of a sample subjected to a steady increase in temperature in a controlled atmosphere. The TGA profile will typically exhibit weight loss corresponding to various stages in the degradation of the substance. The thermal degradation behavior of the catalyst was performed on the dried sample to obtain the optimum calcination temperature and hence before the calcination step above. This was carried out with a Perkin Elmer TGA7 bench model thermogravimeter analyzer. The dried sample (20 g) was heated from room temperature to 900°C with high flow of nitrogen (100 ml/min) at a heating rate of 20°C/min. The weight change presented in **Figure 4** corresponds to water removal, possible carbon burning, and metals oxidation (Eqs. (1) and (2)) stages.

$$\text{Ca(OH)}\_{2}\text{(s)} \xrightarrow{\text{A}} \text{CaO(s)} + H\_{2}\text{O(g)}\tag{1}$$

**Figure 6** shows the elemental composition of areas examined (determined by 4 replicates of EDX) for the catalyst sample. The SEM-EDX analysis of the catalyst confirmed the presence

**Figure 5.** SEM-EDX micrograph of (a) the 80% CaO and (b) showing the areas chosen for EDX analysis at different

The SEM image also shows that Ca particles were well distributed on Al regardless of the 4.6:1 ratio obtained instead of the expected 4:1 which could have been caused by the impurities in

The morphology of the particles of the 80% CaO catalyst was studied with the transmission electron microscopy (TEM). **Figure 7** shows the micrograph of the catalyst particles. Most of

O3

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 101

catalyst which was vis-

of Ca(CaO) and Al(Al2

magnifications.

O3 ).

*3.1.3. Transmission electron microscopy analysis*

the salts. It also showed a significant homogeneity of the CaO/Al<sup>2</sup>

ible in the value of Al and Ca acquired from the EDX analysis.

**Figure 4.** TGA curve for 80% CaO/20% alumina catalyst before calcination.

$$2Al(OH)\_3(s) \overset{\Lambda}{\longrightarrow} Al\_2O\_3(s) + 3H\_2O(g) \tag{2}$$

There was a sharp weight loss at 300°C and then at 600°C to around 750°C. These reduction are as a result of the decomposition of the respective hydroxides to the oxides. Using the thermal profile, 750°C is selected as the calcination temperature for this study.

#### *3.1.2. Scanning electron microscopy analysis*

After calcination, the morphology of the catalyst was studied with SEM as shown in **Figure 5**. The figure shows aggregated (interconnected) particles.

**Figure 4.** TGA curve for 80% CaO/20% alumina catalyst before calcination.

Samples of the catalyst were characterized to determine among others the thermal behavior, the morphological properties, and elemental compositions. The BET, SEM-EDX, and TEM analyses were used to determine the surface area, particle size, particle size distribution, pore size, the pore volume distribution, elemental composition, and distribution. The bulk phases present were studied using XRD, whereas the reducibility and the maximum degree of reduc-

Thermogravimetry analysis (TGA) continuously measures the mass and the rate of change in the weight of a sample subjected to a steady increase in temperature in a controlled atmosphere. The TGA profile will typically exhibit weight loss corresponding to various stages in the degradation of the substance. The thermal degradation behavior of the catalyst was performed on the dried sample to obtain the optimum calcination temperature and hence before the calcination step above. This was carried out with a Perkin Elmer TGA7 bench model thermogravimeter analyzer. The dried sample (20 g) was heated from room temperature to 900°C with high flow of nitrogen (100 ml/min) at a heating rate of 20°C/min. The weight change presented in **Figure 4** corresponds to water removal, possible carbon burning, and metals oxidation (Eqs. (1) and (2)) stages.

There was a sharp weight loss at 300°C and then at 600°C to around 750°C. These reduction are as a result of the decomposition of the respective hydroxides to the oxides. Using the ther-

After calcination, the morphology of the catalyst was studied with SEM as shown in **Figure 5**.

mal profile, 750°C is selected as the calcination temperature for this study.

*3.1.2. Scanning electron microscopy analysis*

The figure shows aggregated (interconnected) particles.

(1)

(2)

tion of the metal oxides were studied by means of the TGA method.

*3.1.1. Thermal stability*

**Figure 3.** Catalyst calcination pattern.

100 Palm Oil

**Figure 5.** SEM-EDX micrograph of (a) the 80% CaO and (b) showing the areas chosen for EDX analysis at different magnifications.

**Figure 6** shows the elemental composition of areas examined (determined by 4 replicates of EDX) for the catalyst sample. The SEM-EDX analysis of the catalyst confirmed the presence of Ca(CaO) and Al(Al2 O3 ).

The SEM image also shows that Ca particles were well distributed on Al regardless of the 4.6:1 ratio obtained instead of the expected 4:1 which could have been caused by the impurities in the salts. It also showed a significant homogeneity of the CaO/Al<sup>2</sup> O3 catalyst which was visible in the value of Al and Ca acquired from the EDX analysis.

#### *3.1.3. Transmission electron microscopy analysis*

The morphology of the particles of the 80% CaO catalyst was studied with the transmission electron microscopy (TEM). **Figure 7** shows the micrograph of the catalyst particles. Most of

There were also some diffraction peaks detected at ~51 and 68°2θ angles which did not correspond to CaO crystalline phases but were identified as hydrated calcium aluminate and alumina crystalline phases. The formation of these phases is expected due to the adsorption

Waste sunflower and waste palm oil were used in this study. The samples FFA contents were found via titration to be 0.3825 and 76.96 mg/g, respectively. These oils were transesterified with a methanol at methanol/oil molar ratio of 9:1 and reaction temperature 65°C for 4 h. The optimum catalyst loading selected for the transesterification of both waste oils was 4 wt% based on previous studies [85, 86]. The effect of basic/acidic oxides ratio on the yield of FAME was investigated by varying the catalyst CaO ratio as 60, 70, and 80%. The yields of the esters

from air which must have occurred during the XRD analysis [84].

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 103

of water and CO2

**3.2. Methyl esters production**

**Figure 8.** XRD pattern of 60, 70, and 80% CaO wt% catalysts.

are presented in **Figure 9**.

**Figure 9.** Methyl ester yield versus catalyst CaO content.

**Figure 6.** EDX spectrum for 80% CaO/Al<sup>2</sup> O3 catalyst.

**Figure 7.** TEM images of the catalyst.

the particles were in the range of 10–100 nm. The porosity of the catalyst particles was confirmed by the TEM image and most of the crystal particles were in rectangular shape.

#### *3.1.4. Bulk phase of catalyst*

The qualitative and quantitative X-ray diffraction spectra XRD patterns of the 60, 70, and 80% CaO on Al2 O3 used in this study are shown in **Figure 8**. The XRD of the catalysts showed expected peaks. A broad reflection of the CaO crystalline phases was clearly observed at 2θ range of 20.0–40.0° for 60, 70, and 80% CaO/Al2 O3 which supports the presence of highly dispersed CaO particles in all CaO on Al2 O3 catalysts.

**Figure 8.** XRD pattern of 60, 70, and 80% CaO wt% catalysts.

There were also some diffraction peaks detected at ~51 and 68°2θ angles which did not correspond to CaO crystalline phases but were identified as hydrated calcium aluminate and alumina crystalline phases. The formation of these phases is expected due to the adsorption of water and CO2 from air which must have occurred during the XRD analysis [84].

#### **3.2. Methyl esters production**

the particles were in the range of 10–100 nm. The porosity of the catalyst particles was con-

The qualitative and quantitative X-ray diffraction spectra XRD patterns of the 60, 70, and 80%

expected peaks. A broad reflection of the CaO crystalline phases was clearly observed at 2θ

catalysts.

O3

used in this study are shown in **Figure 8**. The XRD of the catalysts showed

which supports the presence of highly dis-

firmed by the TEM image and most of the crystal particles were in rectangular shape.

O3

*3.1.4. Bulk phase of catalyst*

**Figure 7.** TEM images of the catalyst.

**Figure 6.** EDX spectrum for 80% CaO/Al<sup>2</sup>

102 Palm Oil

O3 catalyst.

O3

range of 20.0–40.0° for 60, 70, and 80% CaO/Al2

persed CaO particles in all CaO on Al2

CaO on Al2

Waste sunflower and waste palm oil were used in this study. The samples FFA contents were found via titration to be 0.3825 and 76.96 mg/g, respectively. These oils were transesterified with a methanol at methanol/oil molar ratio of 9:1 and reaction temperature 65°C for 4 h. The optimum catalyst loading selected for the transesterification of both waste oils was 4 wt% based on previous studies [85, 86]. The effect of basic/acidic oxides ratio on the yield of FAME was investigated by varying the catalyst CaO ratio as 60, 70, and 80%. The yields of the esters are presented in **Figure 9**.

**Figure 9.** Methyl ester yield versus catalyst CaO content.

A 60% CaO/40% Al2 O3 catalyst was found to be optimum for waste palm oil, whereas the optimum catalyst ratio for the waste sunflower oil was 80% CaO/20% Al<sup>2</sup> O3 at the same reaction conditions. This is due to the fact that waste palm oil contains higher amount of FFAs, and hence requires more acidic sites on the catalyst to esterify the FFA to FAME. The high yield of FAME obtained despite the low quality of the oils used demonstrated that the use of a bifunctional catalyst will provide an opportunity to lower the cost of production as well as assist in disposal of the waste vegetable oils.

## **4. Surfactants productions from the methyl esters**

Currently, increasing research efforts are going into formulating cheaper, biodegradable, and nontoxic surfactants, because the existing commercial surfactants are mostly slow-degrading compounds produced from petrochemicals [13]. In many instances, the products from their degradation are detrimental to the environment or to humans [87]. The high cost of commercial surfactants imposes additional challenges and limits their widespread application in the petroleum industry. Therefore, to cut down on the surfactant production cost and to satisfy the intended specifications, increasing attention is being giving to agriculturally and waste resources [13] as substitutive feedstock to petroleum for surfactants manufacturing.

Waste and nonedible vegetable oils for the production of surfactant are of interest because utilizing these waste materials will result in low material and processing costs, thus making biosurfactants attractive in large scale applications. It is also biodegradable [18] and the relatively high interfacial tension reduction potential or surface active properties are comparable to synthetic surfactants [15]. Most of ionic and nonionic surfactants are derived from C12 and C14 fatty acids which are abundant in palm kernel and palm oil [1]. The longer chain fatty acids exhibit a high hydrophobicity making it unsuitable for micelle formation and, hence, are used only after necessary modification to increase their polarity [1]. The esters produced in the preceding step were further subjected to epoxidation reaction to reduce the mono- and polyunsaturated esters content and obtain more stable epoxides. Finally, the sulfonated surfactant is produced using sulfonating agents such as sulfuric acid, oleum or chlorosulfonic acid. The fatty acid composition of the methyl esters produced used is analyzed using a GC-MS. The spectra are as shown in **Figure 10**.

Moreover, to generate peracetic acid in high concentrations, the use of a catalyst is required [89]. The chemicals utilized for the epoxidation of methyl esters are formic acid (99.81%

O2

The epoxidation reaction was performed in a temperature controlled batch reactor. About

wise to the vessel through the top of the condenser which then formed peroxyformic acid by reacting with the formic acid (Eq. (3)) and allowed to stand for 4 h. The principal product is epoxidized methyl ester (EFAME) with oxirane rings at the position of double bonds. Possible by-products include keto compounds due to the redisposition of oxirane group or vicinal

excess acid. About 20 ml of diethyl ether (Sigma Aldrich, 99.9%) is added to the EFAME in a 250 ml separation funnel and stirred well. First, the EFAME/ether solution is washed thrice with deionized water to get rid of the excess acid. Then, the product was washed again with

and 100 g of FAME is added to the reaction vessel. The vessel is connected to

), n-hexane (anhydrous, 95% C6

Epoxidized FAME purification step was carried out to remove the unreacted H<sup>2</sup>

), sodium chloride (ACS reagent, ≥99.0%

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771

> (CH2 )2

H14), and propan-2-ol (anhydrous,

O2

O), toluene

105

was added drop-

O2

(3)

and the

), diethyl ether (≥99.0% CH<sup>3</sup>

), sodium bicarbonate (7.5% aqueous NaHCO3

99.5% CH₃CHOHCH₃). These were purchased from Sigma Aldrich.

a condenser and placed in a water bath maintained at 25°C. 58.8 g of H2

NaCl), hydrogen peroxide (30% aqueous H2

**Figure 10.** Chromatogram of the palm oil methyl esters.

dihydroxy because of oxirane hydrolysis.

H8

CH2 O2

(anhydrous, 99.8% C7

10.7 g of CH2

**4.1. Epoxidation with no solvent**

O2

The GC-MS confirmed the fatty acids distribution as, saturated fatty acids: palmitic acid (16:0), stearic acid (18:0), arachidic acid (20:0), heneicosylic acid (21:0), behenic acid (22:0), and palmitoleic acid (16:1). The monounsaturated groups are gadoleic acid (20:1) and oleic acid (18:1) while the polyunsaturated fatty acids are linoleic acid (18:2) and linolenic (18:3). The saturated fatty acids content was found to be 19.95%, which is considered to be quite high.

To reduce the saturated fatty acids contents and to epoxidize the unsaturated fatty acids, investigations regarding the effects of solvent-free and solvent in the epoxidation reaction at 25, 30, and 50°C using formic acid were conducted. Formic acid was utilized in this study owing to the fact that the performic acid formation rate is superior in comparison to that of peracetic acid and the formic acid method is well-known to progress at a faster rate [88, 89].

**Figure 10.** Chromatogram of the palm oil methyl esters.

A 60% CaO/40% Al2

104 Palm Oil

O3

assist in disposal of the waste vegetable oils.

spectra are as shown in **Figure 10**.

optimum catalyst ratio for the waste sunflower oil was 80% CaO/20% Al<sup>2</sup>

**4. Surfactants productions from the methyl esters**

tion conditions. This is due to the fact that waste palm oil contains higher amount of FFAs, and hence requires more acidic sites on the catalyst to esterify the FFA to FAME. The high yield of FAME obtained despite the low quality of the oils used demonstrated that the use of a bifunctional catalyst will provide an opportunity to lower the cost of production as well as

Currently, increasing research efforts are going into formulating cheaper, biodegradable, and nontoxic surfactants, because the existing commercial surfactants are mostly slow-degrading compounds produced from petrochemicals [13]. In many instances, the products from their degradation are detrimental to the environment or to humans [87]. The high cost of commercial surfactants imposes additional challenges and limits their widespread application in the petroleum industry. Therefore, to cut down on the surfactant production cost and to satisfy the intended specifications, increasing attention is being giving to agriculturally and waste

Waste and nonedible vegetable oils for the production of surfactant are of interest because utilizing these waste materials will result in low material and processing costs, thus making biosurfactants attractive in large scale applications. It is also biodegradable [18] and the relatively high interfacial tension reduction potential or surface active properties are comparable to synthetic surfactants [15]. Most of ionic and nonionic surfactants are derived from C12 and C14 fatty acids which are abundant in palm kernel and palm oil [1]. The longer chain fatty acids exhibit a high hydrophobicity making it unsuitable for micelle formation and, hence, are used only after necessary modification to increase their polarity [1]. The esters produced in the preceding step were further subjected to epoxidation reaction to reduce the mono- and polyunsaturated esters content and obtain more stable epoxides. Finally, the sulfonated surfactant is produced using sulfonating agents such as sulfuric acid, oleum or chlorosulfonic acid. The fatty acid composition of the methyl esters produced used is analyzed using a GC-MS. The

The GC-MS confirmed the fatty acids distribution as, saturated fatty acids: palmitic acid (16:0), stearic acid (18:0), arachidic acid (20:0), heneicosylic acid (21:0), behenic acid (22:0), and palmitoleic acid (16:1). The monounsaturated groups are gadoleic acid (20:1) and oleic acid (18:1) while the polyunsaturated fatty acids are linoleic acid (18:2) and linolenic (18:3). The saturated fatty acids content was found to be 19.95%, which is considered to be quite high.

To reduce the saturated fatty acids contents and to epoxidize the unsaturated fatty acids, investigations regarding the effects of solvent-free and solvent in the epoxidation reaction at 25, 30, and 50°C using formic acid were conducted. Formic acid was utilized in this study owing to the fact that the performic acid formation rate is superior in comparison to that of peracetic acid and the formic acid method is well-known to progress at a faster rate [88, 89].

resources [13] as substitutive feedstock to petroleum for surfactants manufacturing.

catalyst was found to be optimum for waste palm oil, whereas the

O3

at the same reac-

Moreover, to generate peracetic acid in high concentrations, the use of a catalyst is required [89]. The chemicals utilized for the epoxidation of methyl esters are formic acid (99.81% CH2 O2 ), sodium bicarbonate (7.5% aqueous NaHCO3 ), sodium chloride (ACS reagent, ≥99.0% NaCl), hydrogen peroxide (30% aqueous H2 O2 ), diethyl ether (≥99.0% CH<sup>3</sup> (CH2 )2 O), toluene (anhydrous, 99.8% C7 H8 ), n-hexane (anhydrous, 95% C6 H14), and propan-2-ol (anhydrous, 99.5% CH₃CHOHCH₃). These were purchased from Sigma Aldrich.

#### **4.1. Epoxidation with no solvent**

The epoxidation reaction was performed in a temperature controlled batch reactor. About 10.7 g of CH2 O2 and 100 g of FAME is added to the reaction vessel. The vessel is connected to a condenser and placed in a water bath maintained at 25°C. 58.8 g of H2 O2 was added dropwise to the vessel through the top of the condenser which then formed peroxyformic acid by reacting with the formic acid (Eq. (3)) and allowed to stand for 4 h. The principal product is epoxidized methyl ester (EFAME) with oxirane rings at the position of double bonds. Possible by-products include keto compounds due to the redisposition of oxirane group or vicinal dihydroxy because of oxirane hydrolysis.

$$\begin{array}{ccccccccc} \text{CH}\_2\text{O}\_2 & + & \text{H}\_2\text{O}\_2 & \underset{\text{H}\_2\text{O}\_2}{\longleftrightarrow} & \text{CH}\_2\text{O}\_3 & + & \text{H}\_2\text{O} & \end{array} \tag{3}$$

Epoxidized FAME purification step was carried out to remove the unreacted H<sup>2</sup> O2 and the excess acid. About 20 ml of diethyl ether (Sigma Aldrich, 99.9%) is added to the EFAME in a 250 ml separation funnel and stirred well. First, the EFAME/ether solution is washed thrice with deionized water to get rid of the excess acid. Then, the product was washed again with about 10 ml of aqueous sodium bicarbonate solution (5 g NaHCO3 /100 g H2 O) which neutralized the residual acid and peroxide. As the bicarbonate solution was added to react with the rest of the acid and slowly agitated, the stopper of the separating funnel was pointed away and into the fume hood and occasionally opened to allow produced gasses to be discharged safely from the funnel. This was repeated until pH paper indicated that it was neutral, showing that the only components remaining in the organic layer was the epoxidized methyl esters. If the solution was too basic, it was rinsed again with water, and if it was too acidic, it was rinsed again with NaHCO3 solution.

that open the epoxy ring and minimization of the rate of hydrolysis (oxirane cleavage) of the product. This is in agreement with Ahmad et al. [92]. At 50°C and in the presence of a solvent, the epoxidized FAME showed a very low or no hydroxyl formation compared to the solventfree epoxidation and at 25°C. Furthermore, increasing temperature demonstrated a favorable influence on the formation of performic acid. The results further showed substantial reduction in the percentage composition of saturated and unsaturated fatty acids in product composition for epoxidation reactions carried at higher temperatures. It can be concluded, therefore, that moderate temperature of 30°C were most suitable for epoxidation of oleic acid with PFA (performic acid generated *in-situ* for optimum oxirane levels and minimal hydrolysis rate).

A number of methods for the preparation of sulfonated fatty acid esters from oleochemicals can be found in literatures. The sulfonation reaction of fatty acid methyl esters using SO<sup>3</sup> was studied in detail by Stein and Baumann [94], and products with distinct carbon chains which have excellent properties for surfactant formulation were obtained. Triglycerides with the required number of carbon chains can be found in coconut oil (~48% C12, 17% C14), palm oil (~46% C16), palm kernel oil (~50% C12, 17% C14), and tallow (~26% C16, 23% C18) as mentioned earlier. In general, unsaturated esters contained in vegetable oils and tallow (comprising approximately 43% oleic acid) result in the bad color of the ester sulfonates. Thus, the esters must be hydrogenated or distilled before sulfonation so that their iodine number is less

> H5 )2

) and enough (approximately 30 g) solid sodium bicarbonate (NaHCO3

CO3

The sulfonated product was extracted into 40 ml of n-butanol (C₄H₉OH) using a separating funnel. The solvent was removed from the crude product via drying with a rotary evaporator. The powder obtained is redissolved in 200 ml of water. Then, the organic impurities were eliminated from the aqueous solution of sodium epoxidized methyl ester sulfonate (SEMES) via extraction with 50 ml of diethyl ether. The crude product is concentrated and dried under

alkali, the sulfonated esters produced were analyzed without further purification so as to

15 ml of pyridine (C₅H₅N) in a 500 ml round bottom flask placed in ice-cooled water bath for 15 min. 2.60 g of the epoxidized fatty acid methyl ester solution obtained above was introduced slowly to the round bottom flask with continuous stirring, for another 30 min. The reactor and its contents were afterward heated to a temperature of 65°C in a water bath until the solution turned clear. For the second step, the reaction was quenched and the solution is poured into an ice-cooled 500 ml flask containing 33 g in 300 ml solution of sodium carbonate

), sodium bicarbonate (7.5% aqueous solution of NaHCO3

Cl), pyridine (99.5% C₅H₅N), sodium

O] were purchased from Sigma Aldrich. About

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771

are typically utilized in CEOR as co-solvent and

Cl) was added very slowly while stirring (at 800 ppm) to

), n-buta-

107

) to keep the

**4.3. Production of epoxidized methyl ester sulfonate**

For surfactant synthesis, chlorosulfonic acid (97% HSO3

CO3

solution saturated with inorganic sodium salts.

vacuum for 24 h. Since C₄H₉OH and Na<sup>2</sup>

reduce the cost of surfactant manufacturing [25].

nol (99.5% C₄H₉OH), and diethyl ether [(C<sup>2</sup>

2.63 g of chlorosulfonic acid (HSO3

than 0.5.

(Na2 CO3

carbonate (99.5% Na2

Then, about 10 ml of sodium chloride solution (5 g NaCl/100 g H2 O) is added to remove the remaining H2 O from the organic phase. The aqueous layer was decanted from the reaction system and disposed of. The organic layer was vacuum distilled in a rotary evaporator (Buchi Rotavapor Model R-205) for 30 min at 80°C to evaporate both the ether and any residual H<sup>2</sup> O from the organic phase.

#### **4.2. Epoxidation with solvent**

Carrying out epoxidation reaction at lower temperatures and in the presence of organic solvents will minimize oxirane degradation and by-products formation [53, 90, 91]. The presence of organic solvents also has some stabilizing effect on the oxirane formed during the peroxyformic or peroxyacids epoxidation of oils and FAMEs [91]. Moreover, solvent can control the reaction temperature thus reducing the adverse temperature effects [92]. Solvent use also offers good solubilization for all inorganic and organic substances thus promoting good mass transfer.

The epoxidation reactions were conducted with toluene at 25, 30, and 50°C. The approach of Akintayo et al. [90] was used. 100 g of FAME was dissolved in 50 ml of toluene and 4 mol of CH2 O2 was added at temperature of 25°C with stirring. Hydrogen peroxide (100 ml) was then added while keeping the temperature constant. Afterward the reaction was allowed to continue for 4 h. Reaction mixture was then allowed to settle and the aqueous layer removed using a separating funnel. The organic layer was repeatedly rinsed with warm H2 O until free of acid. The residual toluene and H2 O were removed under reduced pressure in the Buchi rotary evaporator. The same procedure was repeated at 30 and 50°C.

The produced epoxy fatty acid methyl esters are analyzed using a GC-MS to detect and determine the different epoxy acids present. From the results, it is noted that performing epoxidation reactions at 30 and 50°C and in presence of the organic solvents minimized sideand by-products formation and ring-opening reactions especially to hydroxyl compounds. Deshpande [93] argued that the presence of an inert solvent-like toluene stabilizes the epoxide product and reduced the adjacent reactions. Reaction at lower temperature of 25°C showed lower rate of epoxidation and high rate of hydrolysis of the product to various by-products.

When the temperature was increased from 30 to 50°C, a change in the composition of the fatty acid methyl esters to epoxy esters and a decrease in side reactions were observed. The results obtained at 50°C with the use of a solvent suggest simultaneous decrease in the side reactions that open the epoxy ring and minimization of the rate of hydrolysis (oxirane cleavage) of the product. This is in agreement with Ahmad et al. [92]. At 50°C and in the presence of a solvent, the epoxidized FAME showed a very low or no hydroxyl formation compared to the solventfree epoxidation and at 25°C. Furthermore, increasing temperature demonstrated a favorable influence on the formation of performic acid. The results further showed substantial reduction in the percentage composition of saturated and unsaturated fatty acids in product composition for epoxidation reactions carried at higher temperatures. It can be concluded, therefore, that moderate temperature of 30°C were most suitable for epoxidation of oleic acid with PFA (performic acid generated *in-situ* for optimum oxirane levels and minimal hydrolysis rate).

#### **4.3. Production of epoxidized methyl ester sulfonate**

about 10 ml of aqueous sodium bicarbonate solution (5 g NaHCO3

solution.

Then, about 10 ml of sodium chloride solution (5 g NaCl/100 g H2

was rinsed again with NaHCO3

remaining H2

106 Palm Oil

transfer.

of CH2 O2

from the organic phase.

**4.2. Epoxidation with solvent**

of acid. The residual toluene and H2

ized the residual acid and peroxide. As the bicarbonate solution was added to react with the rest of the acid and slowly agitated, the stopper of the separating funnel was pointed away and into the fume hood and occasionally opened to allow produced gasses to be discharged safely from the funnel. This was repeated until pH paper indicated that it was neutral, showing that the only components remaining in the organic layer was the epoxidized methyl esters. If the solution was too basic, it was rinsed again with water, and if it was too acidic, it

system and disposed of. The organic layer was vacuum distilled in a rotary evaporator (Buchi Rotavapor Model R-205) for 30 min at 80°C to evaporate both the ether and any residual H<sup>2</sup>

Carrying out epoxidation reaction at lower temperatures and in the presence of organic solvents will minimize oxirane degradation and by-products formation [53, 90, 91]. The presence of organic solvents also has some stabilizing effect on the oxirane formed during the peroxyformic or peroxyacids epoxidation of oils and FAMEs [91]. Moreover, solvent can control the reaction temperature thus reducing the adverse temperature effects [92]. Solvent use also offers good solubilization for all inorganic and organic substances thus promoting good mass

The epoxidation reactions were conducted with toluene at 25, 30, and 50°C. The approach of Akintayo et al. [90] was used. 100 g of FAME was dissolved in 50 ml of toluene and 4 mol

then added while keeping the temperature constant. Afterward the reaction was allowed to continue for 4 h. Reaction mixture was then allowed to settle and the aqueous layer removed

The produced epoxy fatty acid methyl esters are analyzed using a GC-MS to detect and determine the different epoxy acids present. From the results, it is noted that performing epoxidation reactions at 30 and 50°C and in presence of the organic solvents minimized sideand by-products formation and ring-opening reactions especially to hydroxyl compounds. Deshpande [93] argued that the presence of an inert solvent-like toluene stabilizes the epoxide product and reduced the adjacent reactions. Reaction at lower temperature of 25°C showed lower rate of epoxidation and high rate of hydrolysis of the product to various by-products. When the temperature was increased from 30 to 50°C, a change in the composition of the fatty acid methyl esters to epoxy esters and a decrease in side reactions were observed. The results obtained at 50°C with the use of a solvent suggest simultaneous decrease in the side reactions

using a separating funnel. The organic layer was repeatedly rinsed with warm H2

rotary evaporator. The same procedure was repeated at 30 and 50°C.

was added at temperature of 25°C with stirring. Hydrogen peroxide (100 ml) was

O were removed under reduced pressure in the Buchi

O from the organic phase. The aqueous layer was decanted from the reaction

/100 g H2

O) which neutral-

O) is added to remove the

O

O until free

A number of methods for the preparation of sulfonated fatty acid esters from oleochemicals can be found in literatures. The sulfonation reaction of fatty acid methyl esters using SO<sup>3</sup> was studied in detail by Stein and Baumann [94], and products with distinct carbon chains which have excellent properties for surfactant formulation were obtained. Triglycerides with the required number of carbon chains can be found in coconut oil (~48% C12, 17% C14), palm oil (~46% C16), palm kernel oil (~50% C12, 17% C14), and tallow (~26% C16, 23% C18) as mentioned earlier. In general, unsaturated esters contained in vegetable oils and tallow (comprising approximately 43% oleic acid) result in the bad color of the ester sulfonates. Thus, the esters must be hydrogenated or distilled before sulfonation so that their iodine number is less than 0.5.

For surfactant synthesis, chlorosulfonic acid (97% HSO3 Cl), pyridine (99.5% C₅H₅N), sodium carbonate (99.5% Na2 CO3 ), sodium bicarbonate (7.5% aqueous solution of NaHCO3 ), n-butanol (99.5% C₄H₉OH), and diethyl ether [(C<sup>2</sup> H5 )2 O] were purchased from Sigma Aldrich. About 2.63 g of chlorosulfonic acid (HSO3 Cl) was added very slowly while stirring (at 800 ppm) to 15 ml of pyridine (C₅H₅N) in a 500 ml round bottom flask placed in ice-cooled water bath for 15 min. 2.60 g of the epoxidized fatty acid methyl ester solution obtained above was introduced slowly to the round bottom flask with continuous stirring, for another 30 min. The reactor and its contents were afterward heated to a temperature of 65°C in a water bath until the solution turned clear. For the second step, the reaction was quenched and the solution is poured into an ice-cooled 500 ml flask containing 33 g in 300 ml solution of sodium carbonate (Na2 CO3 ) and enough (approximately 30 g) solid sodium bicarbonate (NaHCO3 ) to keep the solution saturated with inorganic sodium salts.

The sulfonated product was extracted into 40 ml of n-butanol (C₄H₉OH) using a separating funnel. The solvent was removed from the crude product via drying with a rotary evaporator. The powder obtained is redissolved in 200 ml of water. Then, the organic impurities were eliminated from the aqueous solution of sodium epoxidized methyl ester sulfonate (SEMES) via extraction with 50 ml of diethyl ether. The crude product is concentrated and dried under vacuum for 24 h. Since C₄H₉OH and Na<sup>2</sup> CO3 are typically utilized in CEOR as co-solvent and alkali, the sulfonated esters produced were analyzed without further purification so as to reduce the cost of surfactant manufacturing [25].

A FTIR spectrophotometer was utilized to analyze the composition and the chemical functional group present in the synthetized surfactants. The synthesized (SEMES) powder was grinded and mixed with potassium bromide (KBr) to obtain a fine powder. The powder was then compressed into a thin pallet for analysis. About 15 mg of this pallet in each case was put on the Attenuated Total Reflectance (ATR) sample holder of a Perkin Elmer spectrum 100 FTIR spectrometer (model JASCO FT/IR-4100). The sample was recorded in the range of 4000–500 cm−1, baseline was corrected, and the spectra smoothened.

result of the discrepancy in their relative molecular mass. This clearly indicates that the for-

performed as expected, despite the presence of free fatty acids. The catalysts synthesized by the co-precipitation method exhibited high dispersion of the Ca and Al particles. The optimum reaction conditions for the production of methyl esters via simultaneous esterification and transesterification reaction of the waste pal oil were found to be: a reaction time of 4h at

was found to be optimum for waste palm oil. The high esters yield obtained despite the low quality of the oils used demonstrated that the use of a bifunctional catalyst will provide an opportunity to lower the cost of production of the esters. Furthermore, the catalyst showed substantial chemical stability and could be used again for at least 8 times with minor losses

It is evident that the saturated fatty acid contents of the methyl esters subjected to epoxidation reaction in the presence and absence of a solvent at 25, 30, and 50°C were reduced while promoting the desired conversion of the unsaturated fatty acid methyl esters to epoxy esters (with oxirane groups). A temperature of 30°C was found to be suitable for epoxidation of oleic acid with PFA (performic) for optimum oxirane levels and hydrolysis rate diminishment. The EFAME was consequently sulfonated to produce the sodium epoxidized methyl ester sulfonate (SEMES) surfactant, which was then compared with the synthetic SDS and CTAB surfactants. The identified FTIR spectrum of SEMES was similar to that of SDS which indicated that the formulated SEMES is an anionic surfactant. The same result has been reported [98]. The sulfonated surfactant has been evaluated in a separate study for performance in petroleum reservoir [15]. It was found to exhibit excellent characteristics comparable to commercial

The study was made possible by the generous fund provided by South Africa Technology

65°C with a methanol:oil ratio of 9:1 and 4 wt% catalyst amount. A 60% CaO/40% Al2

employed as the catalyst to produce methyl esters used from the waste oil

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771

> O3 ratio

109

mulated surfactant SEMES is an anionic surfactant.

**5. Conclusion**

O3

in its catalytic activity.

petroleum-based anionic surfactant.

Ademola Rabiu\*, Samya Elias and Oluwaseun Oyekola

Cape Peninsula University of Technology, Cape Town, South Africa

\*Address all correspondence to: rabiua@cput.ac.za

**Acknowledgements**

Innovation Agency (TIA).

**Author details**

The CaO/Al2

FTIR spectra in the range of 500–4000 cm−1 of SEMES are shown in **Figure 11**. All the IR absorption bands were investigated with respect to the spectrometric identification of organic compounds by Silverstein et al. [95].

The peak at 1450 cm−1 is typically assigned to the disproportional stretching vibration band of methyl group (C─H). Elraies et al. [25] obtained a similar peak for epoxidized methyl ester sulfonate from jatropha oil. The symmetric and asymmetric C─H stretching vibration of the ─CH3 group appears at 2497 and 2926 cm−1. Analogous peaks between 2473 and 2955 cm−1 were reported by Babu et al. [96] for sulfonated methyl esters synthetized from castor oil and the ricinoleic acid methyl ester was sulfonated without the epoxidation step. The peak at 3679 cm−1 in the SEMES is attributed to the OH stretching of the sorbed water. This sorbed water vibration band suggests that the surface property of SEMES changed from hydrophobic to hydrophilic [96]. The existence of the epoxy ring in the SEMES was shown by the presence of C─O stretching absorption band in the area of 988–830 cm−1.

The strong vibration (absorbance) peak at 1614 cm−1 corresponds to the existence of sulfonate group due to S═O stretching which is also an indication of the presence of esters [95, 97]. These results clearly indicate that the substance synthetized is a sodium epoxidized methyl ester sulfonate. For better understanding the structural arrangement of the surfactants investigated in this study, commercial anionic, SDS, and cationic, CTAB surfactants were also characterized using the same procedure. The FTIR spectra of pure SDS showed similar pattern with the synthetized SEMES, but the percentage of transmission were different as a

**Figure 11.** FTIR spectrum of SEMES.

result of the discrepancy in their relative molecular mass. This clearly indicates that the formulated surfactant SEMES is an anionic surfactant.

## **5. Conclusion**

A FTIR spectrophotometer was utilized to analyze the composition and the chemical functional group present in the synthetized surfactants. The synthesized (SEMES) powder was grinded and mixed with potassium bromide (KBr) to obtain a fine powder. The powder was then compressed into a thin pallet for analysis. About 15 mg of this pallet in each case was put on the Attenuated Total Reflectance (ATR) sample holder of a Perkin Elmer spectrum 100 FTIR spectrometer (model JASCO FT/IR-4100). The sample was recorded in the range of 4000–500 cm−1,

FTIR spectra in the range of 500–4000 cm−1 of SEMES are shown in **Figure 11**. All the IR absorption bands were investigated with respect to the spectrometric identification of organic

The peak at 1450 cm−1 is typically assigned to the disproportional stretching vibration band of methyl group (C─H). Elraies et al. [25] obtained a similar peak for epoxidized methyl ester sulfonate from jatropha oil. The symmetric and asymmetric C─H stretching vibration of the ─CH3 group appears at 2497 and 2926 cm−1. Analogous peaks between 2473 and 2955 cm−1 were reported by Babu et al. [96] for sulfonated methyl esters synthetized from castor oil and the ricinoleic acid methyl ester was sulfonated without the epoxidation step. The peak at 3679 cm−1 in the SEMES is attributed to the OH stretching of the sorbed water. This sorbed water vibration band suggests that the surface property of SEMES changed from hydrophobic to hydrophilic [96]. The existence of the epoxy ring in the SEMES was shown by the presence of C─O stretching absorption band in the area

The strong vibration (absorbance) peak at 1614 cm−1 corresponds to the existence of sulfonate group due to S═O stretching which is also an indication of the presence of esters [95, 97]. These results clearly indicate that the substance synthetized is a sodium epoxidized methyl ester sulfonate. For better understanding the structural arrangement of the surfactants investigated in this study, commercial anionic, SDS, and cationic, CTAB surfactants were also characterized using the same procedure. The FTIR spectra of pure SDS showed similar pattern with the synthetized SEMES, but the percentage of transmission were different as a

baseline was corrected, and the spectra smoothened.

compounds by Silverstein et al. [95].

of 988–830 cm−1.

108 Palm Oil

**Figure 11.** FTIR spectrum of SEMES.

The CaO/Al2 O3 employed as the catalyst to produce methyl esters used from the waste oil performed as expected, despite the presence of free fatty acids. The catalysts synthesized by the co-precipitation method exhibited high dispersion of the Ca and Al particles. The optimum reaction conditions for the production of methyl esters via simultaneous esterification and transesterification reaction of the waste pal oil were found to be: a reaction time of 4h at 65°C with a methanol:oil ratio of 9:1 and 4 wt% catalyst amount. A 60% CaO/40% Al2 O3 ratio was found to be optimum for waste palm oil. The high esters yield obtained despite the low quality of the oils used demonstrated that the use of a bifunctional catalyst will provide an opportunity to lower the cost of production of the esters. Furthermore, the catalyst showed substantial chemical stability and could be used again for at least 8 times with minor losses in its catalytic activity.

It is evident that the saturated fatty acid contents of the methyl esters subjected to epoxidation reaction in the presence and absence of a solvent at 25, 30, and 50°C were reduced while promoting the desired conversion of the unsaturated fatty acid methyl esters to epoxy esters (with oxirane groups). A temperature of 30°C was found to be suitable for epoxidation of oleic acid with PFA (performic) for optimum oxirane levels and hydrolysis rate diminishment. The EFAME was consequently sulfonated to produce the sodium epoxidized methyl ester sulfonate (SEMES) surfactant, which was then compared with the synthetic SDS and CTAB surfactants. The identified FTIR spectrum of SEMES was similar to that of SDS which indicated that the formulated SEMES is an anionic surfactant. The same result has been reported [98]. The sulfonated surfactant has been evaluated in a separate study for performance in petroleum reservoir [15]. It was found to exhibit excellent characteristics comparable to commercial petroleum-based anionic surfactant.

## **Acknowledgements**

The study was made possible by the generous fund provided by South Africa Technology Innovation Agency (TIA).

