**Meet the editor**

Prof Dr Manar El-Sayed Abdel-Raouf is a Professor of polymer chemistry for the Petroleum Application Department at the Egyptian Petroleum Research Institute. She studied at the faculty of science and got her MS. In 1995. The title of her Msc thesis was "Ethylene Oxide – Propylene Oxide Block Copolymers as Demulsifiers for Water-in-Oil Emulsions". She obtained her PhD in

organic chemistry in 2000 with her thesis on "Alleviation of the Environmental Pollution by Recycling of Poly (Ethylene terephthalate) into useful Products". Prof. Dr Manar El-Sayed has published over 30 papers in international journals,attended 7 international conferences and, participated in two scientific projects for waste recycling. She is a member of an American-Egyptian joint project in Polyethylene terephthalate recycling, and a member in Tanks Services Center at EPRI.

Contents

**Preface IX** 

Chapter 1 **Asphaltenes – Problems** 

Chapter 2 **Petroleum Asphaltenes 27**  Lamia Goual

Chapter 3 **Adsorption and Aggregation** 

Chapter 4 **Natural Surfactants** 

B. Borges

Chapter 7 **Determination of** 

Jamilia O. Safieva, Kristofer G. Paso, Ravilya Z. Safieva and Rustem Z. Syunyaev

**from Venezuelan Extra Heavy** 

Romain Privat and Jean-Noël Jaubert

Jung-Nan Oung and Jentaie Shiea

**Metal Ions in Crude Oils 121**  M.Y. Khuhawar, M. Aslam Mirza

**Part 2 Characterization of Crude Oil 69** 

Chapter 5 **Thermodynamic Models for** 

Chapter 6 **Analysis of Polar Components** 

and T.M. Jahangir

**Part 1 Asphaltenes in Crude Oil 1** 

**and Solutions in E&P of Brazilian Crude Oils 3**  Erika Chrisman, Viviane Lima and Príscila Menechini

**of Asphaltenes in Petroleum Dispersed Systems 43** 

**Crude Oil - Study of Interfacial and Structural Properties 59** 

**the Prediction of Petroleum-Fluid Phase Behaviour 71** 

**in Crude Oil by Ambient Mass Spectrometry 107**  Chu-Nian Cheng, Jia-Hong Lai, Min-Zong Huang,

### Contents

#### **Preface** XI


M.Y. Khuhawar, M. Aslam Mirza and T.M. Jahangir

X Contents

#### **Part 3 Crude Oil Biology 145**

	- **Part 4 Natural Components in Crude Oil 181**

### Preface

We live in what has been called the Petroleum Age. This hydrocarbon-rich mixture of crude oil and gases runs our factories, our cars, heats homes and has changed the face of life on the earth since it's discovery on 1901.

Crude oil is an extremely versatile, naturally occurring, flammable liquid consisting of a complex combination of various molecular hydrocarbons weights and other organic liquid compounds that are found in geologic formations beneath the Earth's surface. Petroleum is recovered principally through oil drilling.

Refining it creates everything from asphalt and gasoline to lighter fluids and natural gas, along with a variety of vital elements such as sulphur and nitrogen. Petroleum products are also vital ingredients ("feedstocks") in the manufacture of medicines, chemicals and plastics.

The aim of this book is to discuss the many topics related to crude oil. It includes five sections. The first section deals with asphaltenes-these are natural surfactants that stabilize petroleum emulsions. The chapters of the second section discuss some advanced methods used in characterization of crude oil and it's components. The third section includes and publishes new discoveries and improvements in crude oil biology. The fourth section discusses the natural components presented in crude oil and those factors affecting crude oil stability. The final chapter involves some innovative ideas and concepts related to the crude oil.

Finally, we would like to thank all the authors who had participated in this book for their valuable contribution. While there is no doubt that this book may have omitted some significant findings in the petroleum field, we hope the information included in will be useful for both petroleum engineers and chemists, in addition to the academic researches working in this field.

