Natural Surfactants: Application in Enhanced Oil Recovery [1 ed.] 3030785475, 9783030785475

Table of contents :
Acknowledgement
Contents
1 Historical View
1.1 History of Surfactants
References
2 Surfactants and Their Types
2.1 Surfactant’s Structure
2.2 Classification of Surfactants
2.2.1 Anionic Surfactants
2.2.2 Cationic Surfactants
2.2.3 Non-ionic Surfactants
2.2.4 Amphoteric Surfactants or Zwitterionic Surfactants
2.2.5 Gemini Surfactants
2.3 Industrial Application of Surfactants
References
3 Surfactants in Petroleum Industry
3.1 Emulsifiers
3.2 Methane Gas Hydrate Promoter
3.3 Cleaning of Oil Spills
3.4 Oil- and Water-Based Drilling Fluids
3.5 Enhanced Oil Recovery
3.5.1 Classification of EOR Techniques
3.5.2 Principles of EOR
References
4 Natural Surfactants
4.1 Synthesis of Natural Surfactants
4.2 Application of Natural Surfactants
4.3 Advantages of Natural Surfactants Over Conventional Surfactants
4.4 Challenges for Industrial Application of Natural Surfactants
References
5 Interfacial and Colloidal Properties of Surfactants for Application in EOR
5.1 Interfacial Tension (IFT)
5.2 Emulsification
5.3 Wettability Alteration Study
References
6 Applications of Natural Surfactants in EOR
6.1 Screening and Performance Evaluation of Surfactants
6.2 Thermal Stability and Compatibility with Reservoir Conditions
6.3 Oil Mobilization and Recovery
6.4 Adsorption of Surfactant onto the Reservoir Rock Surface
References
Conclusions
Bibliography

Citation preview

SPRINGER BRIEFS IN APPLIED SCIENCES AND TECHNOLOGY

Neha Saxena Ajay Mandal

Natural Surfactants Application in Enhanced Oil Recovery 123

SpringerBriefs in Applied Sciences and Technology

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Neha Saxena · Ajay Mandal

Natural Surfactants Application in Enhanced Oil Recovery

Neha Saxena Department of Petroleum Engineering Indian Institute of Technology (ISM) Dhanbad Dhanbad, Jharkhand, India

Ajay Mandal Department of Petroleum Engineering Indian Institute of Technology (ISM) Dhanbad Dhanbad, Jharkhand, India

ISSN 2191-530X ISSN 2191-5318 (electronic) SpringerBriefs in Applied Sciences and Technology ISBN 978-3-030-78547-5 ISBN 978-3-030-78548-2 (eBook) https://doi.org/10.1007/978-3-030-78548-2 © The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Acknowledgement

I wish to express my sincerest appreciation and gratitude to the Co-Author of this book Dr. Ajay Mandal, Professor, Department of Petroleum Engineering, for his continuous guidance, rigorous supervision, effective suggestions and the hours spent for discussing and reviewing the intricate aspects of this work. Most importantly, my special gratitude is due to my parents, my in-laws, Siddharth Sabharwal––my life partner, and my friends for their love, blessing, encouragement and never-ending kindness which made everything easier to achieve. I would like to pay sincere thanks to IIMT University for motivating me to develop a research-oriented aptitude and to utilize my knowledge in the right direction.

v

Contents

1 Historical View . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 History of Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 1 2

2 Surfactants and Their Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Surfactant’s Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Classification of Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 Anionic Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2 Cationic Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3 Non-ionic Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4 Amphoteric Surfactants or Zwitterionic Surfactants . . . . . . . . 2.2.5 Gemini Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Industrial Application of Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3 3 3 4 5 5 7 7 8 9

3 Surfactants in Petroleum Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Emulsifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Methane Gas Hydrate Promoter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 Cleaning of Oil Spills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Oil- and Water-Based Drilling Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5 Enhanced Oil Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.1 Classification of EOR Techniques . . . . . . . . . . . . . . . . . . . . . . . 3.5.2 Principles of EOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

11 11 12 12 13 13 14 14 17

4 Natural Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 Synthesis of Natural Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2 Application of Natural Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3 Advantages of Natural Surfactants Over Conventional Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4 Challenges for Industrial Application of Natural Surfactants . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

19 19 21 22 22 23

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5 Interfacial and Colloidal Properties of Surfactants for Application in EOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1 Interfacial Tension (IFT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2 Emulsification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3 Wettability Alteration Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

25 25 26 27 29

6 Applications of Natural Surfactants in EOR . . . . . . . . . . . . . . . . . . . . . . . 6.1 Screening and Performance Evaluation of Surfactants . . . . . . . . . . . . . 6.2 Thermal Stability and Compatibility with Reservoir Conditions . . . . 6.3 Oil Mobilization and Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4 Adsorption of Surfactant onto the Reservoir Rock Surface . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

31 31 36 38 38 40

Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

Chapter 1

Historical View

1.1 History of Surfactants Surfactants are compounds having the properties of detergents and have been identified with human civilization. Plants or different parts of plants like stem, leaves have these detergent-like properties, e.g. soap-nut pericarp was used as a source for washing hairs, and leaves of Jatropha were crushed to use it as a source of washing clothes in Indian culture previously. Hence, it becomes very tough to report the exact time when the surfactants were identified and used by the humans. Though for manmade surfactants, their manufacturing and application are well known, and the exact time can be reported, the same cannot be said about natural surfactants. Few historical applications of these soap-like compounds were identified around 600 B.C. Phoenicians filed the application of surfactant around 3000 years ago (Sagir et al. 2020). The origin of these compound has been identified in Mediterranean culture. From the beginning, the soap was manufactured using wood ash, fats and many other plant products. It has been found in the literature that surfactants from industry have been brought about 2000 years ago where they were used to neutralize animal fats. Many non-soap materials like sulphated oil were used as surface-active agents. These oils became famous with trade names like “turkey red oil” produced by reacting sulphuric acid with castor oil producing a form which has a polar head and long non-polar chain. During World War I, synthetic surfactants gained application to reduce the deficiency from the vegetables and animal fats produced. In the past century, the development in the field of surfactant science boomed in the 1920s and 1930s, where the process of sulphation of long-chain alkyl and aryl alcohols was developed. The product obtained has detergent properties and was used as washing agents. By the end of World War II, the long-chain aryl sulphonates replaced the sulphates obtained from alcohol and were commercially available in the market as washing compounds. Alcoholic sulphates procured the market and found application in shampoo and personal care products.

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2_1

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After World War II, in UK, few secondary olefin sulphates were synthesized using byproducts obtained from petroleum refineries and they also found their application in the petroleum industry. In 1950–65, compounds based on alkyl benzene sulphonates (ABS) and the propylene tetramer (PT) gained much importance industrially as surfactants and detergents. With the advancement in technology, the ABSbased surfactants were replaced by linear alkyl benzene sulphonates (LABS) as a primary compound for the detergent industry. Till today, surfactants have found their major application in the cleaning industry but with the growing demands surfactants have found their applications in multiple areas like polluting industry (Brycki et al. 2014), removal of pigments and dyes (Janoš and Šmídová 2005), synthesis of nanoparticles (Khan et al. 2016), the stability of blood (Zhang and Reineccius 2016), recovery of oil (Sofla et al. 2016) and many other applications, where surfactants are used as additives as wetting agents and foaming agents.

