Demulsification, Viscosity Index Improver, Pour Point Depressant

#### **Chapter 1**

## Acrylic Polymers as Additives for Engine Oil: A Historical Perspective

*Rabab M. Nasser*

#### **Abstract**

Oil undergoes temporary viscosity changes under operating conditions in engines. Therefore, engine oils usually contain polymeric additives called viscosity modifiers. These additives are oil soluble polymers; enable the oil to provide adequate hydrodynamic lubrication at high temperatures and good starting/ pumping performance at low temperatures. Pour point depressants are additives which add to engine oil to lower/decrease the probability of wax argument formation under lower temperature conditions. The aim of this chapter is to present the historical synthesis of different types of acrylic polymers, there effect as lubricating oil additives (viscosity index improvers and pour point depressants). In addition, the mechanisms by which viscosity modifiers and pour point depressants work, and method of evaluation.

**Keywords:** Acrylic polymers, Free radical polymerization, Engine oil additives, Viscosity index improvers, Pour point depressants

#### **1. Introduction**

Almost all commercial manufacturing and general-use equipment have mating surfaces that rub against each other, creating a lot of wear and tear. There is always resistance between the mating surfaces as a result of frictional reactions. As a result of wear and tear, material is removed from the top surface. Lubricants create a protective layer between mating surfaces, minimizing friction and, hence, wear and tear. Lubrication is a technique that is commonly used to maintain a protective layer between moving surfaces in order to reduce frictional effects and material degradation due to wear and tear [1–4].

#### **1.1 Lubricant uses**

#### **The main functions of the lubricant may be dominated as follow:**

1.To reduce mating layer wear and tear by limiting direct surface-to-surface contact, particularly in metallic surfaces, by introducing a lubricating layer between mating layers [4–6].


#### **1.2 Lubrication methods**

The concepts of lubrication can be elucidated using the mechanisms described below.

#### *1.2.1 Use of thick films for lubrication*

The moving/sliding faces are isolated with a thick layer of liquid, with the purpose of allowing for occasional top layer to layer contact. The lubricant layer fills the space at the irregularities of mating layers and creates a not-so-thin layer between them, preventing immediate mating among the top layers of the material in use. As a result, wear and tear is greatly reduced. The lubrication oil must be consistent during typical operation in machine parts, and it must also remain viscous enough to isolate the layers [14–17].

#### *1.2.2 Lubrication through the use of thin films*

Maintaining a continuous layer of lubricant between the mating surfaces can be problematic in some instances. Then a process is used in which the region between layers sliding over one another is lubricated by an adsorbing substance that, according to its adsorption qualities, remains on the higher layers. This reduces friction between moving peak regions of mated surfaces. Adsorption can occur as a result of physical or chemical attributes [18–22].

#### *1.2.3 Extreme pressure lubrication*

When the moving/sliding surfaces are subjected to strong loading, a high temperature is reached. Under such conditions, liquid lubricating oils fail to adhere and may crumble or even evaporate. To solve these ridiculous circumstances, unique additives are added to mineral oils. These are referred to as exceptional weight included compounds. On metal surfaces, these extra chemicals form more intense films (capable of withstanding high loads and temperatures). The most fundamental contained compounds are regular mixtures containing dynamic radicals [23–26].

#### **1.3 Type of lubricants**

Lube oils are generally classified depending on their condition, which is as follows;

#### *1.3.1 Lubricants in liquid form or lubricating oils*

There are three types of oils:

*Acrylic Polymers as Additives for Engine Oil: A Historical Perspective DOI: http://dx.doi.org/10.5772/intechopen.98867*

#### *1.3.1.1 Animal and vegetable oils*

They are derived from unrefined fatty oils and vegetable extracts. They are also called bio-lubricants [27–35]. They have a high degree of smoothness and, as a result, may stick to metallic surfaces for extended periods of time and under harsh conditions.

#### *1.3.1.2 Mineral or petroleum oils*

These are readily available and reasonably priced lubricants. They are relatively stable in regular operating settings and so commonly used. In general, bulkier chemicals are added to them to increase their oiliness. For example, oleic acid and stearic acid are added to improve oiliness [36–39].

#### *1.3.1.3 Blended oils*

Because no individual oil provides all of the desired qualities, these are the most regularly utilized oils. These oils perform better and are often manufactured to order with the addition of larger molecular components [40, 41].

#### *1.3.2 Semi-solid lubricants or grease*

These are typically created by combining thickening additives with base oil. Grease can withstand heavy loads at low speeds but is a poor heat dissipater and is hence utilized in low temperature bearings [42–45].

#### *1.3.3 Lubricants in solid form*

These are to be used when even grease cannot tolerate the temperature and pressure, when contamination must be avoided, when combustible lubricants are undesirable. They keep the lubricating film persistent even in conditions that grease cannot. To improve their adhesion to metallic layers, these are manufactured in powder form, dry form, and as coalescent [46–54].

#### **1.4 The role and importance of engine oil**

In addition to decreasing friction and wear, the engine lubricant is required to aid in sealing, cooling, protecting components against corrosion, cleaning surfaces of deposits, and transporting particles in suspension to the oil filter. All of this must be accomplished while fulfilling customer expectations for low costs and, in some circumstances, considerable intervals between oil changes.

The lubricant base stock, which accounts for 75 to 85 percent of the oil by volume, is a combination of hydrocarbons chosen to offer a starting point for viscosity and lubrication performance. The molecules that make up this base stock might be refined straight from crude oil or generated through chemical processing (synthetic lubricants).

In either scenario, the hydrocarbon compositions may be very similar, with the chemical makeup being more tightly controlled in synthetic oils. Depending on the hydrocarbon sources utilized to make the synthetic oil, it may also be free of the undesired sulfur and ash found in crude oils and which are costly to remove. The remaining lubricating oil is an additive package made up of a variety of chemical compounds chosen to give the anticipated lubrication performance [55].

#### **1.5 Additives to engine oil**

Engine oils are composed primarily of base oil, with the majority consisting of friction modifier additives used to increase performance. Typically, additives reduce wear, prevent oxidation, aid in dispersion, and add detergents to the base, which helps to keep the engine clean and improves viscosity index. Furthermore, the engine oil must maintain proper viscosity across a wide operating temperature range [56–60].

These features are carried by the additives added to base oil, which are necessary for the engine to run smoothly and efficiently. Oil is now produced with the stringent demands of today's engines in mind. The amount of additives ranges from 5 to 30% from total engine oil, **Figure 1**.

This, without a doubt, makes them tough and costly to create, but they can now be tailored to meet the application they are required to serve for engine safety and economical fuel efficiency. They can also be engineered to be exceedingly stable at both low and high temperatures. We will discuss viscosity index improvers and pour point depressants for lube oil.

#### *1.5.1 Viscosity index improvers*

The viscosity of hydrocarbon lubricants varies dramatically with temperature roughly. Two orders of magnitude between cold ambient and full-load oil operating temperature for an unaltered mixture. Because of this reliance, ensuring adequate oil flow under all operating conditions and effectively balancing supply and leakage rates for acceptable lubrication of important surfaces is particularly difficult. Longchain polymers called viscosity index improvers coil up at low temperatures and uncoil as the temperature rises [61–63].

As temperatures drop, the viscosity of ordinary petroleum oil increases, making it flow more slowly; conversely, as temperatures rise, the oil thins out and flows more freely, **Figure 2**. When there are large fluctuations in ambient temperature, it is often advantageous to use an oil whose viscosity remains as close to the ideal value as feasible despite the temperature fluctuation.

The "viscosity index" (V.I) is the rate at which viscosity changes with temperature. A liquid's viscosity is more consistent the greater its V.I. Depending on the source of the crude [paraffinic crude oils have the greatest natural viscosity

**Figure 1.** *Main components of engine oil.*

*Acrylic Polymers as Additives for Engine Oil: A Historical Perspective DOI: http://dx.doi.org/10.5772/intechopen.98867*

**Figure 2.** *Mechanism of viscosity index improvers.*

index], lubricants extracted from crude oil by simple distillation can have a wide range of viscosity indexes. Viscosity index can be calculated according to ASTM D -2270-10 [64].

However, by adding a viscosity improver or viscosity modifier to an oil, the V.I can be increased. Long chain polymers with a very high molecular weight, such as polyisobutylene, polyacrylates or polymethacrylates, are commonly used as viscosity index improvers.