#### **Manar El-Sayed Abdel-Raouf**

Professor of Petroleum Chemistry Petroleum Application Department Egyptian Petroleum Research Institute Egypt

**Part 1** 

**Asphaltenes in Crude Oil** 

**Part 1** 

**Asphaltenes in Crude Oil** 

**1** 

*Brazil* 

**Asphaltenes – Problems and Solutions** 

The history of oil in Brazil began in 1858, when the Marquis of Olinda signed Decree No. 2266 granting Barros Pimentel the right to extract mineral asphalt for the manufacture of kerosene, on land situated on the banks of the Rio Marau in the province of Bahia. But who really came to be known as the discoverer of oil in Brazil was Monteiro Lobato that on January 21, 1939, already under the jurisdiction of the newly created Department of

Only in 1953 began the research of Brazilian oil by the government of Vargas, which

Petrobras - Petroleo Brasileiro S/A was founded on October 3, 1953 and headquartered in Rio de Janeiro, now operates in 28 countries in the energy sector, primarily in the areas of exploration, production, refining, marketing and transportation of oil and derivatives in Brazil and abroad. Its current motto is "An integrated energy company that works with

Since its creation, Petrobras has discovered oil in several states, and in every decade, new oil fields are discovered. Oil production in Brazil grew from 750 m3/day at the time of the creation of Petrobras to more than 182,000 m3/day in the late '90s thanks to continuous

In 2006, Brazil managed to achieve sustainable self-sufficiency in oil production with the operations of the FPSO (Floating Production Storage Offloading) P-50 in giant Albacora East field, in northern of Bacia de Campos in the state of Rio de Janeiro

In 2007, Brazil announced the discovery of oil in the so-called pre-salt, which later turned out to be a large oil field, extending over 800km off the Brazilian coast, from the state of Espírito Santo to Santa Catarina, below thick layer of salt (rock salt) and covering sedimentary basins of Espirito Santo, Campos and Santos. The first pre-salt oil extracted in

The year 2009 was marked by the beginning of production in pre-salt layer in the Santos Basin, and in August 2010, Brazil had a record of oil production, with 2, 078 million barrels

social and environmental responsibility" (http://pt.wikipedia.org/wiki/Petrobras).

technological advances in drilling and production on the continental shelf.

National Production, began drilling the well DNPM-163 in Bahia.

established the state oil monopoly, with the creation of Petrobras.

**1. Introduction**

(www.autosuficiencia.com.br).

2008 (www.petrobras.com.br).

per day, up 6% over the same period in 2009.

**in E&P of Brazilian Crude Oils** 

*Federal University of Rio de Janeiro/DOPOLAB* 

Erika Chrisman, Viviane Lima and Príscila Menechini

### **Asphaltenes – Problems and Solutions in E&P of Brazilian Crude Oils**

Erika Chrisman, Viviane Lima and Príscila Menechini *Federal University of Rio de Janeiro/DOPOLAB Brazil* 

#### **1. Introduction**

The history of oil in Brazil began in 1858, when the Marquis of Olinda signed Decree No. 2266 granting Barros Pimentel the right to extract mineral asphalt for the manufacture of kerosene, on land situated on the banks of the Rio Marau in the province of Bahia. But who really came to be known as the discoverer of oil in Brazil was Monteiro Lobato that on January 21, 1939, already under the jurisdiction of the newly created Department of National Production, began drilling the well DNPM-163 in Bahia.

Only in 1953 began the research of Brazilian oil by the government of Vargas, which established the state oil monopoly, with the creation of Petrobras.

Petrobras - Petroleo Brasileiro S/A was founded on October 3, 1953 and headquartered in Rio de Janeiro, now operates in 28 countries in the energy sector, primarily in the areas of exploration, production, refining, marketing and transportation of oil and derivatives in Brazil and abroad. Its current motto is "An integrated energy company that works with social and environmental responsibility" (http://pt.wikipedia.org/wiki/Petrobras).

Since its creation, Petrobras has discovered oil in several states, and in every decade, new oil fields are discovered. Oil production in Brazil grew from 750 m3/day at the time of the creation of Petrobras to more than 182,000 m3/day in the late '90s thanks to continuous technological advances in drilling and production on the continental shelf.

In 2006, Brazil managed to achieve sustainable self-sufficiency in oil production with the operations of the FPSO (Floating Production Storage Offloading) P-50 in giant Albacora East field, in northern of Bacia de Campos in the state of Rio de Janeiro (www.autosuficiencia.com.br).