## **Author details**

Ademola Rabiu\*, Samya Elias and Oluwaseun Oyekola

\*Address all correspondence to: rabiua@cput.ac.za

Cape Peninsula University of Technology, Cape Town, South Africa

## **References**

[1] Noor Armylisas AH, Siti Hazirah MF, Yeong SK, Hazimah AH. Modification of olefinic double bonds of unsaturated fatty acids and other vegetable oil derivatives via epoxidation: A review. Grasas y Aceites. 2017;**68**(1). http://grasasyaceites.revistas.csic.es/index. php/grasasyaceites/rt/captureCite/1640/2040/ApaCitationPlugin

[15] Rabiu AM, Elias S, Oyekola O. Evaluation of surfactant synthesized from waste vegetable oil to enhance oil recovery from petroleum reservoirs. Energy Procedia. 2016;**100**:188-192

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 111

[16] Marti M, Colonna W, Patra P, Zhang H, Green C, Reznik G, et al. Production and characterization of microbial biosurfactants for potential use in oil-spill remediation. Enzyme

[17] Buist I, Potter S, Nedwed T, Mullin J. Herding surfactants to contract and thicken oil spills in pack ice for in situ burning. Cold Regions Science and Technology. 2011;**67**(1-2):3-23

[18] Ishak SA, Ghazali R, Abd Maurad Z, Zolkarnain N. Ecotoxicology study of various homologues of methyl ester sulfonates (MES) derived from palm oil. Journal of

[19] Elias SD, Rabiu AM, Oyekola O, Seima B. Adsorption characteristics of surfactants on different petroleum reservoir materials. Online Journal of Science and Technology.

[20] Lechuga M, Fernández-Serrano M, Jurado E, Núñez-Olea J, Ríos F. Acute toxicity of anionic and non-ionic surfactants to aquatic organisms. Ecotoxicology and Environmental

[21] Babu K, Maurya NK, Mandal A, Saxena VK. Synthesis and characterization of sodium methyl ester sulfonate for chemically-enhanced oil recovery. Brazilian Journal of

[22] Al-Sulaimani H, Joshi S, Al-Wahaibi Y, Al-Bahry S, Elshafie A, Al-Bemani A. Microbial biotechnology for enhancing oil recovery: Current developments and future prospects.

[23] Rahman P, Joshi S, Makkar R. Recent developments in Biosurfactants. Frontiers in

[24] Zulina AM, Razmah G, Parthiban S, Zahariah I, Salmiah A. Alpha-sulfonated methyl ester as an active ingredient in palm-based powder detergents. Journal of Surfactants

[25] Elraies KA, Isa MT, Saaid I. Synthesis and performance of a new surfactant for enhanced oil recovery. International Journal of Petroleum Science and Technology. 2009;**3**(1):1-9

[26] Roschat W, Siritanon T, Yoosuk B, Sudyoadsuk T, Promarak V. Rubber seed oil as potential non-edible feedstock for biodiesel production using heterogeneous catalyst in

[27] Mba OI, Dumont M-J, Ngadi M. Palm oil: Processing, characterization and utilization in

[28] Bhuiya MMK, Rasul MG, Khan MMK, Ashwath N, Azad AK. Prospects of 2nd generation biodiesel as a sustainable fuel—Part: 1 selection of feedstocks, oil extraction techniques and conversion technologies. Renewable and Sustainable Energy Reviews.

Biotechnology, Bioinformatics and Bioengineering. 2011;**1**(2):147-158

and Microbial Technology. 2014;**55**:31-39

2016;**6**(4):6-16

Safety. 2016;**125**:1-8

Surfactants and Detergents. 2017;**20**(6):1467-1473

Chemical Engineering. 2015;**32**(03):795-803

Microbiology, Published online. July 2017

Thailand. Renewable Energy. 2017;**101**:937-944

the food industry—A review. Food Bioscience. 2015;**10**:26-41

Detergent. 2006;**9**:161-167

2016;**55**:1109-1128


[15] Rabiu AM, Elias S, Oyekola O. Evaluation of surfactant synthesized from waste vegetable oil to enhance oil recovery from petroleum reservoirs. Energy Procedia. 2016;**100**:188-192

**References**

110 Palm Oil

2011;**50**:3854-3871

2016;**7**:11709

2017;**182**:185-196

2018;**120**(1):1700190

Central Journal. 2014;**8**(1):30

International Ltd.; 2008

2018;**14**:23-32

diesel production. Energies. 2008;**1**(1):3-18

production of advanced biofuels. Nature. 2012;**488**:320-328

[1] Noor Armylisas AH, Siti Hazirah MF, Yeong SK, Hazimah AH. Modification of olefinic double bonds of unsaturated fatty acids and other vegetable oil derivatives via epoxidation: A review. Grasas y Aceites. 2017;**68**(1). http://grasasyaceites.revistas.csic.es/index.

[2] Fiorentino G, Ripa M, Ulgiati S. Chemicals from biomass: Technological versus environmental feasibility. A review. Biofuels, Bioproducts and Biorefining. 2017;**11**(1):195-214

[3] Biermann U, Bornscheuer U, Meier MAR, Metzger JO, Schäfer HJ. Oils and fats as renewable raw materials in chemistry. Angewandte Chemie (International Ed. in English).

[4] Zhou YJ, Buijs NA, Zhu Z, Qin J, Siewers V, Nielsen J. Production of fatty acid-derived oleochemicals and biofuels by synthetic yeast cell factories. Nature Communications.

[5] Werth K, Kaupenjohann P, Skiborowski M. The potential of organic solvent nanofiltration processes for oleochemical industry. Separation and Purification Technology.

[6] Rupilius W, Ahmad S. Palm oil and palm kernel oil as raw materials for basic oleochemicals and biodiesel. European Journal of Lipid Science and Technology. 2007;**109**(4):433-439

[7] Tan SG, Chow WS. Biobased epoxidized vegetable oils and its greener epoxy blends: A review. Polymer-Plastics Technology and Engineering. 2010;**49**(15):1581-1590

[8] Vanbésien T, Le Nôtre J, Monflier E, Hapiot F. Hydroaminomethylation of oleochemicals: A comprehensive overview. European Journal of Lipid Science and Technology.

[9] Chhetri AB, Watts KC, Islam MR. Waste cooking oil as an alternate feedstock for bio-

[10] Peralta-Yahya PP, Zhang F, del Cardayre SB, Keasling JD. Microbial engineering for the

[11] Lee HV, Juan JC, Binti Abdullah NF, Nizah Mf R, Taufiq-Yap YH. Heterogeneous base catalysts for edible palm and non-edible Jatropha-based biodiesel production. Chemistry

[12] Geetha S, Banat IM, Joshi SJ. Biosurfactants: Production and potential applications in microbial enhanced oil recovery (MEOR). Biocatalysis and Agricultural Biotechnology.

[13] Permadi P, Fitria R, Hambali E. Palm oil based surfactant products for petroleum industry. IOP Conference Series: Earth and Environmental Science. 2017;**65**(1):012034

[14] Rust D, Wildes S. A Market Opportunity Study Update. Midland, MI: OmniTech

php/grasasyaceites/rt/captureCite/1640/2040/ApaCitationPlugin


[29] Maddikeri GL, Gogate PR, Pandit AB. Improved synthesis of sophorolipids from waste cooking oil using fed batch approach in the presence of ultrasound. Chemical Engineering Journal. 2015;**263**:479-487

[43] Lu J, Goudarzi A, Chen P, Kim DH, Delshad M, Mohanty KK, Sepehrnoori K, Weerasooriya UP, Pope GA. Enhanced oil recovery from high-temperature, high-salinity naturally fractured carbonate reservoirs by surfactant flood. Journal of Petroleum

Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 113

[44] Berger PD, Lee CH.Improved ASP process using organic alkali. In: SPE/DOE Symposium

[45] Gupta R, Mohanty KK. Temperature effects on surfactant-aided imbibition into frac-

[46] RVF P, Carvalho MS, Alvarado V. Oil recovery modeling of macro-emulsion flooding at low capillary number. Journal of Petroleum Science and Engineering. 2014;**119**:112-122

[47] Bera A, Kumar T, Ojha K, Mandal A. Adsorption of surfactants on sand surface in enhanced oil recovery: Isotherms, kinetics and thermodynamic studies. Applied Surface

[48] De Almeida DG, Soares Da Silva RdCF, Luna JM, Rufino RD, Santos VA, Banat IM, et al. Biosurfactants: Promising molecules for petroleum biotechnology advances. Frontiers in

[49] Demirbas A. Studies on cottonseed oil biodiesel prepared in non-catalytic SCF condi-

[50] Jacobson KGRMLC, Dalai AK. Solid acid catalyzed biodiesel production from waste

[51] Balat M. Potential alternatives to edible oils for biodiesel production—A review of cur-

[52] Ferreira ML, Tonetto GM. Enzymatic Synthesis of Structured Triglycerides: From Laboratory to Industry. Cham, Switzerland: Springer International Publishing; 2017

[53] Goud VV, Patwardhan AV, Pradha NC. Kinetics of in-situ epoxidation of natural triglycerides catalyzed by acidic ion exchange resin. Industrial and Engineering Chemistry

[54] Babajide OO. Optimisation of Biodiesel Production Via Different. Department of

[55] Ali O, Yusaf T, Mamat R, Abdullah N, Abdullah A. Influence of chemical blends on palm oil methyl esters' cold flow properties and fuel characteristics. Energies. 2014;**7**(7):4364

[56] Yasin MHM, Mamat R, Najafi G, Ali OM, Yusop AF, Ali MH. Potentials of palm oil as new feedstock oil for a global alternative fuel: A review. Renewable and Sustainable

[57] Hansen SB, Padfield R, Syayuti K, Evers S, Zakariah Z, Mastura S. Trends in global palm

oil sustainability research. Journal of Cleaner Production. 2015;**100**:140-149

cooking oil. Applied Catalysis B: Environmental. 2008;**85**:86-91

rent work. Energy Conversion and Management. 2011;**52**(2):1479-1492

Chemistry. MSc. Cape Town: University of the Western cape; 2011

on Improved Oil Recovery. Society of Petroleum Engineers; 2006

Science and Engineering. 2014;**124**:122-131

Science. 2013;**284**:87-99

Microbiology 2016;**7**:1718

Research. 2007;**46**:3078-3085

Energy Reviews. 2017;**79**:1034-1049

tions. Bio/Technology. 2008;**99**:1125-1130

tured carbonates. SPE Journal. 2010;**15**(3):588-597


[43] Lu J, Goudarzi A, Chen P, Kim DH, Delshad M, Mohanty KK, Sepehrnoori K, Weerasooriya UP, Pope GA. Enhanced oil recovery from high-temperature, high-salinity naturally fractured carbonate reservoirs by surfactant flood. Journal of Petroleum Science and Engineering. 2014;**124**:122-131

[29] Maddikeri GL, Gogate PR, Pandit AB. Improved synthesis of sophorolipids from waste cooking oil using fed batch approach in the presence of ultrasound. Chemical

[30] Pashley RM, Karaman ME. Applied Colloid and Surface Chemistry. England: John

[31] Elraies KA, Tan I, Fathaddin M, Abo-Jabal A. Development of a new polymeric surfactant for chemical enhanced oil recovery. Petroleum Science and Technology. 2011;

[32] Joshi SJ, Abed RM. Biodegradation of polyacrylamide and its derivatives. Environmental

[33] Mohsenzadeh A, Al-Wahaibi Y, Al-Hajri R, Jibril B, Mosavat N. Sequential deep eutectic solvent and steam injection for enhanced heavy oil recovery and in-situ upgrading. Fuel.

[34] Rudyk S, Spirov P, Samuel P, Joshi SJ. Vaporization of crude oil by supercritical CO<sup>2</sup>

[35] Blesic M, Dichiarante V, Milani R, Linder M, Metrangolo P. Evaluating the potential of natural surfactants in the petroleum industry: The case of hydrophobins. Pure and

[36] Bera A, Mandal A. Microemulsions: A novel approach to enhanced oil recovery: A review. Journal of Petroleum Exploration and Production Technology. 2015;**5**(3):255-268

[37] Zargartalebi MKR, Barati N. Enhancement of surfactant flooding performance by the

[38] Kamari ASMMAH, Ramjugernath D. Reliable method for the determination of surfactant retention in porous media during chemical flooding oil recovery. Fuel. 2015;**158**:

[39] Zolfaghari R, Fakhru'l-Razi A, Abdullah LC, Elnashaie SSEH, Pendashteh A. Demulsification techniques of water-in-oil and oil-in-water emulsions in petroleum industry.

[40] Koh A, Wong A, Quinteros A, Desplat C, Gross R. Influence of sophorolipid structure on interfacial properties of aqueous-Arabian light crude and related constituent emulsions.

[41] Ahmadi MA, Shadizadeh SR. Experimental investigation of a natural surfactant adsorption on shale-sandstone reservoir rocks: Static and dynamic conditions. Fuel. 2015;**159**:

[42] Spildo KSLDK, Skauge A. A strategy for low cost, effective surfactant injection. Journal

different temperatures and pressures: Example from Gorm field in the Danish North

at

Engineering Journal. 2015;**263**:479-487

Wiley & Sons; 2004

112 Palm Oil

**29**(14):1521-1528

2017;**187**:417-428

122-128

15-26

Processes. 2017;**4**(2):463-476

Sea. Energy & Fuels. 2017;**31**(6):6274-6283

use of silica nanoparticles. Fuel. 2015;**143**:21-27

Separation and Purification Technology. 2016;**170**:377-407

of Petroleum Science and Engineering. 2014;**117**:8-14

Journal of the American Oil Chemists' Society. 2017;**94**(1):107-119

Applied Chemistry. 2018;**90**:305


[58] Choong YY, Chou KW, Norli I. Strategies for improving biogas production of palm oil mill effluent (POME) anaerobic digestion: A critical review. Renewable and Sustainable Energy Reviews. 2018;**82**:2993-3006

[73] Janaun J, Ellis N. Perspectives on biodiesel as a sustainable fuel. Renewable and

[74] Zabeti M, Wan Daud MAW, Aroua MK. Biodiesel production using alumina-supported calcium oxide: An optimization study. Fuel Processing Technology. 2010;**91**(2):243-248

[75] Wen Z, Yu X, Tu ST, Yan J, Dahlquist E. Biodiesel production from waste cooking oil

[76] Math MC, Kumar SP, Chetty SV. Technologies for biodiesel production from used cook-

[77] Teng G, Gao L, Xiao G, Liu H. Transesterification of soybean oil to biodiesel over hetero-

[78] Hayyan A, Alam M, Mirghani M, Kabbashi N, Hakimi N, Siran Y, et al. Sludge palm oil as a renewable raw material for biodiesel production by two-step processes. Bioresource

[79] Hayyan A, Alam M, Mirghani M, Kabbashi N, Hakimi N, Siran Y, et al. Production of biodiesel from sludge palm oil by esterification process. Journal of Energy and Power

[80] Patil P, Deng S, Rhodes JI, Lammers PJ. Conversion of waste cooking oil to biodiesel using ferric sulfate and supercritical methanol processes. Fuel. 2010;**89**:360-364

[81] Liu X, He H, Wang Y, Zhu S. Transesterification of soybean oil to biodiesel as a solid base

[82] Lotero E, Liu Y, Lopez DE, Suwannakarn K, Bruce DA, Goodwin JG. Synthesis of biodiesel via acid catalysis. Industrial & Engineering Chemistry Research. 2005;**44**:5353-5363

[83] Pasupulety N, Gunda K, Liu Y, Rempel GL, Ng FTT. Production of biodiesel from soybean

[84] Balakrishnan K, Olutoye MA, Hameed BH. Synthesis of methyl esters from waste cooking oil using construction waste material as solid base catalyst. Bioresource Technology.

[85] Farooqa M, Ramlib A, Subbaraoa D. Biodiesel production from waste cooking oil using bifunctional heterogeneous solid catalysts. Journal of Cleaner Production. 2013;**59**:

[86] Saifuddin M, Goh PE, Ho WS, Moneruzzaman KM, Fatima A. Biodiesel production from waste cooking palm oil and environmental impact analysis. Bulgarian Journal of

[87] Gervajio GC. Fatty Acids and Derivatives from Coconut Oil. In: Shahidi F, editor. Bailey's Industrial Oil and Fat Products. 6th ed. New Jersey: John Wiley and Sons, Inc.;

solid base catalysts. Applied Catalysis A: General. 2013;**452**:189-202

ing oil—A review. Energy for Sustainable Development. 2010;**14**:339-345

geneous solid base catalyst. Energy & Fuels. 2009;**23**:4630-4634

catalyst. Catalysis Communication. 2007;**8**:1107-1111


Oleochemicals from Palm Oil for the Petroleum Industry http://dx.doi.org/10.5772/intechopen.76771 115

Sustainable Energy Reviews. 2010;**14**:1312-1320

catalyzed by TiO2

Technology. 2010;**101**:7804-7811

Engineering. 2010;**4**:13-14

oil on CaO/Al2

2013;**128**:788-791

131-140

O3

Agricultural Science. 2014;**20**(1):186-192

2005. DOI: DOI: 10.1002/047167849X.bio039


[73] Janaun J, Ellis N. Perspectives on biodiesel as a sustainable fuel. Renewable and Sustainable Energy Reviews. 2010;**14**:1312-1320

[58] Choong YY, Chou KW, Norli I. Strategies for improving biogas production of palm oil mill effluent (POME) anaerobic digestion: A critical review. Renewable and Sustainable

[59] Kadarusman YB, Herabadi AG. Improving Sustainable Development within Indonesian Palm Oil: The Importance of the Reward System. Sustainable Development 2018.

[60] Indonesia Investments. Palm Oil. 2017. https://www.indonesia-investments.com/busi-

[61] Yaakob ZMMAMAZ, Sopian K. Overview of the production of biodiesel from waste

[62] Yang H, Chien S, Lo M, Lan JC, Lu W, Ku Y. Effects of biodiesel on emissions of regulated air pollutants and polycyclic aromatic hydrocarbons under engine durability test-

[63] Eze VC, Phan AN, Harvey AP. Intensified one-step biodiesel production from high

[64] Amoah J, Quayson E, Hama S, Yoshida A, Hasunuma T, Ogino C, et al. Simultaneous conversion of free fatty acids and triglycerides to biodiesel by immobilized *Aspergillus oryzae* expressing Fusarium heterosporum lipase. Biotechnology Journal 2017;**12**(3):1600400 [65] Demirbas A. Progress and recent trends in biodiesel fuels. Energy Conversion and

[66] Photaworn S, Tongurai C, Kungsanunt S. Process development of two-step esterification plus catalyst solution recycling on waste vegetable oil possessing high free fatty acid.

[67] Helwani Z, Othman MR, Aziz N, WJN F, Kim J. Technologies for production of biodiesel focusing on green catalytic techniques: A review. Fuel Processing Technology.

[68] Schuchardta USR, Vargas RM. Transesterification of vegetable oils: A review. Journal of

[69] Arzamendi G, Campoa I, Arguinarena E, Sanchez M, Montes M, Gandia LM. Synthesis of biodiesel with heterogeneous NaOH/alumina catalysts: Comparison with homoge-

[70] Di Serio M, Tesser R, Pengmei L, Santacesaria E. Heterogeneous catalysts for biodiesel

[71] Hara M. Environmentally benign production of biodiesel using heterogeneous catalysts.

[72] Lopez-Granados M, Alba-Rubio AC, Vila F, Martín AD, Marisacl R. Surface chemical promotion of calcium oxide catalyst in biodiesel production reaction by the addition of monoglycerides, diglycerides and glycerol. Journal of Catalysis. 2010;**276**:229-236

Chemical Engineering and Processing: Process Intensification. 2017;**118**:1-8

cooking oil. Renewable and Sustainable Energy Reviews. 2013;**18**:186-191

water and free fatty acid waste cooking oils. Fuel. 2018;**220**:567-574

Published online in Wiley Online Library. DOI: 10.1002/sd.1715

ness/commodities/palm-oil/item166? [Accessed: 3 March 2018]

ing. Atmospheric Environment. 2007;**41**(34):7232-7240

Energy Reviews. 2018;**82**:2993-3006

114 Palm Oil

Management. 2009;**50**(1):14-34

Brazilian Chemical Society. 1998;**9**(1):199-210

production. Energy & Fuels. 2008;**22**:207-217

neous NaOH. Chemical Engineering Journal. 2007;**134**:123-130

Chemical Engineering Communications. 2009;**2**(2):129-135

2009;**90**:1502-1514


[88] Scala J, Wool RP. Effect of FA composition on epoxidation kinetics of TAG. Journal of American Oil Chemistry Society. 2002;**79**:373-378

**Chapter 7**

Provisional chapter

**The Inclusion of Palm Oil Ash Biomass Waste in**

DOI: 10.5772/intechopen.76632

Oil palm ash (OPA) is a waste material produced by countries having a blooming palm oil industry. Recycling of oil palm ash is receiving increasing attention because of its huge potential in improving economic benefits and environmental awareness. Recently, it has been used as a partial replacement to cement in concrete, mortar and other cementitious materials. OPA is considered a new member of the supplementary cementing materials. Therefore, it is imperative to have a complete understanding of this material and its effects. In this chapter, a thorough literature review involving OPA will be presented. The physical and chemical properties of OPA will be listed as well as its effect when used as a partial cement replacement on the fresh state, mechanical and durability properties of a number of cementitious products. Capitalising such waste products in the production of concrete will not only benefit the recycling chain process but also produce a green product which enables the reduction of cement quantities used and also produce an energy-

The surge in fossil fuel prices and the fear of future supply shortages alongside the increasing awareness of greenhouse gas emissions increased the shift towards the search for alternative fuels. These alternative fuels are conditioned to be technically feasible, environmentally friendly, competitive from an economic perspective and readily available [1]. Vegetable oils, which are from plant origin, are considered to be an alternative to fossil fuels. The alternative fuel is named as biodiesel. Bio-diesel is biodegradable, non-toxic and has low CO2 emission profiles in comparison to

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and eproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

Keywords: biomass waste, concrete, cement replacement, properties

The Inclusion of Palm Oil Ash Biomass Waste in

**Concrete: A Literature Review**

Concrete: A Literature Review

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

Hanizam Bt. Awang and

Hanizam Bt. Awang and

Abstract

1. Introduction

Mohammed Zuhear Al-Mulali

Mohammed Zuhear Al-Mulali

http://dx.doi.org/10.5772/intechopen.76632

efficient building material.


#### **The Inclusion of Palm Oil Ash Biomass Waste in Concrete: A Literature Review** The Inclusion of Palm Oil Ash Biomass Waste in Concrete: A Literature Review

DOI: 10.5772/intechopen.76632

Hanizam Bt. Awang and Mohammed Zuhear Al-Mulali Hanizam Bt. Awang and Mohammed Zuhear Al-Mulali

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76632

#### Abstract

[88] Scala J, Wool RP. Effect of FA composition on epoxidation kinetics of TAG. Journal of

[89] Campanella A, Baltanas MA, Fontanini C. High yield epoxidation of fatty methyl esters with performic acid generated in-situ. Chemical Engineering Journal. 2008;**118**:141-152

[90] Akintayo E, Ziegler T, Onipede A. Gas chromatographic and spectroscopic analysis of epoxidised canola oil. Bulletin of the Chemical Society of Ethiopia. 2006;**20**(1):75-81 [91] Espinoza Perez JD, Haagenson DM, Pryor SW, Ulven CA, Wiesenborn DP. Production and characterization of epoxidized canola oil. American Society of Agricultural and

[92] Ahmad M, Khan MA, Zafar M, Sultana S. Biodiesel from Non Edible Oil Seeds: a Renewable Source of Bioenergy. In: Marco Aurelio Dos Santos Bernardes, editor. Economic Effects of Biofuel Production. Rijeka, Croatia: InTech; 2011. ISBN: 978-953- 307-178-7. http://www.intechopen.com/books/economic-effects-of-biofuel-production/

[93] Deshpande PS. Chapter 3 Epoxidation of oleic acid and vegetable oils: Synthesis, characterization and utilization as biolubricants and additives for plastics. Journal of Cleaner

[94] Stein W, Baumann H. α-Sulfonated fatty acids and esters: Manufacturing process, properties, and applications. Journal of the American Oil Chemists Society. 1975;**52**(9):323-329

[96] Babu K, Pal N, Bera A, Saxena VK, Mandal A. Studies on interfacial tension and contact angle of synthesized surfactant and polymeric from castor oil for enhanced oil recovery.

[97] Awang M, Seng GM. Sulfonation of phenols extracted from the pyrolysis oil of oil palm

[98] Elraies KA, Tan IM. The Application of a New Polymeric Surfactant for Chemical EOR. In: Romero-Zerón L, editor. Introduction to Enhanced Oil Recovery (EOR) Processes and Bioremediation of Oil-Contaminated Sites. Rijeka, Croatia: InTech; 2012. ISBN: 978-953-51-0629-6. Available from: http://www.intechopen.com/books/introduction-toenhanced-oil-recovery-eor-processes-and-bioremediationof-oil-contaminated-sites/

biodiesel-from-non-edible-oil-seeds-a-renewable-source-of-bioenerg

[95] Silverstein RM, Webster FX, Kiemle DJ. John Wiley & Sons, Inc; 2005

shells for enhanced oil recovery. ChemSusChem. 2008;**1**(3):210-214

the-application-of-a-new-polymeric-surfactant-for-chemical-eor

American Oil Chemistry Society. 2002;**79**:373-378

Biological Engineers. 2009;**52**(4):1289-1297

Applied Surface Science. 2015;**353**:1126-1136

Production. 2013;**59**:89-152

116 Palm Oil

Oil palm ash (OPA) is a waste material produced by countries having a blooming palm oil industry. Recycling of oil palm ash is receiving increasing attention because of its huge potential in improving economic benefits and environmental awareness. Recently, it has been used as a partial replacement to cement in concrete, mortar and other cementitious materials. OPA is considered a new member of the supplementary cementing materials. Therefore, it is imperative to have a complete understanding of this material and its effects. In this chapter, a thorough literature review involving OPA will be presented. The physical and chemical properties of OPA will be listed as well as its effect when used as a partial cement replacement on the fresh state, mechanical and durability properties of a number of cementitious products. Capitalising such waste products in the production of concrete will not only benefit the recycling chain process but also produce a green product which enables the reduction of cement quantities used and also produce an energyefficient building material.

Keywords: biomass waste, concrete, cement replacement, properties

#### 1. Introduction

The surge in fossil fuel prices and the fear of future supply shortages alongside the increasing awareness of greenhouse gas emissions increased the shift towards the search for alternative fuels. These alternative fuels are conditioned to be technically feasible, environmentally friendly, competitive from an economic perspective and readily available [1]. Vegetable oils, which are from plant origin, are considered to be an alternative to fossil fuels. The alternative fuel is named as biodiesel. Bio-diesel is biodegradable, non-toxic and has low CO2 emission profiles in comparison to

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and eproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

conventional fossil diesel. Using bio-diesel will allow a balance to occur between agricultural economic development and the environment [2]. Various plants have been identified as a raw stock for the production of bio-diesel such as rapeseed and soybeans in the United Sates and palm oil and jatropha in the Asian region [3]. However, among these resources of bio-diesel, palm oil is considered to be the cheapest and has the highest oil yield per hectare of plantation [1].

burned biomass [12]. In this section, the physical and chemical properties of OPA will be discussed thoroughly. In addition, the effects of OPA integration on the properties of concrete,

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When lower temperatures are used to incinerate the palm oil biomass, a black to dark grey OPA is produced due to the high amounts of unburned carbon [13]. Higher incineration temperatures will reduce the amounts of unburned carbon, thus producing OPA with a lighter colour and improved characteristics [14]. Therefore, every OPA is unique to its mill and there is no OPA similar to another. When received from the source, OPA is a coarse-sized particle which is at the same time porous in structure. In order to change its physical characteristics, OPA is usually ground. The grinding process not only will increase the fineness of the OPA particles but will also increase its specific gravity [15]. Grinding of OPA is done through the use of a modified Los Angeles machine [12, 13] or by ball mill [12, 16, 17]. Table 1 lists a

Due to the different production processes, every OPA is unique in its chemical composition. No OPA is chemically similar to another OPA from another source. OPAS used in different studies were compliant to a chemical composition of a Class N pozzolan [15, 19], Class C pozzolan [20] and a Class F pozzolan [21]. However, when insufficient incineration temperatures are used, impurities such as unburned shell and fibre and unburned carbon exist. Therefore, extra processing procedures are needed to enhance the properties of OPA before

The usual procedure for processing OPA starts with sieving. The sieving process discards any large unburned fibre or shell. To increase OPA's pozzolanic reactivity, the sieved OPA will undergo the process of grinding. As stated earlier, grinding the OPA will create a finer substance possessing a heavier specific gravity. OPA is usually ground until a median particle size of 10 μm is achieved [14]. When the OPA is of poor quality, the grinding process will not change the

> Median particle size (μm)

Sata et al. [12] 1.97 41.2 62.5 2.33 1.5 10.1 Tangchirapat et al. [17] 1.89 94.4 183.0 2.43 1.0 7.4 Tangchirapat et al. [15] 1.97 41.2 65.6 2.33 1.5 10.1 Megat Johari et al. [18] 2.42 — 15.76 2.50 — 2.99

Specific gravity

Retained on 45-μm sieve (%) Median particle size (μm)

number of physical properties for OPA used in different studies.

Author(s) Unground OPA Ground OPA

Retained on 45-μm sieve (%)

Table 1. Physical properties of OPA used in different studies (Al-Mulali et al. [14]).

Specific gravity

mortar and paste will be discussed.

2.1. Physical properties of OPA

2.2. Chemical properties of OPA

using it in concrete.

Today, Malaysia is the world's largest producer and exporter of palm oil, and its palm oil industry is an important contributor to the country's gross domestic product (GDP) [4]. Before the bio-diesel boom, 90% of the oil was used in food-related commodities with the remaining 10% being used as a raw material in soap production [5]. However, after realising the potential of palm oil in producing bio-diesel, the Malaysian palm oil industry grew from a shy 400 hectares in 1920 [6] to 4.17 million hectares in 2006 and nearly 4.5 million tonnes in 2008 [7]. In 2008, about 17.7 million tonnes of crude palm oil have been produced from the 410 palm oil mills in Malaysia reaching 41% of the world's palm oil production [8].

As a result to the thriving Malaysian palm oil industry, the amount of biomass produced will increase. A single hectare of palm oil plantation can generate up to 70 tonnes of biomass residues [9]. As a rough estimate, 1 kg of palm oil results in 4 kg of biomass produced alongside it [7]. About 90 million metric tonnes of biomass is produced in Malaysia annually [10]. This biomass residue consists of empty fruit bunch, fibre, shell, wet shell, palm kernel, fronds and trunks. Each oil palm tree fruit bunch produces about 21% palm oil, 6–7% palm kernel oil, 14–15% fibre, 6–7% shell and 23% empty fruit bunch [11].

It has been a common practice for palm oil mills to burn their biomass instead of using conventional fossil fuels for heating up their boilers and generate steam [1, 5]. According to Shuit et al. [9], more than 300 palm oil mills are operated by self-generated electricity using palm oil biomass in Malaysia. In addition, the generated electricity is not only used for their internal use in crude palm oil extraction but also provided the surrounding remote areas with electricity. Due to the abundant amounts of biomass produced, Malaysia has the potential to utilise these quantities in power generation. Using such alternative fuels to partially or fully replace fossil fuels used in all Malaysian industries to generate energy will result in a significant drop in CO2 emissions, achieving the vision to be a developed country without degrading the environment and promoting the utilisation of renewable energy in power generation.

However, the process of burning palm oil biomass will result in a new type of waste. This waste is called oil palm ash (OPA) which is causing numerous problems to the environment. OPA quantities are expected to increase in quantities due to the increasing demand for energy and the booming palm oil industry.

## 2. Oil palm ash (OPA)

It was mentioned earlier in the previous chapter that OPA is the result of incinerating palm oil biomass to generate necessary energy for the palm oil mill. Incineration of biomass occurs at temperatures ranging from 800 to over 1000C. OPA is produced at a rate of 5% by weight of burned biomass [12]. In this section, the physical and chemical properties of OPA will be discussed thoroughly. In addition, the effects of OPA integration on the properties of concrete, mortar and paste will be discussed.

#### 2.1. Physical properties of OPA

conventional fossil diesel. Using bio-diesel will allow a balance to occur between agricultural economic development and the environment [2]. Various plants have been identified as a raw stock for the production of bio-diesel such as rapeseed and soybeans in the United Sates and palm oil and jatropha in the Asian region [3]. However, among these resources of bio-diesel, palm oil is

Today, Malaysia is the world's largest producer and exporter of palm oil, and its palm oil industry is an important contributor to the country's gross domestic product (GDP) [4]. Before the bio-diesel boom, 90% of the oil was used in food-related commodities with the remaining 10% being used as a raw material in soap production [5]. However, after realising the potential of palm oil in producing bio-diesel, the Malaysian palm oil industry grew from a shy 400 hectares in 1920 [6] to 4.17 million hectares in 2006 and nearly 4.5 million tonnes in 2008 [7]. In 2008, about 17.7 million tonnes of crude palm oil have been produced from the 410 palm oil

As a result to the thriving Malaysian palm oil industry, the amount of biomass produced will increase. A single hectare of palm oil plantation can generate up to 70 tonnes of biomass residues [9]. As a rough estimate, 1 kg of palm oil results in 4 kg of biomass produced alongside it [7]. About 90 million metric tonnes of biomass is produced in Malaysia annually [10]. This biomass residue consists of empty fruit bunch, fibre, shell, wet shell, palm kernel, fronds and trunks. Each oil palm tree fruit bunch produces about 21% palm oil, 6–7% palm

It has been a common practice for palm oil mills to burn their biomass instead of using conventional fossil fuels for heating up their boilers and generate steam [1, 5]. According to Shuit et al. [9], more than 300 palm oil mills are operated by self-generated electricity using palm oil biomass in Malaysia. In addition, the generated electricity is not only used for their internal use in crude palm oil extraction but also provided the surrounding remote areas with electricity. Due to the abundant amounts of biomass produced, Malaysia has the potential to utilise these quantities in power generation. Using such alternative fuels to partially or fully replace fossil fuels used in all Malaysian industries to generate energy will result in a significant drop in CO2 emissions, achieving the vision to be a developed country without degrading the environment and promoting the utilisation of renewable energy in power generation.

However, the process of burning palm oil biomass will result in a new type of waste. This waste is called oil palm ash (OPA) which is causing numerous problems to the environment. OPA quantities are expected to increase in quantities due to the increasing demand for energy

It was mentioned earlier in the previous chapter that OPA is the result of incinerating palm oil biomass to generate necessary energy for the palm oil mill. Incineration of biomass occurs at temperatures ranging from 800 to over 1000C. OPA is produced at a rate of 5% by weight of

considered to be the cheapest and has the highest oil yield per hectare of plantation [1].

mills in Malaysia reaching 41% of the world's palm oil production [8].

kernel oil, 14–15% fibre, 6–7% shell and 23% empty fruit bunch [11].

and the booming palm oil industry.

2. Oil palm ash (OPA)

118 Palm Oil

When lower temperatures are used to incinerate the palm oil biomass, a black to dark grey OPA is produced due to the high amounts of unburned carbon [13]. Higher incineration temperatures will reduce the amounts of unburned carbon, thus producing OPA with a lighter colour and improved characteristics [14]. Therefore, every OPA is unique to its mill and there is no OPA similar to another. When received from the source, OPA is a coarse-sized particle which is at the same time porous in structure. In order to change its physical characteristics, OPA is usually ground. The grinding process not only will increase the fineness of the OPA particles but will also increase its specific gravity [15]. Grinding of OPA is done through the use of a modified Los Angeles machine [12, 13] or by ball mill [12, 16, 17]. Table 1 lists a number of physical properties for OPA used in different studies.

#### 2.2. Chemical properties of OPA

Due to the different production processes, every OPA is unique in its chemical composition. No OPA is chemically similar to another OPA from another source. OPAS used in different studies were compliant to a chemical composition of a Class N pozzolan [15, 19], Class C pozzolan [20] and a Class F pozzolan [21]. However, when insufficient incineration temperatures are used, impurities such as unburned shell and fibre and unburned carbon exist. Therefore, extra processing procedures are needed to enhance the properties of OPA before using it in concrete.

The usual procedure for processing OPA starts with sieving. The sieving process discards any large unburned fibre or shell. To increase OPA's pozzolanic reactivity, the sieved OPA will undergo the process of grinding. As stated earlier, grinding the OPA will create a finer substance possessing a heavier specific gravity. OPA is usually ground until a median particle size of 10 μm is achieved [14]. When the OPA is of poor quality, the grinding process will not change the


Table 1. Physical properties of OPA used in different studies (Al-Mulali et al. [14]).

chemical characteristics of the OPA drastically. Therefore, the fine OPA is usually burned in an electric furnace at a temperature of 500C for at least an hour to remove any carbon content [22]. Table 2 lists different OPA chemical compositions utilised in a number of studies.

2.3. The effect of OPA incorporation on the properties of concrete

2.3.1. Workability

2.3.2. Setting times

OPA particles due to their grinding [27].

In the following sections, the effect of OPA's incorporation on the properties of concrete, mortar,

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In general, increasing OPA content in concrete reduces its workability. Fresh concrete with 50% of its cement replaced by coarse OPA (passing through a 150-μm sieve) achieved a slump reading of 120 mm which is lower than the 150 mm exhibited by the control mix [25]. When using the compacting factor, concrete with a 50% coarse OPA replacement showed a compacting

Using the slump test and the amount of superplasticizer used to obtain a spread between 175 and 225 mm, high-strength concrete with increasing amounts of OPA exhibited less spread and used more superplasticizer to achieve the required spread [29]. The authors reasoned the increase in superplasticizer dose to the high porous nature of the OPA particles resulting in the absorption of a higher water quantity. Reduced workability of high-strength concrete with 20% by weight of cement is replaced by fine OPA is reasoned to the increased surface area of the

The increased water demand for OPA concrete to achieve a required workability limit is due to the shape and nature of the OPA particles themselves. OPA particles are known for their angularity, irregularity and their porous nature [18, 30, 31], and as a result, demanding an increased amount of water for their lubrication and by that attaining similar workability as their control mixes. Chindaprasirt et al. [30] discovered this aspect when comparing the OPA particles to those of fly ash which required less water due to their spherical shape and solid nature.

Sieved through a 300-μm sieve, OPA was used to replace cement at levels of 5, 10 and 15% by weight in conventional concrete. These OPA concrete mixes were compared to concrete with 10% replacement levels of fly ash and quarry dust also sieved through 300-μm sieve. Ahmad et al. [20] found that even with a dose of superplasticizer, OPA concrete mixes showed reduced slump readings and low compacting factors than those of the control and the fly ash mixes. The same observation is made in concrete with 50, 60 and 70% OPA replacement levels (35% retained on 45-μm sieve) and a superplasticizer dose of 2% by weight of binding material [31].

The initial and final setting times of concrete incorporating OPA as a cement replacement are investigated by a number of researchers. In general, OPA concretes showed prolonged initial and final setting times [14]. Concrete containing OPA (sieved through a 150-μm sieve) as a cement replacement exhibited a delay in both initial and final setting times; however, they were within the limits stated by ASTM 150 [25]. The retardation of initial and final setting

The particle size of OPA plays a role in defining the setting times [17]. The authors found that concrete with 40% of its cement replaced by coarse OPA (d50 = 183 μm) exhibited an initial

times increased with increasing OPA replacement levels [28].

cement paste, high-strength concrete and aerated concrete will be discussed thoroughly.

factor reading of 0.93 which was lower than the 0.99 exhibited by the control mix [28].

When compared to fly ash, OPA is known to have a higher percentage of organic residue, a higher alkali content and a larger particle size [25]. Coarse OPA is proven to be of low pozzolanic reactivity when no reduction in strength occurred. This is achieved after a curing period of 1 year is used and 10% of cement used in the production of concrete was replaced by OPA sieved through 150-μm sieve [25]. Increasing the pozzolanic reactivity of OPA is achieved through the grinding process to produce a finer particle sized ash [12]. When OPA with three different median particle sizes is used as a partial cement replacement in conventional concrete, the finest OPA with a median particle size of 7.4 μm showed a higher compressive strength than the control mix at a replacement level of 20–30% by weight of cement [17]. Mortars with cement partially replaced by coarse (55 μm), medium (25 μm) and fine (7 μm) OPA showed the same behaviour [26]. Mortar with fine OPA partially replacing cement shows superior strength in comparison to the control mortar and mortars containing the medium and coarse OPA.