#### *1.5.1.1 Mechanism of viscosity index improvement*

Viscosity index improvers work by enhancing viscosity at high temperatures proportionally more than at low temperatures. Their behavior in oil shows that at higher temperatures, they distend or stretch, limiting flow and giving the oil more viscous qualities [62]. In doing so, they compensate to a significant extent for the oil's tendency to thin out when heated. Increasing the molecular weight of a polymer increases its volume in an oil solution. Viscosity improvers respond to temperature in the same way that springs do. When cold, the molecules in the V.I improver contract and expand or thicken when heated. These changes in the physical properties of the V.I improver serve to adjust for variations in the basic oil stock. As a result, the oil's temperature stability is improved throughout a wide temperature range [65].

#### *1.5.2 Pour point depressants*

All oils contain dissolved wax; however, the percentage of dissolved wax varies depending on the source of the oil. As the temperature dropped, the wax particles began to interlock like a sponge, attracting oil molecules into its microscopic pockets and so impeding oil transport [66–68].

Many approaches were employed to reduce the amount of wax in the generated oil, ranging from mechanical agitation to the inclusion of chemicals known as pour point depressants. The interaction mechanism of action of pour point depressants in oils is explained theoretically. Examples of these theories include adsorption, co-crystallization, nucleation, and improved wax solubility [69].

A good pour point depressant additive must have the following structural characteristics:


#### *1.5.2.1 What is the mechanism of action of a pour point depressant?*

Pour point depressants work by modifying the wax – crystal bond. The main question is how they work based on crystal size? This can happen through one of two ways:

1) adsorption onto the surface of newly formed crystals, or 2) co-crystallization with the precipitating wax [70–75]. Pour point can be evaluated using ASTM D 97–17 [76].

#### *1.5.3 Rheological characteristics*

Polymer molecules are mostly hydrocarbon compounds. When dissolved in oil, they form a random coil. Under significant shear stress, the polymer molecules will separate into two or more polymeric particles. Polymers with higher molecular weights are more resistant to distortion and mechanical degradation, whereas polymers with sufficiently low molecular weight may not even undergo permanent shearing. Because the sheared polymer molecules have a sufficiently low molecular weight to be resistant to further breakdown, the degradation process is self-limiting [77–79].

#### **1.6 Acrylic polymers**

Acrylic polymers are "polymers based on acrylic acid, its homologues, and derivatives." Acrylic acid, methacrylic acid are the most common commercial polymers in this class, as are acrylic acid esters, methacrylic acid esters, acrylonitrile, acrylamide, cyanoacrylates, and copolymers of these compounds. Styrene–acrylonitrile, acrylonitrile-butadiene-styrene terpolymers, as well as acrylonitrile-butadienebutadiene terpolymers [80–82].

Acrylate polymers are easily polymerized (Homo-polymers, co-polymers and terpolymers) using free radical polymerization, where polymerization occur according to free radical polymerization; using initiator such as benzoyl peroxide, H2O2 … etc. the general mechanism of acrylate polymerization is illustrated at **Figure 3**.

#### **Figure 3.** *General mechanism of acrylate polymerization.*


#### *Acrylic Polymers as Additives for Engine Oil: A Historical Perspective DOI: http://dx.doi.org/10.5772/intechopen.98867*



#### *Acrylic Polymers as Additives for Engine Oil: A Historical Perspective DOI: http://dx.doi.org/10.5772/intechopen.98867*


### **Table 1.**

*Application of acrylate polymers in petroleum sector as engine oil additives.*

#### *Acrylic Polymers as Additives for Engine Oil: A Historical Perspective DOI: http://dx.doi.org/10.5772/intechopen.98867*

The incorporation of acrylic polymers with other green ingredients such as (jojoba oil [83–87], sunflower oil [88–90], castor oil [91] … etc.) has been reported. Acrylic polymers have been evaluated as motor oil additives (viscosity index improvers, pour point depressants, anti-wear, and anti-friction … .etc.) as tabulated at **Table 1**.

#### **2. Conclusions**

In this chapter we summarize the important uses of acrylate polymers, copolymers, and terpolymers and their uses as viscosity index improvers, pour point depressant, anti-wear, corrosion inhibitors, and rheology modifiers for engine oil. We can conclude the important of this category of polymers in the petroleum sector.

### **Acknowledgements**

I would like to acknowledge this work to my Mother, and my Sons (Abd El-Rahman, Mostafa, and Faty).

### **Conflict of interest**

I have no conflict of interest.

### **List of abbreviations**


#### **Author details**

Rabab M. Nasser Department of Petroleum Applications, Egyptian Petroleum Research Institute, Cairo, Egypt

\*Address all correspondence to: rabab\_nasser@yahoo.com

© 2021 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.

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#### **Chapter 2**

## Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives

*Manar Elsayed Abdel-Raouf, Mohamed Hasan El-Keshawy and Abdulraheim M.A. Hasan*

#### **Abstract**

The concept of green chemistry has been established to find safe methodologies and environmentally benign solutions for the present and the onset problems. In this regard, extensive work has been carried out worldwide to replace the currently used materials with green ones. The terminology green relies on all the non-pollutive or the degradable materials regardless of their source. Therefore, there are biobased green materials and non-biobased green materials. This review sheds light on several green polymers used in different petroleum industries. The polymers are reviewed according to the stage of oil processing in which they are applied. Furthermore, different modification methodologies of natural polymers are revised. Also, the role of green non-biopolymers in different petroleum industries is investigated. It is worth mentioning that we concentrate our efforts on the utilization of different natural polymers in petroleum applications. Thereafter, some natural polymers such as chitosan and cellulose and their derivatives were specifically reviewed.

**Keywords:** Green polymers, corrosion inhibitors, demulsifiers, oil spill dispersants

#### **1. Introduction**

The majority of raw materials used today derived from non-renewable sources such as coal and petroleum. This caused many drawbacks such as a severe depletion of non-renewable resources, continuous growth in petroleum prices, environmental impact with the rise in the emission of greenhouse gases, and accumulation of nonbiodegradable waste on earth [1–3]. Currently, major global attention has shifted to other sources, for many reasons such as, need for enormous novel and sustainable material resources; supplement, reuse, and replace of petroleum-based polymeric materials; biodegradability of materials to prevent a buildup of waste; the toxicity associated with the preparation, usage, and environmental safety. Therefore, the utilization of natural resources as alternatives for petroleum-based products has been increased (**Figure 1**).

Consequently, some new terms have been developed, such as green, environmentally benign, biodegradable … etc. Therefore, polymers are referred "green" if they exhibit one or more of the following properties: source renewability,

*Crude Oil - New Technologies and Recent Approaches*

**Figure 1.**

*Worldwide use of renewable resources for materials in 2008.*

biodegradability, composability after end of the life and environmentally friendly processing [3, 4].

Many materials can be categorized under this term such as:


Sustainable polymers from renewable resources can be prepared through chemical modification of natural polymers, such as cellulose, starch, chitin, etc. Bio-based polymers also synthesized through a two-step process from biomass (lignin, cellulose, starch, plant oils) [5–7]. Carbohydrates are the most prominent raw materials for industrial chemicals as they account for around 95% of annually produced biomass. The conversion methods including chemical and biological methods, direct extraction and selected technological advancements will be discussed. Furthermore, the application of green polymers in some petroleum processes also will be investigated.

#### **2. Biopolymers versus green polymers**

Macromolecules which are produced by living organisms and given the term biopolymers have numerous functions. Some of them, as DNA molecule, have so specific functions in information storing and convey. Others are formed in considerable level (scale) and offer protection in the form of hard shells or structural integrity [8–11]. These 'structural' biopolymers symbolize a various range of chemical functionality and compositions and can be largely categorized as polysaccharides, triglycerides, polypeptides (**Figure 2**). As general, all biopolymers are green but not all green polymers are derived from natural sources, there are green synthetic polymers such as polyesters and some green polymers are derived from crude oil such as polycaprolactam (PCL) (**Figure 3**).

*Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

**Figure 2.** *Different types of biopolymers.*

**Figure 3.** *Classification of green polymers.*

#### **2.1 Advantages of green polymers**

The green polymers show superior and unique properties incomparable to other materials, these properties are [12–14]:


The green chemistry concept, which was initiated in the 1990, is linked to the term green economy. Both terms aim to minimize the claim for energy and resources, lessen wastes, avoid ecological pollution and hazards, reduce greenhouse gas release, optimize industrialization processes, and establish efficient recycling of wastes [15–17]. These elements are essential parts of sustainable chemistry.