References M. Sagir, M. Muhammad, M.S. Tahir, M.B. Tahir, A.R. Shaik, Surfactants for Enhanced Oil Recovery Applications (Springer International Publishing, 2020) B. Brycki, M. Waligórska, A. Szulc, The biodegradation of monomeric and dimeric alkylammonium surfactants. J. Hazard. Mater. 280, 797–815 (2014) P. Janoš, V. Šmídová, Effects of surfactants on the adsorptive removal of basic dyes from water using an organomineral sorbent—iron humate. J. Colloid Interface Sci. 291(1), 19–27 (2005) Z. Khan, S.A. Al-Thabaiti, O. Bashir,Natural sugar surfactant capped gold nano-disks: Aggregation, green synthesis and morphology. Dyes Pigments 124, 210–221 (2016) J. Zhang, G.A. Reineccius, Factors controlling the turbidity of submicron emulsions stabilized by food biopolymers and natural surfactant. LWT-Food Sci. Technol. 71, 162–168 (2016) S.J.D. Sofla, S. Mohammad, A.H. Sarapardeh,Toward mechanistic understanding of natural surfactant flooding in enhanced oil recovery processes: the role of salinity, surfactant concentration and rock type. J. Mol. Liquids 222, 632–639 (2016)

Chapter 2

Surfactants and Their Types

2.1 Surfactant’s Structure Surfactants are organic compounds possessing short- and long-chain fatty acids, which are amphiphilic in nature, i.e. both hydrophilic and hydrophobic groups. These surfactant molecules orient themselves to show their surface active. The typical structure of a surfactant with polar head and non-polar tail is shown in Fig. 2.1. In the detergent industry, the surfactants are said to produce micelle structure in order to present effective cleaning in detergent industry. The polar head group interacts effectively with an aqueous layer and the forces involved in this interaction are dipole–dipole, ion–dipole interactions. The surfactant molecules at the air–water interface adhere themselves in such a manner that the hydrophobic tail subjects itself opposite to the water molecules as shown in Fig. 2.2. At the oil–water interface, the hydrophobic tail extends itself towards the oleic phase indicating their hydrophobic nature. The self-arrangement of surfactant molecules according to their polarity creates an opportunity to be employed in various other applications.

2.2 Classification of Surfactants Based on the polarity, of the head group, the surfactant molecules are divided into five classes mainly: (1) non-ionic surfactants having no charge on their head group, hence these are more resistant to electrolyte-rich solvents; (2) anionic surfactants have a negative charge on the head group and are exploited a lot in detergent industry; (3) cationic surfactants have a positive charge on their head group and are employed as disinfectant and preservatives; (4) zwitterionic surfactant is a combination of both positive and negative charge constituting the head group; (5) gemini surfactants are another class of surfactant molecules that have two polar heads and two non-polar tails © The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2_2

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Fig. 2.1 Typical structure of anionic surfactant

Fig. 2.2 Arrangements of surfactants at the air–water interface and oil–water interface

Fig. 2.3 Types of surfactants a non-ionic b anionic c cationic d zwitterionic and e gemini surfactants

which are attached via spacer forming a dimer-like structure. The typical structure of the five types of surfactant is shown in Fig. 2.3.

2.2.1 Anionic Surfactants Anionic surfactants are most popular and widely used class of surfactants as they have been employed in most of the industrial and household applications. The polar head group of anionic surfactants retains the negative charge in aqueous solutions. The most common anionic polar head groups include sulphonates, carboxylates,

2.2 Classification of Surfactants

5

Fig. 2.4 Structures of some anionic surfactants

sulphates, and phosphates as shown in Fig. 2.4. Sulphonates have been majorly used in the petroleum industry for their application in enhanced oil recovery (EOR). In the past decades, a trend of green and natural anionic surfactants produced from natural resources has been identified and widely employed in various industries due to their biodegradable nature and environment-friendly impacts.

2.2.2 Cationic Surfactants This class of surfactants having a positive moiety are dissociated in water into an amphiphilic cationic part and an anionic part, often a halogen type. A major proportion of these cationic surfactants class includes nitrogen derivatives such as quaternary ammoniums and fatty amine salts having one or several long alkyl chains frequently coming from natural fatty acid sources. Generally, cationic surfactants are more costly than anionic surfactants, because during synthesis they require highpressure hydrogenation. As a result, they found limited application due to their high cost and only employed in the areas where no cheaper substitute is available, i.e. (1) as a bactericide; (2) as cationic substance adsorbing on the anionic substrate to produce hydrophobant effect that has found immense commercial importance in areas like corrosion inhibition. Some of the cationic surfactants are shown in Fig. 2.5.

2.2.3 Non-ionic Surfactants These surfactants cover the second largest application in industrial production with a share of approximately 45% in the market. The non-ionic surfactants do not dissociate in the aqueous solution like water, alcohol ether, etc. The major proportion of

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Fig. 2.5 Structures of some cationic surfactants (Ghomi et al. 2013)

polyethoxylated non-ionics have been produced using polycondensation of ethylene oxide that results in hydrophilic polyethylene glycol chain (Pei et al. 2016). With consideration of key aspects of the surfactant biodegradability, in line with the principles of Green Chemistry, sugar-based head groups have been employed for non-ionic surfactants as they were found to be less toxic in nature. The alkyl chain from fatty acids or alkylbenzene group is often used as a lipophilic group. The polymeric chains synthesized from polycondensation of polyether and propylene oxide as a lipophilic group have also gained much importance in the commercial market and are often referred as poly-EO-poly-PO copolymers (Zhang et al. 2017). Some of the non-ionic surfactants are shown in Fig. 2.6.

Fig. 2.6 Structures of some non-ionic surfactants (Chu et al. 2010)

2.2 Classification of Surfactants

7

Fig. 2.7 Structures of some zwitterionic surfactants

2.2.4 Amphoteric Surfactants or Zwitterionic Surfactants Zwitterionic surfactants is are another class of surfactants, which are electrically neutral in nature due to the presence of hydrophilic polar head groups having both positive and negative charge. The cationic part is generally quaternary salt of ammonia and the anionic part is contributed by the phosphate group and sulphonate group. The zwitterionic surfactants have found diverse applications in household products and cosmetics (Chu et al. 2010). The doubly polarized head group is responsible for their special properties. The increase in charge separation between the molecules enhances the area per molecule that results in a better activity of surfactant. Betaines and carboxybetaines are common examples of zwitterionic surfactants (Tondo et al. 2010). Some of the zwitterionic surfactants are shown in Figure 2.7.

2.2.5 Gemini Surfactants Structure and design of surfactant plays an important role in defining its properties and application in different fields. Menger and his research group (Menger et al.

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Fig. 2.8 Structure of cationic gemini surfactants (Pisárˇcik et al. 2017)

1991, 1993) identified an efficient group of surfactants known as gemini or dimeric surfactants. Unlike conventional surfactants that possess a hydrophilic head and hydrophilic tail, gemini surfactants have a different structure with two amphiphilic groups that are separated with a spacer chain. The spacer chain can vary between 2 and 7 methylene groups of short or long chains with flexible or rigid entities. The presence of two polar heads enhances the hydrophilicity and hydrophobicity of the surfactants that result in the overall efficiency of surfactants. Some of the gemini surfactants are shown in Fig. 2.8.

2.3 Industrial Application of Surfactants Surfactants have revolutionized the world through their vast application in almost every field from medicinal use to the recovery of oil. These applications and properties of surfactants are dependent on the lyophilic and lyophobic balance between the surfactant molecules at equilibrium. The specific characteristics of surfactants like solubilization, emulsification, detergency power, wetting properties, foaming, reduction of surface tension, etc. are responsible for the performance of surfactants in numerous applications. The different applications of surfactants are shown in Figure 2.9.