In high-strength concrete, mixes containing fine OPA as a partial cement replacement exhibited the same behaviour. High-strength concrete mixes incorporating 20% of fine OPA (d50 = 10 μm) as a partial cement replacement showed a higher compressive strength and an increased resistance to chloride penetration, acid and sulphate attack [27]. High-strength concrete containing 20% fine OPA (d50 = 10.1 μm) achieved a compressive strength of 70 N/mm2 at the age of 90 days proving that fine OPA is a good mineral admixture [15].

In blended cement pastes, the effect of OPA fineness and pozzolanic reaction is studied by Kroehong et al. [16]. Ground OPAs with a particle size of 15 1 and 2 1 μm along with ground river sand were used to partially replace cement at levels of 10–40% by weight of cementing materials. At the age of 90 days, blended cement pastes containing 10–30% of 2-μm OPA exhibited higher compressive strengths than that exhibited by the control paste at a percentage of 105–111%. This increase was reasoned to the high pozzolanic reactivity of the 2 μm OPA.


Table 2. OPA chemical compositions used in different studies.

#### 2.3. The effect of OPA incorporation on the properties of concrete

In the following sections, the effect of OPA's incorporation on the properties of concrete, mortar, cement paste, high-strength concrete and aerated concrete will be discussed thoroughly.

### 2.3.1. Workability

chemical characteristics of the OPA drastically. Therefore, the fine OPA is usually burned in an electric furnace at a temperature of 500C for at least an hour to remove any carbon content [22].

When compared to fly ash, OPA is known to have a higher percentage of organic residue, a higher alkali content and a larger particle size [25]. Coarse OPA is proven to be of low pozzolanic reactivity when no reduction in strength occurred. This is achieved after a curing period of 1 year is used and 10% of cement used in the production of concrete was replaced by OPA sieved through 150-μm sieve [25]. Increasing the pozzolanic reactivity of OPA is achieved through the grinding process to produce a finer particle sized ash [12]. When OPA with three different median particle sizes is used as a partial cement replacement in conventional concrete, the finest OPA with a median particle size of 7.4 μm showed a higher compressive strength than the control mix at a replacement level of 20–30% by weight of cement [17]. Mortars with cement partially replaced by coarse (55 μm), medium (25 μm) and fine (7 μm) OPA showed the same behaviour [26]. Mortar with fine OPA partially replacing cement shows superior strength in comparison to the control mortar and mortars containing the

In high-strength concrete, mixes containing fine OPA as a partial cement replacement exhibited the same behaviour. High-strength concrete mixes incorporating 20% of fine OPA (d50 = 10 μm) as a partial cement replacement showed a higher compressive strength and an increased resistance to chloride penetration, acid and sulphate attack [27]. High-strength concrete containing 20% fine OPA (d50 = 10.1 μm) achieved a compressive strength of 70 N/mm2 at the age of 90 days

In blended cement pastes, the effect of OPA fineness and pozzolanic reaction is studied by Kroehong et al. [16]. Ground OPAs with a particle size of 15 1 and 2 1 μm along with ground river sand were used to partially replace cement at levels of 10–40% by weight of cementing materials. At the age of 90 days, blended cement pastes containing 10–30% of 2-μm OPA exhibited higher compressive strengths than that exhibited by the control paste at a percentage of 105–111%. This increase was reasoned to the high pozzolanic reactivity of the 2-

Sata et al. [12] 65.3 2.60 2.00 6.40 3.10 5.70 0.30 0.50 69.9 10.10 Tangchirapat et al. [17] 57.71 4.56 3.30 6.55 4.23 8.27 0.50 0.25 65.57 10.52 Chindaprasirt et al. [23] 63.6 1.60 1.40 7.60 3.90 6.90 0.10 0.20 66.6 9.60 Altwair et al. [24] 66.91 6.44 5.72 5.56 3.13 5.20 0.19 0.33 79.07 2.30 Megat Johari et al. [23] 65.01 5.72 4.41 8.19 4.58 6.48 0.07 0.33 75.14 2.53

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 SUM LOI

Table 2 lists different OPA chemical compositions utilised in a number of studies.

medium and coarse OPA.

120 Palm Oil

μm OPA.

proving that fine OPA is a good mineral admixture [15].

Author(s) Oxides present in OPA (%)

Table 2. OPA chemical compositions used in different studies.

In general, increasing OPA content in concrete reduces its workability. Fresh concrete with 50% of its cement replaced by coarse OPA (passing through a 150-μm sieve) achieved a slump reading of 120 mm which is lower than the 150 mm exhibited by the control mix [25]. When using the compacting factor, concrete with a 50% coarse OPA replacement showed a compacting factor reading of 0.93 which was lower than the 0.99 exhibited by the control mix [28].

Using the slump test and the amount of superplasticizer used to obtain a spread between 175 and 225 mm, high-strength concrete with increasing amounts of OPA exhibited less spread and used more superplasticizer to achieve the required spread [29]. The authors reasoned the increase in superplasticizer dose to the high porous nature of the OPA particles resulting in the absorption of a higher water quantity. Reduced workability of high-strength concrete with 20% by weight of cement is replaced by fine OPA is reasoned to the increased surface area of the OPA particles due to their grinding [27].

The increased water demand for OPA concrete to achieve a required workability limit is due to the shape and nature of the OPA particles themselves. OPA particles are known for their angularity, irregularity and their porous nature [18, 30, 31], and as a result, demanding an increased amount of water for their lubrication and by that attaining similar workability as their control mixes. Chindaprasirt et al. [30] discovered this aspect when comparing the OPA particles to those of fly ash which required less water due to their spherical shape and solid nature.

Sieved through a 300-μm sieve, OPA was used to replace cement at levels of 5, 10 and 15% by weight in conventional concrete. These OPA concrete mixes were compared to concrete with 10% replacement levels of fly ash and quarry dust also sieved through 300-μm sieve. Ahmad et al. [20] found that even with a dose of superplasticizer, OPA concrete mixes showed reduced slump readings and low compacting factors than those of the control and the fly ash mixes. The same observation is made in concrete with 50, 60 and 70% OPA replacement levels (35% retained on 45-μm sieve) and a superplasticizer dose of 2% by weight of binding material [31].

#### 2.3.2. Setting times

The initial and final setting times of concrete incorporating OPA as a cement replacement are investigated by a number of researchers. In general, OPA concretes showed prolonged initial and final setting times [14]. Concrete containing OPA (sieved through a 150-μm sieve) as a cement replacement exhibited a delay in both initial and final setting times; however, they were within the limits stated by ASTM 150 [25]. The retardation of initial and final setting times increased with increasing OPA replacement levels [28].

The particle size of OPA plays a role in defining the setting times [17]. The authors found that concrete with 40% of its cement replaced by coarse OPA (d50 = 183 μm) exhibited an initial setting time of 390 min and a final setting time of 740 min. The authors reasoned these prolonged initial and final setting times to a number of factors. These factors are reduced cement quantity and the large and porous unground OPA particles that increase the water binder ratio used in the mix. However, the authors stated that increasing the fineness of OPA decreased the setting times, making them closer to those exhibited by the control mix. Highstrength concrete mixes with fine OPA (d50 = 2 μm) replacement levels show prolonged setting times to those exhibited by the control mix [18]. The authors reasoned this retardation to the pozzolanic reaction which is slower than cement hydration.

Increasing OPA content reduces the compressive strength of aerated concrete [35]. However, it is still possible to replace cement by OPA at levels ranging from 10 to 35% without effecting the compressive strength of aerated concrete [14]. Aerated concrete sample containing fine OPA (Class F pozzolan) at a replacement level of 20% exhibits compressive strengths higher than that of the control aerated concrete mix at the same age [34]. Foamed concrete mixes containing 10 and 20% sand replacements by OPA sieved through a 600-μm sieve showed increased compressive strengths than that exhibited by the control mix due to the increase in density [31]. Table 3 summarises the studies that investigated the effect of OPA replacement

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High-strength concrete samples containing 10 and 20% replacement levels of fine OPA (d50 = 10.1 μm) exhibit higher splitting tensile strengths than their corresponding control mix at 90 days of age [29]. The authors reasoned this increase to the high fineness of OPA and its pozzolanic reaction with cement, creating increased CSH compounds. Even though a fine OPA was used, higher replacement levels of cement by OPA (50% by weight of cement) exhibit lower tensile splitting strengths than the control mix [32]. Higher tensile splitting strengths are exhibited by foamed concrete samples containing OPA (passing through a 600-μm sieve)

High-strength concrete samples containing 20% of fine OPA (d50 = 10.1 μm) exhibited similar modulus of elasticity readings as that of the control mix [12, 29]. Concrete samples containing fine OPA (10.1 μm) at cement replacement levels of 10 and 25% by weight of cement exhibit higher modulus of elasticity readings than that of the control mix. However, concrete samples containing coarse OPA (d50 = 19.9 μm) exhibit lower modulus of elasticity readings than the

In aerated concrete samples using fine OPA (1% retained on 45-μm sieve), samples containing 20% replacement of cement by OPA exhibited higher modulus of elasticity readings than the control mix [21]. The authors reasoned this increase to the pozzolanic reaction between the fine OPA particles and the calcium hydroxide emitted by cement hydration, creating a refined and stiffer microstructure. The modulus of elasticity readings of concrete samples containing recycled aggregate and a 20% fine OPA replacement level was lower than that of the control mix and was similar to those exhibited by a concrete sample with recycled aggregate and 100%

Limited studies have endeavoured on studying the effects of OPA incorporation into concrete on its flexural strength. High-strength concrete samples containing OPA as cement replacements exhibit a lower flexural strength than those exhibited by the control mix [40]. However, the author states that the samples containing a 30% fine OPA replacement level exhibit flexural strengths near to that of the control mix. On the other hand, Lim et al. [31] states that foamed concrete mixes having their sand replaced by 10 and 20% of OPA (sieved through a 600-μm

sieve) exhibit higher flexural strengths than those exhibited by the control mix.

on the compressive strength.

control mix [38].

cement [33].

2.3.5. Flexural strength

2.3.4. Tensile strength and modulus of elasticity

replacing sand at 10 and 20% than those of the control mix [31].

#### 2.3.3. Compressive strength

Numerous studies investigated the effect of OPA incorporation as a cement replacement on the strength of concrete, mortar and cement paste. Increasing OPA content in concrete decreases the compressive strength [14]. Concrete with OPA (sieved through a 150-μm sieve) at replacement levels of 0–50% by weight of cement experienced a drop in compressive strength with increasing OPA content [25, 28]. Compressive strength reduction was less observed at the age of 365 days in comparison to that at 28 days due to the pozzolanic activity of the OPA. The researchers recommended an optimum OPA replacement level of 10% by weight of cement because the reduction in compressive strength is found to be 1% at the age of 1 year.

Increasing the fineness of OPA increases its pozzolanic reactivity, hence increasing the compressive strength of concrete. Chindaprasirt et al. [30] concluded that a 20% replacement level of OPA (d50 = 8 μm) possessed a slightly higher compressive strength than the control mix. Increasing the fineness of OPA further makes it possible to increase the replacement level used in the concrete and achieve a higher compressive strength. Concrete samples containing OPA with a median particle size of 7.4 μm at a replacement level of 30% managed to possess 99% of the control mix's strength at 90 days [17]. Fine OPA replacing 50% of cement in concrete showed double the compressive strength of concrete having half of their cement replaced by raw OPA [32].

Even when using different water cement ratios in concrete (0.5, 0.55 and 0.6), samples containing a 10% fine OPA (2% retained on a 45-μm sieve) exhibit higher compressive strengths at all water cement ratios at 14 days of age than its corresponding control mixes [29]. Fine OPA (d50 = 10. 7 μm) at a replacement level of 20% enhanced the compressive strength of concrete with recycled aggregate in comparison to the same concrete samples without OPA [33]. High-strength concrete samples containing 20% cement replacement by fine OPA (d50 = 10 μm) exhibited higher compressive strengths than both the control mix and the mix containing 5% silica fume at the same age [12]. In another study, high-strength concrete samples containing OPA (d50 = 10.1 μm) at a replacement level of 30% exhibit higher compressive strengths than those of mixes containing Type I and Type V Portland cements at the same age [15].

Ultrafine OPA (d50 = 2 μm) is capable of replacing cement at a level of 60% and achieve a higher compressive strength than that exhibited by the control mix at 28 days [18]. The increase in compressive strength is due to the pozzolanic reaction between the high silica oxide content of OPA and calcium hydroxide emitted by the cement hydration. This pozzolanic reaction will produce extra amounts of calcium silicate hydrates (C-S-H); hence, an increase in compressive strength is experienced [15, 18, 27, 29].

Increasing OPA content reduces the compressive strength of aerated concrete [35]. However, it is still possible to replace cement by OPA at levels ranging from 10 to 35% without effecting the compressive strength of aerated concrete [14]. Aerated concrete sample containing fine OPA (Class F pozzolan) at a replacement level of 20% exhibits compressive strengths higher than that of the control aerated concrete mix at the same age [34]. Foamed concrete mixes containing 10 and 20% sand replacements by OPA sieved through a 600-μm sieve showed increased compressive strengths than that exhibited by the control mix due to the increase in density [31]. Table 3 summarises the studies that investigated the effect of OPA replacement on the compressive strength.

#### 2.3.4. Tensile strength and modulus of elasticity

setting time of 390 min and a final setting time of 740 min. The authors reasoned these prolonged initial and final setting times to a number of factors. These factors are reduced cement quantity and the large and porous unground OPA particles that increase the water binder ratio used in the mix. However, the authors stated that increasing the fineness of OPA decreased the setting times, making them closer to those exhibited by the control mix. Highstrength concrete mixes with fine OPA (d50 = 2 μm) replacement levels show prolonged setting times to those exhibited by the control mix [18]. The authors reasoned this retardation to the

Numerous studies investigated the effect of OPA incorporation as a cement replacement on the strength of concrete, mortar and cement paste. Increasing OPA content in concrete decreases the compressive strength [14]. Concrete with OPA (sieved through a 150-μm sieve) at replacement levels of 0–50% by weight of cement experienced a drop in compressive strength with increasing OPA content [25, 28]. Compressive strength reduction was less observed at the age of 365 days in comparison to that at 28 days due to the pozzolanic activity of the OPA. The researchers recommended an optimum OPA replacement level of 10% by weight of cement because the

Increasing the fineness of OPA increases its pozzolanic reactivity, hence increasing the compressive strength of concrete. Chindaprasirt et al. [30] concluded that a 20% replacement level of OPA (d50 = 8 μm) possessed a slightly higher compressive strength than the control mix. Increasing the fineness of OPA further makes it possible to increase the replacement level used in the concrete and achieve a higher compressive strength. Concrete samples containing OPA with a median particle size of 7.4 μm at a replacement level of 30% managed to possess 99% of the control mix's strength at 90 days [17]. Fine OPA replacing 50% of cement in concrete showed double the

Even when using different water cement ratios in concrete (0.5, 0.55 and 0.6), samples containing a 10% fine OPA (2% retained on a 45-μm sieve) exhibit higher compressive strengths at all water cement ratios at 14 days of age than its corresponding control mixes [29]. Fine OPA (d50 = 10. 7 μm) at a replacement level of 20% enhanced the compressive strength of concrete with recycled aggregate in comparison to the same concrete samples without OPA [33]. High-strength concrete samples containing 20% cement replacement by fine OPA (d50 = 10 μm) exhibited higher compressive strengths than both the control mix and the mix containing 5% silica fume at the same age [12]. In another study, high-strength concrete samples containing OPA (d50 = 10.1 μm) at a replacement level of 30% exhibit higher compressive strengths than those of mixes

Ultrafine OPA (d50 = 2 μm) is capable of replacing cement at a level of 60% and achieve a higher compressive strength than that exhibited by the control mix at 28 days [18]. The increase in compressive strength is due to the pozzolanic reaction between the high silica oxide content of OPA and calcium hydroxide emitted by the cement hydration. This pozzolanic reaction will produce extra amounts of calcium silicate hydrates (C-S-H); hence, an increase

compressive strength of concrete having half of their cement replaced by raw OPA [32].

pozzolanic reaction which is slower than cement hydration.

reduction in compressive strength is found to be 1% at the age of 1 year.

containing Type I and Type V Portland cements at the same age [15].

in compressive strength is experienced [15, 18, 27, 29].

2.3.3. Compressive strength

122 Palm Oil

High-strength concrete samples containing 10 and 20% replacement levels of fine OPA (d50 = 10.1 μm) exhibit higher splitting tensile strengths than their corresponding control mix at 90 days of age [29]. The authors reasoned this increase to the high fineness of OPA and its pozzolanic reaction with cement, creating increased CSH compounds. Even though a fine OPA was used, higher replacement levels of cement by OPA (50% by weight of cement) exhibit lower tensile splitting strengths than the control mix [32]. Higher tensile splitting strengths are exhibited by foamed concrete samples containing OPA (passing through a 600-μm sieve) replacing sand at 10 and 20% than those of the control mix [31].

High-strength concrete samples containing 20% of fine OPA (d50 = 10.1 μm) exhibited similar modulus of elasticity readings as that of the control mix [12, 29]. Concrete samples containing fine OPA (10.1 μm) at cement replacement levels of 10 and 25% by weight of cement exhibit higher modulus of elasticity readings than that of the control mix. However, concrete samples containing coarse OPA (d50 = 19.9 μm) exhibit lower modulus of elasticity readings than the control mix [38].

In aerated concrete samples using fine OPA (1% retained on 45-μm sieve), samples containing 20% replacement of cement by OPA exhibited higher modulus of elasticity readings than the control mix [21]. The authors reasoned this increase to the pozzolanic reaction between the fine OPA particles and the calcium hydroxide emitted by cement hydration, creating a refined and stiffer microstructure. The modulus of elasticity readings of concrete samples containing recycled aggregate and a 20% fine OPA replacement level was lower than that of the control mix and was similar to those exhibited by a concrete sample with recycled aggregate and 100% cement [33].

#### 2.3.5. Flexural strength

Limited studies have endeavoured on studying the effects of OPA incorporation into concrete on its flexural strength. High-strength concrete samples containing OPA as cement replacements exhibit a lower flexural strength than those exhibited by the control mix [40]. However, the author states that the samples containing a 30% fine OPA replacement level exhibit flexural strengths near to that of the control mix. On the other hand, Lim et al. [31] states that foamed concrete mixes having their sand replaced by 10 and 20% of OPA (sieved through a 600-μm sieve) exhibit higher flexural strengths than those exhibited by the control mix.


to binder ratios of 0.33, 0.36 and 0.38. The OPA that the authors use in this study was sieved through a 300-μm sieve, then ground using a ball mill and afterwards heat-treated at 450C for 90 min to eliminate any glassy phase crystallisation and agglomeration of the OPA particles. They state that an ECC mix containing OPA at 0.4 by weight of cement and water to binder ratio of 0.36 exhibits the highest flexural strength among the conducted ECC mixes. In addition, a decrease in flexural strengths is exhibited with increasing OPA content and increasing water to binder ratio. Furthermore, ECC mixes containing OPA at 0.4 and 0.8 by weight of cement and water to binder ratio of 0.33 exhibit higher flexural strengths than the

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Concrete samples containing cement replacements by OPA (sieved through a 150-μm) sieve show higher drying shrinkage readings than those exhibited by the control mix [25]. In addition, drying shrinkage is proportional to the increase in OPA content. Concrete samples with 50% of its cement replaced by OPA (sieved through a 45-μm sieve) exhibit a drying shrinkage reading higher by 21% than that of the control mix at the age of 90 days [32]. The authors reason this increase in drying shrinkage to the variation in moisture loss rate caused

Different sized OPA particles exhibit different readings of drying shrinkage [38]. At the age of 6 months, concrete samples having 30% of its cement replaced by coarse OPA exhibit slightly lower drying shrinkage than the control mix. On the other hand, concrete samples containing fine OPA (d50 = 10.1 μm) at the same replacement level of 30% exhibit lower drying shrinkage readings than both the control mix and the mixes with coarse OPA. Tangchirapat and Jaturapitakkul [38] and Tangchirapat et al. [15] reason this reduction in drying shrinkage to the pozzolanic reaction and the packing effect of the fine OPA particles, hence, transforming the large pores into smaller pores and as a result reducing the

Added fine OPA (1% retained on a 45-μm sieve) to aerated concrete at an addition percentage of 20% by weight of cement reduced the drying shrinkage [21]. Drying shrinkage readings of aerated concrete samples containing OPA exhibit lesser drying shrinkage readings than the plain aerated concrete samples. The authors reason this reduction in drying shrinkage to the more compact paste caused by the pozzolanic activity of the fine OPA and to its packing effect.

Using fine OPA as a cement replacement delays the time for the concrete to reach its peak temperature [29]. Concrete specimens containing 30% fine OPA cement replacement is capable of causing a 15% reduction in peak temperature in comparison to the control mix [12, 21, 41]. Fine OPA and heat-treated fine OPA exhibit different behaviours when it comes to heat evolution [42]. Cement pastes containing fine-treated OPA emit a higher heat evolution temperature than the control paste. The researchers reason this raised temperature to the high pozzolanic activity of the treated fine OPA. On the other hand, fine OPA pastes emit lower

Table 4 summarises the studies that tested the effect of OPA on drying shrinkage.

control mix at 90 days of age.

by different porosity and pore distribution.

2.3.6. Drying shrinkage

moisture loss.

2.3.7. Heat evolution

Table 3. Summary of studies investigated the effect of OPA incorporation on compressive strength.

In another study conducted by Altwair et al. [24], engineering cementitious composites (ECCs) are tested for their flexural behaviour. These ECCs are designed to exhibit enhanced ductility and toughness; therefore, they use higher amounts of cementing materials and have their coarse aggregates eliminated from their design. The ECCs in this study used different amounts of added fine OPA 0, 0.4, 0.8 and 1.2 by weight of cement and used different water to binder ratios of 0.33, 0.36 and 0.38. The OPA that the authors use in this study was sieved through a 300-μm sieve, then ground using a ball mill and afterwards heat-treated at 450C for 90 min to eliminate any glassy phase crystallisation and agglomeration of the OPA particles. They state that an ECC mix containing OPA at 0.4 by weight of cement and water to binder ratio of 0.36 exhibits the highest flexural strength among the conducted ECC mixes. In addition, a decrease in flexural strengths is exhibited with increasing OPA content and increasing water to binder ratio. Furthermore, ECC mixes containing OPA at 0.4 and 0.8 by weight of cement and water to binder ratio of 0.33 exhibit higher flexural strengths than the control mix at 90 days of age.

#### 2.3.6. Drying shrinkage

Concrete samples containing cement replacements by OPA (sieved through a 150-μm) sieve show higher drying shrinkage readings than those exhibited by the control mix [25]. In addition, drying shrinkage is proportional to the increase in OPA content. Concrete samples with 50% of its cement replaced by OPA (sieved through a 45-μm sieve) exhibit a drying shrinkage reading higher by 21% than that of the control mix at the age of 90 days [32]. The authors reason this increase in drying shrinkage to the variation in moisture loss rate caused by different porosity and pore distribution.

Different sized OPA particles exhibit different readings of drying shrinkage [38]. At the age of 6 months, concrete samples having 30% of its cement replaced by coarse OPA exhibit slightly lower drying shrinkage than the control mix. On the other hand, concrete samples containing fine OPA (d50 = 10.1 μm) at the same replacement level of 30% exhibit lower drying shrinkage readings than both the control mix and the mixes with coarse OPA. Tangchirapat and Jaturapitakkul [38] and Tangchirapat et al. [15] reason this reduction in drying shrinkage to the pozzolanic reaction and the packing effect of the fine OPA particles, hence, transforming the large pores into smaller pores and as a result reducing the moisture loss.

Added fine OPA (1% retained on a 45-μm sieve) to aerated concrete at an addition percentage of 20% by weight of cement reduced the drying shrinkage [21]. Drying shrinkage readings of aerated concrete samples containing OPA exhibit lesser drying shrinkage readings than the plain aerated concrete samples. The authors reason this reduction in drying shrinkage to the more compact paste caused by the pozzolanic activity of the fine OPA and to its packing effect. Table 4 summarises the studies that tested the effect of OPA on drying shrinkage.

#### 2.3.7. Heat evolution

In another study conducted by Altwair et al. [24], engineering cementitious composites (ECCs) are tested for their flexural behaviour. These ECCs are designed to exhibit enhanced ductility and toughness; therefore, they use higher amounts of cementing materials and have their coarse aggregates eliminated from their design. The ECCs in this study used different amounts of added fine OPA 0, 0.4, 0.8 and 1.2 by weight of cement and used different water

Author(s) Particle size

Abdullah et al. [35] 1% retained on

Jaturapitakkul et al. [36] 183.0, 15.9, and

Tangchirapat et al. [17] 183.0, 15.9, and

Chindaprasirt et al. [23] 1–3% retained on

Hussin et al. [21] 1% retained on a

Lim et al. [31] Passing through a

Tay [25] Tay and Show [28]

124 Palm Oil

Rukzon and Chindaprasirt [26]

Tangchirapat and Jaturapitakkul [38] tested (μm)

Passing through a 150-μm sieve

Sata et al. [12] 10.0 10–30% by weight of

45-μm sieve

Sata et al. [29] 10.1 μm 10–30% by weight of

Chindaprasirt et al. [30] 10.2 μm 20, 40, and 55% by

45-μm sieve

55.0, 20.0, and 7.4 μm

Tangchirapat et al. [15] 10.1 μm 10–30% by weight of

Sata et al. [37] 9.2 μm 10–30% by weight of

45-μm sieve

Megat Johari et al. [18] 2.06 μm 20, 40, and 60% by

Sata et al. [39] 13 μm 10–40% by weight of

600-μm sieve

7.4

7.4

Replacement levels of OPA investigated

10–50% by weight of

10–50% by weight of

10–40% by weight of

weight of cement

20 and 40% by weight of cement

20 and 40% by weight of cement

10–40% by weight of

cement

cement

cement

cement

cement

cement

cement

cement

cement

Table 3. Summary of studies investigated the effect of OPA incorporation on compressive strength.

19.9 and 10.1 10–30% by weight of cement

20% by weight of cement

weight of cement

10 and 20% by weight of sand Tested median

Highstrength concrete

Aerated concrete

Highstrength concrete

Highstrength concrete

Aerated concrete

Highstrength concrete

Foamed concrete

Concrete BS 1881 10%

100 200-mm cylinders

BS1881:116 (70.6 mm3 )

100 200-mm cylinders

Concrete 100 200-mm cylinders

Concrete 100 200-mm cylinders

Concrete 100 200-mm cylinders

Mortar ASTM C109 (50mm<sup>3</sup> )

Mortar ASTM C39 20%

100 200-mm cylinders

BS 1881:116 20%

BSEN 12390–3 40%

BSEN 12390–3 10–20%

Mortar ASTM C109 10–20%

Concrete ASTM C39 10%

Concrete 100 200-mm cylinders

Standard Recommended particle

20%

10–30%

20%

20%

20%

7.4 μm to 20%

15.9 μm to 10% 7.4 μm to 20%

7.4 μm to 20%

19.9 μm to 20% 10.1 μm to 30%

size/replacement level

Using fine OPA as a cement replacement delays the time for the concrete to reach its peak temperature [29]. Concrete specimens containing 30% fine OPA cement replacement is capable of causing a 15% reduction in peak temperature in comparison to the control mix [12, 21, 41]. Fine OPA and heat-treated fine OPA exhibit different behaviours when it comes to heat evolution [42]. Cement pastes containing fine-treated OPA emit a higher heat evolution temperature than the control paste. The researchers reason this raised temperature to the high pozzolanic activity of the treated fine OPA. On the other hand, fine OPA pastes emit lower


replacement level of fine OPA as an outcome of their study. In another study, a 30% replacement level of cement by fine OPA (d50 = 10.1 μm) is recommended in achieving impermeable high-strength concrete [15]. The reduced permeability is attributed to the pozzolanic reaction and to the packing effect of fine OPA particles which results in filling the voids and increasing

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Concrete samples containing fine and coarse OPA replacement levels show a different behaviour when testing their permeability. Concrete samples containing coarse OPA as partial cement replacements are more permeable than the control mix at an earlier age but lower at later ages [38]. The higher permeability readings are attributed to the increased water to binder

In contrast to coarse OPA, concrete samples containing fine OPA replacement levels are less permeable than the control mix. Concrete samples containing recycled aggregate and fine OPA replacement level of 20% by weight of cement show that they are less permeable than the control mix [33]. High-strength concrete samples containing partial cement replacements at levels of 20, 40 and 60% by weight of cement by ultrafine OPA (d50 = 2.06 μm) are tested for their absorption, permeability and porosity [18]. The authors state that the incorporation of ultrafine OPA reduced the porosity of high-strength concrete, reduced its water absorption

Mortars containing OPA having 3 of fineness at replacement levels of 20 and 40% by weight of cement are tested for their carbonation ingress depth [26]. The fineness of OPA particles are coarse OPA (70% retained on a 45-μm sieve), medium OPA (15% retained on the 45-μm sieve) and fine OPA (3% retained on the 45-μm sieve). The carbonation ingress depth is conducted according to RILEM's CPC18, and readings are taken at the ages of 3, 7, 14, 28 and 60 days of age. In general, OPA mortars show an increase in carbonation depth in comparison to the control mortar. However, the behaviour of OPA mortars differs according to the fineness of OPA. Mortar samples containing fine OPA show less increase in carbonation ingress depth with increasing age than mortars containing medium sized and coarse OPA. The authors reason this decrease to the better dispersion and to the filler effect of fine OPA despite its higher pozzolanic activity. This made the mortars with finer OPA incorporations denser and

High-strength, high-workability concrete containing 10–30% OPA replacement levels by weight of cement are tested for their chloride penetration resistance and corrosion resistance [43]. The OPA used in this study has a median particle size of 20 μm. The chloride penetration test is conducted in accordance with ASTM 1202. Results for the chloride penetration show that chloride penetration decreases with an increasing OPA content. The authors reason this decrease in chloride penetration to the separation of large pores to the increase in nucleation sites caused by the increase in pozzolanic reaction products in the cement paste. The study states that replacing cement by fine OPA at a level of 30% by weight of cement shows increased resistance

ratio to achieve the same workability as that of the control mix.

and reduced the water permeability at the age of 28 days.

the density of the mix [30].

2.3.9. Carbonation

better to resist carbonation.

2.3.10. Chloride penetration and corrosion resistance

Table 4. Effect of OPA incorporation on drying shrinkage readings.

temperatures compared to that of the control paste. This is reasoned to the low pozzolanic activity of the fine OPA in comparison to the treated fine OPA. The reduced pozzolanic activity is due to the decreased content of glassy phases within the particles of fine OPA in comparison to that of the fine-treated OPA.

#### 2.3.8. Porosity, permeability and water absorption

Concrete samples containing OPA (sieved through a 150-μm sieve) show the tendency in absorbing more water with an increasing OPA content [25, 28]. Higher readings of water absorption are exhibited by concrete samples containing OPA as cement replacements in comparison to those exhibited by the control mix. The authors reason this increase in water absorption to the porous nature of concrete containing OPA. However, high-strength concrete containing fine OPA (10.1 μm) at a cement replacement level of 10% exhibits less water absorption readings than that of the control mix [43]. The authors reason this reduction in water absorption to a refined pore structure which results in a concrete sample with a reduced porosity.

High-strength concrete samples containing fine OPA (d50 = 8 μm) replacement levels of 20, 40 and 55% are tested for their water permeability by Chindaprasirt et al. [30]. At the ages of 28 and 90 days, high-strength concrete samples incorporating fine OPA at replacement levels of 20 and 40% by weight of cement exhibit less permeability readings than that of the control mix. In addition, samples containing fine OPA replacement levels show lower permeability readings, even though requiring higher water to binder ratios. The researchers recommend a 20% replacement level of fine OPA as an outcome of their study. In another study, a 30% replacement level of cement by fine OPA (d50 = 10.1 μm) is recommended in achieving impermeable high-strength concrete [15]. The reduced permeability is attributed to the pozzolanic reaction and to the packing effect of fine OPA particles which results in filling the voids and increasing the density of the mix [30].

Concrete samples containing fine and coarse OPA replacement levels show a different behaviour when testing their permeability. Concrete samples containing coarse OPA as partial cement replacements are more permeable than the control mix at an earlier age but lower at later ages [38]. The higher permeability readings are attributed to the increased water to binder ratio to achieve the same workability as that of the control mix.

In contrast to coarse OPA, concrete samples containing fine OPA replacement levels are less permeable than the control mix. Concrete samples containing recycled aggregate and fine OPA replacement level of 20% by weight of cement show that they are less permeable than the control mix [33]. High-strength concrete samples containing partial cement replacements at levels of 20, 40 and 60% by weight of cement by ultrafine OPA (d50 = 2.06 μm) are tested for their absorption, permeability and porosity [18]. The authors state that the incorporation of ultrafine OPA reduced the porosity of high-strength concrete, reduced its water absorption and reduced the water permeability at the age of 28 days.

#### 2.3.9. Carbonation

temperatures compared to that of the control paste. This is reasoned to the low pozzolanic activity of the fine OPA in comparison to the treated fine OPA. The reduced pozzolanic activity is due to the decreased content of glassy phases within the particles of fine OPA in

Median Effect Recommended replacement

mix

—

control mix

20%

10% replacement slightly increased the shrinkage strain but it does not adversely affect the change in volume of concrete

30% showed a lower drying shrinkage strain than the control

10–30% fine OPA exhibited a lower drying shrinkage than the

Concrete Drying shrinkage

Highstrength concrete

Aerated concrete increased with OPA replacement level

Decrease in drying shrinkage with increase in OPA level

Concrete OPA concrete samples showed a higher drying shrinkage than the control mix

Concrete Coarse OPA up to 30% exhibited similar shrinkage to that of the

control mix.

OPA aerated concrete exhibited less drying shrinkage strains than the control mix

Concrete samples containing OPA (sieved through a 150-μm sieve) show the tendency in absorbing more water with an increasing OPA content [25, 28]. Higher readings of water absorption are exhibited by concrete samples containing OPA as cement replacements in comparison to those exhibited by the control mix. The authors reason this increase in water absorption to the porous nature of concrete containing OPA. However, high-strength concrete containing fine OPA (10.1 μm) at a cement replacement level of 10% exhibits less water absorption readings than that of the control mix [43]. The authors reason this reduction in water absorption to a refined pore structure which results in a concrete sample with a reduced porosity. High-strength concrete samples containing fine OPA (d50 = 8 μm) replacement levels of 20, 40 and 55% are tested for their water permeability by Chindaprasirt et al. [30]. At the ages of 28 and 90 days, high-strength concrete samples incorporating fine OPA at replacement levels of 20 and 40% by weight of cement exhibit less permeability readings than that of the control mix. In addition, samples containing fine OPA replacement levels show lower permeability readings, even though requiring higher water to binder ratios. The researchers recommend a 20%

comparison to that of the fine-treated OPA.

Author (s) OPA particle

Tay [25] 100% passing

Tangchirapat et al. [15]

126 Palm Oil

Abdul Awal and Nguong [32]

Tangchirapat and Jaturapitakkul [38]

Hussien et al. [21]

size (μm)

sieve

through 150-μm

100% passing through 45-μm sieve

19.9 and 10.1 μm

99% passing through 45-μm sieve

10.1 μm 10–30% by

Replacement level investigated

10–50% by weight of cement

weight of cement

50% by weight of cement

10–30% by weight of cement

20% by weight of cement

Table 4. Effect of OPA incorporation on drying shrinkage readings.

2.3.8. Porosity, permeability and water absorption

Mortars containing OPA having 3 of fineness at replacement levels of 20 and 40% by weight of cement are tested for their carbonation ingress depth [26]. The fineness of OPA particles are coarse OPA (70% retained on a 45-μm sieve), medium OPA (15% retained on the 45-μm sieve) and fine OPA (3% retained on the 45-μm sieve). The carbonation ingress depth is conducted according to RILEM's CPC18, and readings are taken at the ages of 3, 7, 14, 28 and 60 days of age. In general, OPA mortars show an increase in carbonation depth in comparison to the control mortar. However, the behaviour of OPA mortars differs according to the fineness of OPA. Mortar samples containing fine OPA show less increase in carbonation ingress depth with increasing age than mortars containing medium sized and coarse OPA. The authors reason this decrease to the better dispersion and to the filler effect of fine OPA despite its higher pozzolanic activity. This made the mortars with finer OPA incorporations denser and better to resist carbonation.

#### 2.3.10. Chloride penetration and corrosion resistance

High-strength, high-workability concrete containing 10–30% OPA replacement levels by weight of cement are tested for their chloride penetration resistance and corrosion resistance [43]. The OPA used in this study has a median particle size of 20 μm. The chloride penetration test is conducted in accordance with ASTM 1202. Results for the chloride penetration show that chloride penetration decreases with an increasing OPA content. The authors reason this decrease in chloride penetration to the separation of large pores to the increase in nucleation sites caused by the increase in pozzolanic reaction products in the cement paste. The study states that replacing cement by fine OPA at a level of 30% by weight of cement shows increased resistance to corrosion. The authors reason this increase to the high pozzolanic reactivity of the fine OPA and to the reduced amount of calcium hydroxide in the paste. Although the 30% replacement level is effective in increasing chloride and corrosion resistance, the researchers recommend a 20% replacement level of cement by fine OPA. This is due to the increased quantity of superplasticizer required for the 30% OPA replacement mix to achieve the required workability, hence making the mix more expensive.

treatment to decrease the amounts of carbon within its particles. Although enhancing the properties of OPA is beneficial, these enhancing processes do apply increased cost. In addition, the problem with OPA is its increased demand of water when mixing. Therefore, controlling the water demand by applying superplasticizer is a good method in reducing its water demand, hence enhancing its properties. Researchers go further in the use of OPA and state that it is compulsory

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This chapter reviews the potential use of OPA as a supplementary cementing material for concrete production. The review emphasises the effects of POFA on the fresh, hardened and durability properties of concrete. Capitalising such waste products in the production of concrete will not only benefit the recycling chain process but also produce a green product which enables the reduction of cement quantities used and also produce an energy-efficient building

The authors gratefully acknowledge the financial support of the Ministry of Education Malay-

to use water-reducing agents when using OPA as the supplementary cementing material.

material. This is in line with the United Nation's Sustainable Development Goals.

\* and Mohammed Zuhear Al-Mulali<sup>2</sup>

1 Department of Building Technology, Universiti Sains Malaysia, Penang, Malaysia

2 Department of Building Technology, Al-Mustaqbal University College, Babylon, Iraq

[1] Sumathi S, Chai SP, Mohamed AR. Utilization of oil palm as a source of renewable energy in Malaysia. Renewable and Sustainable Energy Reviews. 2008;12(9):2404-2421

[2] Meher LC, Vidya Sagar D, Naik SN. Technical aspects of biodiesel production by transesterification—A review. Renewable and Sustainable Energy Reviews. 2006;10(3):

[3] Mekhilef S, Siga S, Saidur R. A review on palm oil biodiesel as a source of renewable fuel.

[4] Yusoff S. Renewable energy from palm oil–innovation on effective utilization of waste.

Renewable and Sustainable Energy Reviews. 2011;15(4):1937-1949

Journal of Cleaner Production. 2006;14(1):87-93

Acknowledgements

Author details

References

248-268

Hanizam Bt. Awang<sup>1</sup>

sia under FRGS (Ref. No. 203/PPBGN/6711610).

\*Address all correspondence to: hanizam@usm.my

However, a 60% cement replacement by ultrafine OPA (d50 = 2.06 μm) in high-strength concrete is more effective in resisting corrosion [18]. The 60% cement replacement by ultrafine OPA reduces the total charge passed in comparison to that of the control mix by 84%.