#### **2.2 Green principles of polymer production**

Important green principles of polymer production handle the following issues [18, 19]:


However, the properties of biopolymers are strongly influenced by their source. Visibly, the structure and characteristics of a polysaccharide are totally different from a polypeptide. Even so, there can still be spectacular variation in properties of a single biopolymer, depending on the species that produce it. A typical model of

*Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

**Figure 4.** *Alginate from different sources.*

this natural variability is alginate, which is an extract from seaweed. Alginate is a linear copolymer of α-L-guluronate and β-D-mannuronate and the segments are not random copolymers but contain blocks of alternating or identical monomers. The strength of this biopolymer count on its composition, which varies significantly between different species and growth environment as well as within different parts of the original plant (**Figure 4**).

#### **2.3 Physico-chemical properties of green polymers**

Gel or viscous solutions formation is one of the most attractive features about green polymers; a lot of them form viscous solutions or gel in water due to intermolecular hydrogen bonding formation (**Figure 5**). This specific property used widely in different industries to control rheological properties and stability [20].

Another important feature that most green polymers possess is their high functionality, which allows versatile modification routes in order to produce endless products [12]. Extensive works are carried out to design and invent green alternative routes for effective biomass transformation to chemicals.

These modification methodologies depend on the nature of the functional group(s), distribution of these functionalities within the polymer chain, the nature, and the usability of the product. The most common modification procedures involve esterification, ethoxylation, depolymerization, amination, etherification … etc. [21]. The next sections include thorough review for modification of green polymers for

**Figure 5.** *Intermolecular hydrogen bondings.*


**Table 1.**

*Utilization of green polymers in the petroleum sector.*

utilization in different petroleum sectors. They are categorized according to the stage they are applied in – as in **Table 1**.

#### **3. Green polymers in petroleum industry**

#### **3.1 Drilling fluids**

The expression drilling mud implies to fluids, which are used to save up well control and transport drill cuttings from the boreholes to the surface. In the drilling process, the fluid is pumped from the surface, down the drill string, through the bit, and back to the surface via the annulus. Drilling mud constitutes an essential part of the drilling process. The appropriate fluid selection is controlled by drilling performance, expected well condition, the safety of workers, cost, and mud cuttings discarding [22]. Drilling muds must be verbalized to eliminate problems associated with formation damage, well chemistry, and other well disturbances. Choosing suitable drilling fluids and control of their properties within desirable ranges are pivotal aspects of successful oil well drilling [23]. Drilling muds are mainly composed of liquid (i.e., water, oil, or brine) and solid materials (i.e., clay, polymer, barite, and additives). The main types of drilling muds are illustrated in **Figure 6**.

There are many green polymers used as thickening agents in drilling mud formulation as either single materials or a blend of components. These include Polyethylene glycol [24], Carboxymethyl cellulose [25, 26], combination of cellulose and clay [27], amide modified polysaccharide [28], cellulose nanofibril [29], chitosan [30]. Based on their superior thickening properties, Green gums were used are excellent candidates in drilling fluid designs. In this regard, Guar gum was used during drilling operations as a first-rate additive for mud systems because of its unique properties. These properties include, but are not exclusive to, loss control agent, viscosifiers and polymer [31, 32].

Xanthan gum has used as a highly beneficial drilling mud additive that reduces related well instabilities [33, 34]. Xanthan gum also, can be used in other applications such as an emulsifier, stabilizer (in some cases), a thickener for mud systems and suspending agent [34–37].

Moreover, other natural water-insoluble cellulosic materials; peanut hulls, bagasse, and sawdust were investigated as lost circulation control materials [38]. The chemical composition of these materials is given in **Table 2**; the data revealed that Peanut hulls have the best results relative to bagasse and sawdust as they have 60% crude fiber and the least content of cellulose.

Furthermore, some mixed green formulations were applied as thickening agents such as Sulfonate-containing polymer/polyanionic cellulose [39], sulphone crosslinked galactomannans [40].

Olatunde et al. [41] introduced a blended water-based drilling fluid based on guar gum, bentonite, polyanionic cellulose (PAC) and arabic gum. The rheological *Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*


#### **Table 2.**

*Chemical composition of some cellulosic materials [38].*

behavior and the filtration loss property of each drilling fluid developed were measured using API standard procedures. Guar gum showed the highest gel strength and the best stable rheological properties. The rheological properties of borateguar gum crosslinked fluids were studied by Oscar [42] and he found that anionic galactomannans, which are derived from guar gum suitable as thickeners. They are capable of enhancing viscosities when used either alone or in combination with a cationic polymer and distributed in a solvent.

#### **3.2 Demulsifiers**

The process of crude oil formation is usually associated by incorporation of salty water within the crude. This formation water constitutes very drastic waterin-oil emulsions, which affect the production process and causes corrosion to the production facilities and equipment. Therefore, crude oil free of water is a significant demand for oil and gas treatment. The demuslification process is a stepwise process starts removing the natural stabilizing agents that present in the crude oil (asphaltenes), then replacing them with demulsifiers which allow water droplets to approach each other and coalescence into bigger and bigger droplets which finally leads to separation of the emulsion into two phases (**Figure 7**).

#### **Figure 7.** *Demulsification process.*

Environmental restrictions limit the use of most traditional demulsifiers despite of its effectiveness in breaking (W/O) emulsions. Since most traditional demulsifiers are pollutive and have high environmental hazards, green demulsifiers have been applied to break down petroleum emulsions. In this regard, Abu-Bakar and Aliyu [43] investigated plant extracts of some vegetable oils such as the coconut, olive oils, and green tea as effective environmentally friendly W/O demulsifiers. The plant extract was obtained by Soxhlet extraction method while the vegetable oil (triglycerides) was obtained from coconut oil (100%), the compositions, and the purity of the extracts and the vegetable oils were determined by gas chromatography (GC) while the non-toxic effect of the tested demulsifiers was proved by potential toxicity tests. The demulsification efficiency of the investigated green demulsifiers was confirmed via bottle tests, the data revealed that the green tea extract and olive oil separated lesser amount of water than the coconut oil for all W/O emulsion samples. Moreover, Abdulraheim [44] developed chitosan-based nonionic surfactants by modification of chitosan (chemically) via esterification then etherification to produce ether amides surfactants (**Figure 8**). The synthesized surfactants were characterized by IR spectroscopy and their thermal properties were investigated. Furthermore, the surface properties of these surfactants were calculated through surface tension measurements at different temperatures and the

**Figure 8.** *Chemical modification of chitosan into nonionic surfactants.*

#### *Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

demulsification efficiency of the prepared surfactants was verified under different conditions. Viscosity of the crude oil before and after demulsification was used as a parameter for demulsification process. Moreover, the demulsification process was monitored by using the optical microscope. Cellulosic materials were extensively used as bases for green demulsifiers for crude oil emulsion. Regarding this, cellulose was separated from saw dust and depolymerized into pure glucose, which is modified into nonionic surfactants via esterification then etherification, Abdel-Raouf et al. [45]. The surface properties of the synthesized surfactants were verified under different conditions. The demulsification efficiency of the prepared demulsifiers was verified for breaking two types of crude oil (light and heavy crudes) at different conditions of aqueous phase [46]. The data revealed that the light crude was more easily demulsified than the heavy crude, besides that, changes in pH or salinity of the aqueous phase of the emulsion enhance its stability and decrease the demulsification efficiency of the applied demulsifiers.

Furthermore, a number of glucose fatty ester ethoxylates were prepared and tested as demulsifiers for oil sludge (**Figure 9**). Results showed that the prepared demulsifiers achieved about 90% water separation from the sludge after 6 h of injection. The hydrocarbon composition of oil phase recovered from the treated sludge was determined.

The oil phase was rich in low molecular weight hydrocarbons this is also an indication of their efficiency as demulsifiers for petroleum sludge [47]. Zhang and Merchant [48] prepared nonionic saccharide surfactants with an amide group linking hydrophilic saccharide segment to hydrophobic alkyl segment and investigated their surface-active properties (**Figure 10**). The surface properties of these surfactants were studied versus the length of hydrophobic and hydrophilic and the obtained data was interrelated to structural variation in the saccharide surfactants. Roostaie et al. [49] used some cellulose, ethylcellulose, microcrystalline cellulose, at different viscosity grades, and the blend of ethylcellulose and ethoxylated coco amine to break the crude oil emulsion through bottle test. According to the obtained results, ethylcellulose was very efficient in breaking emulsion but with slow dehydration rate, which is the main weakness of that agent. Finally, the effect of temperature, agent composition, and demulsifier amount on the dehydration capacity and rate of selected agents were evaluated. Three unrefined fatty oils were used as sources for demulsifiers. The hydrolyzed form of each type of oil was adducted

**Figure 9.** *Synthesis of ethoxylated glucose fatty esters.*

#### **Figure 10.**

*The chemical structures of three water-soluble chemically modified guar derivatives with different functional lateral groups.*

with maleic anhydride then modified by esterification with polyethylene glycols or ethyleneoxide-propyleneoxide block copolymers. The demulsification efficiency, coalescence rate, some surface active, thermodynamic properties, and partition coefficient of a selected demulsifier were investigated [50].