Personal

Cleaning

care

Agent

• Loon • Body Wash • Face cream • Hair shampoo • Shaving cream

• Domesc dishwash cleaners • Surface cleaning agent • Detergents • Emulsifying agent

Fig. 2.9 Some industrial application of surfactants

Industry

Oil Removing

• Metal purificaon and recovery • Food emulsifier • Fabric soner • Ink and Adhesive

• Degreasers • Chemical Enhanced oil recovery • Auto industry • Soil remediaon

2.3 Industrial Application of Surfactants

9

Table 2.1 Characteristics for surfactants for different industrial applications Industrial application

Characteristic of surfactant

Pharmaceutical industry

Bio-compatibility, less toxic in nature, good emulsifying properties (Nachari et al. 2021)

Detergent industry

Low CMC, good salt tolerance and pH stability, non-toxicity, biodegradability, foaming properties (Lee et al. 2016)

Lubrication

Stability, surface adsorption (Serreau et al. 2009)

Petroleum industry

Alteration of wettability, microemulsion formation, reduction of surface tension, high solubilization ratio, foaming agent, low surfactant absorption (Saxena et al. 2019)

Extraction of minerals

Chemical stability, suitable adsorption of ore(s), cost-effective process (Saitoh et al. 2005)

Emulsifying agent

Hydrophilic-lyophilic balance, good solubilization, environmental and biological component (Zheng et al. 2013)

Every application mentioned above has some specific requirements, and certain essential properties required for a surfactant for being employed in a particular application as are shown in Table 2.1.

References B. Rafiei, F.A. Ghomi,Preparation and characterization of the Cloisite Na+ modified with cationic surfactants. J. Crystallogr. Mineral. 21(2), 25–32 (2013) M. Zhang, Gu. Jiali, X. Zhu, L. Gao, X. Li, X. Yang, Tu. Yingfeng, Y.L. Christopher, Synthesis of poly (butylene terephthalate)-block-poly (ethylene oxide)-block-poly (propylene oxide)-blockpoly (ethylene oxide) multiblock terpolymers via a facile PROP method. Polymer 130, 199–208 (2017) Z. Chu, Y. Feng, Su. Xin, Y. Han, Wormlike micelles and solution properties of a C22-tailed amidosulfobetaine surfactant. Langmuir 26(11), 7783–7791 (2010) L. Pei, Wu. Ping, J. Liu, J. Wang, Effect of nonionic surfactant on the micro-emulsifying water in silicone media. J. Surfactants Deterg. 20(1), 247–254 (2017) D.W. Tondo, E.C. Leopoldino, B.S. Souza, G.A. Micke, A.C. Costa, H.D. Fiedler, C.A. Bunton, F. Nome, Synthesis of a new zwitterionic surfactant containing an imidazolium ring: evaluating the chameleon-like behavior of zwitterionic micelles. Langmuir 26(20), 15754–15760 (2010) F.M. Menger, C.A. Littau, Gemini-surfactants: synthesis and properties. J. Am. Chem. Soc. 113(4), 1451–1452 (1991) F.M. Menger, C.A. Littau, Gemini surfactants: a new class of self-assembling molecules. J. Am. Chem. Soc. 115(22), 10083–10090 (1993) M. Pisárˇcik, J. Jampílek, M. Lukáˇc, R. Horáková, F. Devínsky, M. Bukovský, M. Kalina, J. Tkacz, T. Opravil, Silver nanoparticles stabilised by cationic gemini surfactants with variable spacer length. Molecules 22(10), 1794 (2017) Y. Nachari, M. Jabbari, A case study on the partitioning of pharmaceutical compound naproxen in edible oil-water system in the presence of ionic and non-ionic surfactants. J. Taiwan Inst. Chem. Eng. (2021)

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SuMin Lee, JuYeon Lee, Yu. HyonPil, JongChoo Lim, Synthesis of environment friendly nonionic surfactants from sugar base and characterization of interfacial properties for detergent application. J. Ind. Eng. Chem. 38, 157–166 (2016) L. Serreau, M. Beauvais, C. Heitz, E. Barthel, Adsorption and onset of lubrication by a doublechained cationic surfactant on silica surfaces. J. Colloid Interface Sci. 332(2), 382–388 (2009) N. Saxena, A. Kumar, A. Mandal, Adsorption analysis of natural anionic surfactant for enhanced oil recovery: the role of mineralogy, salinity, alkalinity and nanoparticles. J. Petrol. Sci. Eng. 173, 1264–1283 (2019) T. Saitoh, S. Suzuki, M. Hiraide, Solid phase extraction of some precious metals from hydrochloric acid to polystyrene-divinylbenzene porous resin impregnated with polyoxyethylenetype nonionic surfactant. J. Chromatogr. A 1097(1–2), 179–182 (2005) K. Zheng, A. Zou, X. Yang, F. Liu, Q. Xia, R. Ye, Mu. Bozhong, The effect of polymer–surfactant emulsifying agent on the formation and stability of α-lipoic acid loaded nanostructured lipid carriers (NLC). Food Hydrocoll. 32(1), 72–78 (2013)

Chapter 3

Surfactants in Petroleum Industry

3.1 Emulsifiers Surfactants are an integral part of emulsification formulations. An emulsifying agent is a chemical compound that concentrates at the interfaces of two immiscible phases like oil and water. Surfactants have an important property of emulsification, which frontrunners their use as emulsifying agents in various industrial processes. The amphiphilic property of surfactants supports solubilizing the water molecules in non-polar liquids like oils. Emulsifiers mix oil and water and make stable emulsions for many household and industrial applications. Surfactants get adsorbed on the oil– water interface to lower the interfacial tension. This consequently leads to a decrease in the total energy required to form the oil–water interface for the emulsion. In the petroleum industry, emulsions are used as viscosity-building agents. Surfactants in the presence of crude oil forms an in situ surfactant that favours better recovery of oil (Zhao et al. 2021). Different phases can co-exist with the microemulsions, forming different types of phases, namely, Winsor Types I, II, III and IV. Winsor Type I phase comprises a microemulsion of the oil-in-water type, where only a portion of oil is solubilized by a lower microemulsion solution. Inversely, Winsor Type II is a water-in-oil microemulsion, where a portion of brine (or water) is solubilized by the upper phase microemulsion. Winsor Type III consists of a bicontinuous middle phase microemulsion that exists in equilibrium condition with both upper oleic and lower aqueous phases. Winsor Type IV is a single microemulsion phase, generally formed at high surfactant concentrations. Figure 3.1 depicts the four types of microemulsion systems that can co-exist along with their hydrophilic-lipophilic deviation (HLD).

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2_3

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Fig. 3.1 Image depicts the types of microemulsion system (https://cosmetics.specialchem.com/ tech-library/article/predictive-formulation-via-hld-nac)

3.2 Methane Gas Hydrate Promoter Gas hydrates are recognized as potential application technologies in the green energy sector. These are very much effective in storing and transporting natural gas, considering their vast reserves and stability under certain conditions (Cox et al. 2018). In the present scenario, research on methane hydrates has gained extensive attention as they are considered as potential unit operations for cool storage (Bi et al. 2010), gas transportation (Erfani et al. 2017) and seawater desalination (Babu et al. 2014). Research has been conducted on methods that enhance the formation of gas hydrate and for this promoters are added that aid up the process of gas hydrate formation. The addition of surfactants during the process is an economical and effective way of promoting the hydrate formation process (Cai et al. 2018). The various surfactants used for enhancing the hydrate formation include anionic surfactants like sodium alcohol ether sulfate and sodium dodecyl sulfate), non-ionic surfactants like alkyl polyglycoside and zwitterionic surfactants like disodium laurylamphoacetate. A typical gas hydrate structure is shown in Fig. 3.2.