#### 2.3.11. Sulphate resistance and alkali silica reaction

Concrete bars containing fine OPA cement replacements are exposed to a 5% solution of magnesium sulphate (MgSo4) for 24 months. Results show that fine OPA concrete bars exhibit less expansion when exposed to the sulphate solution [36]. Finer OPA replacements not only cause the reduction of calcium hydroxide (Ca(OH)2) in the concrete but also reduce the voids between the aggregate and hydration products, creating a denser concrete. No adverse effect was found on the concrete expansion or on the compressive strength when replacing 20% of cement by fine OPA [15, 17]. High-strength concrete bars containing cement replacements of both 45- and 10-μm OPA are tested for their sulphate resistance and compressive strength loss [27]. The authors state that concrete bars containing 10-μm OPA show more resistance to sulphate attack and less reduction in compressive strength than those exhibited by the control and 45-μm concrete bars. The high sulphate resistance is attributed to the high pozzolanic reactivity of the finer OPA particles which in return reduces the Ca(OH)2 and reduces the amount of voids in the mix making it denser, hence, more resistant to sulphate attack. Concrete samples made from recycled aggregate show a higher resistance to sulphate attack when 20% of their cement is replaced by fine OPA [33]. The higher resistance in this case is also attributed to the reduced amounts of Ca(OH)2 and tricalcium aluminate (C3A) when cement is replaced by fine OPA, hence reducing gypsum formation and ettringite re-crystallisation.

Mortar bars containing OPA having a fineness of 519 m<sup>2</sup> /kg replacing cement levels of 10, 30 and 50% by weight of cement experience less expansion due to the alkali silica reaction (ASR) [19]. Increased suppressing of the ASR is observed with increasing OPA content. Abdul Awal and Hussin [19] reason this increased suppressing of the ASR to the pozzolanic reaction occurring between OPA's high amounts of silica with the alkalis existing in the concrete, hence limiting the amounts of alkalis reacting with aggregate.

#### 3. Conclusion

OPA is a relatively new pozzolanic material that has been introduced in partially replacing sand or cement in manufacturing concrete, mortar, aerated concrete and high-strength concrete. The studies discussed showed that OPA needed further processing in order for it to work as a pozzolan. The further processing includes grinding to increase the fineness of OPA and heat

treatment to decrease the amounts of carbon within its particles. Although enhancing the properties of OPA is beneficial, these enhancing processes do apply increased cost. In addition, the problem with OPA is its increased demand of water when mixing. Therefore, controlling the water demand by applying superplasticizer is a good method in reducing its water demand, hence enhancing its properties. Researchers go further in the use of OPA and state that it is compulsory to use water-reducing agents when using OPA as the supplementary cementing material.

This chapter reviews the potential use of OPA as a supplementary cementing material for concrete production. The review emphasises the effects of POFA on the fresh, hardened and durability properties of concrete. Capitalising such waste products in the production of concrete will not only benefit the recycling chain process but also produce a green product which enables the reduction of cement quantities used and also produce an energy-efficient building material. This is in line with the United Nation's Sustainable Development Goals.

## Acknowledgements

to corrosion. The authors reason this increase to the high pozzolanic reactivity of the fine OPA and to the reduced amount of calcium hydroxide in the paste. Although the 30% replacement level is effective in increasing chloride and corrosion resistance, the researchers recommend a 20% replacement level of cement by fine OPA. This is due to the increased quantity of superplasticizer required for the 30% OPA replacement mix to achieve the required workability,

However, a 60% cement replacement by ultrafine OPA (d50 = 2.06 μm) in high-strength concrete is more effective in resisting corrosion [18]. The 60% cement replacement by ultrafine

Concrete bars containing fine OPA cement replacements are exposed to a 5% solution of magnesium sulphate (MgSo4) for 24 months. Results show that fine OPA concrete bars exhibit less expansion when exposed to the sulphate solution [36]. Finer OPA replacements not only cause the reduction of calcium hydroxide (Ca(OH)2) in the concrete but also reduce the voids between the aggregate and hydration products, creating a denser concrete. No adverse effect was found on the concrete expansion or on the compressive strength when replacing 20% of cement by fine OPA [15, 17]. High-strength concrete bars containing cement replacements of both 45- and 10-μm OPA are tested for their sulphate resistance and compressive strength loss [27]. The authors state that concrete bars containing 10-μm OPA show more resistance to sulphate attack and less reduction in compressive strength than those exhibited by the control and 45-μm concrete bars. The high sulphate resistance is attributed to the high pozzolanic reactivity of the finer OPA particles which in return reduces the Ca(OH)2 and reduces the amount of voids in the mix making it denser, hence, more resistant to sulphate attack. Concrete samples made from recycled aggregate show a higher resistance to sulphate attack when 20% of their cement is replaced by fine OPA [33]. The higher resistance in this case is also attributed to the reduced amounts of Ca(OH)2 and tricalcium aluminate (C3A) when cement is replaced

OPA reduces the total charge passed in comparison to that of the control mix by 84%.

by fine OPA, hence reducing gypsum formation and ettringite re-crystallisation.

and 50% by weight of cement experience less expansion due to the alkali silica reaction (ASR) [19]. Increased suppressing of the ASR is observed with increasing OPA content. Abdul Awal and Hussin [19] reason this increased suppressing of the ASR to the pozzolanic reaction occurring between OPA's high amounts of silica with the alkalis existing in the concrete, hence

OPA is a relatively new pozzolanic material that has been introduced in partially replacing sand or cement in manufacturing concrete, mortar, aerated concrete and high-strength concrete. The studies discussed showed that OPA needed further processing in order for it to work as a pozzolan. The further processing includes grinding to increase the fineness of OPA and heat

/kg replacing cement levels of 10, 30

Mortar bars containing OPA having a fineness of 519 m<sup>2</sup>

limiting the amounts of alkalis reacting with aggregate.

3. Conclusion

hence making the mix more expensive.

128 Palm Oil

2.3.11. Sulphate resistance and alkali silica reaction

The authors gratefully acknowledge the financial support of the Ministry of Education Malaysia under FRGS (Ref. No. 203/PPBGN/6711610).

## Author details

Hanizam Bt. Awang<sup>1</sup> \* and Mohammed Zuhear Al-Mulali<sup>2</sup>

\*Address all correspondence to: hanizam@usm.my


## References


[5] Mahlia TMI, Abdulmuin MZ, Alamsyah TMI, Mukhlishien D. An alternative energy source from palm wastes industry for Malaysia and Indonesia. Energy Conversion and Management. 2001;42(18):2109-2118

[20] Ahmad MH, Omar RC, Malek MA, Noor NM and Thiruselvam S. Compressive strength of palm oil fuel ash concrete. In: International Conference on Construction and Building

The Inclusion of Palm Oil Ash Biomass Waste in Concrete: A Literature Review

http://dx.doi.org/10.5772/intechopen.76632

131

[21] Hussin MW, Muthusamy K, Zakaria F. Effect of mixing constituent toward engineering properties of pofa cement-based aerated concrete. Journal of Materials in Civil Engineer-

[22] Chandara C, Sakai E, Azizli KM, Ahmad ZA, Hashim SFS. The effect of unburned carbon in palm oil fuel ash on fluidity of cement pastes containing superplasticizer. Construction

[23] Chindaprasirt P, Rukzon S, Sirivivatnanon V. Resistance to chloride penetration of blended Portland cement mortar containing palm oil fuel ash, rice husk ash and fly ash.

[24] Altwair NM, Megat Johari MA, Saiyid Hashim SF. Flexural performance of green engineered cementitious composites containing high volume of palm oil fuel ash. Con-

[25] Tay JH. Ash from oil-palm waste as concrete material. Journal of Materials in Civil

[26] Rukzon S, Chindaprasirt P. Strength and chloride resistance of blended Portland cement mortar containing palm oil fuel ash and fly ash. International Journal of Minerals, Metal-

[27] Hussin MW, Ismail MA, Budiea A, Muthusamy K. Durability of high strength concrete containing palm oil fuel ash of different fineness. Malaysian Journal of Civil Engineering.

[28] Tay JH, Show KY. Use of ash derived from oil-palm waste incineration as a cement replacement material. Resources, Conservation and Recycling. 1995;13(1):27-36

[29] Sata V, Jaturapitakkul C, Kiattikomol K. Influence of pozzolan from various by-product materials on mechanical properties of high-strength concrete. Construction and Building

[30] Chindaprasirt P, Homwuttiwong S, Jaturapitakkul C. Strength and water permeability of concrete containing palm oil fuel ash and rice husk–bark ash. Construction and Building

[31] Lim SK, Tan CS, Lim OY, Lee YL. Fresh and hardened properties of lightweight foamed concrete with palm oil fuel ash as filler. Construction and Building Materials. 2013;4639-47

[32] Awal ASMA, Abubakar SI. Properties of concrete containing high volume palm oil fuel ash: A short-term investigation. Malaysian Journal of Civil Engineering. 2011;23:54-66 [33] Tangchirapat W, Khamklai S, Jaturapitakkul C. Use of ground palm oil fuel ash to improve strength, sulfate resistance, and water permeability of concrete containing high amount of

recycled concrete aggregates. Materials & Design. 2012;41(0):150-157

Technology ICCBT; 2008. pp. 297-306

and Building Materials. 2010;24(9):1590-1593

Construction and Building Materials. 2008;22(5):932-938

struction and Building Materials. 2012;37(0):518-525

ing. 2010;22:287-295

Engineering. 1990;2:94-105

2009;21:180-194

lurgy and Materials. 2009;16(4):475-481

Materials. 2007;21(7):1589-1598

Materials. 2007;21(7):1492-1499


[20] Ahmad MH, Omar RC, Malek MA, Noor NM and Thiruselvam S. Compressive strength of palm oil fuel ash concrete. In: International Conference on Construction and Building Technology ICCBT; 2008. pp. 297-306

[5] Mahlia TMI, Abdulmuin MZ, Alamsyah TMI, Mukhlishien D. An alternative energy source from palm wastes industry for Malaysia and Indonesia. Energy Conversion and

[6] Abdullah AZ, Salamatinia B, Mootabadi H, Bhatia S. Current status and policies on biodiesel industry in Malaysia as the world's leading producer of palm oil. Energy Policy.

[7] Sulaiman F, Abdullah N, Gerhauser H, Shariff A. An outlook of Malaysian energy, oil palm industry and its utilization of wastes as useful resources. Biomass and Bioenergy.

[8] Chiew YL, Iwata T, Shimada S. System analysis for effective use of palm oil waste as

[9] Shuit SH, Tan KT, Lee KT, Kamaruddin AH. Oil palm biomass as a sustainable energy

[10] Safiuddin M, Salam MA, Jumaat MZ. Utilization of palm oil fuel ash in concrete: A review.

[11] Dalimin MN. Renewable energy update: Malaysia. Renewable Energy. 1995;6(4):435-439

[12] Sata V, Jaturapitakkul C, Kiattikomol K. Utilization of palm oil fuel ash in high-strength

[13] Abdul Awal ASM, Warid HM. Effect of palm oil fuel ash in controlling heat of hydration

[14] Al-Mulali MZ, Awang H, Abdul Khalil HPS, Aljoumaily ZS. The incorporation of oil palm ash in concrete as a means of recycling: A review. Cement and Concrete Composites. 2015;

[15] Tangchirapat W, Jaturapitakkul C, Chindaprasirt P. Use of palm oil fuel ash as a supplementary cementitious material for producing high-strength concrete. Construction and

[16] Kroehong W, Sinsiri T, Jaturapitakkul C. Effect of palm oil fuel ash fineness on packing effect and pozzolanic reaction of blended cement paste. Procedia Engineering. 2011;14(0):

[17] Tangchirapat W, Saeting T, Jaturapitakkul C, Kiattikomol K, Siripanichgorn A. Use of waste ash from palm oil industry in concrete. Waste Management. 2007;27(1):81-88

[18] Megat Johari MA, Zeyad AM, Muhamad Bunnori N, Ariffin KS. Engineering and transport properties of high-strength green concrete containing high volume of ultrafine palm

[19] Awal ASMA, Hussin MW. The effectiveness of palm oil fuel ash in preventing expansion due to alkali-silica reaction. Cement and Concrete Composites. 1997;19(4):367-372

oil fuel ash. Construction and Building Materials. 2012;30(0):281-288

energy resources. Biomass and Bioenergy. 2011;35(7):2925-2935

source: A Malaysian case study. Energy. 2009;34(9):1225-1235

Journal of Civil Engineering and Management. 2011;17(2):234-247

concrete. Journal of Materials in Civil Engineering. 2004;16:623-628

of concrete. Procedia Engineering. 2011;14(0):2650-2657

Building Materials. 2009;23(7):2641-2646

Management. 2001;42(18):2109-2118

2009;37(12):5440-5448

130 Palm Oil

2011;35(9):3775-3786

55(0):129-138

361-369


[34] Abdullah K, Hussin MWI, Nordin N and Zakaria Z. Properties of aerated concrete containing various amount of palm oil fuel ash, water content and binder sand ratio. In: 2nd International Conference on Chemical, Biological and Environmental Engineering (ICBEE 2010); 2010. pp. 391-395

**Chapter 8**

**Provisional chapter**

**Mixture Proportioning for Oil Palm Kernel Shell**

**Mixture Proportioning for Oil Palm Kernel Shell**

DOI: 10.5772/intechopen.75601

Oil palm kernel shell (OPKS) is an organic lightweight aggregate (LWA) used as coarse aggregate in tropical countries for concrete in low-cost buildings. Concrete mixture proportioning is used to calculate the quantities of different constituents required to achieve different properties. For LWA concrete with mineral aggregate, there exist mix design methods that follow rigorous sequence of steps that consider performance specifications. However, no such method exists for concrete using organic coarse aggregate, namely, OPKS. The methods that exist for OPKS concrete that satisfy technical specifications for structural lightweight concrete (LWC) are based on trial and error or empirical methods. With trial and error method, it is not always possible to predict the value of specific properties of the concrete; however, engineers are mainly concerned with obtaining specific properties when proportioning a concrete mixture. The present topic presents a structured method for trial mix proportioning of structural LWC using OPKS as coarse aggregate. Based on the principle of the absolute volume method in ACI 213, the method is presented, following the below headings: (1) properties of constituents of OPKS concrete; (2) mix design procedure; and (3) results and discussion. Technicians in tropical oil-palm-

producing countries for low-cost buildings can use the presented method.

**Keywords:** lightweight concrete, mix proportioning, compressive strength, oil palm

The oil palm sector in the Republic of Benin is experiencing a revival since the last 10 years with a production estimated to be more than 505,000 tons in 2015 [1]. This production, according to the Ministry in charge of agriculture, is expected to increase to reach 800,000 tons by 2030. From

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

Mohamed Gibigaye and Gildas Fructueux Godonou

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.75601

Mohamed Gibigaye and Gildas Fructueux Godonou

**Abstract**

kernel shell, Benin

**1. Introduction**


#### **Mixture Proportioning for Oil Palm Kernel Shell Mixture Proportioning for Oil Palm Kernel Shell**

DOI: 10.5772/intechopen.75601

Mohamed Gibigaye and Gildas Fructueux Godonou Mohamed Gibigaye and Gildas Fructueux Godonou

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.75601

#### **Abstract**

[34] Abdullah K, Hussin MWI, Nordin N and Zakaria Z. Properties of aerated concrete containing various amount of palm oil fuel ash, water content and binder sand ratio. In: 2nd International Conference on Chemical, Biological and Environmental Engineering

[35] Abdullah K, Hussi MW, Zakaria F, Muhamad R, and Hamid ZA. Pofa: A potential partial cement replacement material in aerated concrete. In: Proceedings of the 6th Asia-Pacific

[36] Jaturapitakkul C, Kiattikomol K, Tangchirapat W, Saeting T. Evaluation of the sulfate resistance of concrete containing palm oil fuel ash. Construction and Building Materials.

[37] Sata V, Jaturapitakkul C, Rattanashotinunt C. Compressive strength and heat evolution of concretes containing palm oil fuel ash. Journal of Materials in Civil Engineering. 2010;22:

[38] Tangchirapat W, Jaturapitakkul C. Strength, drying shrinkage, and water permeability of concrete incorporating ground palm oil fuel ash. Cement and Concrete Composites. 2010;

[39] Sata V, Tangpagasit J, Jaturapitakkul C, Chindaprasirt P. Effect of W/B ratios on pozzolanic reaction of biomass ashes in Portland cement matrix. Cement and Concrete Compos-

[40] Eldagal OEA. Study on the Behaviour of High Strength Palm Oil Fuel Ash (pofa) Concrete

[41] Awal ASMA, Hussin MW. Influence of palm oil fuel ash in reducing heat of hydration of

[42] Chandara C, Mohd Azizli KA, Ahmad ZA, Saiyid Hashim SF, Sakai E. Heat of hydration of blended cement containing treated ground palm oil fuel ash. Construction and Building

[43] Chindaprasirt P, Chotetanorm C, Rukzon S. Use of palm oil fuel ash to improve chloride and corrosion resistance of high-strength and high-workability concrete. Journal of Mate-

Structural Engineering and Construction Conference; 2006. pp. 132-140

(ICBEE 2010); 2010. pp. 391-395

2007;21(7):1399-1405

1033-1038

132 Palm Oil

32(10):767-774

ites. 2012;34(1):94-100

Materials. 2012;27(1):78-81

rials in Civil Engineering. 2011;23:499-503

Project Report. 2008. Universiti Teknologi Malaysia

concrete. Journal of Civil Engineering (IEB). 2010;38:153-157

Oil palm kernel shell (OPKS) is an organic lightweight aggregate (LWA) used as coarse aggregate in tropical countries for concrete in low-cost buildings. Concrete mixture proportioning is used to calculate the quantities of different constituents required to achieve different properties. For LWA concrete with mineral aggregate, there exist mix design methods that follow rigorous sequence of steps that consider performance specifications. However, no such method exists for concrete using organic coarse aggregate, namely, OPKS. The methods that exist for OPKS concrete that satisfy technical specifications for structural lightweight concrete (LWC) are based on trial and error or empirical methods. With trial and error method, it is not always possible to predict the value of specific properties of the concrete; however, engineers are mainly concerned with obtaining specific properties when proportioning a concrete mixture. The present topic presents a structured method for trial mix proportioning of structural LWC using OPKS as coarse aggregate. Based on the principle of the absolute volume method in ACI 213, the method is presented, following the below headings: (1) properties of constituents of OPKS concrete; (2) mix design procedure; and (3) results and discussion. Technicians in tropical oil-palmproducing countries for low-cost buildings can use the presented method.

**Keywords:** lightweight concrete, mix proportioning, compressive strength, oil palm kernel shell, Benin

#### **1. Introduction**

The oil palm sector in the Republic of Benin is experiencing a revival since the last 10 years with a production estimated to be more than 505,000 tons in 2015 [1]. This production, according to the Ministry in charge of agriculture, is expected to increase to reach 800,000 tons by 2030. From

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

the industrial and artisanal transformation of this product, we obtain among others, oil palm kernel shells (OPKSs), considered as vegetable waste. In areas of production, traditionally near rural populations, OPKS is often used in the building of houses with and without multiple storeys. The OPKSs are used as coarse aggregate for the concrete of structural elements (**Figure 1**). To date, it is permissible to note the apparent good record of service of most of these buildings, constructed more than 30 years back. However, despite the wide availability of OPKSs, the lack of reliable technical information behind OPKS concrete making has led to reluctance by conventional professionals. For the moment, in Republic of Benin as in other oil-palm-producing countries, these materials have little commercial value, despite their technical qualities: (1) they have a relatively low weight and are naturally sized; (2) they are hard enough to break and are of organic origin; and (3) once embedded in the cement matrix of concrete, they do not have any toxic effects on the concrete because they are imputrescible [2]. Moreover, in some of the production areas, the OPKSs are recovered and burned in the cement industry under conditions that do not necessarily satisfy the requirements relating to good management of air pollution. As in Benin, OPKSs are available in large quantities in almost all tropical countries and the problem of managing OPKSs is posed almost in the same way. In such countries as Malaysia and Nigeria, several studies have been undertaken in the past 30 years with success in studying the mix design of structural lightweight concrete using OPKSs as aggregate [2–9]. Most mix design methods for OPKS concrete that satisfy the requirements of technical specifications for structural lightweight concrete were based on trial and error or on empirical methods because the methods based on the proven structured methods for normal and lightweight structural concrete with mineral aggregates had failed. With the trial and error method, it is not always possible to predict the value of specific properties of the concrete, whereas an engineer is mainly concerned with obtaining these specific properties in the process of proportioning a concrete mixture. To lead to that, one of the ways consists of the determination of ranges of values for the ratios of water/cement, cement/aggregates, coarse aggregate/fine aggregate, as well for the cement content that can permit to get the targeted specifications. Some results are available [10], but it is still necessary to work to further refine the range of values of the coarse/fine aggregate ratio in the process of designing structural lightweight concrete using OPKSs as coarse aggregate.

This approach is conducive to recommending mix proportions of concrete that allow its use for structural elements in low- and moderate-cost buildings in tropical countries and in earthquake-

Mixture Proportioning for Oil Palm Kernel Shell http://dx.doi.org/10.5772/intechopen.75601 135

OPKS concrete (OPKSC) is a judicious mix of cement, sand, OPKSs, and water. As the mechanical properties of OPKSC are largely influenced by the physical properties of OPKS, in the present chapter, the emphasis is on the study of the properties of OPKS. OPKSs used as coarse aggregate in OPKSC are one of the wastes produced during the process of obtaining palm oil. For that six stages are necessary: sterilization, threshing, pressing, depericarping, separation of kernel and shell, and clarification [11]. For the present study, the OPKSs used were collected from an artisanal mill at Missérété 6°35′43.4″N; 2°35′26.9″E and were freshly

They were thoroughly rinsed with potable water and dried in the sun for 4 h, in order to remove impurities, present on the shells. Then, they had been stored in containers. After the pretreatment, OPKS aggregate needs to be treated before using in concrete [12]. Various treatment processes are mentioned in the literature to remove the impurities (dust and oil coating)

• Put 30 kg of OPKS in an aqueous solution of potassium hydroxide with a mass concentra-

• Wash the shells with potable water in the sun, until the shells surface became dry.

**2. Properties of constituents of OPKS concrete**

In this study, the treatment method used consists of the following:

prone areas.

discarded (**Figure 2**).

from aggregates [13–18].

tion of 7.4 g/l for 2 h.

**Figure 2.** OPKS waiting for a transaction at Missérété.

In the present study, a trial mix is proposed for a structural lightweight concrete using OPKSs of Benin as coarse aggregate, based on the principle of absolute volume methodology of ACI 213.

**Figure 1.** An example of a one-storeyed house in Missérété, constructed in 2014 with the use of OPKS concrete for the supporting elements. (a) Overview of the ongoing building. (b) Zoom on the columns of the main facade, showing on their surface the oil palm kernel shells in the cement matrix.

This approach is conducive to recommending mix proportions of concrete that allow its use for structural elements in low- and moderate-cost buildings in tropical countries and in earthquakeprone areas.

## **2. Properties of constituents of OPKS concrete**

the industrial and artisanal transformation of this product, we obtain among others, oil palm kernel shells (OPKSs), considered as vegetable waste. In areas of production, traditionally near rural populations, OPKS is often used in the building of houses with and without multiple storeys. The OPKSs are used as coarse aggregate for the concrete of structural elements (**Figure 1**). To date, it is permissible to note the apparent good record of service of most of these buildings, constructed more than 30 years back. However, despite the wide availability of OPKSs, the lack of reliable technical information behind OPKS concrete making has led to reluctance by conventional professionals. For the moment, in Republic of Benin as in other oil-palm-producing countries, these materials have little commercial value, despite their technical qualities: (1) they have a relatively low weight and are naturally sized; (2) they are hard enough to break and are of organic origin; and (3) once embedded in the cement matrix of concrete, they do not have any toxic effects on the concrete because they are imputrescible [2]. Moreover, in some of the production areas, the OPKSs are recovered and burned in the cement industry under conditions that do not necessarily satisfy the requirements relating to good management of air pollution. As in Benin, OPKSs are available in large quantities in almost all tropical countries and the problem of managing OPKSs is posed almost in the same way. In such countries as Malaysia and Nigeria, several studies have been undertaken in the past 30 years with success in studying the mix design of structural lightweight concrete using OPKSs as aggregate [2–9]. Most mix design methods for OPKS concrete that satisfy the requirements of technical specifications for structural lightweight concrete were based on trial and error or on empirical methods because the methods based on the proven structured methods for normal and lightweight structural concrete with mineral aggregates had failed. With the trial and error method, it is not always possible to predict the value of specific properties of the concrete, whereas an engineer is mainly concerned with obtaining these specific properties in the process of proportioning a concrete mixture. To lead to that, one of the ways consists of the determination of ranges of values for the ratios of water/cement, cement/aggregates, coarse aggregate/fine aggregate, as well for the cement content that can permit to get the targeted specifications. Some results are available [10], but it is still necessary to work to further refine the range of values of the coarse/fine aggregate ratio in the process of designing structural lightweight concrete using OPKSs as coarse aggregate. In the present study, a trial mix is proposed for a structural lightweight concrete using OPKSs of Benin as coarse aggregate, based on the principle of absolute volume methodology of ACI 213.

134 Palm Oil

**Figure 1.** An example of a one-storeyed house in Missérété, constructed in 2014 with the use of OPKS concrete for the supporting elements. (a) Overview of the ongoing building. (b) Zoom on the columns of the main facade, showing on

their surface the oil palm kernel shells in the cement matrix.

OPKS concrete (OPKSC) is a judicious mix of cement, sand, OPKSs, and water. As the mechanical properties of OPKSC are largely influenced by the physical properties of OPKS, in the present chapter, the emphasis is on the study of the properties of OPKS. OPKSs used as coarse aggregate in OPKSC are one of the wastes produced during the process of obtaining palm oil. For that six stages are necessary: sterilization, threshing, pressing, depericarping, separation of kernel and shell, and clarification [11]. For the present study, the OPKSs used were collected from an artisanal mill at Missérété 6°35′43.4″N; 2°35′26.9″E and were freshly discarded (**Figure 2**).

They were thoroughly rinsed with potable water and dried in the sun for 4 h, in order to remove impurities, present on the shells. Then, they had been stored in containers. After the pretreatment, OPKS aggregate needs to be treated before using in concrete [12]. Various treatment processes are mentioned in the literature to remove the impurities (dust and oil coating) from aggregates [13–18].

In this study, the treatment method used consists of the following:


**Figure 2.** OPKS waiting for a transaction at Missérété.

**Figure 3.** Different size of Oil Palm Kernel Shell for the concrete mixing.

**Figure 4.** Curve of water absorption of the used OPKS.

Most of the shells were within the thickness range of 2.00–6.00 mm. The shape of the OPKS aggregate varies irregularly as flaky shaped, angular, or polygonal as shown in **Figure 3**. The surface texture of the shell was fairly smooth for both concave and convex faces. The broken edges were rough and spiky. To take into account the fact that the shells absorb water (**Figure 4**), we used them in saturated surface dry condition as shown in **Figure 5**. Particle size distribution for OPKS and sand are shown in **Figure 6**. The other measured physical properties of OPKS were compared with those obtained by previous authors and are shown in **Table 1**.

The lightweight concrete (LWC) mix design is usually established by trial mixes [19]. In the preliminary investigation of OPKS concrete mix proportion, the procedure followed was the

**3. Mix design procedure for OPKS concrete**

**Table 1.** Physical properties of constituents of OPKS concrete.

**Figure 6.** Particle size distribution of sand and OPKS.

AGGREGATES (SAND = Fine, OPKS=Coarse)

Loose bulk density (kg/m3

Aggregate abrasion value (Los

Angeles),%

**Properties Constituents of OPKS concrete** 

**from Benin**

Specific gravity 2.59 1.31 2.60 1.17

Water absorption, 24 h, (%) — 19.93 — 23.32 Fineness modulus 2,4 — 2.56 —

Type of cement CEM II 32.5 CEM I 42.5

**Constituents of OPKS concrete used** 

Mixture Proportioning for Oil Palm Kernel Shell http://dx.doi.org/10.5772/intechopen.75601 137

**elsewhere [10]**

Sand OPKS Sand OPKS

— 5.02 — 4.80

) 1410 530 — 500-600

**3.1. Trial mixture proportions**

**Figure 5.** Draining of OPKSC after imbibition to obtain saturated surface dry (SSD) status.

**Figure 6.** Particle size distribution of sand and OPKS.


**Table 1.** Physical properties of constituents of OPKS concrete.

Most of the shells were within the thickness range of 2.00–6.00 mm. The shape of the OPKS aggregate varies irregularly as flaky shaped, angular, or polygonal as shown in **Figure 3**. The surface texture of the shell was fairly smooth for both concave and convex faces. The broken edges were rough and spiky. To take into account the fact that the shells absorb water (**Figure 4**), we used them in saturated surface dry condition as shown in **Figure 5**. Particle size distribution for OPKS and sand are shown in **Figure 6**. The other measured physical properties of OPKS were compared with those obtained by previous authors and are shown in **Table 1**.

## **3. Mix design procedure for OPKS concrete**

#### **3.1. Trial mixture proportions**

**Figure 4.** Curve of water absorption of the used OPKS.

**Figure 3.** Different size of Oil Palm Kernel Shell for the concrete mixing.

136 Palm Oil

**Figure 5.** Draining of OPKSC after imbibition to obtain saturated surface dry (SSD) status.

The lightweight concrete (LWC) mix design is usually established by trial mixes [19]. In the preliminary investigation of OPKS concrete mix proportion, the procedure followed was the method for lightweight concrete proposed by Georges Dreux [20]. As mentioned in **Table 2**, the obtained cylindrical compressive strength was far below the targeted designed strength, and what that means is that the method is not appropriate for the mixing of structural lightweight concrete using OPKS.

According to [21], the best approach to making a first trial mixture of lightweight concrete, which has given properties and uses a particular aggregate from a lightweight aggregate source, is to use proportions previously established for a similar concrete using aggregate from the same aggregate source. Based on the similarity of the physical properties of the constituents of OPKS concrete (**Table 1**), in a second approach, the mix proportions proposed by Mannan [3] was used. The obtained results were presented in **Table 3**. The 28-day cylindrical compressive strength of 23.50 MPa obtained is greater than the 17 MPa required by ACI [22]. This shows that the said method of mix proportioning is suitable for mix design of structural lightweight concrete, using OPKS from Benin, and therefore can be recommended. Though effective, the method proposed by Mannan is a trial and error method. It does not give the flexibility to vary the mix ratio in order to change the technical specifications of the concrete in the event of need.

#### **3.2. Experimental method of mix proportioning**

According to ACI 213 [23], the absolute volume method considers that the volume of fresh concrete, produced by any combination of materials, is considered equal to the sum of the absolute volumes of cementitious materials, aggregate, net water, and entrapped air. The approach proposed by ACI 213 is based on the use of the indications of the ACI 211 [24], which is a method of mix proportioning, often used for concrete of normal weight aggregates. Mannan [3] has proven that this approach does not give good results for the mix design of structural lightweight OPKS aggregate. In this study, we agree to use the principle defined by said method, through its definition, that is to say:

$$V\_{\text{OKPS}} + V\_{\text{Sand}} + V\_{\text{Coment}} + V\_{\text{Water}} + V\_{\text{Air}} = 1\tag{1}$$

where *S* denotes the sand content in *kg*/*m*<sup>3</sup>

**Table 3.** Mix design for OPKS concrete according to [3].

sity (specific gravity) of the cement in *kg*/*m*<sup>3</sup>

(specific gravity) of the sand in *kg*/*m*<sup>3</sup>

**Proportion by weight of cement** 

**Cement Sand OPKS**

Compressive strength obtained by Mannan [3].

Compressive strength obtained by authors.

**(cement = 480 kg/m3**

(specific gravity) of the OPKS in *kg*/*m*<sup>3</sup>

contents range from 285 to 510 kg/m3

air volume *VAir* and the ratio *<sup>k</sup>*

cement content, *C*, and the *k*

classes from 400 to 550 kg/m3

of concrete, *C* denotes the cement content in *kg*/*m*<sup>3</sup>

B1 1.00 1.71 0.77 1890–1905 7 24.20<sup>a</sup> B2 1.00 1.71 0.77 1889–1941 9 23.50<sup>b</sup>

lightweight concrete. The obtained results were presented in **Table 4**.

of concrete, *ρ<sup>S</sup>*

of concrete.

with a step of 50 kg/m3

As the specific gravity of all constituents of the mix were known (see Section 2), the entrapped

previous authors [10, 25]. Thus, the only unknown quantities in the formula (Eq. (3)) were the

*OPKS* ratio from 0.50 to 0.75. Indeed, according to the practice of traditional use of OPKS concrete in Benin, the average value of this ratio is 0.6 for the mix proportion of structural

in *litres*/*m*<sup>3</sup>

a

b

**Mix order**

content = 530 kg/m3

**OPKS/Sand Ratio (by absolute volume)** **Mix proportion C:S:OPKS**

proportion by weight, C = cement, S = sand, OPKS = oil palm kernel shell].

**), w/c = 0.41**

the *k*

of concrete, *VAir* denotes the entrapped air content

of concrete, *ρ<sup>C</sup>*

of concrete, and *ρOPKS* denotes the mean particle density

**Fresh property (slump, mm)**

; we agreed in this study to vary the cement content

*<sup>W</sup>* were fixed, taking into account the values obtained by most of

*OPKS* ratio. Knowing that, according to Basri et al. [26], the cement

denotes the mean particle density

**28-Day compressive strength** 

Mixture Proportioning for Oil Palm Kernel Shell http://dx.doi.org/10.5772/intechopen.75601

> **Targeted design strength**

139

**(N/mm2 )**

**Obtained strength (EN12390-3)**

**Demoulded density** 

**Table 2.** Mix design for OPKS concrete according to Dreux [OPKS aggregates: saturated surface dry (SSD) conditions, bulk density = 0.53, specific gravity = 1.43; cement: CPJ 35 (type CEM II, 32.5), Density = 3.10, genuine class = 450 bar,

> **Demoulded density (kg/m3**

**) (NF EN 12350-6)**

; sand: Bulk density = 1.41, specific gravity = 2.63; w/c ratio = 0.48; wished slump = 5 cm; mix

**)**

**(kg/m3**

A1 2.1 1:1.05:1.21 1570.59 4.67 25.00 A2 1.6 1:1.26:1.09 1766.52 7.27 25.00 A3 1.0 1:1.64:0.89 1826.65 8.11 25.00 A4 0.8 1:1.82:0.79 1881.30 9.25 25.00 A5 0.6 1:2.04:0.67 1893.16 10.65 25.00

. For each class of cement, we varied

denotes the den-

**28-Day compressive strength (N/mm2)**

Using the specific gravity, the formula (Eq. (1)) can be rewritten:

$$\frac{C}{\rho\_c} + \frac{S}{\rho\_s} + \frac{W}{\rho\_W} + \frac{\text{OPKS}}{\rho\_{\text{OWS}}} + V\_{\text{Ar}} = 1 \tag{2}$$

By applying \_\_ *W <sup>C</sup>* <sup>=</sup> *<sup>k</sup> W* and \_\_\_\_\_ *OPKS <sup>S</sup>* <sup>=</sup> *<sup>k</sup> OPKS* we have:

$$
\mathcal{L}\left(\frac{1}{\rho\_c} + \frac{k\_w}{\rho\_w}\right) + \mathcal{S}\left(\frac{1}{\rho\_s} + \frac{k\_{\rm OWS}}{\rho\_{\rm OWS}}\right) + V\_{\rm Air} = 1
$$

$$
\mathcal{S} = \frac{(1 - V\_{\rm Air}) - \mathcal{C}\left(\frac{1}{\rho\_c} + \frac{k\_w}{\rho\_w}\right)}{\left(\frac{1}{\rho\_s} + \frac{k\_{\rm OWS}}{\rho\_{\rm OWS}}\right)}\tag{3}
$$


**Table 2.** Mix design for OPKS concrete according to Dreux [OPKS aggregates: saturated surface dry (SSD) conditions, bulk density = 0.53, specific gravity = 1.43; cement: CPJ 35 (type CEM II, 32.5), Density = 3.10, genuine class = 450 bar, content = 530 kg/m3 ; sand: Bulk density = 1.41, specific gravity = 2.63; w/c ratio = 0.48; wished slump = 5 cm; mix proportion by weight, C = cement, S = sand, OPKS = oil palm kernel shell].


**Table 3.** Mix design for OPKS concrete according to [3].

method for lightweight concrete proposed by Georges Dreux [20]. As mentioned in **Table 2**, the obtained cylindrical compressive strength was far below the targeted designed strength, and what that means is that the method is not appropriate for the mixing of structural light-

According to [21], the best approach to making a first trial mixture of lightweight concrete, which has given properties and uses a particular aggregate from a lightweight aggregate source, is to use proportions previously established for a similar concrete using aggregate from the same aggregate source. Based on the similarity of the physical properties of the constituents of OPKS concrete (**Table 1**), in a second approach, the mix proportions proposed by Mannan [3] was used. The obtained results were presented in **Table 3**. The 28-day cylindrical compressive strength of 23.50 MPa obtained is greater than the 17 MPa required by ACI [22]. This shows that the said method of mix proportioning is suitable for mix design of structural lightweight concrete, using OPKS from Benin, and therefore can be recommended. Though effective, the method proposed by Mannan is a trial and error method. It does not give the flexibility to vary the mix ratio in order to change the technical specifications of the concrete in the event of need.

According to ACI 213 [23], the absolute volume method considers that the volume of fresh concrete, produced by any combination of materials, is considered equal to the sum of the absolute volumes of cementitious materials, aggregate, net water, and entrapped air. The approach proposed by ACI 213 is based on the use of the indications of the ACI 211 [24], which is a method of mix proportioning, often used for concrete of normal weight aggregates. Mannan [3] has proven that this approach does not give good results for the mix design of structural lightweight OPKS aggregate. In this study, we agree to use the principle defined by

*VOKPS* + *VSand* + *VCement* + *VWater* + *VAir* = 1 (1)

+ \_\_\_\_\_ *OPKS ρOPKS*

> \_\_1 *ρS* + *k* \_\_\_\_ *OPKS*

( \_\_1 *ρS* + *k* \_\_\_\_ *OPKS ρOPKS*)

*<sup>ρ</sup>OPKS*) <sup>+</sup> *VAir* <sup>=</sup> <sup>1</sup>

\_\_1 *ρC* + *k* \_\_\_*W ρW*)

\_\_\_\_\_\_\_\_\_\_\_\_\_\_

+ *VAir* = 1 (2)

(3)

weight concrete using OPKS.

138 Palm Oil

**3.2. Experimental method of mix proportioning**

said method, through its definition, that is to say:

\_\_*<sup>C</sup>*

*W* and \_\_\_\_\_ *OPKS <sup>S</sup>* <sup>=</sup> *<sup>k</sup>*

*<sup>S</sup>* <sup>=</sup> (<sup>1</sup> <sup>−</sup> *VAir*) <sup>−</sup> *<sup>C</sup>*(

*W <sup>C</sup>* <sup>=</sup> *<sup>k</sup>*

*C*(

By applying \_\_

Using the specific gravity, the formula (Eq. (1)) can be rewritten:

*ρC* + \_\_*<sup>S</sup> ρS* + \_\_\_ *<sup>W</sup> ρW*

\_\_1 *ρC* + *k* \_\_\_*W <sup>ρ</sup>W*) <sup>+</sup> *<sup>S</sup>*(

*OPKS* we have:

where *S* denotes the sand content in *kg*/*m*<sup>3</sup> of concrete, *VAir* denotes the entrapped air content in *litres*/*m*<sup>3</sup> of concrete, *C* denotes the cement content in *kg*/*m*<sup>3</sup> of concrete, *ρ<sup>C</sup>* denotes the density (specific gravity) of the cement in *kg*/*m*<sup>3</sup> of concrete, *ρ<sup>S</sup>* denotes the mean particle density (specific gravity) of the sand in *kg*/*m*<sup>3</sup> of concrete, and *ρOPKS* denotes the mean particle density (specific gravity) of the OPKS in *kg*/*m*<sup>3</sup> of concrete.