Atta and Elsaeed [51] prepared some nonionic polymeric surfactants from rosin by esterification of it with different molecular weights of polyethylene glycol to produce rosin ester surfactants. The surfactants were tested as sludge dispersants via viscosity measurements of sludge crude oil mixtures at different times.

Demulsifiers from green non-bio polymers were also prepared. A series of propylene oxide (PO) ethylene oxide (EO) block copolymers with different EO/PO ratios and molecular weights have been synthesized and tested for their demulsification potency in breaking water-in-benzene emulsions stabilized by asphaltenes. The demulsification competence of the prepared surfactants was studied versus the change in molecular weight and HLB, the data revealed that the amounts of separated water are directly proportional to both of them., also the effects of temperature, NaCl concentration (salinity), pH value, and solvents on the demulsification effectiveness were thoroughly inspected [52, 53].

Dalmazzone and Noïk [54] performed large screening of different chemicals that could be used as demulsifiers for oil production by classical bottle tests. Silicone derivatives were proved as effective demulsifiers in breaking two types of emulsions come from an asphaltenic and a paraffinic crude oil. According to this first round study, silicone demulsifiers appeared as good candidates for the further development of new green formulations for oil production and demulsification. Alsabagh et al. [55] studied the demulsification process of Water-in-oil emulsion at petroleum field using some demulsifiers derived from propylene and polyethylene oxides. The data revealed that the chemical structures, which containing propylene oxide, might play a vital role to ease and enhance the demulsification competence and that rising of the surfactant dosage (100–600 ppm) decreases the time taken for complete water separation.

#### **3.3 Corrosion inhibitors**

Corrosion is a severe engineering problem in this current era of industrial evolution, which causes economic losses and irreversible damage to metallic

structures [56]. **Figure 11** illustrates the electrochemical corrosion process. Several efforts have been made to control the destructive effects of corrosion using several preventive methodologies.

Corrosion inhibitors are essential petroleum additives during transport and refinery stages. In general, corrosion inhibition technology uses more than one of the following techniques:


Many green inhibitors have been developed, which are safe, biodegradable, eco-friendly and have proven effectiveness in controlling the corrosion of different metallic equipments and facilities made from steel, mild steel, stainless steel, iron, copper, aluminum, 2024-T3 aluminum alloy, steel in concrete structures, carbon steel, AA5083 Al-Mg alloy, nickel and zinc [57]. The use of inhibitors for the control of corrosion of metals and alloys, which are in contact with an aggressive environment, is highly recommended [58, 59]. The general requirements for selection of a proper inhibitor are illustrated in **Figure 12**.

The inhibitors are absorbed on the metal surface and suppress the corrosion. They are classified as cathodic, anodic and mixed type inhibitors, depending upon whether the inhibitor affects the anodic metal dissolution reaction or the cathodic oxygen reduction in near-neutral solutions or hydrogen discharge reaction in acid solutions [60]. Great numbers of organic compounds have been studied to investigate their corrosion inhibition potential [61–64].

All these studies have revealed that organic compounds particularly those with N, S, and O show significant inhibition efficiency. Plant extracts and organic species have become important as an environmentally acceptable, readily obtainable and renewable source for wide range of inhibitors [65–67].

**Figure 11.** *Representation of electrochemical corrosion.*

#### **Figure 12.**

*General requirements for corrosion inhibitors selection.*

The most common green polymers that can be made into corrosion inhibitor formulations are cellulose and cellulose derivatives, chitosan, fatty acids and alcohols, guar gum and starch. They can be used either in their original forms or chemically modified or blended in different formulations or as nanocomposites. This variability leads to countless designs of green inhibitors. Therefore, the most effective designs are summarized in **Table 3**.

The bigger size and the greater number of characteristic anchoring groups of polymeric corrosion inhibitors afforded superior performance. These functional groups facilitate the adsorption on the surface of metal and coat greatly more surface than the matching repeating units.

Therefore, efficient protection operation is influenced by the corrosion alleviation properties of polymers such as molecular weight, molecular size, composition, and nature of the anchoring groups. However, corrosion inhibitors from green non-biopolymers are well known. Organic inhibitors have been the most extensively used in petroleum refining processes because of their ability to form a shielding layer on the metal surface in media with high hydrocarbons content. Currently there are many of organic inhibitors belonging to diverse chemical families i.e. fatty amides [85, 86], pyridines [64, 87], imidazolines [68, 88–90] and other 1, 3-azoles [91–93] and polymers [94] have showed outstanding performance as CIs (**Table 4**).

Moreover, protonated polyanilines were identified as a pioneer corrosion inhibitor in acid for a number of metals of the last century. Also, polyanilines as anticorrosive coatings were reported by several authors [95].

Most aniline-based polymeric materials show efficient inhibition due to their good of adhesion on the surface of metals. The metal/polymer interactions are mostly of hydrogen-bridge type or secondary interaction due to dispersion, dipole interactions, or van der Waals forces. Polyethylene terephthalate waste was modified into powerful corrosion inhibitors for API XL65 carbon steel, in a solution of 2 M HCl [96].

*Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*


#### **Table 3.**

*The most effective inhibitor formulations based on biopolymers.*

Amines polymer are superb corrosion inhibitors for iron in acid solutions. Jeyaprabha et al. [97, 98] investigated the corrosion inhibition act of poly(diphenylamine) and poly(aminoquinone) on iron in 0.5 M H2SO4. Other imine- and amide-based polymers have been employed as potent corrosion inhibitors for different metallic systems [99–101].

#### **3.4 Coating materials**

A coating material is an anticorrosion agent applied in the form of a thin layer covering the metallic surface. The selected coating materials shall be appropriate for the intended use and shall be chosen after verifying the following properties:

#### **Table 4.**

*Structural groups of green non-biopolymer inhibitors.*


Based on the above-mentioned criteria, green polymers specially biopolymers are excellent candidates for coating formulations. In the last few years, cellulosebased materials (sp. Nano and micro cellulose) have recognized themselves among the most frequently used materials for superhydrophobic coatings.

In this regard, A number of polyurethane nanocrystalline cellulose composite (PNCCC) and polyurethane micro-powdered cellulose composite (PMPCC) coatings were prepared with various loading levels of NCC and MPC, these coatings were applied onto the pretreated mild steel substrate at room temperature. The results showed that the NCC and MPC affected positively on the properties of the polyurethane coating [102].

Cleide et al. [103] studied the effect of aminopropyl triethoxysilane (APS), cellulose and polyaniline emeraldine-salt (PAni ES) as an additives to epoxy coating on the corrosion protection of mild steel. Microcrystalline cellulose (MCC) and cellulose nanowhiskers (CNW) functionalized or not with PAni ES were used and compared. The coating properties were checked by electrochemical impedance

#### *Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

spectroscopy (EIS), salt spray test and scanning electron microscopy (SEM). The surface of the carbon steel, after 1000 h of exposure, did not present evidence of surface corrosion. Polymer coatings using CNW and PAni ES displayed amended corrosion protection properties even after 90 days of immersion in 3.5 wt% NaCl solution.

Another series of epoxy resin-based nanocomposites were prepared in the form of coatings with different amounts of NC loadings, and the coatings were applied onto mild steel at room temperature. The corrosion protection properties of the coated mild steel substrates immersed in a 3.5% NaCl solution were studied relatively by electrochemical impedance spectroscopy (EIS). The results showed that all of the nanocomposite coatings with NC clearly influenced the epoxy-diamine liquid pre-polymer, both physically and chemically [104].

Lignin occupies the second rank in most widespread organic polymer. It contains benzyl alcohol, carboxyl, hydroxyl, methoxyl, phenolic and aldehydic characteristic groups. Extracted alkali lignin has shown corrosion inhibition behavior on various metal alloys in HCl solutions [105].

Chitin and chitosan are nitrogen derivative of cellulose. Chitosan is polyelectrolyte (cationic type), which can gel with polyanions and form complexes with metal ions. In our work [106], Chitosan was mixed as natural organic filler with epoxy coating in various loading levels from 2–20% to get chitosan − epoxy coating composite. The corrosion resistance and the antimicrobial activity of coatings formed by chitosan and epoxy were investigated. The corrosion resistance was evaluated via a salt spray test and the antimicrobial activity of the prepared composites was investigated against different pathogens. The obtained results demonstrated that the chitosan − epoxy coating composite showed uniform and lower corrosion rates than that of absolute epoxy coating. The DMA proved that chitosan improved the viscoelastic characteristics of epoxy coating; the mechanical and chemical resistance were also enhanced with increasing chitosan. Other chitosan derivates such as acetyl thiourea, carboxymethyl, and hydroxyapatite composites were used as efficient corrosion inhibitors [107].