3.3 Cleaning of Oil Spills Surfactants have found their application in the cleaning of oil spills and soil remediation. Surfactants being a good emulsifying agent can emulsify oil and water to emulsions and microemulsions so that they are effective in the removal of oil. These emulsifying agents break the oil layers to small droplets at the interface that enhances the cleaning process (Rosales et al. 2010). During subsurface oil spills and recovery processes, surfactants are effective in altering the capillary pressure by reducing the interfacial tension (IFT) at the oil aqueous interface, alter wettability to water-wet and enhances the oil flow from contaminated areas.

3.4 Oil- and Water-Based Drilling Fluids

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Fig. 3.2 Schematic diagram of natural gas hydrate formation in molecular scale (Lee et al. 2011)

3.4 Oil- and Water-Based Drilling Fluids Surfactants are generally used in numerous applications for drilling muds and drilling fluids. Drilling muds are of different types for example oil-based mud, water-based mud, emulsion drilling mud, synthetic-based mud and invert emulsion mud. Surfactants are commonly employed as an emulsifying agent and wetting agent in oil-based drilling mud. Other applications like foaming and deforming agents in water-based drilling muds also found applications where surfactants play a key role in producing the appropriate ratio of gas and water foam and also in removing undesired foam.

3.5 Enhanced Oil Recovery The enhanced oil recovery (EOR) process encourages the use of chemical compounds and numerous other methods and mechanisms to recover oil after secondary oil recovery. Tertiary recovery techniques or EOR techniques includes miscible, gas injection, thermal methods and chemical flooding methods. When the same techniques to recover oil are engaged at any stage, then it is called enhanced oil recovery technique (EOR). Another term linked with oil recovery is improved oil recovery (IOR) that comprises EOR methods and other techniques like reservoir characterization, improved reservoir management (IRM), seismic surveying, geological modeling and drilling process (Wu et al. 1989). The residual oil after secondary recovery can be produced by the development of cost-effective and efficient EOR technology such as thermal, chemical, microbial or miscible EOR to upsurge the overall oil production from the matured reservoirs. Injected fluids and the reservoir rock components interact with crude oil and formation water to provide favourable conditions for EOR (Green and Willhite 1998). EOR is considered to be one of the most promising oil recovery techniques for low-pressure depleted reservoirs. The mechanisms involved

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in oil recovery include lowering of interfacial tension at the oil-aqueous interface, mobility control, emulsification, wettability alteration and oil swelling (Arabloo et al. 2016; Golabi et al. 2012; Qi et al. 2013). The EOR application is governed by various factors which include crude oil price, reservoir characteristic after conventional water flooding, technical and economic feasibility of the processes (Nazar et al. 2011). It has been assessed that designing and application of EOR projects at the appropriate time can produce up to 30–60% of OOIP over the secondary recovery method (Dong et al. 2009). Foam-based EOR is another technique used to recover crude oil, in this technique gas is used to generate the foam along with the dispersant mixture of surfactant. This method is beneficial as foam elevate the viscosity of the injected fluid and block the porous layers (Massarweh and Ahmad 2020). More applications: Surfactants have found their application in various other operations of the petroleum industry. They have become an integral component in drilling, cement slurries, hydraulic fracturing, de-emulsification, water flooding corrosion inhibition, transportation, cleaning, chemical, foam and steam flooding for the recovery process (Bhardwaj and Hartland 1993).

3.5.1 Classification of EOR Techniques The enhanced oil recovery techniques follow the two mechanisms of improving the sweep efficiency and displacement efficiency (Zhao et al. 2006). Figure 3.3 depicts the EOR classifications functional in the oil and gas industry. The chemical oil recovery process (CEOR) comprises the injection of chemical slug comprising mainly surfactant, polymer and alkali. The thermal oil recovery method amends the reservoir temperature that affects the rock and fluid properties that facilitate the movement of oil hence, oil recovery is improved indirectly. Reservoirs comprising of crude oil with gravity of approximately 12–25°API and formation with high porosity are predominantly appropriate for the thermal EOR. Miscible flooding comprises injection of gases like natural gas, nitrogen (N2 ) and carbon dioxide (CO2 ) into the reservoir that follows a mass transfer mechanism by the formation of a miscible oil bank. It has been reported that for low viscous oils gas, the injection method can serve as a potential oil recovery process (Srivastava et al. 1999).

3.5.2 Principles of EOR The amount of oil present in the mature reservoir, type of crude oil, rock properties, and oil transmissibility through the porous rocks are the major factors that govern oil recovery. To evaluate the reservoir performance, and distribution of organic components in the reservoir, it is essential to analyse the physical properties of rock formations and the formation fluids (crude oil/water/gas). Porosity is considered to be the most important property for a rock reservoir and is defined as the available space for

3.5 Enhanced Oil Recovery

15

Fig. 3.3 Classification of EOR methods

the storage of hydrocarbon available. Mathematically, it is the ratio of pore volume (void space) to bulk volume. Permeability of the rock is another significant parameter of the porous rock and is defined as the measure of the ability and capacity of the rock to channelize the fluid. Porosity, permeability and pore size distribution are non-uniform and show variation even in the same reservoir. Initially, the porous reservoir rock is entirely occupied by brine, and hydrocarbon, in the form of oil and gases, which are accumulated in the pores, displacing brine. The prolonged contact of crude oil and the reservoir rocks alters the wettability of rock. The crude oil distribution in a reservoir is reliant on capillary pressure in the reservoir. The capillary forces acting at the interface are influenced by the viscosity of crude oil, IFT, wettability and pore dimensions. The capillary forces are responsible for trapping the oil in the pores and they needed to be overcome during the production of oil. The greater value of IFT at the oil-water interface and oil-wetting state of reservoir rock results in increase in the capillary forces, causing lower oil recovery during primary and secondary recovery processes. Thus, the principle of EOR focuses on altering these properties and depressing capillary forces acting at the oil-water interface. Figure 3.4 demonstrates the IFT reduction mechanism and alteration of wettability during chemical slug injection in EOR. The common sequence of fluid injection during the EOR process is depicted in Figure 3.5.

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Fig. 3.4 a IFT reduction mechanism b alteration of wettability during chemical slug injection in EOR

Fig. 3.5 Common chemical EOR fluid injection sequence (Druetta and Picchioni 2018)