As the specific gravity of all constituents of the mix were known (see Section 2), the entrapped air volume *VAir* and the ratio *<sup>k</sup> <sup>W</sup>* were fixed, taking into account the values obtained by most of previous authors [10, 25]. Thus, the only unknown quantities in the formula (Eq. (3)) were the cement content, *C*, and the *k OPKS* ratio. Knowing that, according to Basri et al. [26], the cement contents range from 285 to 510 kg/m3 ; we agreed in this study to vary the cement content classes from 400 to 550 kg/m3 with a step of 50 kg/m3 . For each class of cement, we varied the *k OPKS* ratio from 0.50 to 0.75. Indeed, according to the practice of traditional use of OPKS concrete in Benin, the average value of this ratio is 0.6 for the mix proportion of structural lightweight concrete. The obtained results were presented in **Table 4**.


**4. Results and discussion**

for cement contents of at least 500 kg/m3

for the cement content of 400 kg/m3

cement classes. The cement contents of 400 and 450 kg/m3

Slump values for cement content of 450, 500, and 550 kg/m3

The workability increased with increasing cement content and sand content but not for all

more than 70% in weight for the solid part of the concrete mix, and in the same moment,

that is to say, more the quantity of OPKSs is, the lower is the workability. This is due to the increase of the specific surface because of the increase in the quantity of OPKSs, thus requiring more water to make the specimens workable. This trend was mentioned elsewhere [5].

range of recommended values for structural lightweight concrete according to ACI 211. 2–98 [24], that is to say, 25.4–101.6 mm. The low value of the workability (slump less than 10 mm)

the cavities and the pores of OPKSs no longer permits to have the needed quantity of cement paste, which allows for good workability. On the other hand, for cement contents higher

the logic of the growth of the slump value according to the decrease of the OPKS quantity as

recommendable range values of OPKS/sand ratio could be in the range of 0.50–0.65 by weight. Thus, to obtain the minimum recommendable values of slump for various types of constructions according to Table 3.1 of [24], the mix ratios designated by C7, C8, C9, and C10 in **Table 4**

In this investigation, we determined the 28-day air-dry density of the specimens, which were kept in ambient laboratory conditions (RH of 74–88%; temp. of 27 ± 2°C). The results were

saying that all the mix proportions were those for lightweight concretes. From **Table 4**, it can be seen that, in each cement content class, the density decreases as the proportion of

tural lightweight concrete, according to Mindess [16]. Thus, it appears that except the sand, the cement content is also a parameter influencing the density of OPKS concrete. Taking into account the results of workability (Section 4.1) and the maximum value of 1900 kg/m3

we could recommend the mix proportions of C7, C8, C9, and C10, with cement content of

and w/c = 0.45 to achieve a density which corresponds to the requirements of

. Mixtures with cement content equal to or higher than 500 kg/m3

Therefore, the optimal cement content relative to the workability would be 450 kg/m3

could be the suitable ones. Note that the ratio of water/cement was 0.45.

shown in **Table 4**. Note that all densities obtained are less than 2000 kg/m3

shells increases, with a maximum value of almost 1880 kg/m3

, the variation of the slump value versus OPKS/sand ratio, does not follow

of concrete, the workability decreases with the increase in the quantity of OPKSs,

gave for each OPKS/sand ratio,

Mixture Proportioning for Oil Palm Kernel Shell http://dx.doi.org/10.5772/intechopen.75601 141

were included mostly in the

, and the

, which allows

had a maximum

,

for cement content of 400 and

, the said quantity was lower than 70%. For 400 and

could be because the quantity of mortar that penetrates

, which is above the maximum value of the density for struc-

**4.1. Workability**

450 kg/m3

than 450 kg/m3

**4.2. Density**

450 kg/m3

450 kg/m3

density of more than 1900 kg/m3

structural lightweight concrete.

proven also by [5, 27].

**Table 4.** Mix design for OPKS concrete based on the variation of the OPKS/Sand ratio and the cement content [w/c=0.45; Stage of OPKS=saturated surface dry; Mix proportion by weight].

## **4. Results and discussion**

#### **4.1. Workability**

**Mix order**

140 Palm Oil

**Cement content**

(kg/m3

**OPKS/Sand ratio**

) C:S:OPKS (kg/m3

C1 0.50 1:2.10:1.05 1872.63 8.5 8.35 C2 400 0.55 1:2.00:1.10 1875.44 7.92 6.14 C3 0.60 1:1.91:1.15 1838.74 6.23 8.91 C4 0.65 1:1.83:1.19 1829.82 5.1 11.22 C5 0.70 1:1.75:1.23 1811.33 4.7 12.03 C6 0.75 1:1.68:1.26 1789.50 3.86 10.70

C7 450 0.50 1:1.76:0.88 1859.40 34.50 10.80 C8 0.55 1:1.67:0.92 1876.81 30.35 13.54 C9 0.60 1:1.60:0.96 1840.09 26.98 15.19 C10 0.65 1:1.53:0.99 1843.79 22.01 18.63 C11 0.70 1:1.47:1.03 1790.92 16.38 9.58 C12 0.75 1:1.41:1.06 1759.35 16.25 9.44

C13 0.45 1:1.56:0.70 1895.35 47.07 12.38 C14 500 0.50 1:1.48:0.74 1887.08 42.36 18.27 C15 0.55 1:1.41:0.78 1901.31 51.12 12.21 C16 0.60 1:1.35:0.81 1879.85 52.67 12.09 C17 0.65 1:1.29:0.84 1849.70 48.16 13.50 C18 0.70 1:1.24:0.86 1798.10 27.07 10.03

C19 550 0.40 1:1.40:0.56 1920.86 86.84 14.91 C20 0.45 1:1.32:0.60 1857.09 125.01 15.36 C21 0.50 1:1.26:0.63 1892.48 80.4 17.54 C22 0.55 1:1.20:0.66 1893.12 80.60 12.28 C23 0.60 1:1.14:0.69 1866.81 77.15 12.21 C24 0.65 1:1.09:0.71 1851.51 83.09 12.21

Stage of OPKS=saturated surface dry; Mix proportion by weight].

**Mix proportion Demoulded** 

0.45 — — — —

0.40 — — — — 0.45 — — — —

0.40 — — — —

0.75 — — — —

0.70 — — — — 0.75 — — — —

**Table 4.** Mix design for OPKS concrete based on the variation of the OPKS/Sand ratio and the cement content [w/c=0.45;

**density**

**Fresh property**

) (Slump, mm)

**Average Cylindrical 28-day Compressive** 

), 28-day

**strength**

(N/mm2

The workability increased with increasing cement content and sand content but not for all cement classes. The cement contents of 400 and 450 kg/m3 gave for each OPKS/sand ratio, more than 70% in weight for the solid part of the concrete mix, and in the same moment, for cement contents of at least 500 kg/m3 , the said quantity was lower than 70%. For 400 and 450 kg/m3 of concrete, the workability decreases with the increase in the quantity of OPKSs, that is to say, more the quantity of OPKSs is, the lower is the workability. This is due to the increase of the specific surface because of the increase in the quantity of OPKSs, thus requiring more water to make the specimens workable. This trend was mentioned elsewhere [5].

Slump values for cement content of 450, 500, and 550 kg/m3 were included mostly in the range of recommended values for structural lightweight concrete according to ACI 211. 2–98 [24], that is to say, 25.4–101.6 mm. The low value of the workability (slump less than 10 mm) for the cement content of 400 kg/m3 could be because the quantity of mortar that penetrates the cavities and the pores of OPKSs no longer permits to have the needed quantity of cement paste, which allows for good workability. On the other hand, for cement contents higher than 450 kg/m3 , the variation of the slump value versus OPKS/sand ratio, does not follow the logic of the growth of the slump value according to the decrease of the OPKS quantity as proven also by [5, 27].

Therefore, the optimal cement content relative to the workability would be 450 kg/m3 , and the recommendable range values of OPKS/sand ratio could be in the range of 0.50–0.65 by weight.

Thus, to obtain the minimum recommendable values of slump for various types of constructions according to Table 3.1 of [24], the mix ratios designated by C7, C8, C9, and C10 in **Table 4** could be the suitable ones. Note that the ratio of water/cement was 0.45.

#### **4.2. Density**

In this investigation, we determined the 28-day air-dry density of the specimens, which were kept in ambient laboratory conditions (RH of 74–88%; temp. of 27 ± 2°C). The results were shown in **Table 4**. Note that all densities obtained are less than 2000 kg/m3 , which allows saying that all the mix proportions were those for lightweight concretes. From **Table 4**, it can be seen that, in each cement content class, the density decreases as the proportion of shells increases, with a maximum value of almost 1880 kg/m3 for cement content of 400 and 450 kg/m3 . Mixtures with cement content equal to or higher than 500 kg/m3 had a maximum density of more than 1900 kg/m3 , which is above the maximum value of the density for structural lightweight concrete, according to Mindess [16]. Thus, it appears that except the sand, the cement content is also a parameter influencing the density of OPKS concrete. Taking into account the results of workability (Section 4.1) and the maximum value of 1900 kg/m3 , we could recommend the mix proportions of C7, C8, C9, and C10, with cement content of 450 kg/m3 and w/c = 0.45 to achieve a density which corresponds to the requirements of structural lightweight concrete.

#### **4.3. Compressive strength**

From the results presented in **Table 4**, it can be noted that for every class of cement content, the 28-day cylindrical compressive strength increased to attain a maximum value, before it decreased, depending on the quantity of shells in the concrete mix. The cement content of 400 kg/m3 showed a maximum of 28-day cylindrical compressive strength of 11.22 MPa for OPKS/sand ratio equal to 0.65, corresponding to almost 27% of OPKS in the rigid part of the concrete. For 450 kg/m3, we recorded the greatest value of the 28-day cylindrical compressive strength of 18.63 MPa, corresponding to 447.36 kg of OPKS in 1 m3 of concrete. This content is in the rangeof values (290–450 kg) for OPKS in structural lightweight concrete, as reported by [25]. The value of 18.63 MPa is higher than the specified cylindrical compressive strength of 17 MPa given by ACI. Relative to cement contents of 500 and 550 kg/m3 , the maximum values of the 28-day cylindrical compressive strength were, respectively 18.27 and 17.54 MPa, and the corresponding OPKS/sand ratio was 0.5, which corresponds to almost 20% of OPKS in the rigid part of the concrete.

**4.** Determine the cement content [10] in the range of 400 to 550 kg/m3

LWC, obtained from the data of previous authors as reported by [10], for concrete without admixture.

**Author (year) as cited by [10] Mix proportion Water/cement 28-day compressive strength (MPa)**

1:2:4 0.50 18.90

**6.** Determine the air content ratio [12] in the range from 4.8 to 5.1

*<sup>S</sup>* <sup>=</sup> (<sup>1</sup> <sup>−</sup> *VAir*) <sup>−</sup> *<sup>C</sup>*(1/*ρ<sup>C</sup>* <sup>+</sup> *kW*/*ρW*) \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ (1/*ρ<sup>S</sup>* <sup>+</sup> *kOPKS* /*ρOPKS*)

**5.** Determine the OPKS/sand ratio depending on the targeted slump value and the 28-day

**Table 5.** Water/cement ratio for compressive strength (≥ 15 MPa), recommended by ACI and British code for structural

**9.** Make a test mixture with sufficient volume to perform the "slump test" coming to 0.008 m3

sand and OPKSs by 5–15% without changing the ratio of OPKS/sand.

that is to say 8 l. If the slump is smaller than the one specified above, then increase the amount of cement and water between 5% and 15%, while respecting the ratio w/c as indicated earlier. If the slump is larger than indicated in the data, then increase the amount of

If despite all the operator does not obtain the results, then review the calculations and

obtain precisely again the characteristics of the materials constituting the concrete.

The mix proportions of C:S:OPKS in weight of 1:1.60:0.96 and 1:1.53:0.99 with cement content

and *w*/*c* = 0.45 had resulted in obtaining appropriate values for workability (≥ 20*mm*),

), and cylindrical compressive strength (≥ 15*MPa*), recommended by ACI

value and the 28-day compressive strength.

Abdullah (1984) 1:2:0.6 0.40 20.50 Okafor (1988) 1:1.70:2.08 0.48 23.00 Okpala (1990) 1:1:2 0.50 22.30

Teo and Lew (2006) 1:1.12:0.80 0.41 22.00

compressive strength.

**7.** Calculate the sand content for 1 m3

Range for water/cement ratio is from 0.40 to 0.50.

**8.** Determine the OPKS content for 1 m3

volume method of ACI 213:

content determined earlier.

**10.** Calculate the final mix proportion

**5. Conclusion**

density (1800 ≤ *d* ≤ 1900*kg*/*m*<sup>3</sup>

of 450 *kg*/*m*<sup>3</sup>

based on the slump

Mixture Proportioning for Oil Palm Kernel Shell http://dx.doi.org/10.5772/intechopen.75601 143

,

of concrete, based on the principles of the absolute

of concrete, using the OPKS/sand ratio and sand

The developing of the compressive strength of the concrete with cement content less than 500 kg/m3 was influenced by the amount of OPKS in the concrete mix, with a maximum value of up to 27% of the rigid part of the concrete. For these cement contents, the compressive strength is controlled by the strength of the shells [28]. During the compressive strength test, it is observed that the cement matrix failed first, which is to say that, the cracks path passed around OPKS aggregates. For cement contents of 500 and 550 kg/m3 , the compressive strength was influenced by the strength of the cement matrix and contrary to 400 and 450 kg/m3 , the cracks path passed through the shells of the concrete.

Thus, to produce economically structural lightweight concrete using OPKS as coarse aggregate and taking into account the recommended mix proportions for good workability and acceptable density, the mix ratios of C9 and C10 could be suggested. They could give the possibility to an engineer to fix efficiently the targeted values of specific properties in the mix proportioning of lightweight concrete, using OPKS as coarse aggregate.

#### **4.4. OPKS concrete mixing proportioning process**

Taking into account the results obtained earlier, we could recommend a general mixture proportioning procedure as follows [9]:



**Table 5.** Water/cement ratio for compressive strength (≥ 15 MPa), recommended by ACI and British code for structural LWC, obtained from the data of previous authors as reported by [10], for concrete without admixture.


$$S\_{\circ} = \frac{\left(1 - V\_{\text{Air}}\right) - C \left(1/\rho\_{\text{c}} + k\_{\text{W}}/\rho\_{\text{W}}\right)}{\left(1/\rho\_{\text{s}} + k\_{\text{OPKS}}/\rho\_{\text{OPKS}}\right)}$$


If despite all the operator does not obtain the results, then review the calculations and obtain precisely again the characteristics of the materials constituting the concrete.

**10.** Calculate the final mix proportion

## **5. Conclusion**

**4.3. Compressive strength**

rigid part of the concrete.

400 kg/m3

142 Palm Oil

500 kg/m3

From the results presented in **Table 4**, it can be noted that for every class of cement content, the 28-day cylindrical compressive strength increased to attain a maximum value, before it decreased, depending on the quantity of shells in the concrete mix. The cement content of

OPKS/sand ratio equal to 0.65, corresponding to almost 27% of OPKS in the rigid part of the concrete. For 450 kg/m3, we recorded the greatest value of the 28-day cylindrical compressive

in the rangeof values (290–450 kg) for OPKS in structural lightweight concrete, as reported by [25]. The value of 18.63 MPa is higher than the specified cylindrical compressive strength of

of the 28-day cylindrical compressive strength were, respectively 18.27 and 17.54 MPa, and the corresponding OPKS/sand ratio was 0.5, which corresponds to almost 20% of OPKS in the

The developing of the compressive strength of the concrete with cement content less than

of up to 27% of the rigid part of the concrete. For these cement contents, the compressive strength is controlled by the strength of the shells [28]. During the compressive strength test, it is observed that the cement matrix failed first, which is to say that, the cracks path passed

was influenced by the strength of the cement matrix and contrary to 400 and 450 kg/m3

Thus, to produce economically structural lightweight concrete using OPKS as coarse aggregate and taking into account the recommended mix proportions for good workability and acceptable density, the mix ratios of C9 and C10 could be suggested. They could give the possibility to an engineer to fix efficiently the targeted values of specific properties in the mix

Taking into account the results obtained earlier, we could recommend a general mixture pro-

**1.** Establish the specific properties of the lightweight OPKSC for structural elements in low-

**2.** Determine the physical properties of constituents of concrete based on the applicable codes. For sand, we consider specific gravity, loose bulk density, fineness of modulus, and grading curve. For OPKS, we consider specific gravity, loose bulk density, water absorp-

**3.** Choose the water/cement ratio based on the targeted 28-day compressive strength using

cost buildings: slump [24], density [10], and 28-day compressive strength [29].

was influenced by the amount of OPKS in the concrete mix, with a maximum value

strength of 18.63 MPa, corresponding to 447.36 kg of OPKS in 1 m3

17 MPa given by ACI. Relative to cement contents of 500 and 550 kg/m3

around OPKS aggregates. For cement contents of 500 and 550 kg/m3

proportioning of lightweight concrete, using OPKS as coarse aggregate.

tion after 24 h, aggregate abrasion value, and grading curve.

the data from previous authors [10], as presented in **Table 5**.

cracks path passed through the shells of the concrete.

**4.4. OPKS concrete mixing proportioning process**

portioning procedure as follows [9]:

showed a maximum of 28-day cylindrical compressive strength of 11.22 MPa for

of concrete. This content is

, the maximum values

, the compressive strength

, the

The mix proportions of C:S:OPKS in weight of 1:1.60:0.96 and 1:1.53:0.99 with cement content of 450 *kg*/*m*<sup>3</sup> and *w*/*c* = 0.45 had resulted in obtaining appropriate values for workability (≥ 20*mm*), density (1800 ≤ *d* ≤ 1900*kg*/*m*<sup>3</sup> ), and cylindrical compressive strength (≥ 15*MPa*), recommended by ACI and British Code for structural lightweight concrete. This study, as part of efforts to develop a structured method of proportioning of eco-friendly composite, demonstrates the possibility of linking mix proportions to properties of lightweight OPKS concrete and therefore makes the use of locally available materials in developing countries more feasible.

[6] Yong M, Liu J, Alengaram UJ, Santhanam M, Zamin M, Hung K. Microstructural investigations of palm oil fuel ash and fly ash based binders in lightweight aggregate foamed geopolymer concrete. Construction and Building Materials. 2016;**120**:112-122. DOI: 10.1016/

Mixture Proportioning for Oil Palm Kernel Shell http://dx.doi.org/10.5772/intechopen.75601 145

[7] Zulkarnain F, Sulieman MZ, Serri E. The effect of mix design on mechanical and thermal properties oil palm Shell (OPS) lightweight concrete. Journal of Civil Engineering

[8] Teo DCL, Mannan MA, Kurian VJ, Ganapathy C. Lightweight concrete made from oil palm shell (OPS): Structural bond and durability properties. Building and Environment.

[9] Gibigaye M, Godonou GF, Katte R, Degan G. Structured mixture proportioning for oil palm kernel shell concrete, case stud. Construction Materials. 2017;**6**:219-224. DOI: 10.1016/

[10] Alengaram UJ, Abdullah B, Muhit A, Zamin M. Utilization of oil palm kernel shell as lightweight aggregate in concrete—A review. Construction and Building Materials. 2013;

[11] Abdullah AA, Palm oil shell aggregate for lightweight concrete. In: Chandra S. Waste

[12] Mannan MA, Ganapathy C. Concrete from an agricultural waste-oil palm shell (OPS). Building and Environment. 2004;**39**:441-448. DOI: 10.1016/j.buildenv.2003.10.007

[13] Spratt BH. The Structural Use of Lightweight Aggregate Concrete. The TRIS and ITRD

[14] Mohd Noor M, Jusoh A, Ghazali A. Management and Utilisation of Oil Palm Wastes—A Review. Malaysia: Regional Information Centre on the Management and Utilisation of

[15] Okafor F, Eze-Uzomaka O, Egbuniwe N. The structural properties and optimum mix proportions of palmnut 9bre-reinforced mortar composite. Cement and Concrete Research.

[17] Salam SA. Lightweight concrete made from palm oil shell aggregates and rice husk. In: Proceeding. A Regional Seminar, Universiti Putra, Malaysia; 15-17 September; 1982.

[18] ShortA, KinniburghW.Lightweight Concrete, 3rd ed. London: Applied Science Publishers;

[19] Shetty SM. Concrete technology theory and practice. In: Chand S, editor. 3rd Multicolor

[16] Mindess S, Young JF. Concrete. Englewood Cliffs, NJ: Prentice Hall; 1981

[20] Dreux G. Nouveau guide du béton [ouvrage]. Paris: Eyrolles; 1981

Mater. New York: Use Concrete Manufacturers, Noyes Publications; 1997

Research and Practice. 2014;**4**:203-207. DOI: 10.5923/c.jce.201402.34

2007;**42**:2614-2621. DOI: 10.1016/j.buildenv.2006.06.013

**38**:161-172. DOI: 10.1016/j.conbuildmat.2012.08.026

wastes, Universiti Putra Malaysia; 1990

Illustrative. Revised edition. India; 2005

j.conbuildmat.2016.05.076

j.cscm.2017.04.004

database; 1974

1996;**26**:45-55

pp. 177-196

1978

## **Acknowledgements**

We would like to thank the managers of the Djaouley Consulting Engineers (DIC-BTP) for the logistical, material, and financial support we received during the various laboratory experiences and office works.

## **Conflict of interest**

There is no conflict of interest in this submission.

## **Author details**

Mohamed Gibigaye\* and Gildas Fructueux Godonou

\*Address all correspondence to: gibigaye\_mohamed@yahoo.fr

Department of Civil Engineering, University of Abomey-Calavi, Abomey-Calavi, Republic of Benin

## **References**


[6] Yong M, Liu J, Alengaram UJ, Santhanam M, Zamin M, Hung K. Microstructural investigations of palm oil fuel ash and fly ash based binders in lightweight aggregate foamed geopolymer concrete. Construction and Building Materials. 2016;**120**:112-122. DOI: 10.1016/ j.conbuildmat.2016.05.076

and British Code for structural lightweight concrete. This study, as part of efforts to develop a structured method of proportioning of eco-friendly composite, demonstrates the possibility of linking mix proportions to properties of lightweight OPKS concrete and therefore makes the use

We would like to thank the managers of the Djaouley Consulting Engineers (DIC-BTP) for the logistical, material, and financial support we received during the various laboratory experi-

of locally available materials in developing countries more feasible.

**Acknowledgements**

144 Palm Oil

ences and office works.

**Conflict of interest**

**Author details**

Republic of Benin

31, 2016]

**30**:251-257

**References**

There is no conflict of interest in this submission.

Mohamed Gibigaye\* and Gildas Fructueux Godonou

\*Address all correspondence to: gibigaye\_mohamed@yahoo.fr

Department of Civil Engineering, University of Abomey-Calavi, Abomey-Calavi,

[1] MAEP. Plan Stratégique de Relance du Secteur Agricole. 2011. 116p. Available from: http://www.inter-reseaux.org/IMG/pdf/PSRSA\_version\_finale.pdf [Accessed: August

[2] Teo DCL, Mannan MA, Kurian VJ. Structural concrete using oil palm shell (OPS) as lightweight aggregate. Turkish Journal of Engineering and Environmental Sciences. 2006;

[3] Mannan MA, Ganapathy C. Mix design for oil palm shell concrete. Cement and Concrete

[4] Olanipekun EA, Olusola KO, Ata O. A comparative study of concrete properties using coconut shell and palm kernel shell as coarse aggregates. Building and Environment.

[5] Osei DY, Jackson EN. Experimental study on palm kernel shells as coarse aggregates in concrete. International Journal of Scientific and Engineering Research. 2012;**3**:1-6

Research. 2001;**31**:1323-1325. DOI: 10.1016/S0008-8846(01)00585-3

2006;**41**:297-301. DOI: 10.1016/j.buildenv.2005.01.029


[21] Barton SG, Bell LW, Berg GRU, Cook JE, Cook RA, Costa WJ, Day KW, Lee SH, Mass GR, Pierce JS, Robinson HC, Crocker DA, Scherocman JA, Taylor MA, Virgalitte SJ, Weber JW, White DJ. Standard Practice for Selecting Proportions for Structural Lightweight Concrete (ACI 211. 2-98) Reported by ACI Committee 211; 1998. pp. 1-18

**Section 4**

**Dietary Applications of Palm Oil**


**Section 4**

**Dietary Applications of Palm Oil**

[21] Barton SG, Bell LW, Berg GRU, Cook JE, Cook RA, Costa WJ, Day KW, Lee SH, Mass GR, Pierce JS, Robinson HC, Crocker DA, Scherocman JA, Taylor MA, Virgalitte SJ, Weber JW, White DJ. Standard Practice for Selecting Proportions for Structural Lightweight

[23] Ries JP, Crocker DA, Sheetz SR. Guide for Structural Lightweight-Aggregate Concrete

[24] Barton SG, Bell LW, Berg GRU, Cook JE, Cook RA, Costa WJ, Day KW, Lee SH, Mass GR, Pierce JS, Robinson HC, Crocker DA, Scherocman JA, Taylor MA, Virgalitte SJ, Weber JW, White DJ. Standard Pratice for Selecting Proportions for Structural Light-

[25] Shafigh P, Jumaat MZ, Mahmud H. Mix design and mechanical properties of oil palm shell lightweight aggregate concrete: A review. International Journal of Physical

[26] Basri HB, Mannan MA, Zain MFM. Concrete using waste oil palm shells as aggregate.

[27] Oyejobi DO, Abdulkadir TS, Yusuf IT, Badiru MJ. Effects of palm kernel shells sizes and mix ratios on lightweight concrete. USEP Journal of Research Information in Civil

[28] Andrew S et al. CEB-FIP Manual of Lightweight Aggregate Concrete, Design and Tech-

[29] Claisse PA.Civil Engineering Materials. Kidlington, Oxford OX5: Elsevier Butterworth-Heinemann; 2016. Available from: http://www.sciencedirect.com/science/book/978008

Concrete (ACI 211. 2-98) Reported by ACI Committee 211; 1998. pp. 1-18 [22] Brooks JJ, Neville AM. Concrete Technology. Malaysia: Prentice Hall; 2008

weight Concrete (ACI 211.2-98), American Concrete Institute; 2004

Reported by ACI Committee 213; 2003. pp. 1-38

Cement and Concrete Research. 1999;**29**:619-622

1002759 [Accessed: March 4, 2017]

Engineering. Nigeria: University of Ilorin; 2012;**9**:217-226

nology. London/Lancaster, England: Longman Group Ltd.; 1977

Sciences. 2010;**5**:2127-2134

146 Palm Oil

**Chapter 9**

**Provisional chapter**

**Chemical Characteristics and Nutritional Properties of**

**Chemical Characteristics and Nutritional Properties of** 

Nutritional guidelines and environmental issues are adversely affecting palm oil's image among consumers. However, hybrid palm oils are currently receiving increasing attention because of their interesting chemical characteristics and nutritional properties. Interspecific hybridization *Elaeis oleifera × E. guineensis* (O×G) has been originally exploited with the main aim of developing disease-resistant varieties. However, available literature data contribute to reinforcing the idea that interspecific hybrid O×G palm oil could be a potential substitute for other vegetable oils rich in monounsaturated fatty acids (i.e., high oleic sunflower and safflower oils). The chapter aims to review current knowledge on various aspects of hybrid palm oil chemical composition (fatty acids, triacylglycerols, partial glycerides, unsaponifiable matter components) and their changes during fruit ripening. The nutritional attributes of hybrid palm oils are compared with the ones of conventional

**Keywords:** interspecific hybrid palm, palm oil, ripening, *Elaeis oleifera*, tocotrienols,

Fruits of palms (drupes) belonging to the genus *Elaeis* have been exploiting to produce edible oils for 5000 years. "Palm oil" is obtained from the reddish pulp (mesocarp) of the fruits, mainly those of the African palm (*Elaeis guineensis* Jacq.) (EG) and, to a considerably small amount, those of the palm native in central and northern South America (*Elaeis oleifera* [H.B.K.] Cortés) (EO), also known as "caiaué." "Palm kernel oil" derives from the kernel inside the shell (endocarp) [1]. The

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

DOI: 10.5772/intechopen.75421

**Hybrid Palm Oils**

**Hybrid Palm Oils**

Urszula Tylewicz

**Abstract**

African palm oils.

**1. Introduction**

Urszula Tylewicz

Massimo Mozzon, Roberta Foligni and

Massimo Mozzon, Roberta Foligni and

http://dx.doi.org/10.5772/intechopen.75421

Additional information is available at the end of the chapter

positional analysis, fatty acids, triacylglycerols

Additional information is available at the end of the chapter

#### **Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils**

DOI: 10.5772/intechopen.75421

Massimo Mozzon, Roberta Foligni and Urszula Tylewicz Massimo Mozzon, Roberta Foligni and Urszula Tylewicz

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.75421

#### **Abstract**

Nutritional guidelines and environmental issues are adversely affecting palm oil's image among consumers. However, hybrid palm oils are currently receiving increasing attention because of their interesting chemical characteristics and nutritional properties. Interspecific hybridization *Elaeis oleifera × E. guineensis* (O×G) has been originally exploited with the main aim of developing disease-resistant varieties. However, available literature data contribute to reinforcing the idea that interspecific hybrid O×G palm oil could be a potential substitute for other vegetable oils rich in monounsaturated fatty acids (i.e., high oleic sunflower and safflower oils). The chapter aims to review current knowledge on various aspects of hybrid palm oil chemical composition (fatty acids, triacylglycerols, partial glycerides, unsaponifiable matter components) and their changes during fruit ripening. The nutritional attributes of hybrid palm oils are compared with the ones of conventional African palm oils.

**Keywords:** interspecific hybrid palm, palm oil, ripening, *Elaeis oleifera*, tocotrienols, positional analysis, fatty acids, triacylglycerols

#### **1. Introduction**

Fruits of palms (drupes) belonging to the genus *Elaeis* have been exploiting to produce edible oils for 5000 years. "Palm oil" is obtained from the reddish pulp (mesocarp) of the fruits, mainly those of the African palm (*Elaeis guineensis* Jacq.) (EG) and, to a considerably small amount, those of the palm native in central and northern South America (*Elaeis oleifera* [H.B.K.] Cortés) (EO), also known as "caiaué." "Palm kernel oil" derives from the kernel inside the shell (endocarp) [1]. The

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

African palm grows spontaneously or in cultivated fields in tropical regions of Africa, Southeast Asia, and South and Central America, whereas the American oil palm only occurs in spontaneous populations from the south of Mexico to Amazon areas in Brazil and Colombia. High productivity, perennial nature of the plant, and low cost of oil production make the palm oil obtained from *E. guineensis* (henceforth referred to as "palm oil") the most produced and marketed vegetable oil worldwide. A total of 66.9 × 106 t of palm oil and 7.8 × 106 t of palm kernel oil were produced in 2017; Malaysia and Indonesia are the most important producers, with 57 × 106 t in all, corresponding to 85% of the world production [2].

biochemical performance of seedlings of O×G hybrids grown in hydroponics was carried out [30]. Nevertheless, very few studies have been conducted on the composition of the mesocarp oil. The chapter aims to review current knowledge about the various aspects of hybrid palm oil chemical composition: FAs, triacylglycerols (TAGs), partial glycerides, and unsaponifiable matter components. Available data on the composition of the hybrid palm oil during ripening are also summarized. Eventually, the nutritional attributes of hybrid palm oils are discussed in view of recently published papers about the consumption of crude oils from O×G hybrids.

Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

http://dx.doi.org/10.5772/intechopen.75421

151

A set of quality parameters (free acidity, unsaponifiable content, water content, and insoluble matter content) gives an overall assessment of the whole amount of non-glyceridic constituents, which is relevant in determining the commercial value of raw fatty substances. In crude oils obtained by pressing pulp of hybrids palm drupes, unsaponifiable matter accounts for about 1 g/100 g oil, without any significant difference due to harvest time [31, 32]; water content ranges from 0.20 to 0.73 g/100 g oil; and insoluble matter content lies in the range 0.09–0.20 g/100 g oil [31]. The free fatty acid (FFA) content ranges between 0.35 (as g/100 g oil, determined by GC areas) and 2.91 (as palmitic acid %, determined by titration) [31–33]. Higher FFA contents (9.7–36.7%, as palmitic acid) were ascribed to improper handling of raw material [34]. In fact, mesocarp lipase (triacylglycerol acyl hydrolase, EC 3.1.1.3) has been associated with the membranes of oleosomes (lipid bodies) and is activated when any kind of damage occurs to fruits, during harvest, transportation, and storage. Due to lipase activity lower than EG, interspecific O×G hybrids are considered as promising crosses with better stability of the

drupes after harvest, if they have been properly handled before oil extraction [35].

with antioxidant properties (tocols, polyphenols).

**3. Acylglycerols**

As regard to the oxidative state, hydroperoxides have not been detected by conventional titrimetry (determination of peroxide number) in samples of freshly pressed oils [3], thus confirming the stability toward oxidation of crude palm oils [36]. Nevertheless, induction times measured at 100°C are spread over a wide range (5.7–17.2 hours) [3]: these inconsistencies could be related to differences in the qualitative and quantitative composition of components

Edible vegetable oils mainly consist of TAGs; however, partial glycerides, namely diacylglycerols (DAGs) and monoacylglycerols (MAGs), are always present and their origin could be traced to both biosynthetic and lipolytic processes, the latter being of enzymatic or chemical nature.

Hardon [10] first quantified the amounts of MAG (0.88%) and DAG (5.55%) in F1 hybrids. Recently, a more detailed data have become available; 1(3)-P, 1(3)-O, and 1(3)-L were detected in the range 70–300 mg/100 g oil, with no significant differences related to ripening stage; small quantities of the corresponding 2-MAGs have also been identified. DAG types identified

**2. Quality parameters**

Palm oil is a typical multipurpose vegetable oil; it is used in food products (cooking oils, margarine and other spreads, crisps, baked food, food additives, confectionary, dairy and dairy replacements, prepared foods, snacks), in food for livestock and household pets (as fat supplement), and in several non-food productions (biodiesel, oleochemicals, cosmetics and textiles). The wide range of applications for mesocarp oil is due to its fatty acid (FA) composition. Palm oil has approximately equal amounts of saturated (SFA) and unsaturated fatty acids (UFA), while the mesocarp oil from EO is much more unsaturated [3–6].

Despite its technological characteristics, public perception of palm oil is getting worse and worse; new evidence concerning the presence of process contaminants [7] and environmental issues [8] have been added to the well-known health impact of high dietary intake of SFA. Palm oil is considered "the worst" edible oil in France, in French Belgium and in Italy, as regard to both people's health and environmental impact, whereas in the extra-European countries (USA, UK, Canada, Australia, China, Saudi Arabia) the negative opinion on palm oil is really low [9]. Campaigning against palm oil has been quite tenacious in Italy; in the last 3 years, several petitions have been promoted by online magazines (Il FattoAlimentare), consumer associations (AltroConsumo), and farmer associations (Coldiretti); even a parliamentary motion to ban palm oil from canteens has been proposed. This induced some important brands (Misura, Mulino Bianco) and retailers (Coop, Esselunga) to meet the consumer demand by introducing foodstuffs without palm oil.

In such a climate, interspecific hybrid between the cultivated oil palm EG and its wild relative EO (O×G) is receiving increasing attention by researchers and stakeholders. The O×G hybrid provides a crude oil that contains significantly higher amount of oleic acid (O) and lower percentages of palmitic (P) and stearic (S) acid than conventional African palm oil. Hardon [10, 11] first provided data on crossability, cytogenetics, fertility, growth, yield, and FA composition of F1 hybrids O×G, with the objective of developing varieties resistant to diseases [12]; in fact, hybrid expresses less severe symptoms and a slower progression of "bud rot" disease than EG. Besides, hybrid is significantly less preferred by *Rhynchophorus palmarum* than African oil palm [13]. O×G hybrids inherit from the American parent other characters of interest, such as slower vertical stem growth [14], which could result in reduced harvesting costs.

Only in recent years, a wide range of characteristics of O×G interspecific hybrids has been thoroughly studied and described: yield and morphology [15–19]; phenological stages [20]; genome size [21, 22]; sensitivity to water stress [23, 24]; physiological and biochemical response to aluminum toxicity [25]; nutritional status [26]; seed germination [27]; fruit abscission process [28]; and mycorrhization process [29]. Even a comparative characterization of the physiological and biochemical performance of seedlings of O×G hybrids grown in hydroponics was carried out [30]. Nevertheless, very few studies have been conducted on the composition of the mesocarp oil. The chapter aims to review current knowledge about the various aspects of hybrid palm oil chemical composition: FAs, triacylglycerols (TAGs), partial glycerides, and unsaponifiable matter components. Available data on the composition of the hybrid palm oil during ripening are also summarized. Eventually, the nutritional attributes of hybrid palm oils are discussed in view of recently published papers about the consumption of crude oils from O×G hybrids.

## **2. Quality parameters**

African palm grows spontaneously or in cultivated fields in tropical regions of Africa, Southeast Asia, and South and Central America, whereas the American oil palm only occurs in spontaneous populations from the south of Mexico to Amazon areas in Brazil and Colombia. High productivity, perennial nature of the plant, and low cost of oil production make the palm oil obtained from *E. guineensis* (henceforth referred to as "palm oil") the most produced and marketed vegetable oil worldwide. A total of 66.9 × 106 t of palm oil and 7.8 × 106 t of palm kernel oil were produced in 2017; Malaysia and Indonesia are the most important producers, with 57 × 106 t in all, correspond-

Palm oil is a typical multipurpose vegetable oil; it is used in food products (cooking oils, margarine and other spreads, crisps, baked food, food additives, confectionary, dairy and dairy replacements, prepared foods, snacks), in food for livestock and household pets (as fat supplement), and in several non-food productions (biodiesel, oleochemicals, cosmetics and textiles). The wide range of applications for mesocarp oil is due to its fatty acid (FA) composition. Palm oil has approximately equal amounts of saturated (SFA) and unsaturated fatty

Despite its technological characteristics, public perception of palm oil is getting worse and worse; new evidence concerning the presence of process contaminants [7] and environmental issues [8] have been added to the well-known health impact of high dietary intake of SFA. Palm oil is considered "the worst" edible oil in France, in French Belgium and in Italy, as regard to both people's health and environmental impact, whereas in the extra-European countries (USA, UK, Canada, Australia, China, Saudi Arabia) the negative opinion on palm oil is really low [9]. Campaigning against palm oil has been quite tenacious in Italy; in the last 3 years, several petitions have been promoted by online magazines (Il FattoAlimentare), consumer associations (AltroConsumo), and farmer associations (Coldiretti); even a parliamentary motion to ban palm oil from canteens has been proposed. This induced some important brands (Misura, Mulino Bianco) and retailers (Coop, Esselunga) to meet the consumer

In such a climate, interspecific hybrid between the cultivated oil palm EG and its wild relative EO (O×G) is receiving increasing attention by researchers and stakeholders. The O×G hybrid provides a crude oil that contains significantly higher amount of oleic acid (O) and lower percentages of palmitic (P) and stearic (S) acid than conventional African palm oil. Hardon [10, 11] first provided data on crossability, cytogenetics, fertility, growth, yield, and FA composition of F1 hybrids O×G, with the objective of developing varieties resistant to diseases [12]; in fact, hybrid expresses less severe symptoms and a slower progression of "bud rot" disease than EG. Besides, hybrid is significantly less preferred by *Rhynchophorus palmarum* than African oil palm [13]. O×G hybrids inherit from the American parent other characters of interest, such as slower vertical stem growth [14], which could result in reduced harvesting costs. Only in recent years, a wide range of characteristics of O×G interspecific hybrids has been thoroughly studied and described: yield and morphology [15–19]; phenological stages [20]; genome size [21, 22]; sensitivity to water stress [23, 24]; physiological and biochemical response to aluminum toxicity [25]; nutritional status [26]; seed germination [27]; fruit abscission process [28]; and mycorrhization process [29]. Even a comparative characterization of the physiological and

acids (UFA), while the mesocarp oil from EO is much more unsaturated [3–6].

ing to 85% of the world production [2].

150 Palm Oil

demand by introducing foodstuffs without palm oil.