#### **Figure 13.**

*Some green polymers used in coating formulations.*

Rosin is another natural polymer that can be adopted into highly durable coatings. In our work [108], Ketone type derivative of rosin was synthesized by dehydrocarboxylation of isomerized abietic acid. Acid-catalyzed Diel-Alder reaction was carried out for coupling of dipimaryl ketone with maleic anhydride. The corresponding tetra glycidyl ester was obtained by epoxidation of the dipimaryl ketone. The thermal properties of the cured resins using a rosin-based crosslinker and p-phenylene diamine (a viable crosslinker) were investigated using dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and some preliminary universal coating tests. Results showed that the fully rosin-based epoxy coatings gave better performance than bisphenol-A based one. These findings and results were attributed to a liquid crystal behavior of the rosin-based crosslinker. Furthermore, a tetrafunctional rosin-based epoxy was prepared and cured with either rosin-based hardener or common phenylene diamine to study the viability of creating high performance thermosetting polymer from a renewable resource. The analytical results indicate that fully bio-based epoxy system holds high glass transition temperature (Tg), high modulus (G`) and enhanced thermal stability [109].

Additional biopolymers such as vegetable oils [110] and Fatty acids [111] have been modified into successful coating formulations. However, other green polymers such as polyesters, polyester amides, polyether amides – (**Figure 13**) – have been used as coatings by many authors [112–114].

#### **3.5 Oil sorbent materials**

Over the past few decades, there have been many oil spill accidents. These accidents occurred during the extraction, transportation, and storage of oil, The spilled oil significantly affects the marine ecological system and the surrounding environment [115, 116]. Oil spill accidents have commended scientists all over the world to advance instant cleaning technology to treat oil spill disasters. Therefore, the removal of spilled oil from water resources is a very worthy matter.

The increased environmental awareness pushed the efforts towards inexpensive, non-toxic and biologically degradable compounds along with diverse biomasses to make multi-sized materials, sponges/aerogel, membranes, etc. for the remediation of oil spill [117]. Generally, there are two methodologies for oil spill remediation; Dispersion and/or recovery of the spilled oil (**Figure 14**).

The selection of the suitable method for oil spill control is dependent on the nature of the spilled oil, its location and the surrounding conditions [118]. When oil sorbents were chosen as a treatment method, environmental designs are required. However, the growing global inhabitant's rate has enlarged the rate of food consuming, producing immense amounts of biological waste. Therefore, the sensible solution is to consume such easily biodegradable waste or biomass to make cheap sorbent materials with higher oil uptake capability that is simple to scale up for the removal of an oil spill, rather than toxic chemicals. The most important natural polymer applied as oil sorbents or modified into gel structures are provided in **Table 5**.

Beside our previous works concerning the utilization of natural polymers as oil sorbents, we paid some attention for modifying some plastic wastes into effective oil sorbents for oil spill remediation. In this context, polymeric sorbents based on polystyrene waste were prepared and evaluated as sorbents for different oil phases under different application conditions. These sorbents are synthesized through radical polymerization of p-CMS with styrene in the presence of benzoyl peroxide as a free radical initiator. The oil uptake of organogel was determined through oil absorption tests; the highest oil absorbencies were 82.6, 74.4, 46.7, and 38.1 g/g in N,N-dimethyl formamide, CHCl3, toluene, and diesel, respectively [126].

*Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

**Figure 14.** *Oil spill treatment processes based on oil dispersion or oil recovery.*


#### **Table 5.**

*The most common natural polymers used as oil sorbers.*

#### **3.6 Oil spill dispersants**

Addition of some chemical agents to breakdown the spilled oil into tiny particles to facilitate the process of biodegradation is another treatment mean for spilled oil. The proposed mechanism of dispersants action is illustrated in **Figure 15**.

Therefore, utilization of natural polymers in dispersant formulation is highly required. Generally, all multifunctional biopolymers can be modified into dispersants due to their high functionality. Water-soluble surfactants based on rosin acids were prepared from condensed rosin acid-formaldehyde, which esterified with different poly (ethylene glycol) chains into rosin esters. The dispersion effectiveness of the prepared surfactants as oil spill dispersants was investigated and linked with the surface activity, concentrations of the surfactants and type of petroleum crude oil. Additionally, Xanthan gum formulation comprised of Polyoxyethylene Sorbitan Fatty Acid Esters (48%), bis (2-ethylhexyl)sulfosuccinate sodium salt (35%) and Xanthan

**Figure 15.**

*Proposed mechanism of action of dispersants.*

Gum was applied as a dispersant for crude oil with dispersion efficiency more than 50% [127]. Some Octyl carboxymethyl chitosan as a green polymer was applied as a dispersant for waxy crude and fresh asphaltic crude with more than 90% dispersion efficacy [128]. Our environmental awareness has been extended to oil spill treatment. In this context, our attention was paid for chemical recycling of plastic wastes such as poly ethylene terephthalate into effective dispersants [129]. Moreover, green some poly oxyethylenated pentaerythritol (PE) ester surfactants have been synthesized and investigated as oil spill dispersants. Furthermore, the biodegradability of the investigated esters was studied at various conditions in order to explore their usability as oil spill dispersants. The data revealed that the investigated esters were very efficient as dispersing agents and they were completely biodegraded after 8 days [130].

#### **4. Future perspectives**

The greatest challenge with the industrial development that is a rocket rising is to maintain the environment and develop environmentally benign multi-purpose materials especially hose designed for the petroleum sector. The sustainability of these materials is guaranteed as they are constructed from natural polymers. The future concern is concentrated on the following points:


Our future concern is to explore more products derived from natural polymers, mainly cellulose and cellulose derivatives, as it is the most abundant biopolymer to be used as multi-purpose products in the petroleum sector and to overcome the disadvantages of the currently applied formulations such as improper mechanical properties, decreased efficiency at higher temperature or at elevated salt concentration. Our current research is the synthesis of cellulose nanocomposites as demulsifiers for petroleum sludge at ambient temperature. The breaking down of sludge requires sophisticated methodology, and the introduction of efficient demulsifiers to recover the oil from the sludge without heating will greatly reduce the sludge treatment costs. So, our future work will be extended on developing new *Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

organic–inorganic nanocomposites to increase the effectiveness of the working agents so as to double its surface area and to include inorganic core material inside a polymer shell to build up nanoparticles of a proper size.

#### **5. Conclusions**

Petroleum is the first and most important energy source. Therefore, the petroleum industry is rapidly growing and necessitates great attention. At the same time, the green chemistry concept is linked to this industry such that most if not all the materials used in this sector become green material. The concept 'green' was demonstrated and the difference between biomaterial and green material is discussed. The advantages of the green materials were mentioned. Moreover, the materials utilized in the petroleum sector were categorized according to the stage of application. Some products such as corrosion inhibitors and coating materials can be used in more than one stage. Furthermore, corrosion inhibitors perform the same function but differ in application methodology. The difference between the oil sorbers and the oil spill dispersant was discussed and the need for each category was identified. The green polymers included in this work are tabulated in **Table 6**.


#### **Table 6.**

*The green polymer reviewed in this work.*

*Crude Oil - New Technologies and Recent Approaches*

#### **Author details**

Manar Elsayed Abdel-Raouf, Mohamed Hasan El-Keshawy\* and Abdulraheim M.A. Hasan Egyptian Petroleum Research Institute, Cairo, Egypt

\*Address all correspondence to: elkeshawy2006@yahoo.com

© 2021 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.

*Green Polymers and Their Uses in Petroleum Industry, Current State and Future Perspectives DOI: http://dx.doi.org/10.5772/intechopen.99409*

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#### **Chapter 3**

## Technologies Involved in the Demulsification of Crude Oil

*Karthika Rajamanickam*

#### **Abstract**

Due to the use of enhanced recovery processes that necessitate the use of a considerable amount of water, mature petroleum reservoirs generate crude oil with huge amounts of water. The majority of this water gets emulsified into crude oil during production, increasing viscosity and making flow more difficult, resulting in production, transportation, and refining operational challenges that have an influence on corporate productivity. Natural surfactants with a strong potential to create stable emulsions are naturally mixed with crude oils. Because crudes with a high amount of stable emulsion have a lower value, the stable emulsion must be adequately processed to meet industrial requirements. As a result, basic research on natural surfactants that contribute to emulsion stability is examined in order to effectively separate emulsions into oil and water. This would need a review of various emulsification methods as well as the proper formulation for effective demulsification. The petroleum industry recognizes the importance of an efficient demulsification procedure for treating emulsions. Numerous studies on the mechanisms of emulsification and demulsification have been undertaken for decades. To guarantee optimal hydrocarbon output, effective treatment is required. The present paper is to review reported works on the formation of petroleum emulsions, demulsification treatments, and characteristics of fit-for-purpose demulsifiers as well as research trends in emulsion treatment.