References

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References M. Arabloo, M.H. Ghazanfari, D. Rashtchian,Wettability modification, interfacial tension and adsorption characteristics of a new surfactant: implications for enhanced oil recovery. Fuel 185, 199–210 (2016) P. Babu, R. Kumar, P. Linga, Unusual behavior of propane as a co-guest during hydrate formation in silica sand: Potential application to seawater desalination and carbon dioxide capture. Chem. Eng. Sci. 117, 342–351 (2014) A. Bhardwaj, S. Hartland, Applications of surfactants in petroleum industry. J. Dispersion Sci. Technol. 14(1), 87–116 (1993) Y. Bi, T. Guo, L. Zhang, L. Chen, F. Sun, Entropy generation minimization for charging and discharging processes in a gas-hydrate cool storage system. Appl. Energy 87(4), 1149–1157 (2010) J. Cai, Xu. Chun-Gang, Z.-Y. Chen, X.-S. Li, Recovery of methane from coal-bed methane gas mixture via hydrate-based methane separation method by adding anionic surfactants. Energy Sources, Part a: Recov. Utilization Environ. Effects 40(9), 1019–1026 (2018) S.J. Cox, D.J.F. Taylor, T.G.A. Youngs, A.K. Soper, T.S. Totton, R.G. Chapman, M. Arjmandi, M.G. Hodges, N.T. Skipper, A. Michaelides,Formation of methane hydrate in the presence of natural and synthetic nanoparticles. J. Am. Chem. Soc. 140(9), 3277–3284 (2018) M. Dong, S. Ma, Q. Liu, Enhanced heavy oil recovery through interfacial instability: a study of chemical flooding for Brintnell heavy oil. Fuel 88(6), 1049–1056 (2009) P. Druetta, F. Picchioni, Surfactant–polymer flooding: influence of the injection scheme. Energy Fuels 32(12), 12231–12246 (2018) A. Erfani, E. Fallah-Jokandan, F. Varaminian, Effects of non-ionic surfactants on formation kinetics of structure H hydrate regarding transportation and storage of natural gas. J. Nat. Gas Sci. Eng. 37, 397–408 (2017) E. Golabi, F.S. Azad, S. Ayatollahi, N. Hosseini, N. Akhlaghi,Experimental study of wettability alteration of limestone rock from oil wet to water wet by applying various surfactants, in SPE Heavy Oil Conference Canada (Society of Petroleum Engineers, 2012) D.W. Green, G.P. Willhite, Enhanced oil recovery. vol. 6 (Henry L. Doherty Memorial Fund of AIME, Society of Petroleum Engineers, Richardson, TX, 1998) J.Y. Lee, B.J. Ryu, T.S. Yun, J. Lee, G.-C. Cho, Review on the gas hydrate development and production as a new energy resource. KSCE J. Civil Eng. 15(4), 689–696 (2011) O. Massarweh, A.S. Abushaikha, The use of surfactants in enhanced oil recovery: a review of recent advances. Energy Rep. 6, 3150–3178 (2020) M.F. Nazar, S.S. Shah, M.A. Khosa, Microemulsions in enhanced oil recovery: a review. Pet. Sci. Technol. 29(13), 1353–1365 (2011) Z. Qi, Y. Wang, H. He, D. Li, Xu. Xiaoli, Wettability alteration of the quartz surface in the presence of metal cations. Energy Fuels 27(12), 7354–7359 (2013) P.I. Rosales, M.T. Suidan, A.D. Venosa, A laboratory screening study on the use of solidifiers as a response tool to remove crude oil slicks on seawater. Chemosphere 80(4), 389–395 (2010) R.K. Srivastava, S.S. Huang, M. Dong, Comparative effectiveness of CO2 produced gas, and flue gas for enhanced heavy-oil recovery. SPE Reservoir Eval. Eng. 2(03), 238–247 (1999) D. Wang, C. Liu, W. Wu, G. Wang, Novel surfactants that attain ultra-low interfacial tension between oil and high salinity formation water without adding alkali, salts, co-surfactants, alcohols and solvents, in SPE EOR Conference at Oil & Gas West Asia (Society of Petroleum Engineers, 2010) Z. Zhao, C. Bi, Z. Li, W. Qiao, L. Cheng, Interfacial tension between crude oil and decylmethylnaphthalene sulfonate surfactant alkali-free flooding systems. Colloids Surf. A 276(1–3), 186–191 (2006) H. Zhao, W. Kang, H. Yang, Z. Huang, B. Zhou, B. Sarsenbekuly, Emulsification and stabilization mechanism of crude oil emulsion by surfactant synergistic amphiphilic polymer system. Colloids Surf. A Physicochem. Eng. Aspects 609, 125726 (2021)

Chapter 4

Natural Surfactants

Holmberg (2001) has defined natural surfactants as compounds that originated from renewable resources like plants or animals and are known as polar lipids. These can be extracted directly or can be synthesized chemically with the polar head or nonpolar tails from natural resources. The polyols, like glucose, amino acid residues and simple sugars serve as a natural raw material source for the synthesis of these natural surface-active agents. Several microbes also act as a source of raw material for the synthesis of biosurfactants (Juwarkar et al. 2007). They are often called as green surfactants because of their less toxic nature and are readily biodegradable (De et al. 2015).

4.1 Synthesis of Natural Surfactants A wide range of surfactants are available in the market at a various prices ranging from very low cost to very high cost (approx. 20 times higher). The starting materials for these surfactants are enormously diverse and originate from different sources, and the synthesis method starting from an easy single-step hydrolysis to high pressurized multistep processes. For few exceptions like rosin, gums and tall oils, the market for raw material is not dependent on the commercial manufacture of surfactant significantly. The outcome of this market analysis is that the starting material price varies noticeably because of market aspects related to the surfactant industry. The unstable market variation has created fluctuations and changed the economical margins in this surfactant business. In order to classify the raw materials for surfactant production, simple ways are selected like their origin from a petroleum source or a natural source. The raw materials commonly deal with the lipophilic group, as there is a variation in the alkyl chain. With the few exceptions, like ethylene and propylene oxides, the starting constituents used as the hydrophilic groups are sulphur, oxygen–nitrogen and phosphorus compounds. © The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2_4

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This classification of raw materials for the surfactant-manufacturing business is as follows: Natural oils, fats and triglycerides Triglycerides obtained from plant or animal sources are tri-esters, which upon hydrolysis yield glycerol and fatty acids, the structure of triglycerides is indicated in the following formula (Fig. 4.1). In few experiments, the esterification process is incomplete, which results in the formation of mono and di-glycerides. Few of the natural products include polyalcohols that are found to be more complicated than simple kinds like glycerol having C5 and C6 monosaccharides. In these cases, hydrolysis of triglycerides favours the removal of the poly-alcohols from the fatty acids. Fatty acid constituents of various oils are listed in Fig. 4.2.

Fig. 4.1 Hydrolysis of triglyceride (Díaz et al. 2014)

Fig. 4.2 Fatty acid constituents of various oils (Canale et al. 2005)

4.1 Synthesis of Natural Surfactants

21

Other Natural Substances Plant sources are the main resources for the preparation of natural surfactants. Plant sources like wood oils, lignin and its derivatives, rosin, gums and leaf extracts also serve as raw materials for the synthesis of natural surfactants. During the process of wood digestion, in order to form pulp, various fatty acids are broken down using a bio-catalyst. In this process, a majority of esters are hydrolyzed and the fatty acids are released that can act as a source of raw material (Cao et al. 2021).

4.2 Application of Natural Surfactants Bio-surfactants and natural surfactants comprises an extensive range of amphiphilic surfactant molecules that are produced by microbes, plants and animals. Synthetic routes designed for the productive synthesis of natural surfactant define their molecular characteristics, which result in wide structural variety and enhances the functional surface-active properties. Having vast structural variation and different functional surface-active properties, natural surfactant plays a key role in various industrial processes (Perfumo et al. 2010; Meshram et al. 2021, pharmaceutical industry (Rodrigues et al. 2006), and environmental applications (Mulligan 2005), including specific applications in detergency, foaming (Hajimohammadi and Johari-Ahar 2018), wetting and emulsification (Ishak et al. 2021), bioremediation (Daverey and Pakshirajan 2011), lubrication, dispersing agent and solubilization (Abouseoud et al. 2010) of hydrophobic and hydrophilic compounds. These natural surfactants are eco-friendly and less toxic to the environment, cost-effective and present as probable substituents for commercial surfactants available in the market for various industrial processes (JJahan et al. 2020). The natural surfactants and bio-surfactants are known for their specific properties such as motility, specificity, adhesion, substrate employment and biofilm interface interactions. The use of bio-surfactants and natural surfactants is increasing in the field of the medicinal and pharmaceutical industry because of their properties like antibacterial, anti-cancerous, antifungal, antiviral and anti-adhesive activities (Rodrigues et al. 2006). Oil remediation methods using natural surfactants and biosurfactant helps to clean the hydrocarbons and metals polluted areas (Juwarkar et al. 2007). Additionally, natural surfactants and biosurfactants are employed in oil recovery techniques popularly known as chemical-enhanced oil recovery (CEOR) and microbial enhanced oil recovery (MEOR) (Zhao et al. 2016; Saxena et al. 2019).