A set of quality parameters (free acidity, unsaponifiable content, water content, and insoluble matter content) gives an overall assessment of the whole amount of non-glyceridic constituents, which is relevant in determining the commercial value of raw fatty substances. In crude oils obtained by pressing pulp of hybrids palm drupes, unsaponifiable matter accounts for about 1 g/100 g oil, without any significant difference due to harvest time [31, 32]; water content ranges from 0.20 to 0.73 g/100 g oil; and insoluble matter content lies in the range 0.09–0.20 g/100 g oil [31]. The free fatty acid (FFA) content ranges between 0.35 (as g/100 g oil, determined by GC areas) and 2.91 (as palmitic acid %, determined by titration) [31–33]. Higher FFA contents (9.7–36.7%, as palmitic acid) were ascribed to improper handling of raw material [34]. In fact, mesocarp lipase (triacylglycerol acyl hydrolase, EC 3.1.1.3) has been associated with the membranes of oleosomes (lipid bodies) and is activated when any kind of damage occurs to fruits, during harvest, transportation, and storage. Due to lipase activity lower than EG, interspecific O×G hybrids are considered as promising crosses with better stability of the drupes after harvest, if they have been properly handled before oil extraction [35].

As regard to the oxidative state, hydroperoxides have not been detected by conventional titrimetry (determination of peroxide number) in samples of freshly pressed oils [3], thus confirming the stability toward oxidation of crude palm oils [36]. Nevertheless, induction times measured at 100°C are spread over a wide range (5.7–17.2 hours) [3]: these inconsistencies could be related to differences in the qualitative and quantitative composition of components with antioxidant properties (tocols, polyphenols).

## **3. Acylglycerols**

Edible vegetable oils mainly consist of TAGs; however, partial glycerides, namely diacylglycerols (DAGs) and monoacylglycerols (MAGs), are always present and their origin could be traced to both biosynthetic and lipolytic processes, the latter being of enzymatic or chemical nature.

Hardon [10] first quantified the amounts of MAG (0.88%) and DAG (5.55%) in F1 hybrids. Recently, a more detailed data have become available; 1(3)-P, 1(3)-O, and 1(3)-L were detected in the range 70–300 mg/100 g oil, with no significant differences related to ripening stage; small quantities of the corresponding 2-MAGs have also been identified. DAG types identified are the α,β- (1,2- + 2,3- racemic mixture) and 1,3-isomers of PP, PS, PO, PL, SO, OO, OL, and LL. The most represented are PO and OO isomers, which globally account for 58–66% of total DAGs, 43–78% of α,β-DAGs, and 62–80% of 1,3-DAGs, in agreement with the of different TAG species [3, 31]. The presence of 1,3-DAGs is not "natural", as they are neither biosynthetic nor lipolytic intermediates; yet their presence may be due to both non-specific (chemical) lipolysis of TAGs and rearrangement of natural α,β-DAGs to the thermodynamically stable 1,3-isomers [3]. Hence, the presence of 1,3-DAGs is associated with mediocre quality of raw materials and unsuitable conditions during extraction and storage of oil. The biosynthesis of DAGs in fruit mesocarps accelerates during the period of maximum oil accumulation (18–22 weeks after anthesis, WAA). A decrease of relative abundance of PP and a corresponding increase of PO and OO were also observed [31]; this finding was consistent with results about changes in TAG composition during ripening described by the same authors.

#### **3.1. Fatty acid composition**

Two main FAs, O and P, account for about 80% of total FAs in hybrid palm oil and their ratio typically lies in the range 1.5–1.9 (**Table 1**), while in African palm oil O/P ratio is close to one and in EO oleic acid is the main FA (36.4–61.7%) and P is the second most represented one (21.0–37.0%) [3, 4]. Several authors have pointed out the wide range of oil composition from EO, reflecting the wider genetic diversity of EO than EG [4, 37]. Oleic acid comes with *cis*-vaccenic acid (C18:1Δ11) in an amount equal to about 0.7–1% of total FAs [3, 4]. Besides FAs listed in **Table 1**, other saturated (C8:0, C10:0, C24:0) and ω9 unsaturated (C22:1Δ13, C24:1Δ15) FAs were identified, which globally account for 0.2% of total FAs [3].

Despite the importance of determining the optimal harvest time for fruit bunches, only a very limited number of studies have been focused on the FA changes during fruit ripening. In cold pressed oils from fruits harvested between 18 and 24 WAA, a significant decrease of P (from 40.3 ± 0.3% to 32.2 ± 0.3%) and S (from 3.8 ± 0.1% to 2.7 ± 0.1%) and a corresponding increase in the relative percentage of O (from 49.7 ± 0.4% to 57.0 ± 0.4%) and L (from 4.1 ± 0.1% to 5.6 ± 0.0%) were observed [31]. Other researchers [33] detected an opposite behavior (an increase of P from 28.1 ± 2.3% to 31.3 ± 1.9% and a decrease of O from 56.4 ± 2.4% to 51.8 ± 2.1%), but in a different ripening period (phenological stages from 806 to 809, which roughly corresponds to 24–27 WAA).

As a rule, the FA composition of oils from F1 O×G interspecific hybrids is intermediate between those of their parents [3, 4, 38], while FAs in the F1 × F1 (i.e. the F2 generation) exhibit the composition of F1 [38]. This behavior has been attributed to a codominant and additive heredity in hybrid palms. The differences in FA composition between oils from African and hybrid palms should be related to the expression of genes encoding β-ketoacyl-ACP synthase (KAS) II, which is specifically used for chain lengthening of C16:0 to C18:0, and stearoyl/palmitoyl-ACP Δ9 -desaturase. Hereditariness and expression of genes linked to FAs and TAGs biosynthesis were explored by several authors [1, 6, 39–41]. Different quantitative trait loci (QTLs) for iodine value (index of total unsaturation) and FAs (C14:0, C16:0, C16:1, C18:0, C18:1, C18:2) have been identified, and a few structural genes encoding the enzymes involved in the *de novo* synthesis of FAs and in the TAG assembly (e.g., acyl-ACP thioesterases, acyl-CoA synthetase, diacylglycerol acyltransferase) have been localized in those genomic intervals. It is interesting to notice

**Reference**

Samples

Congo,

Nigeria,

Nigeria

Malaysia

Malaysia

Malaysia

Colombia

Colombia

Colombia

Malaysia

Malaysia

Costa Rica

Colombia

Malaysia,

Colombia

origin

Hybrid

Oil

extraction

system

N. of

3

7

14

126

3

21b

12c

85

111

2

samples

Fatty acid

C12:0 (La) C14:0 (M)

C15:0 C16:0 (P)

C16:1Δ9

C17:0 C17:1 C18:0 (S) C18:1 (O) C18:2Δ9,12

11.3–11.8

10.3–13.9

9.3–11.5

6.5–9.3 tr – 0.1 0.1–0.7

0.5–0.5

0.4–0.4 0.2–0.2

0.1–0.2

153

8.2–16.8

10.8–16.5

10.7–11.5

0.2–0.3

0.3–0.4

0.1–0.2

0.40–0.65

0..00–0.53

0.3–0.4

9.4–10.4

4.1–5.6

10.45–

8.15–17.65

10.7–12.7

http://dx.doi.org/10.5772/intechopen.75421

15.15

(L)

C20:0 (A)

C18:3

0.4–1.3

Δ9,12,15

(Ln)

C20:1 Δ11

0.0–0.11

48.0–52.5

50.2–53.4

44.9–56.0

3.4–6.1

3.0–4.6

3.3–5.9

0.4–1.5

1.4–4.9 36.9–60.1

34.4–51.8

53.5–55.2

51.8–56.4

49.7–57.0

48.20–

37.58–

38.7–43.4

61.45

54.48

3.2–4.1

2.6–3.1

2.3–2.7

2.7–3.8

1.50–3.10

2.11–9.43

4.0–4.3

Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

27.3–32.5

29.3–35.5

28.9–38.6

36.2–41.4

tr

0.1–0.3

0.3–0.4 0.1–0.2

tr

0.3–0.5 0.1–0.4

0.1–0.1

0.20–0.83

0.07–0.34

0.2–0.2

22.4–44.7

32.2–43.1

27.7–29.5

28.1–31.3

32.2–40.3

22.25–

24.73–

37.0–43.5

34.33

41.69

0.47–0.9

0.4–0.9

0.3–0.9

0.4–0.8

0.1–0.5

0.5–1.6

0.5–0.9

tr

0.01–0.1

tr

tr

0.5–1.7

0.4–0.5

0.4–0.4 0.1–0.1

0.14–0.55

0.14–0.75

0.9–0.9

F1

F1

BC1

F1; BC1

F1

F1; BC1

F1

F1

F1

F1

BC2 (with

BC3 (with

EG)

EG); BC3 × EO

solvent

(with EG)

pressure

pressure

pressure

(with

(with EG and

EG)

pressure

pressure

EO); F2

**[10]**

**[34]**

**[42]**

**[38]**

**a**

**[5]**

**[44]**

**[3]**

**[33]**

**[31]**

**[6]**

**[6]**

**[4]**


are the α,β- (1,2- + 2,3- racemic mixture) and 1,3-isomers of PP, PS, PO, PL, SO, OO, OL, and LL. The most represented are PO and OO isomers, which globally account for 58–66% of total DAGs, 43–78% of α,β-DAGs, and 62–80% of 1,3-DAGs, in agreement with the of different TAG species [3, 31]. The presence of 1,3-DAGs is not "natural", as they are neither biosynthetic nor lipolytic intermediates; yet their presence may be due to both non-specific (chemical) lipolysis of TAGs and rearrangement of natural α,β-DAGs to the thermodynamically stable 1,3-isomers [3]. Hence, the presence of 1,3-DAGs is associated with mediocre quality of raw materials and unsuitable conditions during extraction and storage of oil. The biosynthesis of DAGs in fruit mesocarps accelerates during the period of maximum oil accumulation (18–22 weeks after anthesis, WAA). A decrease of relative abundance of PP and a corresponding increase of PO and OO were also observed [31]; this finding was consistent with results about changes in TAG

Two main FAs, O and P, account for about 80% of total FAs in hybrid palm oil and their ratio typically lies in the range 1.5–1.9 (**Table 1**), while in African palm oil O/P ratio is close to one and in EO oleic acid is the main FA (36.4–61.7%) and P is the second most represented one (21.0–37.0%) [3, 4]. Several authors have pointed out the wide range of oil composition from EO, reflecting the wider genetic diversity of EO than EG [4, 37]. Oleic acid comes with *cis*-vaccenic acid (C18:1Δ11) in an amount equal to about 0.7–1% of total FAs [3, 4]. Besides FAs listed in **Table 1**, other saturated (C8:0, C10:0, C24:0) and ω9 unsaturated (C22:1Δ13, C24:1Δ15) FAs

Despite the importance of determining the optimal harvest time for fruit bunches, only a very limited number of studies have been focused on the FA changes during fruit ripening. In cold pressed oils from fruits harvested between 18 and 24 WAA, a significant decrease of P (from 40.3 ± 0.3% to 32.2 ± 0.3%) and S (from 3.8 ± 0.1% to 2.7 ± 0.1%) and a corresponding increase in the relative percentage of O (from 49.7 ± 0.4% to 57.0 ± 0.4%) and L (from 4.1 ± 0.1% to 5.6 ± 0.0%) were observed [31]. Other researchers [33] detected an opposite behavior (an increase of P from 28.1 ± 2.3% to 31.3 ± 1.9% and a decrease of O from 56.4 ± 2.4% to 51.8 ± 2.1%), but in a different ripening period (phenological stages from 806 to 809, which roughly corresponds to 24–27 WAA).

As a rule, the FA composition of oils from F1 O×G interspecific hybrids is intermediate between those of their parents [3, 4, 38], while FAs in the F1 × F1 (i.e. the F2 generation) exhibit the composition of F1 [38]. This behavior has been attributed to a codominant and additive heredity in hybrid palms. The differences in FA composition between oils from African and hybrid palms should be related to the expression of genes encoding β-ketoacyl-ACP synthase (KAS) II, which is specifically used for chain lengthening of C16:0 to C18:0, and stearoyl/palmitoyl-ACP


composition during ripening described by the same authors.

were identified, which globally account for 0.2% of total FAs [3].

**3.1. Fatty acid composition**

152 Palm Oil

Δ9

153


**Table 1.** FA composition (% w/w) of O×G interspecific hybrid palm oil.

SFA =

saturated fatty acids. MUFA

 =

monounsaturated fatty acids. PUFA

 =

polyunsaturated fatty acids.

that, while most of the FAs and total unsaturation indicate additive or co-dominance effects, L seems to be an exception; in fact, the percentage of this essential FA does not undergo signifi

While great emphasis in breeding has been given to the mesocarp oil, less attention has been focused on the composition of kernel oils from EG, EO and their hybrids. Medium chain FAs characterize the composition of *Elaeis* kernel oils. Lauric acid (La) represents the most abun

dant FA, followed by myristic acid (M) and O; these three FAs account for 75–80% of total

the mesocarp oils, the kernel oils of the hybrids do not display an intermediate composition between their American and West African parents (**Table 2**); hybrids and back-crosses show a

A TAG type is defined by its three constitutive FAs. Data on the FA composition of individual TAG molecular species can be achieved through the combination of the separation properties

5, 34, 43].

**[34 ]**

6

= number of double bonds, x

= saturated fatty acids. MUFA

FAs. Besides, *cis*-vaccenic acid was only present at trace levels in kernel oil (

**[ 5, 43 ]**

Oil extraction system Solvent Solvent Solvent Solvent

5

C8:0 3.2–3.4 4.0 1.3–3.2 1.2–2.3 C10:0 2.7–2.9 3.5 1.8–3.2 1.1–2.2 C12:0 (La) 44.4–46.8 50.0 40.6–49.0 35.0–42.3 C14:0 (M) 18.1–18.6 16.5 17.4–22.1 19.6–24.7 C16:0 (P) 7.9–8.8 7.8 8.0–9.5 9.1–10.2 C18:0 (S) 2.1–2.2 2.2 1.5–2.5 2.4–3.5 C18:1 (O) 14.8–16.3 13.1 14.1–18.5 17.2–19.1 C18:2Δ9,12 (L) 3.2–3.4 2.4 1.0–4.5 4.4. – 4.7 ΣSFA 75.9–78.2 ΣMUFA 17.5–19.3 ΣPUFA 4.4–4.7 ΣSFA/ ΣUFA 3.2–3.7

= number of carbon atoms, n

= sum of oleic and *cis*-vaccenic acids. SFA

**Table 2.** FA composition (% w/w) of O×G interspecific hybrid palm kernel oil.

Samples origin Malaysia Malaysia Nigeria, Colombia Costa Rica

Hybrid F1 BC1 (with EO) F1 BC3 (with EG); BC3

3,

cant changes between African palm and O×G hybrids [

dominant and dictates the level of L in the hybrid.

composition close to the one of EG kernel oil [

**[ 5, 43 ]**

C6:0 0.2–0.2 0.2 tr

**Reference**

BCn

PUFA

= trace. C18:1

= back-cross. Cm:nΔx: m

= polyunsaturated fatty acids.

N. of samples 12

**3.2. Composition and structure of triacylglycerols**


155


4]. Unlike

× EO

= position of double bonds. tr.

= monounsaturated fatty acids.

4, 38, 42]. In this case, EG seems to be

http://dx.doi.org/10.5772/intechopen.75421

Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

**[ 4 ]**

2

∼0.1%) [

that, while most of the FAs and total unsaturation indicate additive or co-dominance effects, L seems to be an exception; in fact, the percentage of this essential FA does not undergo significant changes between African palm and O×G hybrids [3, 4, 38, 42]. In this case, EG seems to be dominant and dictates the level of L in the hybrid.

While great emphasis in breeding has been given to the mesocarp oil, less attention has been focused on the composition of kernel oils from EG, EO and their hybrids. Medium chain FAs characterize the composition of *Elaeis* kernel oils. Lauric acid (La) represents the most abundant FA, followed by myristic acid (M) and O; these three FAs account for 75–80% of total FAs. Besides, *cis*-vaccenic acid was only present at trace levels in kernel oil (∼0.1%) [4]. Unlike the mesocarp oils, the kernel oils of the hybrids do not display an intermediate composition between their American and West African parents (**Table 2**); hybrids and back-crosses show a composition close to the one of EG kernel oil [5, 34, 43].

#### **3.2. Composition and structure of triacylglycerols**

A TAG type is defined by its three constitutive FAs. Data on the FA composition of individual TAG molecular species can be achieved through the combination of the separation properties


BCn = back-cross. Cm:nΔx: m = number of carbon atoms, n = number of double bonds, x = position of double bonds. tr. = trace. C18:1 = sum of oleic and *cis*-vaccenic acids. SFA = saturated fatty acids. MUFA = monounsaturated fatty acids. PUFA = polyunsaturated fatty acids.

**Table 2.** FA composition (% w/w) of O×G interspecific hybrid palm kernel oil.

**Reference**

C22:0 ΣSFA ΣMUFA

ΣPUFA ΣSFA/ ΣUFA

amol %.

bSamples collected between the phenological stages 806 and 809.

cSamples collected between 18 and 24

BCn =

SFA =

**Table 1.**

back-cross. Cm:nΔx: m

 = saturated fatty acids. MUFA

 = FA composition (% w/w) of O×G interspecific hybrid palm oil.

number of carbon atoms, n

 = monounsaturated fatty acids. PUFA

 =

number of double bonds, x

 = polyunsaturated fatty acids.

position of double bonds. tr. = trace. C18:1

 =

sum of oleic and *cis*-vaccenic acids.

weeks after anthesis (WAA).

**[10]**

**[34]**

**[42]**

**[38]**

**a**

**[5]**

**[44]**

**[3]**

**[33]**

**[31]** 0.1–0.1

33.2–34.1 53.8–55.8 11.1–11.9 0.50–0.52

0.58–0.84

4.2–5.8

50.6–57.6

31.5–34.7

36.6–46.1

42.4–49.1

39.8–44.5

11.1–13.1

0.7–1

**[6]**

**[6]**

**[4]**

154 Palm Oil

of instrumental chromatographic techniques, both in liquid [45, 46] and gas [3] phase, and the powerful of mass spectrometers, as detection system.

Mozzon et al. [3, 31] identified 23 TAG molecular species (**Table 3**), by direct GC-MS analysis of oils. Other 14 TAG molecular species characterized by the presence of medium chain SFAs (8:0, 10:0, 12:0, and 14:0), which globally accounted for about 0.7% of oil samples, have been identified after TLC fractionation of oil. These are the TSTAGs 32:0 (LaLa8:0), 34:0 (LaLa10:0), 36:0 (LaLaLa), 38:0 (LaLaM), 40:0 (LaMM+LaLaP), 42:0 (LaMP), 44:0 (LaPP+MMP), and the DSTAGs 42:1 (LaLaO), 44:1 (LaMO). TAG structures with three (LaLaLa) and two (LaLaM, LaLaP, LaLaO) lauryl groups constitute 69.4–72.0% of medium chain TAGs.

No qualitative differences between TAG species of O×G hybrid palm oil and its African parent have been detected. From a quantitative viewpoint, most (about 80%) of total TAGs are made up of both saturated (16:0, 18:0) and unsaturated (18:1, 18:2) FAs (DSTAG + MSTAG). Lower percentages of MPP, PPP, MOP, PPS, PPO, PPL, POS, and higher contents of OOO (2.5 times), OOL (three times), POO, PLO, SOA (from 0.1–0.2% to 0.9–1.2%) than African parent were observed in oil samples from O×G hybrid. Grouped data reflect the discoveries summarized above: oil samples from the hybrid are characterized by higher contents of MSTAGs (47.5–51.0% vs 36.7–37.1%) and TUTAGs (15.5–15.6% vs 5.2–5.4%) than EG [3]. Despite similar FA compositions, other authors [33, 35] observed different TAG profiles, namely lower percentages of POO and PPO, and higher percentages of PPL, PLO, OOL, PLL + POLn.

The pattern of TAGs of mesocarp oils, according to the number of acyl carbon atoms (CN), follows a typical unimodal distribution with an apex at CN 52 for the hybrid palm oil, at CN 50–52 in African palm oil, and at CN 52–54 in EO oils [3, 5]. In kernel oils of EG and its interspecific hybrids (F1 hybrids, back-crosses), the major TAG groups range from CN 36–38 (the most represented) to CN 44 (**Table 3**), whereas in EO kernel oils they range from C36 to C54. A bimodal distribution with maxima at CN 38 and C 48 characterizes the TAG profile of EO kernel lipids [5, 43].

Pancreatic lipase degradation of TAGs was extensively applied in the TAGs structure studies [47–49]. Experimental data reveal an asymmetric structure of the hybrid palm oil TAGs, thus suggesting that the length of carbon chain and the number of double bonds could constitute discriminating factors in the acylation steps. SFAs (C16:0, C18:0) are acylated mainly in positions sn-1,3, while unsaturated fatty acids (C18:1Δ9, C18:2Δ9,12) are preferably acylated in position sn-2 [3, 38]. The conservation of FAs regiodistribution in TAGs of O×G hybrid with respect to its African parent could indicate that hybridization cannot affect the general pattern of stereospecific acylation of glycerol [3].

Trends in FAs availability during ripening (18–24 WAA) mainly affect TSTAGs and TUTAGs: total TSTAG relative percentage halves from 3.6 ± 0.1 to 1.8 ± 0.1, whereas ΣTUTAG increased from 16.9 ± 0.1% to 18.9 ± 0.3%, mainly because of the increase of OOO and decrease in PPP. As saturated and unsaturated FAs have opposite trends during ripening, ΣDSTAG and ΣMSTAG overall changes are very inconspicuous, although they are statistically significant. No significant differences have been observed for medium chain TAGs [31].

**Reference** Samples origin

Hybrid Oil extraction system

N. of samples

TAG m:n

ΣC28 ΣC30 ΣC32 ΣC34 ΣC36 ΣC38 ΣC40 ΣC42 ΣC44

46:0 46:1 ΣC46

48:0 48:1 48:2 ΣC48

50:0

PPS

0.0–0.2

n.d.

0.4 ± 0.3

0.2–0.6

PPP MOP

MLP

0.0–0.7

> 0.9–8.9

0.4 ± 0.0

0.2 ± 0.1

tr - 0.1

7.1–8.0

6.0

157

0.0–0.6

1.3 ± 1.3 0.8 ± 0.0

0.4–0.6

1.5–2.8

MPP MMO + LaPO 0.0–1.1

TAG ABC

**[5]** **Mesocarp oil**

Malaysia

F1

F1 Pressure

> 38

21a

3b

3c

12d

12 0.1–0.2 0.4–0.7 2.9–3.9 4.8–6.0 17.9–19.6 17.2–18.0 10.9–11.3

9.9–10.6

8.0–8.8

> 0.1 ± 0.0

0.3 ± 0.2

tr – 0.3

6.3–7.2

5.1

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Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

0.1–0.5

6.7

9.1

10.3

18.9

24.5

7.1

4.7

0.7

0.1

5

Pressure

Pressure

Pressure

F1

F1

F1

F1

BC1 (with EO)

Colombia

Colombia

Colombia

Colombia

Malaysia

Malaysia

**[33]**

**[35]**

**[3]**

**[31]**

**[5, 43]** **Kernel oil**

**[5, 43]**


of instrumental chromatographic techniques, both in liquid [45, 46] and gas [3] phase, and the

Mozzon et al. [3, 31] identified 23 TAG molecular species (**Table 3**), by direct GC-MS analysis of oils. Other 14 TAG molecular species characterized by the presence of medium chain SFAs (8:0, 10:0, 12:0, and 14:0), which globally accounted for about 0.7% of oil samples, have been identified after TLC fractionation of oil. These are the TSTAGs 32:0 (LaLa8:0), 34:0 (LaLa10:0), 36:0 (LaLaLa), 38:0 (LaLaM), 40:0 (LaMM+LaLaP), 42:0 (LaMP), 44:0 (LaPP+MMP), and the DSTAGs 42:1 (LaLaO), 44:1 (LaMO). TAG structures with three (LaLaLa) and two (LaLaM,

No qualitative differences between TAG species of O×G hybrid palm oil and its African parent have been detected. From a quantitative viewpoint, most (about 80%) of total TAGs are made up of both saturated (16:0, 18:0) and unsaturated (18:1, 18:2) FAs (DSTAG + MSTAG). Lower percentages of MPP, PPP, MOP, PPS, PPO, PPL, POS, and higher contents of OOO (2.5 times), OOL (three times), POO, PLO, SOA (from 0.1–0.2% to 0.9–1.2%) than African parent were observed in oil samples from O×G hybrid. Grouped data reflect the discoveries summarized above: oil samples from the hybrid are characterized by higher contents of MSTAGs (47.5–51.0% vs 36.7–37.1%) and TUTAGs (15.5–15.6% vs 5.2–5.4%) than EG [3]. Despite similar FA compositions, other authors [33, 35] observed different TAG profiles, namely lower percentages of POO and PPO, and higher percentages of PPL, PLO, OOL,

The pattern of TAGs of mesocarp oils, according to the number of acyl carbon atoms (CN), follows a typical unimodal distribution with an apex at CN 52 for the hybrid palm oil, at CN 50–52 in African palm oil, and at CN 52–54 in EO oils [3, 5]. In kernel oils of EG and its interspecific hybrids (F1 hybrids, back-crosses), the major TAG groups range from CN 36–38 (the most represented) to CN 44 (**Table 3**), whereas in EO kernel oils they range from C36 to C54. A bimodal distribution with maxima at CN 38 and C 48 characterizes the TAG profile of EO kernel

Pancreatic lipase degradation of TAGs was extensively applied in the TAGs structure studies [47–49]. Experimental data reveal an asymmetric structure of the hybrid palm oil TAGs, thus suggesting that the length of carbon chain and the number of double bonds could constitute discriminating factors in the acylation steps. SFAs (C16:0, C18:0) are acylated mainly in positions sn-1,3, while unsaturated fatty acids (C18:1Δ9, C18:2Δ9,12) are preferably acylated in position sn-2 [3, 38]. The conservation of FAs regiodistribution in TAGs of O×G hybrid with respect to its African parent could indicate that hybridization cannot affect the general pattern

Trends in FAs availability during ripening (18–24 WAA) mainly affect TSTAGs and TUTAGs: total TSTAG relative percentage halves from 3.6 ± 0.1 to 1.8 ± 0.1, whereas ΣTUTAG increased from 16.9 ± 0.1% to 18.9 ± 0.3%, mainly because of the increase of OOO and decrease in PPP. As saturated and unsaturated FAs have opposite trends during ripening, ΣDSTAG and ΣMSTAG overall changes are very inconspicuous, although they are statistically significant. No signifi-

LaLaP, LaLaO) lauryl groups constitute 69.4–72.0% of medium chain TAGs.

powerful of mass spectrometers, as detection system.

PLL + POLn.

156 Palm Oil

lipids [5, 43].

of stereospecific acylation of glycerol [3].

cant differences have been observed for medium chain TAGs [31].


**Reference**

**[5]** **Mesocarp oil**

> ΣDSTAG

ΣMSTAG ΣTUTAG aSamples collected between the phenological stages 806 and 809.

bPhenological stage 807.

c24

weeks after anthesis (WAA).

dSamples collected between 18 and 24 WAA.

 BCn =

abbreviations, e.g. PLO, does not mean the binding position of each FA.

back-cross. m:n

 = FAs like in **Table 1**. tr

been grouped according to the type of FA bonded to the glycerol moiety as TSTAG, trisaturated TAGs (MPP, PPP, PPS, PSS); DSTAG, disaturated TAGs (MMO

MOP, MLP, PPO, PPL, POS, PLS, SSO, SOA); MSTAG, monosaturated TAGs (MOO, POO, PLO, PLL

Triacylglycerol (TAG) composition (% w/w) of O×G interspecific hybrid mesocarp oil and kernel oil.

OOL, OLL).

**Table 3.**

 =

 +

acyl carbon number:double bonds number. In TAG species composition (TAG ABC), the order of the

trace values (< 0.1%). n.d. = not detected. TAG types listed in **Table 3** have

 + LaPO, Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

http://dx.doi.org/10.5772/intechopen.75421

159

POLn, SOO, SLO, AOO); TUTAG, triunsaturated TAGs (OOO,

**[33]**

**[35]**

**[3]** 33.3 ± 0.3 49.6 ± 1.8 15.5 ± 0.1

16.9–18.9

47.7–49.5

29.8–31.5

**[31]**

**[5, 43]** **Kernel oil**

**[5, 43]**


**Reference**

50:1 50:2 50:2 ΣC50

52:0 52:1 52:2 52:2 52:3 52:4 ΣC52

54:1 54:2 54:3 54:3 54:4 54:5 ΣC54

56:1 56:2 ΣC56

SOA AOO 0.0–0.6

ΣTSTAG

SSO SOO SLO OOO

OOL OLL

8.5–12.8 8.5–11.3

3.9–5.0

> 21.8–44.7

3.2 ± 0.3

0.2 ± 0.1 1.1 ± 0.1 0.1 ± 0.0 1.6 ± 1.6

1.8–3.6

0.1–0.1

0.9–1.1

tr - 0.3

3.0–3.5

2.6

7.6 ± 0.6

4.7 ± 0.1

4.6–5.2

7.6 ± 1.0

10.7 ± 0.2

12.2–14.2

0.2–0.4 1.1–2.5

1.8 ± 0.3

2.6 ± 0.1 0.7 ± 0.7

1.4–1.5

2.3–3.5

n.d.

0.3 ± 0.0

0.3–0.4

PSS POS PLS POO PLO PLL + POLn

21.9–24.8 17.8–20.2

7.4–9.4

> 43.5–50.5

6.7 ± 0.6

2.0 ± 0.0

1.1–1.9

2.9–3.3

1.9

17.7 ± 0.8

11.2 ± 0.2

7.4–8.9

23.4 ± 0.7

32.6 ± 2.4

33.1–35.8

1.5–1.8

2.8 ± 0.5

3.3 ± 0.2 1.6 ± 0.3

1.7–2.0

2.8–3.8

PPO PPL MOO 11.1–25.5

**[5]** **Mesocarp oil** 10.4–15.3

5.6–9.4

9.4 ± 0.9

5.5 ± 0.2 0.5 ± 0.1

tr

tr

0.3–0.5

3.3–3.9

2.3

2.5–3.2

17.0 ± 2.4

20.4 ± 0.2

20.3–21.1

**[33]**

**[35]**

**[3]**

**[31]**

**[5, 43]** **Kernel oil**

**[5, 43]**

158 Palm Oil

c24weeks after anthesis (WAA).

dSamples collected between 18 and 24 WAA. BCn = back-cross. m:n = acyl carbon number:double bonds number. In TAG species composition (TAG ABC), the order of the abbreviations, e.g. PLO, does not mean the binding position of each FA. FAs like in **Table 1**. tr = trace values (< 0.1%). n.d. = not detected. TAG types listed in **Table 3** have been grouped according to the type of FA bonded to the glycerol moiety as TSTAG, trisaturated TAGs (MPP, PPP, PPS, PSS); DSTAG, disaturated TAGs (MMO + LaPO, MOP, MLP, PPO, PPL, POS, PLS, SSO, SOA); MSTAG, monosaturated TAGs (MOO, POO, PLO, PLL + POLn, SOO, SLO, AOO); TUTAG, triunsaturated TAGs (OOO, OOL, OLL).

**Table 3.** Triacylglycerol (TAG) composition (% w/w) of O×G interspecific hybrid mesocarp oil and kernel oil.

## **4. Unsaponifiable matter**

A full characterization of the unsaponifiable matter (UM) of the hybrid palm oil is required to assess its potential as a source of health-promoting bioactive compounds. However, only few specific studies have been conducted about the composition of UM of the O×G hybrid oil (**Table 4**).

**Reference [10] [44] [33] [32] [31]**

Total Isoprenoid alcohols 269.3 ± 60.0 160.7–251.3

Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

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161

*n*-docosanol 1.8 ± 1.3 0.5–1.4 *n*-tetracosanol 1.2 ± 0.5 0.4–1.2 *n*-hexacosanol 2.7 ± 0.2 0.4–2.5 *n*-octacosanol 7.3 ± 0.8 3.0–5.2

*n*-triacontanol 15.6 ± 1.6 7.2–12.9

*n*-dotriacontanol 18.1 ± 6.5 6.9–13.1

*n*-tetratriacontanol 8.2 ± 7.6 2.2–37.4 Total *n*-Alkanols 61.7 ± 17.0 24.9–37.4

obtusifoliol 2.7–5.2 citrostadienol 4.2–9.8 Total 4-methylsterols 12.7 ± 1.5 6.9–14.9

Cycloartenol 14.6–24.9

Isoarborinol 2.0–3.9

9,19-cyclopropanesterol 0.8–1.6 Total 4,4-dimethylsterols 74.0 ± 12.3 20.0–33.7

α-tocopherol 11–24% 27.1 ± 7.4/10.0 ± 0.2% 1.5–7.4

γ-tocotrienol 42–51% 148.1 ± 23.3/59.7 ± 1.1% 9.4–18.9

β- tocopherol tr/0.3 ± 0.3% γ- tocopherol tr/0.3 ± 0.4%

α-tocotrienol 22–31% 44.7 ± 13.7/15.0 ± 1.9% β-tocotrienol 3.7 ± 1.2/1.4 ± 0.4%

2.0–3.4

) tr

*n*-octadecanol 5.3 ± 2.1

*n*-nonacosanol tr

*n*-hentriacontanol 0.7 ± 1.2

*n*-tritriacontanol 0.7 ± 1.2

Isoprenoid alcohol (X<sup>2</sup>

*n***-Alkanols (Ak**)

**4-methylsterols** gramisterol

**4,4-dimethylsterols**

24-methylenecycloartanol

Unknown

**Tocols**



**Reference [10] [44] [33] [32] [31]**

A full characterization of the unsaponifiable matter (UM) of the hybrid palm oil is required to assess its potential as a source of health-promoting bioactive compounds. However, only few specific studies have been conducted about the composition of UM of the O×G hybrid oil (**Table 4**).

Oil extraction system pressure cold pressed cold pressed

Cholesterol 3–5% 10.0 ± 2.6/1.8 ± 0.4% 7,8–10.2/3.5–5.4% Campesterol 20–22% 93.1 ± 23.4/19.3 ± 1.2% 18,8–47.6/11.8–

Stigmasterol 13–19% 62.8 ± 10.8/13.1 ± 0.6% 25,8–45.2/15.3–



Total 4-desmethylsterols 700–1400 469–1417 472.7 ± 102.8 158.7–293.8

Phytol 120.7 ± 26.1 127.5–175.0

Geranylgeraniol 129.0 ± 31.7 31.3–76.3

) tr

2.1 ± 1.4/0.5 ± 0.2%

11.3 ± 2.1

7.7 ± 1.5

N. of samples 3 21a 3<sup>b</sup> 12<sup>c</sup> **Squalene** 247.4 ± 3.3 20.3–83.1

Malaysia Colombia Colombia Colombia

F1 F1 F1

16.3%

16.3%

62.4%

Samples origin Congo,

**4. Unsaponifiable matter**

160 Palm Oil

**4-desmethylsterols**

Δ7

Δ5

sterols

Other unidentified

**Isoprenoid alcohols**

hexadien-1-ol

3,7,11,15-tetramethyl-2,6-

3,7,11,15-tetramethyl-2,6,10-hexatrien-1-ol

Isoprenoid alcohol (X<sup>1</sup>

Hybrid F1 F1; BC1

Malaysia, Colombia

> (with EG)

Ergosterol 11.0 ± 3.4/1.9 ± 0.3%

Fucosterol 5.6 ± 2.9/1.1 ± 0.6%


[31, 32, 45]. As described above, an increase in total sterols content of oil samples occurs during ripening, whereas no significant variations in the composition of the desmethylsterol frac-

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163

Very little information is available on the occurrence of 4,4-dimethylsterols (or triterpenic alcohols, or triterpenols) in hybrid palm oil. Three 9,19-cyclopropanesterol have been identified: cycloartenol, 24-methylenecycloartanol, and a third triterpenol characterized by a mass spectrum very similar to 24-methylenecycloartanol, compatible with cyclobranol or cyclolaudenol. The structure of isoarborinol was tentatively attributed by Mozzon et al. [32] to a fourth triterpenol. The content of 4,4-dimethylsterols ranges between 20 and 85 mg/Kg g oil (corresponding to 0.6% of total unsaponifiable matter), with no significant differences between African and hybrid palm oils. The composition of the triterpenol fraction does not show significant variations between the African and hybrid palm oils, as well; cycloartenol (70–75% of total triterpenols), and 24-methylenecycloartanol (14–20%) are the two most represented components [31, 32]. Oil levels of 4,4-dimethylsterols increase from 200 mg/Kg at 18

WAA (beginning of inolition) to 340 mg/Kg at 24 WAA (maximum of inolition) [31].

Citrostadienol was the main 4-methylsterol in hybrid palm oil, followed by obtusifoliol (4,14-dimethylergosta-8,24(28)-dien-3-ol). Gramisterol (24-methylenelophenol) was also identified. The content of 4-methylsterols ranges 7–15 mg/Kg g oil (corresponding to 0.1– 0.2% of total unsaponifiable matter), with no significant differences between African and hybrid oils. The composition of the 4-methylsterols fraction does not show significant variations between the African and hybrid palm oils too; cytrostadienol ranged from 44.5 to 50.3% of total 4-methylsterols, obtusifoliol from 14.3 to 31.5%, and gramisterol from 24.0 to 35.4%. Total content of 4-methylsterols does not significantly change during ripening [31, 32].

A complete series of aliphatic alcohols of even number of carbon atoms from 18 to 34 was identified in mesocarp oil from hybrid palm fruits. Odd carbon number alkanols C29, C31, and C33 were also identified [31, 32]. *n*-alkanols level ranges 25–80 mg/Kg oil, without significant differences between African and hybrid palm oil. The pattern of *n*-alkanols, according to the number of carbon atoms, follows a typical unimodal distribution with a maximum abundance of alcohol C32, in both EG and hybrid oil types [32]. Ripening stage affects aliphatic

After 4-desmethylsterols, isoprenoid alcohols (terpenols) are the most represented class of alcoholic components of unsaponifiable matter of hybrid pal oil. A series of terpenols with 20 carbon atoms and 1 (phytol), 2, 3, and 4 (geranylgeraniol) double bonds has been identified. Hybrid palm oil is characterized by higher (160–330 mg/Kg), although not statistically significant, contents of isoprenoid alcohols, and by a higher phytol/geranylgeraniol ratio than EG

alcohol fraction neither from a qualitative nor from quantitative viewpoint [31].

tion were observed [31].

**4.2. 4,4-dimethylsterols**

**4.3. 4-methylsterols**

**4.4. Aliphatic alcohols**

mesocarp oil [32].

a Samples collected at phenological stages 806–809. b Ripe fruit (24 WAA).

c Samples collected between 18 and 24 WAA.

**Table 4.** Literature data on composition of the unsaponifiable fraction of O×G interspecific hybrid palm oil. Data are provided as mg/Kg oil unless % is indicated. Percentages refer to within class of unsaponifiable components.

Carotenoids are responsible for the color of the oils obtained from mesocarp of palm fruits. A wide range (500–10,000 mg/Kg oil) of their level in hybrid palm oils was reported in literature [3, 10, 33, 44]. Eleven types of carotenes have been identified (α-, β-, ζ-, γ-, and δ-carotene, phytoene, phytofluene, neurosporene, α- and β-zeacarotene, and lycopene), with no qualitative variations among EO, EG and their hybrids. β-carotene is the most represented (52–60% of total carotenes), followed by α-carotene (33–36% of total carotenes). Major quantitative differences are related to lycopene, whose levels account for 1–8% of total carotenes in EG whereas in EO and O×G hybrids lycopene percentages are less than 0.1% [44]. Squalene ranges from 20 to 250 mg/Kg oil [31, 32]. African palm oil was characterized by higher contents of carotenes [44] and squalene [32] than O×G interspecific hybrid oil.