In 2007, Brazil announced the discovery of oil in the so-called pre-salt, which later turned out to be a large oil field, extending over 800km off the Brazilian coast, from the state of Espírito Santo to Santa Catarina, below thick layer of salt (rock salt) and covering sedimentary basins of Espirito Santo, Campos and Santos. The first pre-salt oil extracted in 2008 (www.petrobras.com.br).

The year 2009 was marked by the beginning of production in pre-salt layer in the Santos Basin, and in August 2010, Brazil had a record of oil production, with 2, 078 million barrels per day, up 6% over the same period in 2009.

Asphaltenes – Problems and Solutions in E&P of Brazilian Crude Oils 5

In 2010, world oil consumption was 3.2% over 2009, totaling 87.4 million barrels/day. The oil was more consumed in the region of Asia-Pacific, with a total of 27.2 million barrels/day or 31.2% of the total. Consumption growth was 5.3% over 2009, especially to China which, after the United States was the country with the second largest consumer in the world, 9.1

The Central and South America also recorded high in its consumption, as a result of increases in almost all countries, except Chile, which had a low of 6.2%. Thus, the increase in consumption in the region was 4.8%, reaching 6.1 million barrels/day or 7% of the world. Brazil was the country with the largest increase in consumption in the region - 8.6% - and reached 2.6 million barrels / day or 3% of world total. Thus, the country jumped to seventh

Compared to 2009, the volume of oil produced worldwide in 2010 increased 2.3%, from 80.3

Fig. 2. Statistical Review of World Energy 2011. Source: www.bp.com

million barrels/day, 10, 4% more than last year.

in the ranking of the largest consumers of oil in the world.

Fig. 3. World consumption of oil. Source: www.anp.gov.br

**3. Consumption** 

to 82.1 million barrels/day.

According to the National Petroleum Agency (ANP), the volume exceeds one thousand barrels the previous record from April 2010. Produced in the Tupi, Jubarte and Cachalote fields, the pre-salt oil contributed 43, 087 thousand barrels per day in volume in August (www.monitormercantil.com.br).

Fig. 1. Pre-salt layer. Source: www.anp.gov.br

The company ranks second among the largest publicly traded oil in the world. In market value, it is the second largest in the Americas and the fourth largest in the world in 2010. In September 2010, it became the second largest energy company in the world, always in terms of market value, according to Bloomberg data and the Agency Brazil.

It became internationally famous for having made in October 2010 the largest capitalization of all publicly traded history of mankind: US\$ 72.8 billion (R\$ 127.4 billion), almost double the record so far, the post office in Japan (Nippon Telegraph and Telephone), with US\$ 36.8 billion capitalized in 1987. In August 2011 the company broke two more records for net income: US\$ 10.94 billion in the second quarter, and also the record of R\$ 21.9 billion in the first half of the year. (Http://pt.wikipedia.org/wiki/Petrobras).

#### **2. Proved reserves**

In 2010, the proved oil reserves in the world reached about 1.38 trillion barrels, after a 0.5% increase over 2009.

In South and Central America, the rise was driven by Colombia, Brazil and Peru, which saw its proved reserves grow 39.7%, 10.7% and 10.6% in that order.

With this increase, partly due to the findings in the pre-salt, the Brazilian proved reserves reached 14.2 billion barrels of oil, and placed the country in 15th position in world ranking of reserves.

Fig. 2. Statistical Review of World Energy 2011. Source: www.bp.com

#### **3. Consumption**

4 Crude Oil Emulsions – Composition Stability and Characterization

According to the National Petroleum Agency (ANP), the volume exceeds one thousand barrels the previous record from April 2010. Produced in the Tupi, Jubarte and Cachalote fields, the pre-salt oil contributed 43, 087 thousand barrels per day in volume in August

The company ranks second among the largest publicly traded oil in the world. In market value, it is the second largest in the Americas and the fourth largest in the world in 2010. In September 2010, it became the second largest energy company in the world, always in terms

It became internationally famous for having made in October 2010 the largest capitalization of all publicly traded history of mankind: US\$ 72.8 billion (R\$ 127.4 billion), almost double the record so far, the post office in Japan (Nippon Telegraph and Telephone), with US\$ 36.8 billion capitalized in 1987. In August 2011 the company broke two more records for net income: US\$ 10.94 billion in the second quarter, and also the record of R\$ 21.9 billion in the

In 2010, the proved oil reserves in the world reached about 1.38 trillion barrels, after a 0.5%

In South and Central America, the rise was driven by Colombia, Brazil and Peru, which saw

With this increase, partly due to the findings in the pre-salt, the Brazilian proved reserves reached 14.2 billion barrels of oil, and placed the country in 15th position in world ranking

of market value, according to Bloomberg data and the Agency Brazil.

first half of the year. (Http://pt.wikipedia.org/wiki/Petrobras).

its proved reserves grow 39.7%, 10.7% and 10.6% in that order.