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4.3 Advantages of Natural Surfactants Over Conventional Surfactants Chemically synthesized surfactants or conventional surfactants are generally petroleum based and usually non-biodegradable in nature, thereby toxic to the ecosystem and environment. These conventional surfactants accumulate in the water bodies and enter the food chain that can be hazardous to the environment. With the increasing awareness among the people about the need to protect the environment, it is very important to switch our applications from synthetic chemical compounds towards natural origin compounds (Benincasa 2007). Conventional surfactants that are employed in various industrial processes possess alkyl chains of 10–12 carbon units, whereas many bio-surfactants possess surprisingly short alkyl chains. Availability of Raw Materials: Natural surfactants and biosurfactants can be synthesized from relatively low-cost raw materials, which are readily available in almost unlimited quantity. The carbon sources like hydrocarbons and carbohydrates can be easily converted into biosurfactants that can be blended with each other easily (Kosaric 2001). Physical Factors: Many natural and biological surfactants are active at extreme range temperatures, salinities and pH. Acceptable Production Economics: Natural surfactants can be easily prepared from industrial wastes and other by-products of the industry and results in an advantage for bulk production. Specificity: Natural surfactants are complex organic molecules that possess specific functional groups which are specific in their action. Specificity has prime importance during detoxification of pollutants, development of cosmetics, de-emulsification process of industrial emulsions, different applications in the pharmaceutical and food industry. Environmental Control: Bio-surfactants are very active in controlling oil spills, industrial emulsions, detoxification and biodegradation process of industrial waste (Rahman and Gakpe 2008).

4.4 Challenges for Industrial Application of Natural Surfactants Despite having various advantages, natural surfactants faces the following challenges for their industrial application: Toxicity: It has been studied by researchers that the specificity of bio-surfactants comes as a disadvantage in some cases. For example, some studies predicted that in certain circumstances bio-surfactants can be toxic to the environment (Millioli et al. 2009). Though the effect is very much lower when compared to synthetic surfactants (CTAB, TTAB, BC and SDS). Moreover, biosurfactants do not cause any harmful effects on human organs.

4.4 Challenges for Industrial Application of Natural Surfactants

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Expensive Large Scale Production: Production of natural processes at a large scale is an expensive affair. However, this problem can be dealt with the utilization of waste material and by combating their polluting effects that compensate the overall costs. Difficulty in Obtaining Pure Substances: Since the natural products are first identified at laboratory scale for their application, it is very difficult to obtain pure substance in bulk, which again increases the cost of the application. Very Low Productivity: High production rates strains of microbes are very rare and hence show very low productivity.

References M. Abouseoud, A. Yataghene, A. Amrane, R. Maachi, Production of a biosurfactant by Pseudomonas fluorescens-Solubilizing and wetting capacity. Chem. Eng. Trans. 20, 291–296 (2010) M. Benincasa, Rhamnolipid produced from agroindustrial wastes enhances hydrocarbon biodegradation in contaminated soil. Curr. Microbiol. 54(6), 445–449 (2007) L. de C.F. Canale, M.R. Fernandes, S.C.M. Agustinho, G.E. Totten, A.F. Farah, Oxidation of vegetable oils and its impact on quenching performance. Int. J. Mater. Product Technol. 24(1–4), 101–125 (2005) Q. Cao, W. Zhang, T. Lian, S. Wang, H. Dong, Short chain carboxylic acids production and dynamicity of microbial communities from co-digestion of swine manure and corn silage. Bioresource Technol. 320, 124400 (2021) A. Daverey, K. Pakshirajan, Recent advances in bioremediation of contaminated soil and water using microbial surfactants. Microbes Microb. Technol. 207–228 (2011) S. De, S. Malik, A. Ghosh, R. Saha, B. Saha, A review on natural surfactants. RSC Adv. 5(81), 65757–65767 (2015) G.C. Díaz, N. de la C. Om Tapanes, L.D.T. Câmara, D.A.G. Aranda, Glycerol conversion in the experimental study of catalytic hydrolysis of triglycerides for fatty acids production using Ni or Pd on Al2O3 or SiO2. Renew. Energy 64, 113–122 (2014) R. Hajimohammadi, S. Johari-Ahar, Synergistic effect of saponin and rhamnolipid biosurfactants systems on foam behavior. Tenside Surfactants Deterg. 55(2), 121–126 (2018) K. Holmberg, Natural surfactants. Curr. Opin. Colloid Interface Sci. 6(2), 148–159 (2001) K.A. Ishak, M.F.A. Fadzil, M.S.M. Annuar, Phase inversion emulsification of different vegetable oils using surfactant mixture of cremophor EL and lipase-synthesized glucose monooleate. LWT 138, 110568 (2021) R. Jahan, A.M. Bodratti, M. Tsianou, P. Alexandridis, Biosurfactants, natural alternatives to synthetic surfactants: physicochemical properties and applications. Adv. Colloid Interface Sci. 275, 102061 (2020) A.A. Juwarkar, A. Nair, K.V. Dubey, S.K. Singh, S. Devotta, Biosurfactant technology for remediation of cadmium and lead contaminated soils. Chemosphere 68(10), 1996–2002 (2007) N. Kosaric, Biosurfactants and their application for soil bioremediation. Food Technol. Biotechnol. 39(4), 295–304 (2001) P.D. Meshram, S. Shingade, C.S. Madankar, Comparative study of saponin for surfactant properties and potential application in personal care products. Mater. Today Proc. (2021) V.S. Millioli, E.L.C. Servulo, L.G.S. Sobral, D.D. De Carvalho, Bioremediation of crude oil-bearing soil: evaluating the effect of rhamnolipid addition to soil toxicity and to crude oil biodegradation efficiency. Global NEST J. 11(2), 181–188 (2009) C.N. Mulligan, Environmental applications for biosurfactants. Environ. Pollut. 133(2), 183–198 (2005)

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A. Perfumo, I. Rancich, I.M. Banat, Possibilities and challenges for biosurfactants use in petroleum industry. Biosurfactants 135–145 (2010) P.K.S.M. Rahman, E. Gakpe, Production, characterisation and applications of biosurfactants-review. Biotechnology (2008) L. Rodrigues, I.M. Banat, J. Teixeira, R. Oliveira, Biosurfactants: potential applications in medicine. J. Antimicrob. Chemother. 57(4), 609–618 (2006) N. Saxena, A. Saxena, A. Mandal, Synthesis, characterization and enhanced oil recovery potential analysis through simulation of a natural anionic surfactant. J. Mol. Liq. 282, 545–556 (2019) Y.-H. Zhao, L.-Y. Chen, Z.-J. Tian, Y. Sun, J.-B. Liu, L. Huang, Characterization and application of a novel bioemulsifier in crude oil degradation by Acinetobacter beijerinckii ZRS. J. Basic Microbiol. 56(2), 184–195 (2016)