More than 40 alcoholic compounds, belonging to six classes (4-desmethylsterols, 4,4-dimethylsterols, isoprenoid alcohols, n-alkanols and tocols) have been identified in screw pressed crude palm oil obtained from interspecific hybrids. Desmethylsterols and isoprenoid alcohols are the most represented classes, accounting for 79–85% of total alcohols, followed by *n*-alkanols (4–8% of total alcohols), 4,4-dimethylsterols (5–6%), tocols (3–4%), and 4-methylsterols (1–3%) [32].

Quantitative data expressed in mg/kg oil show a trend of progressive accumulation of squalene, desmethylsterols, isoprenoid alcohols, tocols, and 4,4-dimethylsterols in crude hybrid palm oil during ripening, whereas *n*-alkanols and 4-methylsterols show apparently stable levels in total lipids, which can be attributed to the increase in their amounts at the same time TAGs were synthesized [32, 33].

#### **4.1. 4-desmethylsterols**

The content of phytosterols in hybrid palm oil ranges from 160 to 1400 mg/kg oil [31–33, 44]. Δ5 -sterols represent 97% of total sterols in hybrid palm oil. The identified molecules are "campesterol" (campesterol +22,23-dihydrobrassicasterol), stigmasterol, β-sitosterol, Δ5 avenasterol, Δ5,24-stigmastadienol, fucosterol, and clerosterol; ergosterol (ergosta-5,7,22-trien-3β-ol) was tentatively identified, whereas Δ7 -campesterol (ergosta-7-en-3β-ol) is the only Δ7 -sterol clearly identified in hybrid palm oil. β-sitosterol is the most represented phytosterol (58–62% of total sterols), followed by campesterol (12–22%) and stigmasterol (13–19%). Cholesterol is a significant component of sterol fraction, accounting for 2–5% of total sterols [31, 32, 45]. As described above, an increase in total sterols content of oil samples occurs during ripening, whereas no significant variations in the composition of the desmethylsterol fraction were observed [31].

#### **4.2. 4,4-dimethylsterols**

Very little information is available on the occurrence of 4,4-dimethylsterols (or triterpenic alcohols, or triterpenols) in hybrid palm oil. Three 9,19-cyclopropanesterol have been identified: cycloartenol, 24-methylenecycloartanol, and a third triterpenol characterized by a mass spectrum very similar to 24-methylenecycloartanol, compatible with cyclobranol or cyclolaudenol. The structure of isoarborinol was tentatively attributed by Mozzon et al. [32] to a fourth triterpenol. The content of 4,4-dimethylsterols ranges between 20 and 85 mg/Kg g oil (corresponding to 0.6% of total unsaponifiable matter), with no significant differences between African and hybrid palm oils. The composition of the triterpenol fraction does not show significant variations between the African and hybrid palm oils, as well; cycloartenol (70–75% of total triterpenols), and 24-methylenecycloartanol (14–20%) are the two most represented components [31, 32]. Oil levels of 4,4-dimethylsterols increase from 200 mg/Kg at 18 WAA (beginning of inolition) to 340 mg/Kg at 24 WAA (maximum of inolition) [31].

#### **4.3. 4-methylsterols**

Carotenoids are responsible for the color of the oils obtained from mesocarp of palm fruits. A wide range (500–10,000 mg/Kg oil) of their level in hybrid palm oils was reported in literature [3, 10, 33, 44]. Eleven types of carotenes have been identified (α-, β-, ζ-, γ-, and δ-carotene, phytoene, phytofluene, neurosporene, α- and β-zeacarotene, and lycopene), with no qualitative variations among EO, EG and their hybrids. β-carotene is the most represented (52–60% of total carotenes), followed by α-carotene (33–36% of total carotenes). Major quantitative differences are related to lycopene, whose levels account for 1–8% of total carotenes in EG whereas in EO and O×G hybrids lycopene percentages are less than 0.1% [44]. Squalene ranges from 20 to 250 mg/Kg oil [31, 32]. African palm oil was characterized by higher contents of carotenes

**Table 4.** Literature data on composition of the unsaponifiable fraction of O×G interspecific hybrid palm oil. Data are

provided as mg/Kg oil unless % is indicated. Percentages refer to within class of unsaponifiable components.

**Reference [10] [44] [33] [32] [31]**

Total Tocols 600–1000 452–2189 259.3 ± 48.4 10.9–26.2

δ-tocotrienol 5–9% 31.8 ± 4.2/11.7 ± 0.8% α-tocomonoenol 4.0 ± 1.7/1.6 ± 0.3%

**Other** (Hc + carotenoids) 1070–1800 800–2400 514–1375 10389.3 ± 1004.9

More than 40 alcoholic compounds, belonging to six classes (4-desmethylsterols, 4,4-dimethylsterols, isoprenoid alcohols, n-alkanols and tocols) have been identified in screw pressed crude palm oil obtained from interspecific hybrids. Desmethylsterols and isoprenoid alcohols are the most represented classes, accounting for 79–85% of total alcohols, followed by *n*-alkanols (4–8% of total alcohols), 4,4-dimethylsterols (5–6%), tocols (3–4%), and 4-methylsterols (1–3%) [32]. Quantitative data expressed in mg/kg oil show a trend of progressive accumulation of squalene, desmethylsterols, isoprenoid alcohols, tocols, and 4,4-dimethylsterols in crude hybrid palm oil during ripening, whereas *n*-alkanols and 4-methylsterols show apparently stable levels in total lipids, which can be attributed to the increase in their amounts at the same time

The content of phytosterols in hybrid palm oil ranges from 160 to 1400 mg/kg oil [31–33,

"campesterol" (campesterol +22,23-dihydrobrassicasterol), stigmasterol, β-sitosterol, Δ5

avenasterol, Δ5,24-stigmastadienol, fucosterol, and clerosterol; ergosterol (ergosta-5,7,22-trien-





[44] and squalene [32] than O×G interspecific hybrid oil.

TAGs were synthesized [32, 33].

3β-ol) was tentatively identified, whereas Δ7

**4.1. 4-desmethylsterols**

Hc = hydrocarbons.

Ripe fruit (24 WAA).

Samples collected at phenological stages 806–809.

Samples collected between 18 and 24 WAA.

a

162 Palm Oil

b

c

44]. Δ5

Δ7

Citrostadienol was the main 4-methylsterol in hybrid palm oil, followed by obtusifoliol (4,14-dimethylergosta-8,24(28)-dien-3-ol). Gramisterol (24-methylenelophenol) was also identified. The content of 4-methylsterols ranges 7–15 mg/Kg g oil (corresponding to 0.1– 0.2% of total unsaponifiable matter), with no significant differences between African and hybrid oils. The composition of the 4-methylsterols fraction does not show significant variations between the African and hybrid palm oils too; cytrostadienol ranged from 44.5 to 50.3% of total 4-methylsterols, obtusifoliol from 14.3 to 31.5%, and gramisterol from 24.0 to 35.4%. Total content of 4-methylsterols does not significantly change during ripening [31, 32].

#### **4.4. Aliphatic alcohols**

A complete series of aliphatic alcohols of even number of carbon atoms from 18 to 34 was identified in mesocarp oil from hybrid palm fruits. Odd carbon number alkanols C29, C31, and C33 were also identified [31, 32]. *n*-alkanols level ranges 25–80 mg/Kg oil, without significant differences between African and hybrid palm oil. The pattern of *n*-alkanols, according to the number of carbon atoms, follows a typical unimodal distribution with a maximum abundance of alcohol C32, in both EG and hybrid oil types [32]. Ripening stage affects aliphatic alcohol fraction neither from a qualitative nor from quantitative viewpoint [31].

After 4-desmethylsterols, isoprenoid alcohols (terpenols) are the most represented class of alcoholic components of unsaponifiable matter of hybrid pal oil. A series of terpenols with 20 carbon atoms and 1 (phytol), 2, 3, and 4 (geranylgeraniol) double bonds has been identified. Hybrid palm oil is characterized by higher (160–330 mg/Kg), although not statistically significant, contents of isoprenoid alcohols, and by a higher phytol/geranylgeraniol ratio than EG mesocarp oil [32].

#### **4.5. Tocols**

At least seven different tocols were identified in mesocarp oil from hybrid palm fruits [31, 32, 44]: 5,7,8-trimethyl (α isomer) tocol and tocotrienol, 5,8-dimethyl (β isomer) tocol and tocotrienol, 7,8-dimethyl (γ isomer) tocol and tocotrienol, and 8-monomethyl (δ isomer) tocotrienol. The whole amount of tocols in hybrid palm oils greatly varies between 10 and 2200 mg/Kg [31–33, 44]. Experimental data about tocols composition of hybrid palm oils [32, 44] report a range of 10–24% for α-tocopherol, 42–60% for γ-tocotrienol, 15–31% for α-tocotrienol, and 5–12% for δ-tocotrienol. A trend of increase in total tocols content was observed during fruit ripening [31, 33].

Hence, the use of unrefined vegetable oils can both avoid the exposure to toxicants originating during processing and provide significant levels of substances (antioxidants) that are able to protect from negative effects of free radicals and reactive oxygen species. Indeed, EVOO is the most famous (among edible fats/oils) source of nutritionally valuable bioactive compounds (polyphenols) and, for the latest decades, a great amount of literature has been producing on the role of EVOO antioxidants in the prevention of chronic and degenerative diseases (cardiovascular diseases, obesity, type 2 diabetes, inflammatory processes, cancer, aging). Recently, tocotrienols have gained attention for their higher biological effectiveness than tocopherols, as antioxidant and anticancer agents. Crude palm oil obtained from O×G interspecific hybrid contains high amount of tocotrienols and carotenoids, together with a more favorable SFA/UFA ratio than the traditional African palm oil. Recently, phenolics of crude hybrid palm oil and their evolution during ripening were studied [51]: total amount of phenolic substances ranges between 190 and 260 mg GAE/kg oil and a decreasing trend during ripening has been observed. Those levels are comparable to phenolic amounts in EVOO and several molecules that already have been identified in EVOO have been found in hybrid palm oil as well (protocatechuic acid, protocatechualdehyde, *p*-salicylic acid, vanillic acid,

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165

Lucci and co-workers [52] found that consumption of crude palm oil from interspecific hybrids has a favorable effect on plasma lipids pattern (total cholesterol, low-density lipoprotein cholesterol, and high-density lipoprotein cholesterol) and that this effect is not statistically different from dietary EVOO. Recently, Ojeda et al. [53] explored the impact of daily crude oil consumption (25 mL/day for 3 months) on plasma/serum antioxidant capacity (trolox equivalent antioxidant capacity, TEAC, and oxygen radical absorbance capacity, ORAC, assays) and total phenolic content in adults aged 50–77; they also compared the effect of hybrid palm oil and EVOO supplementations. Palm oil significantly increases the total phenolic content and the antioxidant capacity of human plasma (measured by both ORAC and TEAC methods); furthermore, no significant differences have been found between crude palm oil and EVOO groups for the measured parameters. Due to those interesting discoveries, it has been suggested to consider crude palm oil from interspecific hybrid as the "tropical

and Urszula Tylewicz<sup>2</sup>

1 Università Politecnica delle Marche, Department of Agricultural, Food and Environmental

2 Alma Mater Studiorum-Università di Bologna, Department of Agricultural and Food

syringic acid, syringaldehyde, ferulic acid).

\*, Roberta Foligni<sup>1</sup>

\*Address all correspondence to: m.mozzon@staff.univpm.it

equivalent of olive oil".

**Author details**

Massimo Mozzon<sup>1</sup>

Sciences, Ancona, Italy

Sciences, Cesena, Italy

## **5. Hybrid palm oil and health**

Several drawbacks contribute to negatively affect the reputation of conventional palm oil among consumers. Involvement of dietary SFAs, mainly P, in the serum lipids profile and in the development of obesity, metabolic syndrome, type 2 diabetes and cancer were thoroughly discussed and confirmed [50]. Besides, it is estimated that only a quarter of palm oil worldwide is used as a crude oil. In EU and USA fatty substances from palm drupes are mostly used in their odorless and pale-yellow forms resulting from refining processes. Refining aims to remove volatile (off-odors, water) and non-volatile (FFA, phospholipids, pigments) oil components other than TAGs. The process causes not only a strong reduction of nutritionally valuable components (antioxidants, such as tocols and polyphenols) but also generates new toxicant. Since late 2000s, non-volatile chloropropanols (3-monochloropropane-1,2-diol, 3-MCPD; 2-monochloropropane-1,3-diol, 2-MCPD), glycidol, and their esters with FAs have been receiving increasing attention. Due to the elevated temperatures reached, the deodorization step is the most important contributor to the generation of those toxicants. Among the most consumed edible fatty substances, palm oil has the highest levels of MCPD and glycidol esters (**Table 5**). On the basis of available data, the European Food Safety Authority (EFSA) have concluded that estimated exposure of the younger aged groups of population to 3-MCPD could substantially exceed the tolerable daily intake (TDI) [7].


**Table 5.** Occurrence (mean values, μg/Kg) of 3-MCPD, 2-MCPD and glycidol (from esters) in edible fats and oils during the period 2012–2015. Data referred to five edible oils most consumed in EU (globally 90% of total edible oil consumption); palm kernel oil as comparison (data from [11]).

Hence, the use of unrefined vegetable oils can both avoid the exposure to toxicants originating during processing and provide significant levels of substances (antioxidants) that are able to protect from negative effects of free radicals and reactive oxygen species. Indeed, EVOO is the most famous (among edible fats/oils) source of nutritionally valuable bioactive compounds (polyphenols) and, for the latest decades, a great amount of literature has been producing on the role of EVOO antioxidants in the prevention of chronic and degenerative diseases (cardiovascular diseases, obesity, type 2 diabetes, inflammatory processes, cancer, aging). Recently, tocotrienols have gained attention for their higher biological effectiveness than tocopherols, as antioxidant and anticancer agents. Crude palm oil obtained from O×G interspecific hybrid contains high amount of tocotrienols and carotenoids, together with a more favorable SFA/UFA ratio than the traditional African palm oil. Recently, phenolics of crude hybrid palm oil and their evolution during ripening were studied [51]: total amount of phenolic substances ranges between 190 and 260 mg GAE/kg oil and a decreasing trend during ripening has been observed. Those levels are comparable to phenolic amounts in EVOO and several molecules that already have been identified in EVOO have been found in hybrid palm oil as well (protocatechuic acid, protocatechualdehyde, *p*-salicylic acid, vanillic acid, syringic acid, syringaldehyde, ferulic acid).

Lucci and co-workers [52] found that consumption of crude palm oil from interspecific hybrids has a favorable effect on plasma lipids pattern (total cholesterol, low-density lipoprotein cholesterol, and high-density lipoprotein cholesterol) and that this effect is not statistically different from dietary EVOO. Recently, Ojeda et al. [53] explored the impact of daily crude oil consumption (25 mL/day for 3 months) on plasma/serum antioxidant capacity (trolox equivalent antioxidant capacity, TEAC, and oxygen radical absorbance capacity, ORAC, assays) and total phenolic content in adults aged 50–77; they also compared the effect of hybrid palm oil and EVOO supplementations. Palm oil significantly increases the total phenolic content and the antioxidant capacity of human plasma (measured by both ORAC and TEAC methods); furthermore, no significant differences have been found between crude palm oil and EVOO groups for the measured parameters. Due to those interesting discoveries, it has been suggested to consider crude palm oil from interspecific hybrid as the "tropical equivalent of olive oil".

## **Author details**

**3-MCPD 2-MCPD Glycidol**

Palm oil 2912 1565 3955 Sunflower oil 503 233 650 Rapeseed oil 232 109 166 Olive oil 48 86 15 Soybean 394 167 171 Palm kernel oil 624 270 421

3-MCPD could substantially exceed the tolerable daily intake (TDI) [7].

consumption); palm kernel oil as comparison (data from [11]).

**4.5. Tocols**

164 Palm Oil

**5. Hybrid palm oil and health**

**Table 5.** Occurrence (mean values, μg/Kg) of 3-MCPD, 2-MCPD and glycidol (from esters) in edible fats and oils during the period 2012–2015. Data referred to five edible oils most consumed in EU (globally 90% of total edible oil

At least seven different tocols were identified in mesocarp oil from hybrid palm fruits [31, 32, 44]: 5,7,8-trimethyl (α isomer) tocol and tocotrienol, 5,8-dimethyl (β isomer) tocol and tocotrienol, 7,8-dimethyl (γ isomer) tocol and tocotrienol, and 8-monomethyl (δ isomer) tocotrienol. The whole amount of tocols in hybrid palm oils greatly varies between 10 and 2200 mg/Kg [31–33, 44]. Experimental data about tocols composition of hybrid palm oils [32, 44] report a range of 10–24% for α-tocopherol, 42–60% for γ-tocotrienol, 15–31% for α-tocotrienol, and 5–12% for δ-tocotrienol.

Several drawbacks contribute to negatively affect the reputation of conventional palm oil among consumers. Involvement of dietary SFAs, mainly P, in the serum lipids profile and in the development of obesity, metabolic syndrome, type 2 diabetes and cancer were thoroughly discussed and confirmed [50]. Besides, it is estimated that only a quarter of palm oil worldwide is used as a crude oil. In EU and USA fatty substances from palm drupes are mostly used in their odorless and pale-yellow forms resulting from refining processes. Refining aims to remove volatile (off-odors, water) and non-volatile (FFA, phospholipids, pigments) oil components other than TAGs. The process causes not only a strong reduction of nutritionally valuable components (antioxidants, such as tocols and polyphenols) but also generates new toxicant. Since late 2000s, non-volatile chloropropanols (3-monochloropropane-1,2-diol, 3-MCPD; 2-monochloropropane-1,3-diol, 2-MCPD), glycidol, and their esters with FAs have been receiving increasing attention. Due to the elevated temperatures reached, the deodorization step is the most important contributor to the generation of those toxicants. Among the most consumed edible fatty substances, palm oil has the highest levels of MCPD and glycidol esters (**Table 5**). On the basis of available data, the European Food Safety Authority (EFSA) have concluded that estimated exposure of the younger aged groups of population to

A trend of increase in total tocols content was observed during fruit ripening [31, 33].

Massimo Mozzon<sup>1</sup> \*, Roberta Foligni<sup>1</sup> and Urszula Tylewicz<sup>2</sup>

\*Address all correspondence to: m.mozzon@staff.univpm.it

1 Università Politecnica delle Marche, Department of Agricultural, Food and Environmental Sciences, Ancona, Italy

2 Alma Mater Studiorum-Università di Bologna, Department of Agricultural and Food Sciences, Cesena, Italy

## **References**

[1] Montoya C, Cochard B, Flori A, Cros D, Lopes R, Cuellar T, Espeout S, Syaputra I, Villeneuve P, Pina M, Ritter E, Leroy T, Billotte N. Genetic architecture of palm oil fatty acid composition in cultivated oil palm (*Elaeis guineensis* Jacq.) compared to its wild Relative *E. oleifera* (H.B.K) Cortés. PLoS One. 2014;**9**:e95412. DOI: 10.1371/journal. pone.0095412

[13] Moura JIL, Santos LPD, Bittencourt MAL, Krug C. Preference of palm weevils for oil palm, caiaué, and for their interspecific hybrid. PesquisaAgropecuariaBrasileira. 2013;**48**:

Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

http://dx.doi.org/10.5772/intechopen.75421

167

[14] Arias D, González M, Prada F, Ayala-Diaz I, Montoya C, Daza E, Romero HM. Genetic and phenotypic diversity of natural American oil palm (*Elaeis oleifera* (H.B.K.) Cortés) accessions. Tree Genetics and Genomes. 2015;**11**:22. DOI: 10.1007/s11295-015-0946-y

[15] Gomes Junior RA, Lopes R, Da Cunha RNV, Pina AJA, Quaresma CE, Santos RR, De Resende MDV. Bunch yield of interspecific hybrids of American oil palm with oil palm in the juvenile phase. Crop Breeding and Applied Biotechnology. 2016;**16**:86-94. DOI:

[16] Peixoto LA, Bhering LL, Gurgel FL, Gomes Junior RA. Parental selection for the formation of interspecific hybrid populations of oil palm.ActaScientiarum. Agronomy. 2015;**37**:155-

[17] Thomas RL, Ng SC, Chan KW. Phyllotaxis in the oil palm: Applications in selection of interspecific hybrids. Annals of Botany. 1970;**34**:1025-1035. DOI: 10.1093/oxfordjournals.

[18] Oboh BO, Fakorede MAB. A factor analysis of vegetative and yield traits in backcross progenies of an interspecific hybrid of oil palm. Journal of Genetics and Breeding. 1997;**51**:

[19] Chia GS, Lopes R, Da Cunha RNV, Da Rocha RNC, Lopes MTG. Repeatability for bunch production in interspecific hybrids between caiaué and African oil palm. Acta Amazonica.

[20] Hormaza P, Mesa F, Mauricio E, Romero H. Phenology of the oil palm interspecific hybrid *Elaeis oleifera* × *Elaeis guineensis*. Scientia Agricola. 2012;**69**:275-280. DOI: 10.1590/S0103-

[21] Madon M, Phoon LQ, Clyde MM, Mohd DA. Application of flow cytometry for estimation of nuclear DNA content in *Elaeis*. Journal of Oil Palm Research. 2008;**20**:447-452

[22] Camillo J, Leão AP, Alves AA, Formighieri EF, Azevedo AL, Nunes JD, De Capdeville G, Mattos JKA, Souza MT. Reassessment of the genome size in *Elaeis guineensis* and *Elaeis oleifera*, and its interspecific hybrid. Genomics Insights. 2014;**7**:13-22. DOI: 10.4137/

[23] Bayona-Rodríguez CJ, Ochoa-Cadavid I, Romero HM. Impacts of the dry season on the gas exchange of oil palm (*Elaeis guineensis*) and interspecific hybrid (*Elaeis oleifera* × *Elaeis guineensis*) progenies under field conditions in eastern Colombia. Agronomia

[24] Méndez YDR, Chacón LM, Bayona CJ, Romero HM. Physiological response of oil palm interspecific hybrids (*Elaeis oleifera* H.B.K. Cortes versus *Elaeis guineensis* Jacq.) to water deficit. Brazilian Journal of Plant Physiology. 2012;**24**:273-280. DOI: 10.1590/

Colombiana. 2016;**34**:329-335. DOI: 10.15446/agron.colomb.v34n3.55565

454-456. DOI: 10.1590/S0100-204X2013000400015

10.1590/1984-70332016v16n2a14

aob.a084433

2009;**39**:249-254

90162012000400007

GEI.S15522

S1677-04202012000400006

257-262

161. DOI: 10.4025/actasciagron.v37i2.19145


[13] Moura JIL, Santos LPD, Bittencourt MAL, Krug C. Preference of palm weevils for oil palm, caiaué, and for their interspecific hybrid. PesquisaAgropecuariaBrasileira. 2013;**48**: 454-456. DOI: 10.1590/S0100-204X2013000400015

**References**

166 Palm Oil

pone.0095412

10.1016/j.rser.2007.10.001

10.1007/BF00397784

2003;**39**:225-240. DOI: 10.1017/S0014479703001315

[1] Montoya C, Cochard B, Flori A, Cros D, Lopes R, Cuellar T, Espeout S, Syaputra I, Villeneuve P, Pina M, Ritter E, Leroy T, Billotte N. Genetic architecture of palm oil fatty acid composition in cultivated oil palm (*Elaeis guineensis* Jacq.) compared to its wild Relative *E. oleifera* (H.B.K) Cortés. PLoS One. 2014;**9**:e95412. DOI: 10.1371/journal.

[2] Oilseeds: World Markets and Trade [Internet]. 2018. Available from: https://apps.fas.

[3] Mozzon M, Pacetti D, Lucci P, Balzano M, Frega NG. Crude palm oil from interspecific hybrid *Elaeis oleifera* × *E. guineensis*: Fatty acids regiodistribution and molecular species of glycerides. Food Chemistry. 2013;**141**:245-252. DOI: 10.1016/j.foodchem.2013.03.016 [4] Lieb VM, Kerfers MR, Kronmüller A, Esquivel P, Alvarado A, Jiménez VM, Schmarr H-G, Carle R, Schweiggert RM, Steingass CB.Characterization of Mesocarp and kernel lipids from *Elaeis guineensis* Jacq., *Elaeis oleifera* [Kunth] Cortés, and their interspecific hybrids. Journal of Agricultural and Food Chemistry. 2017;**65**:3617-3626. DOI: 10.1021/acs.jafc.7b00604 [5] Tan BK, Ong SH, Rajanaidu N, Rao V. Biological modification of oil composition. Journal of the American Oil Chemists' Society. 1985;**62**:230-236. DOI: 10.1007/BF02541383

[6] Ting N-C, Yaakub Z, Kamaruddin K, Mayes S, Massawe F, Sambanthamurthi R, Jansen J, Low LET, Ithnin M, Kushairi A, Arulandoo X, Rosli R, Chan K-L, Amiruddin N, Sritharan K, Lim CC, Nookiah R, Amiruddin MD, Singh R. Fine-mapping and cross-validation of QTLs linked to fatty acid composition in multiple independent interspecific crosses of oil

[7] EFSA Panel on Contaminants in the Food Chain. Risks for human health related to the presence of 3- and 2-monochloropropanediol (MCPD), and their fatty acid esters, and glycidyl fatty acid esters in food. EFSA Journal. 2016;**14**:4426. DOI: 10.2903/j.efsa.2016.4426

[8] Tan KT, Lee KT, Mohamed AR, Bhatia S. Palm oil: Addressing issues and towards sustainable development. Renewable and Sustainable Energy Reviews. 2009;**13**:420-427. DOI:

[9] Palm Oil: Awareness, Attitudes and Consumer Behaviours [Internet]. 2016. Available from: http://www.palmoilandfood.eu/sites/default/files/Laurent%20Cremona%20-%20

[10] Hardon JJ. Interspecific hybrids in the genus *Elaeis*. II. Vegetative growth and yield of F1 hybrids *E. guineensis* × *E. oleifera*. Euphytica. 1969;**18**:380-388. DOI: 10.1007/BF00397785

[11] Hardon JJ, Tan GY. Interspecific hybrids in the genus *Elaeis*. I. Crossability, cytogenetics and fertility of F1 hybrids of *E. guineensis* × *E. oleifera*. Euphytica. 1969;**18**:372-379. DOI:

[12] De Franqueville H. Oil palm bud rot in Latin America. Experimental Agriculture.

TNS%20survey%20on%20Palm%20Oil%202016.pdf [Accessed: 2018-01-08]

palm. BMC Genomics. 2016;**17**:289. DOI: 10.1186/s12864-016-2607-4

usda.gov/psdonline/circulars/oilseeds.pdf [Accessed: January 08, 2018]


[25] Rivera-Méndez YD, Chacón ALM Romero HM. Response of the roots of oil palm O×G interspecific hybrids (*Elaeis oleifera* × *Elaeis guineensis*) to aluminum (Al3+) toxicity. Australian Journal of Crop Science. 2014;**8**:1526-1533

[36] Rudzińska M, Hassanein MMM, Abdel-Razek AG, Kmiecik D, Siger A, Ratusz K. Influence of composition on degradation during repeated deep-fat frying of binary and ternary blends of palm, sunflower and soybean oils with health-optimised saturated-to-unsaturated fatty acid ratios. International Journal of Food Science and Technology. **53**:1021-1029.

Chemical Characteristics and Nutritional Properties of Hybrid Palm Oils

http://dx.doi.org/10.5772/intechopen.75421

169

[37] Barcelos E, Amblard P, Berthaud J, Seguin M. Genetic diversity and relationship in American and African oil palm as revealed by RFLP and AFLP molecular markers. Pesquisa Agropecuària Brasileira. 2002;**37**:1105-1114. DOI: 10.1590/S0100-204X2002000800008

[38] Ong SH, Chuah CC, Sow HP. The co-dominance theory: Genetic interpretations of analyses of mesocarp oils from *Elaeis guineensis*, *Elaeis oleifera* and their hybrids. Journal of

the American Oil Chemists' Society. 1981;**58**:1032-1038. DOI: 10.1007/BF02679320

[39] Zulkifli Y, Rajinder S, Mohd Din A, Ting NC, Rajanaidu N, Kushairi A, Musa B, Mohamad O, Ismanizan I. Inheritance of SSR and SNP loci in an oil palm interspecific hybrid backcross (BC2) population. Journal of Oil Palm Research. 2014;**26**:203-213

[40] Nordiana HMN, Ngoot-Chin T, Singh R, Clyde MM, Madon M. Evaluation of intersimple sequence repeat (ISSR) markers for genetic mapping of an oil palm interspecific

[41] Singh R, Tan SG, Panandam JM, Rahman RA, Ooi LC-L, Low E-TL, Sharma M, Jansen J, Cheah S-C. Mapping quantitative trait loci (QTLs) for fatty acid composition in an interspecific cross of oil palm. BMC Plant Biology. 2009;**9**:114. DOI: 10.1186/1471-2229-9-114

[42] Opute FI, Obasola CO. Breeding for short-stemmed oil palm in Nigeria: Fatty acids, their significance and characteristics. Annals of Botany. 1979;**43**:677-681. DOI: 10.1093/

[43] Tan BK, Berger KG. Characteristics of kernel oils from *Elaeis oleifera*, F1 hybrids and backcross with *Elaeis guineensis*. Journal of the Science of Food and Agriculture. 1982;**33**:204-

[44] Choo YM, Yap S. Carotenes, vitamin E and sterols in oils from *Elaeis guineensis*, *Elaeis* 

[45] Haddad I, Mozzon M, Strabbioli R, Frega NG. Electrospray ionization tandem mass spectrometry analysis of triacylglycerols molecular species in camel milk (*Camelus dromedarius*). International Dairy Journal. 2011;**21**:119-127. DOI: 10.1016/j.idairyj.2010.09.003

[46] Haddad I, Mozzon M, Strabbioli R, Frega NG. A comparative study of triacylglycerols molecular species composition in equine and human milks. Dairy Science and

[47] Haddad I, Mozzon M, Frega NG. Trends in fatty acids positional distribution in human colostrum, transitional and mature milk. European Food Research and Technology.

hybrid mapping population. Journal of Oil Palm Research. 2014;**26**:214-225

DOI: 10.1111/ijfs.1367

oxfordjournals.aob.a085680

208. DOI: 10.1002/jsfa.2740330213

*oleifera* and their hybrids. Palmas. 1998;**19**:79-85

Technology. 2012;**92**:37-56. DOI: 10.1007/s13594-011-0042-5

2012;**235**:325-332. DOI: 10.1007/s00217-012-1759-y


[36] Rudzińska M, Hassanein MMM, Abdel-Razek AG, Kmiecik D, Siger A, Ratusz K. Influence of composition on degradation during repeated deep-fat frying of binary and ternary blends of palm, sunflower and soybean oils with health-optimised saturated-to-unsaturated fatty acid ratios. International Journal of Food Science and Technology. **53**:1021-1029. DOI: 10.1111/ijfs.1367

[25] Rivera-Méndez YD, Chacón ALM Romero HM. Response of the roots of oil palm O×G interspecific hybrids (*Elaeis oleifera* × *Elaeis guineensis*) to aluminum (Al3+) toxicity. Australian

[26] De Matos GSB, Fernandes AR, Wadt PGS, Pina AJA, Franzini VI, Ramos HMN. The use of DRIS for nutritional diagnosis in oil palm in the state of Pará. Revista Brasileira de

[27] Lima WAA, Lopes R, Green M, Cunha RNV, Abreu SC, Cysne AQ. Heat treatment and germination of seeds of interspecifc hybrid between American oil palm (*Elaeis oleifera* (H.B.K) Cortes) and African oil palm (*Elaeis guineensis* Jacq.). Journal of Seed Science.

[28] Fooyontphanich K, Morcillo F, Amblard P, Collin M, Jantasuriyarat C, Verdeil J-L, Tangphatsornruang S, Tranbarger TJ. A phenotypic test for delay of abscission and nonabscission oil palm fruit and validation by abscission marker gene expression analysis.

[29] Galindo-Castañeda T, Romero HM. Mycorrhization in oil palm (*Elaeis guineensis* and *E. oleifera* × *E. guineensis*) in the pre-nursery stage. Agronomia Colombiana. 2013;**31**:95-102

[30] Rivera Méndez YD, Moreno Chacón AL, Romero HM. Biochemical and physiological characterization of oil palm interspecific hybrids (*Elaeis oleifera* × *Elaeis guineensis*) grown

[31] Lucci P, Pacetti D, Frega NG, Mozzon M. Phytonutrient concentration and unsaturation of glycerides predict optimal harvest time for *Elaeis oleifera* × *E. guineensis* palm oil hybrids. European Journal of Lipid Science and Technology. 2015;**117**:1027-1036. DOI:

[32] Mozzon M, Pacetti D, Frega NG, Lucci P. Crude palm oil from interspecific hybrid *Elaeis oleifera* × *E. guineensis*: Alcoholic constituents of unsaponifiable matter. Journal of the American Oil Chemists' Society. 2015;**92**:717-724. DOI: 10.1007/s11746-015-2628-1

[33] Rincón SM, Hormaza PA, Moreno LP, Prada F, Portillo DJ, García JA, Romero HM. Use of phenological stages of the fruits and physico chemical characteristics of the oil to determine the optimal harvest time of oil palm interspecific O×G hybrid fruits. Industrial

[34] Macfarlane N, Swetman T, Cornelius JA. Analysis of mesocarp and kernel oils from the American oil palm and F1 hybrids with the west African oil palm. Journal of the Science

[35] Cadena T, Prada F, Perea A, Romero HM. Lipase activity, mesocarp oil content, and iodine value in oil palm fruits of *Elaeis guineensis*, *Elaeis oleifera*, and the interspecific hybrid O×G (*E. oleifera* × *E. guineensis*). Journal of the Science of Food and Agriculture. 2013;**93**:674-680.

Crops and Products. 2013;**49**:204-210. DOI: 10.1016/j.indcrop.2013.04.035

of Food and Agriculture. 1975;**26**:1293-1298. DOI: 10.1002/jsfa.2740260907

Acta Horticulturae. 2016;**1119**:97-104. DOI: 10.17660/ActaHortic.2016.1119.13

Ciencia do Solo. 2017;**41**:e0150466: DOI: 10.1590/18069657rbcs20150466

Journal of Crop Science. 2014;**8**:1526-1533

168 Palm Oil

2014;**36**:451-457. DOI: 10.1590/2317-1545v36n41034

in hydroponics. Acta Biologica Colombiana. 2013;**18**:465-472

10.1002/ejlt.201400599

DOI: 10.1002/jsfa.5940


[48] Haddad I, Mozzon M, Strabbioli R, Frega NG. Fatty acid composition and regiodistribution in mare's milk triacylglycerols at different lactation stages. Dairy Science and Technology. 2011;**91**:397-412. DOI: 10.1007/s13594-011-0020-y

**Chapter 10**

**Provisional chapter**

**Effects of Dietary Palm Oil on the Whole-Body Mineral**

**Effects of Dietary Palm Oil on the Whole-Body Mineral** 

A 50-day feeding trial was carried out to determine the effect of the graded incorporation of crude palm oil on the whole-body mineral composition of African catfish juveniles *Heterobranchus longifilis.* Six diets were formulated to contain from 3–21% crude palm oil (CPO). Whole-body macromineral composition represented by calcium (Ca), potassium (K), sodium (Na), phosphorus (P) and magnesium (Mg) showed significant variations (p < 0.05) with the different dietary palm oil levels. The same trend was observed in whole-body micromineral composition in iron (Fe), zinc (Zn), manganese (Mn) and copper (Cu). Regardless of the micromineral, the increase in the body was related with increasing dietary palm oil levels between 3 and 9%. In summary, the results of this study suggest that an incorporation of palm oil into the fish diet modifies the mineral body

**Keywords:** *Heterobranchus longifilis*, palm oil, feeding, whole-body mineral composition,

Fish plays an important role in human nutrition. It represents an important source of proteins and lipids. In terms of nutrition, fish provides high-value proteins and long-chain (omega-3) polyunsaturated fatty acids that are beneficial to human health [1]. According to the Food and Agriculture Organization (FAO) of the United Nations [2], world consumption of fish per

composition without major effects on health and nutritional quality of fish.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

DOI: 10.5772/intechopen.76615

**Composition of African Catfish,** *Heterobranchus*

**Composition of African Catfish,** *Heterobranchus* 

*longifilis* **(Teleostei, Clariidae)**

**longifilis (Teleostei, Clariidae)**

Laurent Alla Yao

**Abstract**

nutritional quality

**1. Introduction**

Laurent Alla Yao

Célestin Mélécony Ble, Olivier Assoi Etchian,

Célestin Mélécony Ble, Olivier Assoi Etchian,

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76615

Athanase Kraidy Otchoumou, Jean Noel Yapi and

Athanase Kraidy Otchoumou, Jean Noel Yapi and


#### **Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish,** *Heterobranchus longifilis* **(Teleostei, Clariidae) Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish,** *Heterobranchus*  **longifilis (Teleostei, Clariidae)**

DOI: 10.5772/intechopen.76615

Célestin Mélécony Ble, Olivier Assoi Etchian, Athanase Kraidy Otchoumou, Jean Noel Yapi and Laurent Alla Yao Célestin Mélécony Ble, Olivier Assoi Etchian, Athanase Kraidy Otchoumou, Jean Noel Yapi and Laurent Alla Yao

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76615

#### **Abstract**

[48] Haddad I, Mozzon M, Strabbioli R, Frega NG. Fatty acid composition and regiodistribution in mare's milk triacylglycerols at different lactation stages. Dairy Science and

[49] Haddad I, Mozzon M, Strabbioli R, Frega NG. Stereospecific analysis of triacylglycerols in camel (*Camelus dromedarius*) milk fat. International Dairy Journal. 2010;**20**:863-867.

[50] Pedersen JI. Health aspects of saturated fatty acids. In: Talbot G, editor. Reducing Saturated Fats in Foods. Cambridge: Woodhead Publishing; 2011. pp. 77-97. DOI: 10.1533/

[51] Rodríguez JC, Gómez D, Pacetti D, Núñez O, Gagliardi R, Frega NG, Ojeda ML, Loizzo MR, Tundis R, Lucci P. Effects of the fruit ripening stage on antioxidant capacity, total phenolics, and polyphenolic composition of crude palm oil from interspecific hybrid *Elaeis oleifera* × *Elaeis guineensis*. Journal of Agricultural and Food Chemistry. 2016;**64**:852-859.

[52] Lucci P, Borrero M, Ruiz A, Pacetti D, Frega NG, Diez O, Ojeda M, Gagliardi R, Parra L, Angel M. Palm oil and cardiovascular disease: A randomized trial of the effects of hybrid palm oil supplementation on human plasma lipid patterns. Food and Function.

[53] Ojeda M, Borrero M, Sequeda G, Diez O, Castro V, García Á, Ruiz Á, Pacetti D, Frega N, Gagliardi R, Lucci P. Hybrid palm oil (*Elaeis oleifera* × *Elaeis guineensis*) supplementation improves plasma antioxidant capacity in humans. European Journal of Lipid Science

and Technology. 2017;**119**. Article ID: 1600070. DOI: 10.1002/ejlt.201600070

Technology. 2011;**91**:397-412. DOI: 10.1007/s13594-011-0020-y

DOI: 10.1016/j.idairyj.2010.06.006

DOI: 10.1021/acs.jafc.5b04990

2016;**7**:347-354. DOI: 10.1039/c5fo01083g

9780857092472.1.77

170 Palm Oil

A 50-day feeding trial was carried out to determine the effect of the graded incorporation of crude palm oil on the whole-body mineral composition of African catfish juveniles *Heterobranchus longifilis.* Six diets were formulated to contain from 3–21% crude palm oil (CPO). Whole-body macromineral composition represented by calcium (Ca), potassium (K), sodium (Na), phosphorus (P) and magnesium (Mg) showed significant variations (p < 0.05) with the different dietary palm oil levels. The same trend was observed in whole-body micromineral composition in iron (Fe), zinc (Zn), manganese (Mn) and copper (Cu). Regardless of the micromineral, the increase in the body was related with increasing dietary palm oil levels between 3 and 9%. In summary, the results of this study suggest that an incorporation of palm oil into the fish diet modifies the mineral body composition without major effects on health and nutritional quality of fish.