**Keywords:** crude oil, demusification, w/o emulsion, treatment

#### **1. Introduction**

Crude oil is a type of petroleum which has not been treated yet. In general, geologists agree that over millions of years crude oil was formed out of remains of small aquatic plants and animals living in ancient seas. Brontosaurus may be cast into bits for good, but petroleum is largely owed to one-cell marine organisms. Geological history of crude oils is the one most important when its characteristics are determined; therefore, crude oils in similar marine deposits can resemble each other on different continents. However, regions characterized by different deposits of the marine environment, pressure and temperature can produce a variety of crude oil, from sweet to greenish, to black, light or heavy, waxy or not.

Water is usually found in crude oil reservoirs or injected into oil production by steam. When rising through the well and passing through the valves and pumps, water and oil can blend into relatively stable dispersions of water droplets in crude oil, usually referred to as emulsions from oil fields [1]. In combination with gas and saline-forming water, crude oil is found. As the reservoir is depleted, the amount

of water produced with oil is co-produced, and the number of water supplies with crude oil is increasing steadily. The simultaneous action of shear and pressure drop on the wellhead, squash, and a valve easily emulsifies these immiscible fluids. It is produced in emulsion at 90 to 95% of the world's crude oil. Due to economic reasons and pipeline corrosion, water in oil causes many trouble; before sending oil for processing, the water needs to be separated fully from petroleum. If a [2] system contains at least two intermixable phases, they are called dispersion. The formation of a dispersed system involves a dispersed phase and a continuous flow.

Two immiscible (unbeatable) liquids are mixed into emulsion. One (the scattered) fluid is scattered into the other (the continuous phase). Many emulsions are emulsions of oil/water, with dietary fats one common type of oil found in daily life. Emulsions tend to look cloudy as the many interfaces of the phases (the interface is called the boundary) dispersion light through the emulsion. Emulsions are unstable and therefore not spontaneously formed. Emulsions tend to return to the stable state of the emulsion-related phases over time. The kinetic stability of emulsions can be greatly increased by surface active substances (surfactants), so that emulsion does not change markedly during stocking years once formed [3]. The formation of an emulsion is undeniable during the extraction and transport of crude oil. The formation occurs when the heterogeneous mix flows into the pipe valves and porous rocks and endures turbulence at high or high temperatures. The principal reasons for improving emulsion are the existence of water surface-active agents, ionic compositions and pH [4].

Transporting and manufacturing companies do not receive emulsions because it is highly capable of producing a stable composition, unless well treated, leading to many problems, especially in the process of refining. During the extraction of crude oil, many fighting can be brought together for an inscription [5].


The primary elements of crude oil may be divided into four: saturates, including waxes, aromatic materials, resins, and asphalt, known as SARA fractions. The raw oil is classified in a solvent according to its polarity and solubility. Demulsification is the division into oil and water of a crude oil emulsion. In distillated piers, heat exchangers and reboilers, emulsions can cause problems of corrosion and under deposits. Commercial processes include settling, heating, distillation, centrifuge, electrical processing, chemical therapy and filtration. In combination, this separation technology can be used to ensure optimal results.

*Technologies Involved in the Demulsification of Crude Oil DOI: http://dx.doi.org/10.5772/intechopen.99743*

Many of the oilfield researchers are concerned about the stability of crude oil emulsions, inventing various efficient and relevant techniques to cut it off. The demulsification process has grown in importance because the development of viscous emulsions of oil, water and clay complicate use of steam and caustic injections or combustion processes for in situ heavy oil recovery.

In the petroleum industry the origin of the emulsion from the oilfield reservoir has become a complex problem. Strengthening future requirements for the best petroleum quality requires impressive and intensive development efforts to improve emulsion demulsification mechanisms. According to [5] Kokal and Aramco (2005), Rough oil is seldom produced on its own. It usually is produced from water, which in the production process creates several complications. The water can produce two ways. The water may be produced as free, immediately settling water, or emulsion formation due to the presence of the water.

#### **2. Classification of oil emulsions**

Three main types of emulsion that are common in the petroleum industry are the emulsions of water in oil (in which the water phase is dispersed in continuous petroleum), oil in water (in the continuous water phase) and multiple emulsions (**Figure 1**). Thermodynamically unstable, but also cinemically stable, these types of emulsion may last forever or even for a long time [5]. Emulsions are divided into three classes based on their kinetic stability: loose, medium and tight emulsions. They differ in their separation rates when the loose emulsions are separated in a couple of minutes and the water is occasionally discussed as free water. In 10 minutes, medium emulsions are to be separated. Tight emulsions however take longer than days, weeks or even completely separate as such to separate.

#### **2.1 Water-in-oil emulsions**

The most significant interest was given to water-in-oil emulsions during crude oil production. These emulsions must be divided into two stages to meet the transport requirements of crude oil and must be sent to refineries. Water in

**Figure 1.** *Types of emulsion.*

oil emulsion is commonly known as regular emulsion, often called "chocolate mousse" or "mouse" while oil in waters emulsion is referred to as reverse or reverse. Some 95% of the world's crude oil produced the emulsion water in oils. It tends to separate into the formation of water droplets throughout the continuous oil phase. During manufacturing, an adequate mixing of emulsifiers/surfactants added to the crude oil volume leads to corrosion in the pipelines and increasing transport costs and refining costs. The crude oil viscosity is one of the important parameters in transport. Droplet size distribution affects the emulsion viscosity, since the smaller the droplet size, the higher the viscosity and stability of the water-in-oil emulsions [6]. The water emulsion in oil is formed when certain raw oils are mixed with water (which has their natural salt, NaCl) and when droplets are produced of water spread through the oils. Wind or wave turbulence supplies the mixing energy required to form emulsions in the ocean.

#### **2.2 Oil-in-water emulsions**

A **"**reverse**"** emulsion is said to be the oil-in-water (O/W) emulsions. Usually O/W emulsions will be identified during the water phase of the oil droplets. In 1994 Porter disclosed that the stabilization and adsorption of an emergency surfactant is more effective in the continuous phase when the surfactant is more soluble. For the formation of O/W emulsions, it consists of two stages: water and oil. The oil phase appeared as globules at a continuous water phase and the surfactant structure (hydrophilic head and hydrophobic tail) are considered to be a soluble type for oil surfactants. Water surfactant is more effective in the case of W/O emulsions.

#### **2.3 Multiple emulsions**

The structure of several emulsions is more complicated and contains small droplets suspended in large droplets, which are continuously suspended. For example, water-in-oil-in-water emulsions include small water droplets that are suspended in larger oil droplets during a constant water period [7]. It is possible to separate multiple emulsions into two classes: water in oil and water emulsions (W/O/W), and oil in water emulsions (O/W/O). Emulsions (W/O/W) are composed of oil globules dispersed in water droplets. Meanwhile, (O/W/O) emulsions consist of water globules dispersed in oil droplets. The intermediate state of these several emulsions is when simple emulsions undergo transformations from W/O emulsions to O/W emulsions.

#### **3. Demulsification of crude oil**

Demulsification is the breakdown of the emulsion into its incompatible individual phases, particularly water and oil. In petroleum industries, the demulsification process is very important, where emulsions occur almost always either naturally or consciously (man made emulsions). Before oil refining, water is to be separated from crude oil in the petrochemical industries and refineries. Emulsion breakers are currently used in large numbers as chemical additives to break the emulsion of water in oils. In terms of technology, the resistance to and response to demulsification technologies such as thermal, mechanical, electrical or chemical emulsions of a w/o emulsion mainly depends on the physico-chemical structure of the oil they are formed from, emulsification, and aging conditions. The effort and strategies for optimizing the demulsification of w/o can therefore vary from one oil field to another [8]. The emul sions must be separated into water and oil phases in several

*Technologies Involved in the Demulsification of Crude Oil DOI: http://dx.doi.org/10.5772/intechopen.99743*

**Figure 2.** *Process of demulsification of crude oil.*

stages during the process of demulsification. Creaming and sedimenting, flocculation, eastwald ripening, coalescence are the mechanisms involved in this process which shown in **Figure 2**.