Chapter 5

Interfacial and Colloidal Properties of Surfactants for Application in EOR

Surfactants have found their application in diverse fields because of their special properties to reduce interfacial tension and the tendency to from colloidal solutions popularly called as emulsions. The properties of IFT, wettability alteration and tendency to form emulsions are very much desirable and have helped the surfactants to find their application in EOR. During tertiary recovery of oil, the chemical slug is generally a combination of surfactants (S), which is used along with specific chemicals like alkali (A) and polymer (P) and these chemical slug injections are popularly known as SP, AS and ASP flooding. The chief screening criteria for surfactants in chemical slug are: (i) IFT reduction ability, usually up to 10−3 mN/m, is desirable; (ii) tendency to form emulsions and generally Winsor III phase is favourable; (iii) alteration of wettability from oil-wet to water-wet. However, surfactants have also found their application in foam-based EOR and for micelle formation that possess viscoelastic properties envisioned for mobility control. The key role of surfactant in EOR is as interfacial tension reducing surface-active compounds. The chemical slug injected in the reservoir must possess an ultralow IF, which increases the capillary number that facilitates in improving the mobility of the trapped oil. The oil recovery rates and its extent are mainly governed by the interaction between three forces, namely viscous drag forces, capillary forces between the channels and the gravitational forces present in the mature reservoirs. The capillary number and bond number present a strong relation between these three forces.

5.1 Interfacial Tension (IFT) Injection of chemical slug eases the movement of the residual oil as there is a decrease in interfacial tension at the oil–water, which in turn enhances the capillary number (Nc) towards the higher range which is desirable for effective oil recovery (Wilson et al. 1976). The interfacial tension between displacing fluid and the trapped oil © The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2_5

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presents a key role in analysing the displacement efficiency. Lowering of IFT in presence of surface-active agents degrades the interfacial rigidness and permits the distortion of the oil-aqueous interface that creates a low-pressure gradient that exists surrounding the oil drop resulting in enhanced oil recovery (Sheng 2015). Laplace equation describes that the resistance to the flow is substantially decreased by a reduction in interfacial tension at the two interfaces into consideration like oil–water (Zhang et al. 2016). The IFT at the interface of oil and surfactant solution should be less than 10−1 mN/m to lessen the capillary trapping throughout the oil recovery process. An ultralow interfacial value ranges from 10–3 mN/m and it can be achieved by the addition of surface-active agents which are very much desired for application in EOR. The IFT value at the interface of crude oil and formation water present in the reservoir generally ranges from 20 to 30 mN/m and is dependent on the crude oil type and constituents. When the solution of surfactant is injected into the reservoir, the surfactant molecules tend to adsorb at the surface and form a micelle structure such that the hydrophobic tail extends towards the oleic phase. The lower value of IFT facilitates the recovery of the trapped oil from the reservoir by increasing the capillary number. The IFT at the oil-aqueous interface is the key parameter in the screening of surfactants for its application in EOR. Several other factors that are important for lowering the interfacial tension are partition coefficient and salt content. Baviere (1976) found that at optimum salinity condition minimum IFT could be achieved and with the partition coefficient being unity. Factors affecting the IFT value in an EOR process are the nature of crude oil components, salinity and temperature variation, the concentration of surfactant, alkali and charge on surfactant. The presence of salts in the reservoir is a chief criterion considered while studying chemical-enhanced oil recovery (CEOR). During the study of interfacial properties of surfactant, the two most important terms taken into account: (i) critical micelle concentration (CMC) which is the concentration at which the efficacy of the surfactant is maximum; (ii) the Kraft point of the surfactant which the lowest temperature at which the surfactant start forming micelle. Ionic interaction between crude oil and brine plays an important role in determining the IFT of the system as there is a development of in situ surfaceactive agent due to the presence of ions and other natural components like organic acids, salts and alkali constituted by crude oil that leads to high accumulation time at the oil-aqueous interface. The surfactants employed are expected to have good salt tolerance to find application in both high saline and low saline reservoir. Figure 5.1 depicts the mechanism of IFT reduction on the addition of salt.

5.2 Emulsification The formation of the emulsions during the surfactant injection process is assumed to be extremely advantageous during flooding because it proposes an extremely low IFT along with high miscibility with the oil trapped in the capillaries, resulting in effective recovery of trapped oil. The formation of emulsions during the flooding procedure reduces the mobility of the displacing fluid and increases the channeling through

5.2 Emulsification

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Fig. 5.1 The mechanism of IFT reduction on the addition of salt (Pal et al. 2018)

microscopic pores which result in improved oil recovery (Gbadamosi et al. 2019). For an emulsion-based oil recovery process, the quantity of surfactant used is much less than the one employed in the conventional surfactant flooding process. However, it is a challenging task to design a formulation forming stable emulsions at reservoir conditions. In an emulsion-based oil recovery process, surfactant molecules should be able to solubilize the oil from the oleic phase to form an emulsion that lowers IFT to an ultralow value. The proficiency of an emulsion-based recovery process is related to the phase behavior of oil-surfactant-brine arrangement (Spildo et al. 2014). The ability of the surfactants to form microemulsion can be analysed by mixing the surfactant solutions with crude oil at varying concentrations and salt content. Various phases can co-exist with the microemulsion system, forming different phases, namely, Winsor Types I, II, III and IV type. Winsor Type I phase that comprises of a microemulsion containing oil-in-water system type having a part of oil solubilized by a microemulsion system found in the lower region. Contrariwise, Winsor Type II is the water-in-oil type microemulsion where a portion of aqueous solution or brine solubilizes the microemulsion found in the upper region. Winsor Type III involves a formation of bicontinuous mid-phase microemulsion that occurs in equilibrium oil and aqueous phase. Lastly, Winsor Type IV forms a single microemulsion phase, usually formed at a higher concentration of surfactant. Figure 5.2 depicts the four types of microemulsion systems that can co-exist.

5.3 Wettability Alteration Study Wettability in a reservoir rock system is defined as the “ability to wet fluid phase to preferentially wet a solid surface in the presence of another non-wetting fluid phase” (Gupta and Mohanty 2008). All through the initial phase of drainage, the water-wet

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Fig. 5.2 Image depicts the types of micro-emulsion system

rock surface is altered to an oil-wet surface that is not appropriate for oil recovery due to high residual oil saturation, which results in improved oil recovery. Wettability alteration of any rock surface is directly associated with the interaction between the crude oil and aqueous system along with the rock surface-crude oil interactions. This process of alteration of wettability of rock surface is possible only because of the charged ions present in the system. The attractive forces existing between the charged ions and the rock surfaces reduce the surface energy of the system and the repulsive forces that result in high surface energy. The resultant forces produced due to the charges present at the interface can be correlated with Young’s law (Standnes and Austad 2000) and the contact angle is calculated using Eq. (5.1): cosθC =

σsw − σso σwo

(5.1)

where θC denotes the contact angle, σwo defines the interfacial tension between the oil and water, σso is interfacial tension at the oil-rock surface and σsw is the interfacial tension at the water and rock surface and these forces are balanced when the system is in equilibrium. Figure 5.3 shows how the contact angle for different interface systems is measured. The presence of salt is a significant parameter to be considered during the wettability study of the rock-surfactant system. The addition of salts improves the wettability of oil-wetted rock as a result of the high adsorption of surfactant molecules at the oil-rock interface. On increasing the salt percentage in the aqueous solution of surfactant, the contact angle keeps on reducing as a result of salting-out of surfactant molecules to the bulk phase (Hou et al. 2015). Besides salinity, capillary pressure, type of rock and crude oil nature, and the surfactant type are also essential parameters that modify the wettability of the rock surface. According to various studies conducted on wettability alteration of rock surface, it has been found that it is the result of physicochemical phenomena like adsorption, ion-ion attraction and attractive/repulsive forces (Zhang and Austad 2005). The water-wet reservoirs are expected to be a good source for high recovery. Hence constant efforts are being

5.3 Wettability Alteration Study

29

Fig. 5.3 Image depicts the contact angle measurement for a three-phase system

made to develop a mechanism to convert oil-wet rock to water-wet. These mechanisms include: (1) interaction of rock with polar components of crude oil; (2) surface precipitation of crude oil due to the presence of asphaltenes; (3) acid-base interaction that relates to the surface charge at the interfaces. Variation in contact angle envisages the alteration of wettability of rock which is the effect of two mechanisms: (i) ion-pair attraction between the polar head groups of the surfactant units; (ii) cationic charged components/carboxylic groups of crude oil present in the crude oil (Standnes and Austad 2000). The interfacial properties form the basis of chemical EOR and are considered to be the screening criteria for the application of a particular surfactant in the oil recovery process.