(www.monitormercantil.com.br).

Fig. 1. Pre-salt layer. Source: www.anp.gov.br

**2. Proved reserves** 

increase over 2009.

of reserves.

In 2010, world oil consumption was 3.2% over 2009, totaling 87.4 million barrels/day. The oil was more consumed in the region of Asia-Pacific, with a total of 27.2 million barrels/day or 31.2% of the total. Consumption growth was 5.3% over 2009, especially to China which, after the United States was the country with the second largest consumer in the world, 9.1 million barrels/day, 10, 4% more than last year.

The Central and South America also recorded high in its consumption, as a result of increases in almost all countries, except Chile, which had a low of 6.2%. Thus, the increase in consumption in the region was 4.8%, reaching 6.1 million barrels/day or 7% of the world. Brazil was the country with the largest increase in consumption in the region - 8.6% - and reached 2.6 million barrels / day or 3% of world total. Thus, the country jumped to seventh in the ranking of the largest consumers of oil in the world.

Compared to 2009, the volume of oil produced worldwide in 2010 increased 2.3%, from 80.3 to 82.1 million barrels/day.

Fig. 3. World consumption of oil. Source: www.anp.gov.br

Asphaltenes – Problems and Solutions in E&P of Brazilian Crude Oils 7

Oil can be defined as to its chemical composition as a naturally occurring complex mixture consisting predominantly of hydrocarbons (up to more than 90% of its composition) and

The oils from different oil reservoirs have different characteristics. Within this complex mixture, there is a fraction with high molecular weight components called asphaltenes that causes serious precipitation problems, since its production by refining (Carvalho, 2003).

The hydrocarbons present in oil can be classified into four main classes: saturated (alkanes and cycloparaffins), aromatics (hydrocarbons, mono, di and polyaromatic), resins (fractions consist of polar molecules containing heteroatoms such as N, O or S) and asphaltenes (they are molecules similar to the resins, but with a higher molecular weight and polyaromatic core). This classification is known as SARA (Wang et al, 2002; Speight, 2001; Tissot and Welt, 1978).

Fig. 4. Structures representing saturated, asphaltenes, aromatics and resins. Source: Bernucci

Table 04 shows the elemental analysis of five Brazilian oils performed in DOPOLAB - Laboratory of Development and Optimization of Process Organic, showing considerable

> **Oil Saturated (%) Aromatics (%) Resins (%) Asphaltenes (%) A** 22.4 22.8 36.4 18.4 **B** 20.7 29.8 30.4 19.1 **C** 16.0 25.1 25.0 33.9 **D** 14.2 40.5 24.7 20.5 **E** 19.4 36.7 12.6 31.2

The relative amounts of individual compounds within each group of hydrocarbons is

Metals can be found at levels ranging from 1 to 1200 ppm, the main being iron, zinc, copper, lead, molybdenum, cobalt, arsenic, manganese, chromium, sodium, nickel and vanadium,

Table 2. Chemical composition of Brazilian oil. Source: DOPOLAB, 2011.

derived organic sulfur, nitrogen, oxygen and organometallic.

**5.1 Constituents of oil** 

et al., 2006.

amounts of asphaltenes present.

characteristic of each type of oil.

the latter two with the highest incidence.

### **4. Production**

Compared to 2009, the volume of oil produced worldwide in 2010 increased 2.3%, from 80.3 to 82.1 million barrels/day.

Oil production in Central and South America rose by 3.5%, driven mainly by increases in Colombia, Peru and Brazil, respectively, 16.8%, 8.2% and 5.3%. With the increase in the volume of oil produced, Brazil reached the 12th position among the world's largest producers of oil in 2010.


£ Excludes Former Soviet Union.