#### **3.1 Creaming and sedimentation**

The difference in density between water and oil is responsible for both sedimentation and creaming; that is, the density of water is higher than oil. Sedimentation is an important mechanism for the demulsification of crude oil and is characterized by water droplets on the ground of the continuous oil phase of an emulsion settling. The growth of oil droplets on the water surface is instead a creaming process. Whether sedimentation or creaming takes place depends, therefore, on whether the dispersed phase is water or oil [9].

#### **3.2 Flocculation**

During flocculation the droplets of the water in crude oil emulsions are aggregated or flocculated together. The flocculation rate depends on a number of factors, such as the emulsion's water content, emulsion temperature, oil viscosity, the difference in oil/water density, and the electrostatic field [10].

#### **3.3 Ostwald ripening**

Ripening of the east forest is another process that demulsifies the crude oil. Ripening in the Eastwald is the process through which the volume drops. The process takes place as soon as in the continuous phase the dispersed phase has a finite solubility, which causes drops of varying sizes to migrate. In large fractions, faster growth generally occurs because the drops are easier to swap materials.

The solubility of oil in water or water in oil is low for heavy oil, which slows down growth processes. The decline of growth through Ostwald maturation plays a crucial part in stabilizing emulsions from oil into water [11].

#### **3.4 Coalescence**

Coalescence is a crucial step in the demulsification of crude oil and an irreversible process by which water droplets merge into or fuse into a larger process. The coalescence process often results in fewer droplets of water. The emulsion of crude oil is permanently demulsified [12]. Factors such as a high flocculation rate and lack of mechanically strong films, high interfacial tension and water cutting, low interfacial speed and high temperature are necessary for an efficient coalescence [13].

#### **4. Techniques involved in the demulsification of crude oil**

Increased temperature, centrifuge, electrical techniques, high resonance time, and chemical treatment separation increase destabilization of crude oil emulsions. The Many demulsification approaches have been found to achieve this, and numerous parameters, including the distribution of the droplet size, dosage and drainage rate, emulsion viscosity/demulsifier type and temperature [5]. The techniques like Chemical, biological, mechanical, Thermal, centrifugal, freeze/thaw, and ultrasonic membrane techniques electric and microwave demulsifications.

#### **4.1 Chemical demulsification**

One of the most important techniques of water in-oil emulsification is chemical demulsification and it is widely applied in the petroleum industries. A demulsifier is a surface-active compound so that the demulsifier moves to an oil–water interface and breaks the film rigid, which causes the water droplets to coalesce. In principle, a huge quantity of surfactants can be prepared just through the manipulation of surfactants in a commercial polymer surfactant long chain by changing accepters, compounds, amounts and sequences [14]. The basic element of the chemical demulsification mechanism of any type of emulsion is the gradual replacement of demulsifiers within the water oil film and eventually causing tremendous changes to the interface viscosity and elasticity [15]. Optimal interruption of the emulsion of crude crude oil by demulsifiers requires careful selection of the chemicals for a given emulsion, an appropriate amount of the chemicals and an appropriate mix of the chemical in an emulsion which represented by **Figure 3**. In addition, the emulsion could be resolved completely by adding heat, electric grids and coalescers [16].

In comparison with the emulsion of heavy raw oil, the surfactant formulated was found to be more effective in demulsifying the medium raw oil emulsion. This difference was attributed to the efficiency of the surfactant because the medium crude oil contains less asphalt than heavy crude oil. In a follow-up study, [17]. Examined the effect on the demulsifying efficiency of W/O emulsions of five demulsifying agents formulated from different polymer ratios. The results showed that the efficiency of water separation increased with increased molecular weight. Calcium chloride was used in demulsifiers used for the demulsification of superheavy petroleum with cationic poly(dimethylamine co-epichlorohydrine) (PDcE) and cationic polyacrylamine (CPAM) [18]. The optimum formulation of the demulsifier with a PDcE/CaCl2/CPAM ratio of 20:600:1,2 (m/m) resulted in effective separation between heavy oil emulsions of mineral oil (98.04 per cent). Contrary to the work of Tonget et al., they have been used as demulsifying medium *Technologies Involved in the Demulsification of Crude Oil DOI: http://dx.doi.org/10.5772/intechopen.99743*

**Figure 3.** *Chemical Demulsification of crude oil.*

for the demulsification of super-heavy crude oil as a series of ionic liquids, such as trioctyl methylammonium [TOA]+]- and ammonium salt [OCD] + [Y]—. Use from [TOA] + [Y]-species of the Ionic Liquid has achieved an efficiency in water extraction of 95 percent. An ionic demulsifier at a concentration of 900 mg/L and resulted in a dewatering efficiency of 89.5 percent. Polymers, such as alkene oxides diester, ethicellul, formulated demulsifiers [19]. Variation at polymer demulsifier concentration has often led to different degrees of demulsification efficiency, and at 97.5 percent the highest demulsification effectiveness recorded with the help of a polyester-based demulsifyer within 45 minutes of the demulsification process. Likewise, a high demulsifying efficiency of 95–99.98 percent was demonstrated in magnetic chemical demulsifiers such as magnetic graphene oxides, januus magnetic submi-cron parts, oleic acid coated magnetite nanoparticles, and alginate [20]. Based on the results of the analysis of range and the relationship between the factors and oil concentration, demulsifying dosage > flocculant dosage > set time > stirring time > intensity of movement were found and optimal conditions for demulsification-flocculation were optimized successfully. The toxicity and nonbiological degradability of chemical substances can be controlled by the use of biodemulsifiers generated by micro-organisms in the water extracted during demu lsification.

#### **4.2 Biological demulsification**

A biodemulsifier has features leading to the destabilization of the crude oil emulsion. Biodemulsifiers are environmentally friendly and do not cause secondary pollution to be used. Biodemulsifiers can function effectively under extreme conditions and can be used for different constituents of complex emulsions of crude oil. In different environments the effectiveness of each bacterial isolation varies greatly from the elements of temperature, soil properties, contaminant type and amount, and the ability to demulsify. *Pseudomona aeruginosa* MSJ isolated for the biodemulsification of W/O and O/W emulsions from oil-contaminated soil. *Alcaligenes sp*. Demulsifying (S-XJ-1) for bio-demulsification of an E/O emulsion, bacterial strain isolated from petroleum-contaminated soil. With a cell concentration of 500 mg/l they achieved 81.3% demulsifying efficiency within 24 hours. It is apparent that organisms or products such as *Alcaligenes Sp.* S-XJ-1, *Rhamnolipids*, ARN63, *Candida sphaerica* UCP 0995 and *Paenibacillus alvei* have been used as demulsifying agents, isolated from various sources of oil-contaminated environments [21].

#### **4.3 Mechanical demulsification**

A series of machines such as a free-water knock-out drum, a 2- and three-phase (low and high-pressure trap), desalting tanks and settlement tanks can be used for the mechanical demulsification of raw oil emulsions. When relative large goutlets are present in the emulsion of crude oil, the flow rate is usually reduced and gravitational forces are used to separate oil, water and small suspended goutlets. Usually, they are present in high volume desalters or separators over the shortest period of time. By concentrating oil traces on the separator, the velocity of the oil separation increases. Normally, when the mixture is very high, the oil in the separator is separated. The centrifuge is one of mechanical equipment rarely used for demulsification as the capital cost and capacity of the centrifuge is high. Emulsions sediment by gravity in a gravity deposition tank separate oil from water. The dispersed-phase droplets are reproached and coalesced when the emulsion is sediment. A centrifugal contactor can be combined with a gravity settling tank for efficient demulsification, as reported by Krebs et al.who studied the demulsification kinetics of an emulsion O/W model in a centrifugal field to imitate the force acting on emulsion droplets on O/ W separators. The study focused mainly on the growth rate of the separate oil stage and on the variation in the mean emulsion layer droplet diameter in terms of centric acceleration and time.

#### **4.4 Thermal demulsification**

The use of temperature for petroleum emulsions is referred to in thermal treatment. Conventional hot plate is used for optimal temperature in laboratory scales. In addition to the fact that some researchers have treated the emulsion by reducing the temperature to more than a point of freezing and then gradually increasing the temperature, this is called a freeze/taw method. Paraffinic petroleum emulsions could break down faster than high asphaltene oil emulsions. The emulsion could be broken slowly, but the separation rate had increased after the addition of chemicals. In fact, the chemical demulsifiers had better be placed at 10°C for viscous emulsion while the demulsifiers should be added after heating up the emulsion for the very viscous emulsion. Emulsion formed from the residues of the distillation could also be broken with moderate heating, while diesel oil did not break up at high temperatures. The viscosity also diminishes as emulsion breaks down. Chantal et al. employed the techniques of insitu emulsion burning to treat emulsions in oil spills. Their emulsion was real emulsion from the scheme. Little samples were placed in a centrifugal bottle and cooled to frost, then thawed back to certain temperatures. The volume of water removed from the emulsion was measured by the centrifugal tube scales (sample holder). It has been found that demulsifying emulsion from

*Technologies Involved in the Demulsification of Crude Oil DOI: http://dx.doi.org/10.5772/intechopen.99743*

water into raw oil strongly depends on certain parameters, including original water, temperature freezing, freezing period as well as temperature and speed of thawing. The optimal freezing temperature for the oil sludge taken from oil used was around −40°C [22].