**Keywords:** *Heterobranchus longifilis*, palm oil, feeding, whole-body mineral composition, nutritional quality

#### **1. Introduction**

Fish plays an important role in human nutrition. It represents an important source of proteins and lipids. In terms of nutrition, fish provides high-value proteins and long-chain (omega-3) polyunsaturated fatty acids that are beneficial to human health [1]. According to the Food and Agriculture Organization (FAO) of the United Nations [2], world consumption of fish per

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

capita has increased from 5.2 kg in 1961 to 20 kg in 2014. In sub-Saharan Africa, fish represents on average 22% of dietary animal protein [3]. Fish consumption is therefore constantly increasing in relation to the growth of world population.

of 0.80 ± 0.7 g. Before the start of the trial, the fish were stored in glass tanks and acclimated to the experimental conditions for a 2-week period during which they were fed with a control diet (CD). After this step the fish were randomly distributed in the glass (50 L) containing 30 fish. The flow of water in the glass tank was ensured at all times by an electric motor pump allowing a flow of 1.5 liter/min. The filtration was carried out by settling and water renewal of 30% was performed daily. During the experimental period the water temperature, pH and dissolved oxygen were considered favorable in fish culture tanks according to Boyd [15].

Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish…

http://dx.doi.org/10.5772/intechopen.76615

173

A control diet (containing no crude palm) and six experimental diets in which different palm oil levels were used were incorporated, and control diets were prepared using a 2 mm diameter pellet press and dried at 37°C. During the experiment, the diets were stored at 20°C. The composition and proximate composition of all diets are given in **Table 1** and mineral composition in **Table 2**. The diet was fed ad libitum, twice daily during 50 days. At the end of the experiment, all fish from the same tank were killed, weighed and individually measured and

The proximate composition of the experimental diets was determined according to the AOAC standard methods [16]. Gross energy (GE) contents of diets were calculated from the lipid and protein contents using the equivalents of 38.9 KJ.g−1 crude fats, 22.2 KJ.g−1 crude protein and

The mineral compositions were determined by atomic absorption spectrophotometry for calcium (Ca), phosphorus (P), potassium (K), sodium (Na), magnesium (Mg), iron (Fe), zinc (Zn), manganese (Mn) and copper (Cu) according to the AOAC standard methods [16].

All data were subjected to analysis of variance (ANOVA) using Statistica, statistical software for Windows (release 7.1). Comparisons among treatment means were carried out by a oneway analysis of variance followed by Duncan's test (0.05) [18]. Standard deviation (±SD) was

Lipids represent an essential component in the diet as they are a major source of energy and essential fatty acids [13]. However, an excess of dietary fat can affect the composition of the carcass due to increased lipid deposits and reduce the use of other nutrients [13]. On the other hand, dietary factor as feeding habits and nutritional status of fish can affect mineral and trace elements in fish. Minerals are inorganic elements that fish need for their different development stage, which they usually obtain through diet and water [19, 20]. In terms of minerals, dietary requirements in several fish distinguish two groups: macrominerals such as Ca, K, Mg, Na and P and microminerals such as Cu, Fe, I, Mn, Se and Zn, and several response

stored in the freezer at −20°C for the further analysis of whole-body composition.

**2.2. Experimental diets and methods**

**2.3. Proximate analysis**

**2.4. Statistical analysis**

**2.5. Results and discussion**

17.2 KJ.g−1 carbohydrate (NFE) [17].

calculated to identify the range of means.

Currently, aquaculture is the main activity likely to meet the need for fish due to the reduction of capture fisheries and the depletion of natural stocks associated with overfishing. Among the factors of production, food represents more than 50% and constitutes one of the major constraints to the development of aquaculture. To maintain aquaculture yields at a satisfactory level, the intensification of production with significant use of compound feed is achieved [4]. In aquafeeds, fish meal and fish oil represent the main ingredients because of their good nutritional quality. Fish oil provides dietary lipids that are an important source of essential fatty acids for growth, health and reproduction [5]. However, the availability of fish oil remains limited by higher price and the decline in fisheries' catches [6]. The use of alternative dietary oil sources such as vegetable oils is being considered and their ability to meet the nutritional requirements of fish has been studied for some years [7].

Among the vegetable oils, palm oil is the one whose world production has increased rapidly in recent years [5, 8]. The oil palm tree (*Elaeis guineensis*) from which crude palm oil (CPO) is extracted is native to West Africa. Palm oil is the richest natural source of the antioxidants ß-carotene and vitamin E. In addition, CPO contains 48.8% of saturated fats, especially 16:0, 37% of monounsaturated fats, mainly 18:1 n-9, and has low concentrations of polyunsaturated fats (9.1% n−6 and 0.2% n−3) with 9.1% linoleic acid [8]. Several studies using palm oil-based diets showed an improvement of growth performance [8–11]. Dietary lipids play important roles of the fish diet as a source of energy and have a sparing action on dietary protein [12]. However, high dietary lipid intake can affect carcass composition and reduce the utilization of other nutrients [13].

Minerals are among the nutrients that fish need to live. Minerals are essential constituents of skeletal structures and play an important role in the maintenance of osmotic pressure. Minerals serve as essential components of many enzymes, vitamins, hormones and respiratory pigments or as cofactors in metabolism, catalysts and enzyme activators.

Fish can satisfy their mineral needs by absorbing minerals dissolved in water or through the diet [14]. Biological factors such as trophic levels, dietary habits and nutritional status, dietary factors such as diet composition, availability and nutrient interactions and environmental factors such as water mineral concentration and temperature of the rearing system can affect dietary levels of minerals and trace elements in fish [14]. The aim of this study was to evaluate the effect of graded incorporation of crude palm oil on the mineral composition of African catfish *Heterobranchus longifilis*, fingerlings.

## **2. Materials and methods**

#### **2.1. Fish and experimental design**

This study was conducted at the hatchery of the Oceanological Research Center in Abidjan, Côte d'Ivoire. The fingerlings of *H. longifilis* used during the experiment had an average weight of 0.80 ± 0.7 g. Before the start of the trial, the fish were stored in glass tanks and acclimated to the experimental conditions for a 2-week period during which they were fed with a control diet (CD). After this step the fish were randomly distributed in the glass (50 L) containing 30 fish. The flow of water in the glass tank was ensured at all times by an electric motor pump allowing a flow of 1.5 liter/min. The filtration was carried out by settling and water renewal of 30% was performed daily. During the experimental period the water temperature, pH and dissolved oxygen were considered favorable in fish culture tanks according to Boyd [15].

#### **2.2. Experimental diets and methods**

A control diet (containing no crude palm) and six experimental diets in which different palm oil levels were used were incorporated, and control diets were prepared using a 2 mm diameter pellet press and dried at 37°C. During the experiment, the diets were stored at 20°C. The composition and proximate composition of all diets are given in **Table 1** and mineral composition in **Table 2**. The diet was fed ad libitum, twice daily during 50 days. At the end of the experiment, all fish from the same tank were killed, weighed and individually measured and stored in the freezer at −20°C for the further analysis of whole-body composition.

#### **2.3. Proximate analysis**

capita has increased from 5.2 kg in 1961 to 20 kg in 2014. In sub-Saharan Africa, fish represents on average 22% of dietary animal protein [3]. Fish consumption is therefore constantly

Currently, aquaculture is the main activity likely to meet the need for fish due to the reduction of capture fisheries and the depletion of natural stocks associated with overfishing. Among the factors of production, food represents more than 50% and constitutes one of the major constraints to the development of aquaculture. To maintain aquaculture yields at a satisfactory level, the intensification of production with significant use of compound feed is achieved [4]. In aquafeeds, fish meal and fish oil represent the main ingredients because of their good nutritional quality. Fish oil provides dietary lipids that are an important source of essential fatty acids for growth, health and reproduction [5]. However, the availability of fish oil remains limited by higher price and the decline in fisheries' catches [6]. The use of alternative dietary oil sources such as vegetable oils is being considered and their ability to meet the

Among the vegetable oils, palm oil is the one whose world production has increased rapidly in recent years [5, 8]. The oil palm tree (*Elaeis guineensis*) from which crude palm oil (CPO) is extracted is native to West Africa. Palm oil is the richest natural source of the antioxidants ß-carotene and vitamin E. In addition, CPO contains 48.8% of saturated fats, especially 16:0, 37% of monounsaturated fats, mainly 18:1 n-9, and has low concentrations of polyunsaturated fats (9.1% n−6 and 0.2% n−3) with 9.1% linoleic acid [8]. Several studies using palm oil-based diets showed an improvement of growth performance [8–11]. Dietary lipids play important roles of the fish diet as a source of energy and have a sparing action on dietary protein [12]. However, high dietary lipid intake can affect carcass composition and reduce the utilization

Minerals are among the nutrients that fish need to live. Minerals are essential constituents of skeletal structures and play an important role in the maintenance of osmotic pressure. Minerals serve as essential components of many enzymes, vitamins, hormones and respira-

Fish can satisfy their mineral needs by absorbing minerals dissolved in water or through the diet [14]. Biological factors such as trophic levels, dietary habits and nutritional status, dietary factors such as diet composition, availability and nutrient interactions and environmental factors such as water mineral concentration and temperature of the rearing system can affect dietary levels of minerals and trace elements in fish [14]. The aim of this study was to evaluate the effect of graded incorporation of crude palm oil on the mineral composition of African

This study was conducted at the hatchery of the Oceanological Research Center in Abidjan, Côte d'Ivoire. The fingerlings of *H. longifilis* used during the experiment had an average weight

tory pigments or as cofactors in metabolism, catalysts and enzyme activators.

increasing in relation to the growth of world population.

nutritional requirements of fish has been studied for some years [7].

of other nutrients [13].

172 Palm Oil

catfish *Heterobranchus longifilis*, fingerlings.

**2. Materials and methods**

**2.1. Fish and experimental design**

The proximate composition of the experimental diets was determined according to the AOAC standard methods [16]. Gross energy (GE) contents of diets were calculated from the lipid and protein contents using the equivalents of 38.9 KJ.g−1 crude fats, 22.2 KJ.g−1 crude protein and 17.2 KJ.g−1 carbohydrate (NFE) [17].

The mineral compositions were determined by atomic absorption spectrophotometry for calcium (Ca), phosphorus (P), potassium (K), sodium (Na), magnesium (Mg), iron (Fe), zinc (Zn), manganese (Mn) and copper (Cu) according to the AOAC standard methods [16].

## **2.4. Statistical analysis**

All data were subjected to analysis of variance (ANOVA) using Statistica, statistical software for Windows (release 7.1). Comparisons among treatment means were carried out by a oneway analysis of variance followed by Duncan's test (0.05) [18]. Standard deviation (±SD) was calculated to identify the range of means.

#### **2.5. Results and discussion**

Lipids represent an essential component in the diet as they are a major source of energy and essential fatty acids [13]. However, an excess of dietary fat can affect the composition of the carcass due to increased lipid deposits and reduce the use of other nutrients [13]. On the other hand, dietary factor as feeding habits and nutritional status of fish can affect mineral and trace elements in fish. Minerals are inorganic elements that fish need for their different development stage, which they usually obtain through diet and water [19, 20]. In terms of minerals, dietary requirements in several fish distinguish two groups: macrominerals such as Ca, K, Mg, Na and P and microminerals such as Cu, Fe, I, Mn, Se and Zn, and several response


the two structural components that play an important role in the body of fish. Ca is involved in bone formation, muscle contraction and enzymatic activation and is also involved in bone development and fish growth [19, 21]. Phosphorus is the most important mineral element in fish. Because of the limited contribution from the aquatic environment, the fish is obliged to satisfy the needs through diet. A phosphorus deficiency results in decreased skeletal growth and bone deformation [21, 22]. The other macrominerals determined in the diets were K, Na and Mg. The diets showed fairly variable contents of K with a higher value (100.2 g.kg−

**Experimental diets**

Palm oil inclusion level 0% 3% 5% 7% 9% 15% 21%

Ca (g.kg−1) 231.34 136.8 105.42 108.68 140.47 72.82 140.88 P (g.kg−1) 8.66 5.83 12.00 5.50 8.16 6.00 6.16 K (g.kg−1) 66.02 78.95 100.25 86.18 82.54 33.56 68.9 Na (g.kg−1) 82.36 75.39 78.31 99.41 61.56 45.36 59.09 Mg (g.kg−1) 2.43 1.40 2.44 2.23 2.41 2.21 2.51 Fe (mg.kg−1) 647.97 225.5 560.25 542.7 680.13 949.14 590.51 Zn (mg.kg−1) 940.02 51.00 267.01 440.01 855.02 609.01 950.02 Mn (mg.kg−1) 651.38 37.83 218.84 309.98 568.05 320.73 667.51

diet D2 and the lowest (33.5 g.kg−−1) in diet D5. Dietary Na and Mg contents did not vary con-

The microminerals analyzed in the experimental diets were Fe, Zn and Mn. Here too, it appeared that the contents were variable from one diet to another. Dietary Fe contents ranged from 225.5 to 949.1 mg.kg−1 with the higher level obtained in diet D5 and the lowest in diet

the lowest in the D1 diet. The minimal and maximal requirements for fish reported in other

Whole-body macromineral composition of fish is presented in **Figure 1**. Body composition in calcium (Ca), potassium (k), sodium (Na), phosphorus (P) and magnesium (Mg) showed significant variations (p < 0.05) with the different dietary palm oil levels. The Ca content of whole body increased with increasing dietary palm oil levels at 5 and 9%. The highest value of Ca (168.49 ± 8.01 g.kg−1) was recorded in fish fed with diet containing 9% of palm oil. Incorporation of palm oil at 3, 5, 7, 15 and 21% in diet increased fish whole-body K content and

1), Zn (36–330 mg.kg−

values recorded in this study were in excess than dietary requirements mentioned for fish.

1.

**CD D1 D2 D3 D4 D5 D6**

Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish…

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175

1. For these last two minerals, the highest levels are obtained in the D6 diet and

1 when Mn contents ranged from 37.8 to

1) and Mn (4.4–226 mg.kg−

siderably and ranged from 45.3–99.4 and 1.4–2.5 g.kg−

**Table 2.** Mineral composition of experimental diets (dry weight basis).

D1. Zn contents were between 51.0 and 950.0 mg.kg−

667.5 mg.kg−

**Mineral composition**

studies were: Fe (65–493 mg.kg−

1) in

1) [19].The

NFE: Nitrogen free extract.<sup>1</sup> Composition for 1 kg of premix: Vitamin A 1.760000 IU, Vitamin D3 880,000, IU Vitamin E 22.000 mg, Vitamin B1 4400 mg, Vitamin B2 5280 mg, Vitamin B6 4400 mg, Vitamin B1236 mg, Vitamin C 151000 mg, (Vitamin K) 4400 mg, Vitamin PP 35200 mg, folic acid 880 mg, choline chloride 220,000 mg, Pantothenic acid D-14080 mg. 2 Composition for 1 kg of premix: cobalt 20 mg, Iron 17,600 mg, Iodine 2000 mg, Copper 1600 mg, Zinc 60.000 mg, Manganese 10000 mg, Selenium 40 mg.

**Table 1.** Formulation and composition of the experimental diets (% dry weight).

criteria have been used to determine mineral requirements in different fish species [14]. In this study, the effect of the gradual incorporation of oil palm in the diet of juveniles *H. longifilis* was investigated.

The mineral proximate composition of the experimental diets in **Table 1** showed that, for the same mineral element, the contents were different according to the diets. As regards macrominerals, it should be noted that dietary Ca contents ranged from 72.8 to 231.3 g.kg−1, with the highest level found in control diet and the lowest in diet D4. These calcium contents are widely higher compared to the dietary calcium requirements of channel catfish that were between 5 and 20 g.kg−1 [13]. P contents in diet ranged from 5.5 to 8.6 g.kg−1 and were in accordance with the fish P requirements which ranged from 0.5 to 0.9% of the diet [21]. Ca and P are


**Table 2.** Mineral composition of experimental diets (dry weight basis).

criteria have been used to determine mineral requirements in different fish species [14]. In this study, the effect of the gradual incorporation of oil palm in the diet of juveniles *H. longifilis*

22.000 mg, Vitamin B1 4400 mg, Vitamin B2 5280 mg, Vitamin B6 4400 mg, Vitamin B1236 mg, Vitamin C 151000 mg, (Vitamin K) 4400 mg, Vitamin PP 35200 mg, folic acid 880 mg, choline chloride 220,000 mg, Pantothenic acid D-14080 mg.

Composition for 1 kg of premix: cobalt 20 mg, Iron 17,600 mg, Iodine 2000 mg, Copper 1600 mg, Zinc 60.000 mg,

Composition for 1 kg of premix: Vitamin A 1.760000 IU, Vitamin D3 880,000, IU Vitamin E

**Experimental diets**

Palm oil inclusion level 0% 3% 5% 7% 9% 15% 21%

Fish meal 30.00 30.00 30.00 30.00 30.00 30.00 30.00 Soybean meal 19.00 19.00 19.50 20.00 21.00 22.50 24.50 Cottonseed meal 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Maize meal 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Wheat bran 29.00 26.00 23.50 21.00 18.00 10.50 2.50 Cassava starch 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Crude palm oil 00.00 3.00 5.00 7.00 9.00 15.00 21.00 Mineral mixture<sup>1</sup> 1.50 1.50 1.50 1.50 1.50 1.50 1.50 Vitamin mixture<sup>2</sup> 1.50 1.50 1.50 1.50 1.50 1.50 1.50

Crude protein (%) 36.41 36.09 36.06 36.00 36.13 36.00 36.04 Crude lipid (%) 5.76 8.60 10.49 12.38 14.27 19.95 25.62 Ash (%) 8.94 8.89 8.88 8.87 8.88 8.85 8.84 Crude fiber (%) 3.73 3.63 3.58 3.52 3.48 3.31 3.15 NFE (%) 43.81 41.41 39.62 37.82 35.84 30.46 24.88 Digestible energy (kJg−1)3 13.97 14.71 15.21 15.71 16.22 17.73 19.25

**DC D1 D2 D3 D4 D5 D6**

The mineral proximate composition of the experimental diets in **Table 1** showed that, for the same mineral element, the contents were different according to the diets. As regards macrominerals, it should be noted that dietary Ca contents ranged from 72.8 to 231.3 g.kg−1, with the highest level found in control diet and the lowest in diet D4. These calcium contents are widely higher compared to the dietary calcium requirements of channel catfish that were between 5 and 20 g.kg−1 [13]. P contents in diet ranged from 5.5 to 8.6 g.kg−1 and were in accordance with the fish P requirements which ranged from 0.5 to 0.9% of the diet [21]. Ca and P are

was investigated.

NFE: Nitrogen free extract.<sup>1</sup>

Manganese 10000 mg, Selenium 40 mg.

**Table 1.** Formulation and composition of the experimental diets (% dry weight).

2

**Ingredients (g/100 g)**

174 Palm Oil

**Proximate analysis**

the two structural components that play an important role in the body of fish. Ca is involved in bone formation, muscle contraction and enzymatic activation and is also involved in bone development and fish growth [19, 21]. Phosphorus is the most important mineral element in fish. Because of the limited contribution from the aquatic environment, the fish is obliged to satisfy the needs through diet. A phosphorus deficiency results in decreased skeletal growth and bone deformation [21, 22]. The other macrominerals determined in the diets were K, Na and Mg. The diets showed fairly variable contents of K with a higher value (100.2 g.kg− 1) in diet D2 and the lowest (33.5 g.kg−−1) in diet D5. Dietary Na and Mg contents did not vary considerably and ranged from 45.3–99.4 and 1.4–2.5 g.kg− 1.

The microminerals analyzed in the experimental diets were Fe, Zn and Mn. Here too, it appeared that the contents were variable from one diet to another. Dietary Fe contents ranged from 225.5 to 949.1 mg.kg−1 with the higher level obtained in diet D5 and the lowest in diet D1. Zn contents were between 51.0 and 950.0 mg.kg− 1 when Mn contents ranged from 37.8 to 667.5 mg.kg− 1. For these last two minerals, the highest levels are obtained in the D6 diet and the lowest in the D1 diet. The minimal and maximal requirements for fish reported in other studies were: Fe (65–493 mg.kg− 1), Zn (36–330 mg.kg− 1) and Mn (4.4–226 mg.kg− 1) [19].The values recorded in this study were in excess than dietary requirements mentioned for fish.

Whole-body macromineral composition of fish is presented in **Figure 1**. Body composition in calcium (Ca), potassium (k), sodium (Na), phosphorus (P) and magnesium (Mg) showed significant variations (p < 0.05) with the different dietary palm oil levels. The Ca content of whole body increased with increasing dietary palm oil levels at 5 and 9%. The highest value of Ca (168.49 ± 8.01 g.kg−1) was recorded in fish fed with diet containing 9% of palm oil. Incorporation of palm oil at 3, 5, 7, 15 and 21% in diet increased fish whole-body K content and the highest value (98.54 ± 1.30 g.kg−1) was obtained in the flesh fish fed with 9% dietary palm oil level. The same trend was observed for whole-body Na content, with the marked increase (87.50 ± 0.73 g.kg−1) in fish fed with the diet containing 9% of palm oil. Change in dietary palm oil levels had significantly affected P on whole-body content of fish. Whole-body P content decreased with increasing palm oil levels in the diet, with the lowest value (6.68 ± 0.34) recorded in fish fed diet containing a 15% palm oil level. These values are generally higher than those reported by other works. For instance, Anthony Jesu Prabhu et al. [14] reported for Rainbow trout and Common carp the following values: for Ca, 5.2 ± 1.2 and 7.1 ± 0.8 g.kg−1; Mg: 0.3 ± 0.2 and 0.25 ± 0.05 g.kg−1; P: 4.8 ± 1 and 4.9 ± 0.7 g.kg−1. In another study, Bogard et al. [23] obtained in Common carp Ca: 0.37 g.kg−1, Mg: 0.26 g.kg−1 and P: 1.8 g.kg−1.

Fish whole-body micromineral composition in iron (Fe), zinc (Zn), manganese (Mn) and copper (Cu) was significantly affected (P < 0.05) by dietary palm oil levels, with different variations according to the mineral (**Figure 2**). Regardless of the mineral, the increase in the body was related with increasing dietary palm oil levels between 3 and 9% and the highest value was obtained in fish fed diet containing a 9% palm oil level. The highest value was: body Fe with 536.88 ± 38.74 ppm and that of Zn, Mn and Cu were 246.43 ± 4.09 , 48.24 ± 4.07 and

Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish…

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177

Despite the variations described above, the whole-body mineral composition of *H. longifilis* was generally increased with increasing dietary palm oil levels. In this study, the diets were formulated to contain from 3 to 21% crude palm oil with dietary lipid levels ranging from 8 to 25%. Wang et al. [24] reported that crude lipid contents in the whole body and muscles were not significantly influenced by the dietary lipid source. It may be thought that the effect of palm oil on body composition may be related to lipid metabolism. Several studies in fish have reported that dietary lipid sources could regulate gene expression. Qui et al. [25] reported that dietary lipid source could influence hepatic fatty acid synthetic gene expression, gene expres-

It appears in the light of various works that fish whole-body mineral contents are highly variable from one species to another and often for the same species. This may be partly attributable to sampling variability and methodological differences in analysis and fish species.

**Figure 2.** Whole-body Fe, Zn, Mn, and Cu contents (wet weight basis) of *H. longifilis* fed graded levels of dietary palm

sion related to fatty acid β-oxidation and lipid deposition in the muscle and liver.

22.63 ± 0.91 mg.kg−1, respectively.

oil for 50 days.

**Figure 1.** Whole-body Ca, k, Na, P, and Mg contents (wet weight basis) of *H. longifilis* fed graded levels of dietary palm oil for 50 days.

Fish whole-body micromineral composition in iron (Fe), zinc (Zn), manganese (Mn) and copper (Cu) was significantly affected (P < 0.05) by dietary palm oil levels, with different variations according to the mineral (**Figure 2**). Regardless of the mineral, the increase in the body was related with increasing dietary palm oil levels between 3 and 9% and the highest value was obtained in fish fed diet containing a 9% palm oil level. The highest value was: body Fe with 536.88 ± 38.74 ppm and that of Zn, Mn and Cu were 246.43 ± 4.09 , 48.24 ± 4.07 and 22.63 ± 0.91 mg.kg−1, respectively.

the highest value (98.54 ± 1.30 g.kg−1) was obtained in the flesh fish fed with 9% dietary palm oil level. The same trend was observed for whole-body Na content, with the marked increase (87.50 ± 0.73 g.kg−1) in fish fed with the diet containing 9% of palm oil. Change in dietary palm oil levels had significantly affected P on whole-body content of fish. Whole-body P content decreased with increasing palm oil levels in the diet, with the lowest value (6.68 ± 0.34) recorded in fish fed diet containing a 15% palm oil level. These values are generally higher than those reported by other works. For instance, Anthony Jesu Prabhu et al. [14] reported for Rainbow trout and Common carp the following values: for Ca, 5.2 ± 1.2 and 7.1 ± 0.8 g.kg−1; Mg: 0.3 ± 0.2 and 0.25 ± 0.05 g.kg−1; P: 4.8 ± 1 and 4.9 ± 0.7 g.kg−1. In another study, Bogard et al.

**Figure 1.** Whole-body Ca, k, Na, P, and Mg contents (wet weight basis) of *H. longifilis* fed graded levels of dietary palm

oil for 50 days.

176 Palm Oil

[23] obtained in Common carp Ca: 0.37 g.kg−1, Mg: 0.26 g.kg−1 and P: 1.8 g.kg−1.

Despite the variations described above, the whole-body mineral composition of *H. longifilis* was generally increased with increasing dietary palm oil levels. In this study, the diets were formulated to contain from 3 to 21% crude palm oil with dietary lipid levels ranging from 8 to 25%. Wang et al. [24] reported that crude lipid contents in the whole body and muscles were not significantly influenced by the dietary lipid source. It may be thought that the effect of palm oil on body composition may be related to lipid metabolism. Several studies in fish have reported that dietary lipid sources could regulate gene expression. Qui et al. [25] reported that dietary lipid source could influence hepatic fatty acid synthetic gene expression, gene expression related to fatty acid β-oxidation and lipid deposition in the muscle and liver.

It appears in the light of various works that fish whole-body mineral contents are highly variable from one species to another and often for the same species. This may be partly attributable to sampling variability and methodological differences in analysis and fish species.

**Figure 2.** Whole-body Fe, Zn, Mn, and Cu contents (wet weight basis) of *H. longifilis* fed graded levels of dietary palm oil for 50 days.

However, the results obtained in this study are within the range of fish reported elsewhere [26]. Indeed, good results have been reported on the use of palm oil in the diets of several catfishes: *H. longifilis* [11, 27], *Mystus nemurus* [28] and *Clarias gariepinus* [9, 10, 29]. Other studies have also shown that inclusion of palm oil in the diet of tilapia did not affect hematology and organoleptic properties [30].

**References**

Penang. 2005. 11 p

2013;**26**(4):303-316

Studies. 2017;**5**(4):171-175

in Aquaculture. 2009;**9**:10-57

Aquaculture. 2001;**202**:101-112

0305-0491/82/090003-13503.00/0

2014;**23**:18-23. DOI: 10.1684/agr.2014.0679

Organisation of the United Nations, Rome; 2014. 223 pp

(*Oncorhyncus mykiss*). Aquaculture. 1995;**133**:257-274

palm oil. Pakistan Journal of Nutrition. 2007;**6**(5):452-459

Aquaculture Feeds. CRC Press; 2010. pp. 99-132

[1] Kaushik S. L'apport de la pisciculture à l'alimentation de l'homme. Cahiers Agricultures.

Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish…

http://dx.doi.org/10.5772/intechopen.76615

179

[2] FAO. The State of World Fisheries and Aquaculture 2014. Food and Agriculture

[3] WorldFish Center. Le poisson et la sécurité alimentaire en Afrique. WorldFish Center,

[4] Yeo GM, Blé MC, Otchoumou KA, Dabonne S, Yao LA, Etchian AO. Digestibility and growth performance in fingerlings of tilapia *Oreochromis niloticus* fed with diet containing high-carbohydrate ingredients. International Journal of Fisheries and Aquatic

[5] Turchini GM, Torstensen BE, Ng WK. Fish oil replacement in finfish nutrition. Reviews

[6] Médale F, Le Boucher R, Dupont-Nivet M, Quillet E, Aubain J, Panserat S. Des aliments à base de végétaux pour les poissons d'élevage. INRA production Animale.

[7] Kaushik SJ, Cravedi JP, Lalles JP, Sumpter J, Fauconneau B, Laroche M. Partial or total replacement of fish meal by soy-bean protein on growth, protein utilization, potential estrogenic or antigenic effects, cholesterolemia and flesh quality in raibow trout,

[8] Ng WK, Gibon V. Palm oil and saturated fatty acid-rich vegetable oils. In: Turchini GM, Ng WK, Tocher DR, editors. Fish Oil Replacement and Alternative Lipid Sources in

[9] Lim PK, Boey PL, Ng WK. Dietary palm oil level affects growth performance, protein retention and tissue vitamin E concentration of African catfish, *Clarias gariepinus*.

[10] Ochang, NS, Fagbenro AO, Adebayo TO. Growth performance, body composition, haematology and product quality of the African catfish (*Clarias gariepinus*) fed diets with

[11] Otchoumou KA, Blé MC, Yao LA, Corraze G, Niamké LS, Diopoh KJ. Effect of crude palm oil incorporation on growth, survival, feed efficiency, and body composition of *Heterobranchus longifilis* fingerlings. Journal of Applied Aquaculture. 2014;**26**:169-178

[12] Watanabe T. Lipid nutrition in fish. Biochemistry & Physiology. 1982;**73B**(1):3-15. DOI:

Although it has been proven that substantial quantities of palm oil can be used as energy substitutes in fish diets without negative effects on growth performance [11, 12, 28, 30, 31] it is important to determine the dietary level for optimal use that does not affect growth, whole-body composition and nutritional quality of fish. In Nile tilapia *Oreochromis niloticus*, [32] reported that 6% of dietary palm oil improved growth performance and fish recorded the highest level of whole-body docosahexaenoic acid (DHA). In view of the different studies on the incorporation of vegetable oils in fish feed, it appeared that palm oil, due to its fatty acid composition, is one of the best lipid sources that can be replaced by fish oil in aquafeed [5].

## **3. Conclusion**

The results of this study showed that the incorporation of palm oil in the diet of juveniles of *H. longifilis* affected their whole-body mineral composition. Increasing the level of dietary palm oil from 3–9% resulted in increased whole-body macrominerals and micromineral contents. Previous studies have shown that dietary palm oil improved fish growth and feed utilization. This study suggests that palm oil modifies the whole-body mineral composition without major effects on health and nutritional quality of fish, confirming the interest of this oil as an ingredient for fish feed. Due to its nutritional value and relative low cost, palm oil is an interesting source of lipid to promote in the aquafeed manufacture for sustainable and profitable aquaculture.

## **Author details**

Célestin Mélécony Ble1 \*, Olivier Assoi Etchian2 , Athanase Kraidy Otchoumou3 , Jean Noel Yapi1,2 and Laurent Alla Yao1

\*Address all correspondence to: melecony@gmail.com

1 Aquaculture Department, Center for Research of Oceanology (CRO), Abidjan, Côte d'Ivoire

2 Laboratory of Biology and Animal Cytology, University Nangui Abrogoua, Abidjan, Côte d'Ivoire

3 Laboratory of Biotechnology, University Felix Houphouet-Boigny, Abidjan, Côte d'Ivoire

## **References**

However, the results obtained in this study are within the range of fish reported elsewhere [26]. Indeed, good results have been reported on the use of palm oil in the diets of several catfishes: *H. longifilis* [11, 27], *Mystus nemurus* [28] and *Clarias gariepinus* [9, 10, 29]. Other studies have also shown that inclusion of palm oil in the diet of tilapia did not affect hematology and

Although it has been proven that substantial quantities of palm oil can be used as energy substitutes in fish diets without negative effects on growth performance [11, 12, 28, 30, 31] it is important to determine the dietary level for optimal use that does not affect growth, whole-body composition and nutritional quality of fish. In Nile tilapia *Oreochromis niloticus*, [32] reported that 6% of dietary palm oil improved growth performance and fish recorded the highest level of whole-body docosahexaenoic acid (DHA). In view of the different studies on the incorporation of vegetable oils in fish feed, it appeared that palm oil, due to its fatty acid composition, is one of the best lipid sources that can be replaced by

The results of this study showed that the incorporation of palm oil in the diet of juveniles of *H. longifilis* affected their whole-body mineral composition. Increasing the level of dietary palm oil from 3–9% resulted in increased whole-body macrominerals and micromineral contents. Previous studies have shown that dietary palm oil improved fish growth and feed utilization. This study suggests that palm oil modifies the whole-body mineral composition without major effects on health and nutritional quality of fish, confirming the interest of this oil as an ingredient for fish feed. Due to its nutritional value and relative low cost, palm oil is an interesting source of lipid to promote in the aquafeed manufacture for sustainable and profitable

, Athanase Kraidy Otchoumou3

,

\*, Olivier Assoi Etchian2

1 Aquaculture Department, Center for Research of Oceanology (CRO), Abidjan,

2 Laboratory of Biology and Animal Cytology, University Nangui Abrogoua, Abidjan, Côte

3 Laboratory of Biotechnology, University Felix Houphouet-Boigny, Abidjan, Côte d'Ivoire

organoleptic properties [30].

178 Palm Oil

fish oil in aquafeed [5].

**3. Conclusion**

aquaculture.

Côte d'Ivoire

d'Ivoire

**Author details**

Célestin Mélécony Ble1

Jean Noel Yapi1,2 and Laurent Alla Yao1

\*Address all correspondence to: melecony@gmail.com


[13] Wang J-T, Liu Y-L, Tiana L-X, Maib K-S, Dua Z-Y, Wanga Y, Hui-Jun Yang HJ. Effect of dietary lipid level on growth performance, lipid deposition, hepatic lipogenesis in juvenile cobia (*Rachycentron canadum*). Aquaculture. 2005;**2005**(249):439-447

[26] FAO/INFOODS. FAO/INFOODS Food Composition Database for Biodiversity Version 2.1 – BioFoodComp2. Vol. 1. Rome: Food and Agriculture Organization of the United

Effects of Dietary Palm Oil on the Whole-Body Mineral Composition of African Catfish…

http://dx.doi.org/10.5772/intechopen.76615

181

[27] Legendre M, Kerdchuan CG, Bergot P. Larval rearing of an African catfish *Heterobranchus longifilis* Teleostei, Clariidae: Effect of dietary lipids on growth, survival and fatty acid

[28] Ng WK, Tee MC, Boey PL. Evaluation of crude palm oil and refined palm olein as dietary lipids in pelleted feeds for a tropical bagrid catfish *Mytus nemurus* (Cuvier and

[29] Ng WK, Lim PK, Boey PL. Dietary lipid and palm oil source affects growth, fatty acid composition and muscle alpha-tocopherol concentration of African catfish, *Clarias gari-*

[30] Ochang SN, Fagbenro OA, Adebayo OT. Influnce of dietary palm oil on growth response, carcass composition, hematology and organoleptic properties of juvenile Nile tilapia

[31] Ayisi CL, Zhao J, Rupia EJ. Growth performance, feed utilization, body and fatty acid composition of Nile tilapia (*Oreochromis niloticus*) fed diets containing elevated levels of

[32] Ng WK. Palm oil as a novel dietary lipid source in aquaculture feeds. Palm oil

*Oreochromis niloticus*. Pakistan Journal of Nutrition. 2007;**6**(5):424-429

composition of fry. Aquatic Living Resources. 1995;**8**:355-363

Valenciennes). Aquaculture Research. 2000;**31**:337-347

palm oil. Aquaculture and Fisheries. 2017;**2**:67-77

*epinus*. Aquaculture. 2003;**215**:229-243

Developments. 2004;**41**:14-18

Nations; 2013


[26] FAO/INFOODS. FAO/INFOODS Food Composition Database for Biodiversity Version 2.1 – BioFoodComp2. Vol. 1. Rome: Food and Agriculture Organization of the United Nations; 2013

[13] Wang J-T, Liu Y-L, Tiana L-X, Maib K-S, Dua Z-Y, Wanga Y, Hui-Jun Yang HJ. Effect of dietary lipid level on growth performance, lipid deposition, hepatic lipogenesis in juve-

[14] Antony Jesu Prabhu P, Schrama JW, Kaushik SJ. Mineral requirements of fish: A systematic review. Reviews in Aquaculture. 2016;**8**:172-219. DOI: 10.1111/raq.12090

[15] Boyd CE. Water Quality in Ponds for Aquaculture, Alabama Agricultural Experimental

[16] AOAC. Official Methods of Analysis. 17th ed. Vol. I. Washington, DC: Association of

[17] Moreau Y. Couverture des besoins énergétiques des poissons tropicaux en aquaculture Purification et comparaison des amylases de deux tilapias *Oreochromis niloticus* et *Sarotherodon melanotheron* [Thèse]. Faculté des Sciences et Techniques de Saint-Jérome,

[19] Lall SP. The Minerals, Fish Nutrition. 3rd ed. Amsterdam: Elsevier; 2002. pp. 259-308

[20] Kalantarian SH, Rafiee GH, Farhangi M, Mojazi Amiri B. Effect of different levels of dietary calcium and potassium on growth indices, biochemical composition and some whole body minerals in rainbow trout (*Oncorhynchus Mykiss*) fingerlings. Aquaculture Research and development. 2013;**4**(3). http://dx.doi.org/10.4172/2155-9546.1000170 [21] Kaushik SJ. Besoins et apport en phosphore chez les poisons. INRA production Animale.

[22] Sikorska J, Wolnicki J, Kaminski R, Stolovich V. Effect of different diets on body mineral content, growth, and survival of barbel, Barbus barbus (L.), larvae under controlled con-

[23] Bogard JR, Thilsted SH, Geoffrey C. Marks GC, Abdul Wahab Md, Hossain MAR, Jakobsen J, Stangoulis J. Nutrient composition of important fish species in Bangladesh and potential contribution to recommended nutrient intakes. Journal of Food Composition

[24] Wang XX, Li YJ, Hou CL, Gao Y, Wang YZ. Influence of different dietary lipid sources on the growth, tissue fatty acid composition, histological changes and peroxisome proliferator-activated receptor γ gene expression in large yellow croaker (Pseudosciaena crocea

[25] Qiu H, Jin M, Li Y, Lu Y, Hou Y, Zhou Q. Dietary lipid sources influence fatty acid composition in tissue of large yellow croaker (*Larmichthys crocea*) by regulating triacylglycerol synthesis and catabolism at the transcriptional level. PLoS One. 2017;**12**(1):e0169985.

nile cobia (*Rachycentron canadum*). Aquaculture. 2005;**2005**(249):439-447

[18] Duncan DB. Multiple range and multiple F-tests. Biometrics. 1995;**11**:1-42

Station. Alabama: Aurburn University; 1990. 483 pp

Analytical; 2003

180 Palm Oil

2005;**18**(3):203-208

Université d'Aix-Marseille III; 2001

ditions. Archives Polish Fisheries. 2012;**20**:3-10

and Analysis. 2014;**42**(2015):120-133

DOI: 10.1371/journal.pone.0169985

R.). Aquaculture Research. 2012;**43**:281-291


## *Edited by Viduranga Waisundara*

Palm oil production is one of the most developed and noteworthy industries in the world, leading to rapid economic growth in countries where the industry has been established. Currently, palm oil is the world's leader in the vegetable oil industry with a yearly production and consumption of approximately 45.3 million tons, which almost covers 60% of the global trade of vegetable oils in the international market. Along these lines, it is expected that the global demand for palm oil will be doubled by 2020. The book focuses on various aspects of palm oil production, primarily, the environmental aspects, its application as an animal feed, chemical and nutritional properties of the oil, and technical aspects of enhancing the efficacy of production.

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Palm Oil

Palm Oil