#### **4.5 Electrical demulsification**

The technology of electric demulsification in the industry gains wide acceptance as a technological path toward crude oil demulsification. The technological advantages include low sludge production, simple appliances and a lack of chemical agents [23]. For consumables that are in contact with crude oil emulsions during electrical demulsification, an electric current is typically applied to a dose of the in situ coagulation resulting in an in situ dose. The dose of coagulants helps to disrupt the repulsive charges of the surfactant molecule, which in turn allows oil droplets to be trapped and forms larger flowers that can be separated easily from water (**Figure 4**). The application of an electric field during electrical demulsification frequently leads to the polarization of droplets and drops can align in chains parallel to the field applied as a result of the interaction between the inducing dipoles. Though the method for adapting the technical to various emulsions with varying properties is considered a substitute for thermal and chemical demulsification.

**Figure 4.** *Electrical Demulsification of crude oil.*

With the direct current fields, the demulsification rate of W/O emulsions in direct current areas increased by the water separation rate. The authors concluded that the demulsification of raw oil emulsions was based on the magnitude and type of electrode of the electric field used [24]. Although electrical derogation has succeeded in the treatment of various industrial effluents from the manufacture of paints and oilfield-produced water for different industrial processes, the focus of research is still on increasing the efficiency of the process.

#### **4.6 Ultrasonic demulsification**

The ultrasound makes it easier to clump droplets into the crude oil, thereby making the separation of oil–water phases easier. The simplicity and effectiveness of the ultrasound demulsification used on crude oil emulsions have drawn more and more attention from research. The acoustophoresis phenomenon influences the scattered droplets in an ultrasonic standing wave field during ultrasound demulsification. The variation in density and compression of the spread droplets and the continuous phase can lead to a uniform combination of the acoustic standing wave [25]. More than one study shows that ultrasound energy is used to demulsify crude oil emulsions. The effect on the efficiency of demulsification by parameters like the input of irradiation and irradiation time, temperature and injected water. The interaction among the parameters resulted in the greatest efficiency of demulsification (99.8 percent) with an optimal capacity of 57.7 W, irradiation time of 6.2 min and temperature of 100μc. A further study focused on the effect of the demulsification of crude oil emulsion by two ultrasound irradiations - primary and secondary. The results showed that irradiance of 75 W was decreased for primary radiation and 50 W was decreased for secondary irradiation at 45 s for irradiation. The use of the low-frequency ultrasound for demulsification of crude oil emulsions is becoming increasingly important. In the absence of a chemical emulsifier, [26] studied the effect of a low frequency ultrasound on demulsification from raw oil emulsions.

#### **4.7 Membrane demulsification**

The membrane demulsification of emulsions of crude oil is based on a tendency to move the spreading phase into the continuing phase via a membrane. The use of membrane technology in the demulsification of crude oil emulsions is an economic and effective way to demulsify the emulsions of crude oil. Several studies on the application of membrane technology to demulsify raw oil emulsions have recently been published. The effect of membrane surface charge on crude oil demulsification and fouling resistance was investigated. For the demulsification process two membranes were used, PP-g-pDMAEMA and PP-g-pOEGMA. In water, the membranes showed positive and negative surface loads. In comparison with the use of PP-gpOEGMA, the efficiency of demulsification increased by 15%. PP-g-pDMAEMA. The authors concluded that the positive charge for the membrane surface increased the demulsification of crude oil. The membrane damage was however exacerbated following demulsification [27]. The membrane has excellent stability because, after several applications, efficiency has not decreased visibly. A similar study, by [24] was carried out with a nylon membrane modified for the demulsification of emulsion from crude oil, as thermosponsive poly(N-isopropylacrylamide) (PNIOAAm). A rough structure, appropriate pore size and thermal responsiveness, the fabricated membrane is able to separate 16 different types of stabilized O / O and W / O crude oil at different temperatures. The membrane was capable of separating any type of crude oil emulsion at a temperature of approximately 25 μC. In contrast, the

membrane showed high hydrophobicity and superoleophilicity at a temperature of about 45 / c which can only be used for separation.

#### **4.8 Microwave demulsification**

The microwave is known as the electromagnetic spectrum of 300 Mhz to 300 GHz. The electrical and magnetic properties of the microwave. Thus, the applied field induces a multi-polarization effect on the medium when projected to the material, according to the transmission, absorption and reflexing rules, depending on the medium properties. The width of the wave varies between 1 mm and 1 m according to the above frequency (300 MHz to 300 GHz). In addition to heating and scientific research, some frequencies, including mobile, radar and television communication, are for specific purposes reserved for the Federal Communications Committee. However, for industrial, scientific and medical purposes the frequency used the most frequently is 915 MHz and 2450 MHz, with 915 in this research. Due to its volumetric heating, the microwave is often preferred in material processing over its conventional counterpart. The heating mechanism in conventional heating takes place by diffusing the heating material from its surface into the bulk. While, in the case of microwave heating, a temperature gradient is almost invariant at different locations in the sample, an important other phenomenon is that a different material has various heating patterns because of the variation in the absorption capacity of the material, which in turn depends on dielectric properties (**Figure 5**). Emulsion was first treated by Wolf via microwave, who initially began the concept of demulsifying the microwave. The emulsion effectiveness of the microwave was shown to induce some impact on the treated emulsion as the temperature increase leads to reduced viscosity, which would increase water droplets' mobility, which can neutralize the zeta potential of the dispersed droplets in turn, and also break the link between hydrogen and molecules of surfactant water. In addition the electromagnetic wave is expected to increase the water droplets' internal pressure, which leads to reduced thickness of the film interface and charges of water droplets free to move toward each other, and downward by gravitational force [28]. The advantage of using microwave energy over its conventional counterpart is that the sample heats better than conventional heating, although local overheating may in some cases cause the sample to hotspots or heat flushes. Crude oil contains large numbers

**Figure 5.** *Oil/ water Seperation by microwave heating.*

of components with a difference of conductivity and polarity, and the main and main charge-bearing component is asphalt [29].

#### **5. Conclusion**

Demulsification by chemical, biological, mechanical, mechanical, thermal, electrical, ultrasonic, and membrane technologies of crude oil emulsions is investigated. It should be noted that each of these techniques depends on its operational parameters and interplay. In addition, the use of synergistic effects by combining one or more of the techniques discussed in the present review could achieve a more effective demulsification process. The efficiency of separation and the rate of demulsification are the main factors of interest in most demulsification techniques. During processing and transport, the occurrence of crude oil emulsions has proven problematic by increasing the cost of production and the use of chemicals that affect the environment. These facts in the petroleum sector have attracted the interest of scientists who are seeking to identify scientific ways to monitor and prevent the formation of raw oil emulsion. A positive demulsification technique therefore is not only robust and applicable to various types of emulsions, it must also be respectful of the environment with minimum environmental impacts, respect for environmental standards and regulations and at lower cost. Recent literature shows that a correct understanding of the properties and types of crude oil involved in the formation or demulsification of emulsions (O/W or W/O) will help to formulate appropriate methods for demulsifying emulsions. It is apparent from the overview of recent studies that different techniques for demulsifying raw oil emulsions vary in efficiency and effectiveness. But the effect of viscosity on the demulsification process was not taken into account by most researchers. Furthermore, most of the crude oil demulsification scenarios are based on laboratory experiments. In field cases or on-site crude oil demulsification cases, there is scarce literature. Therefore, research should be aimed at proposing, at site with real operating parameters used in crude oil treatment plants in small scale or on the pilot scale.

#### **Author details**

Karthika Rajamanickam

PG and Research Department of Biotechnology, Mahendra Arts and Science College (Autonomous), Namakkal, Tamil Nadu, India

\*Address all correspondence to: karthibtanish@gmail.com

© 2021 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.

*Technologies Involved in the Demulsification of Crude Oil DOI: http://dx.doi.org/10.5772/intechopen.99743*

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Section 2