References P.M. Wilson, C.L. Murphy, W.R. Foster, The Effects of Sulfonate Molecular Weight and Salt Concentration on the Interfacial Tension of Oil-Brine-Surfactant Systems (Society of Petroleum Engineers, In SPE Improved Oil Recovery Symposium, 1976) M. Baviere, Phase diagram optimization in micellar systems, in SPE Annual Fall Technical Conference and Exhibition. Society of Petroleum Engineers (1976) N. Pal, N. Saxena, A. Mandal, Studies on the physicochemical properties of synthesized tailor-made gemini surfactants for application in enhanced oil recovery. J. Mol. Liq. 258, 211–224 (2018) K. Spildo, L. Sun, K. Djurhuus, A. Skauge, A strategy for low cost, effective surfcatant injection. J. Pet. Sci. Eng. 117, 8–14 (2014) J.J. Sheng, Status of surfactant EOR technology petroleum. 1, 95–106 (2015) J. Zhang, G.A. Reineccius, Factors controlling the turbidity of submicron emulsions stabilized by food biopolymers and natural surfactant. Food Sci. Technol. 71, 162–168 (2016) O.A. Gbadamosi, R. Junin, M.A. Manan, A. Agi, A.S. Yusuff, An overview of chemical enhanced oil recovery: recent advances and prospects. Int. Nano Lett. 1–32 (2019) R. Gupta, K.K. Mohanty, Wettability alteration of fractured carbonate reservoirs. SPE Symp. Improv. Oil Recover. 19–23 (2008). D.C. Standnes, T. Austad, Wettability alteration in chalk 2: mechanism for wettability alteration from oil-wet to water-wet using surfactants. J. Pet. Sci. Eng. 28, 123–143 (2000)

30

5 Interfacial and Colloidal Properties of Surfactants …

B.F. Hou, Y.F. Wang, Y. Huang, Mechanistic study of wettability alteration of oil-wet sandstone surface using different surfactants. Appl. Surf. Sci. 330, 56–64 (2015) P. Zhang, T. Austad, The relative effects of acid number and temperature on chalk wettability, in Paper SPE 92999 presented at the SPE International Symposium on Oilfield Chemistry held in Houston 2005. Texas

Chapter 6

Applications of Natural Surfactants in EOR

6.1 Screening and Performance Evaluation of Surfactants In the present global scenario, crude oil production and consumption provide an economically mature market having the potential to meet the global energy demands. The mature reservoir contains high concentrations of hydrocarbon in the reservoir rocks, which can be recovered through various oil techniques like primary, secondary and tertiary oil recovery process (Pal et al. 2018; Saxena et al. 2019a, b). Primary and secondary method to recover oil is generally employed where employed for oil two-thirds of original oil in place (OOIP) remains unrecovered from the mature fields. Chemical-enhanced oil recovery (EOR) process is the tertiary recovery technique involving the injection of chemical compounds popularly known as surfactants. Surfactant flooding is considered to be a well-established method of oil recovery process. Surfactant-based EOR has proven to be efficient in mature fields as it enhances the recovery of oil on application using different mechanisms. The mechanism essential for the recovery process is lowering of interfacial tension (IFT), foam generation, wettability alteration and emulsion formation. Despite the popularity in the oil and gas industry, surfactant flooding still faces application issues like unevenness under strict (or normal) conditions in the reservoir and unnecessary surfactant adsorption onto the reservoir rock surface (Green and Willhite 1998). These factors disturb the probable oil recoveries, and hence reduces the profitable yields of chemical EOR projects. Though the choice of surface-active agents is totally dependent on reservoir conditions and rock type. For this purpose, surfactant screening methods are employed. These include IFT, adsorption of surfactant, wettability and additional factors under certain temperature and saline conditions. The efficient and economically feasible oil recovery process is the major distress for the researchers and oil and gas industry throughout the world and henceforth, it is important to investigate the reservoir properties according to their ranges wherever enhanced oil recoveries are expected. The main criteria governing the potential of

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2_6

31

32

6 Applications of Natural Surfactants in EOR

EOR techniques, such as viscosity, permeability, temperature, etc. are listed in Table 6.1. Most of the reservoir rocks are heterogeneous in nature with complex porosity and permeability. Craig (1980) studied the various types of heterogeneities present in the reservoir having a difference in areal and vertical permeability. The variation in permeability is due to the heterogeneous nature of the reservoir result in poor recovery of oil because of poor sweep efficiency and unbalanced displacement of oil. Macroscopic efficiency can be defined “as the product of vertical and areal sweep efficiency” whereas microscopic efficiency (displacement efficiency) can be defined as “how the oil mobilizes into the porous rock upon the injection of fluid”. Interfacial tension, viscosity of oil, rock permeability, wettability of rock and capillary pressure and capillary number affect the displacement efficiency of fluid. The displacement efficiency can be enhanced by: (1) lowering the interfacial tension by injection of the polymer-surfactant slug and (2) reducing the viscosity of oil by steam injection method. Experimentally macroscopic efficiency is defined as how the displacing fluid (surfactant slug) comes in contact with the displacing fluid in the reservoir. Factors affecting the macroscopic efficiency are reservoir heterogeneity, mobility of injected slug, geological disturbances like faults, folds and fractures, well spacing, etc. EO is called the oil recovery efficiency which is the product of macroscopic efficiency and microscopic efficiency. Equation (6.1) shows oil recovery efficiency. EO = EV ol × ED

(6.1)

where E V represents the volumetric efficiency, E D depicts the displacement efficiency or microscopic efficiency. E Vol is the volumetric efficiency and is defined as the product of areal sweep efficiency (E A ) and vertical sweep efficiency (EV ). The total oil recovery factor (RF) is defined as the ratio of cumulative oil produced (NP ) to the original oil in place (N) as shown in Eqs. (6.2) and (6.3): RF =

NP N

NP = ED × EA × EV × where ED = displacement efficiency, EA = areal sweep efficiency, EV = vertical sweep efficiency, SO = oil saturation, VP = pore volume, BO = oil formation volume factor.

(6.2) SO × VP BO

(6.3)

Gravity (API)

>23–41

>22–36

>12

Hydrocarbon

OO2

Immiscible gases

>15

Polymer flooding

>10–16

>8–13

Combustion

Steam

Thermal/Mechanical

>20–35

Polymer, alkaline flooding

(Enhanced) Water flooding

>23–41

Nitrogen and flue gas

30–80

>40–75

Oil saturation

High porosity sand/sandstone

High porosity sand/sandstone

Sandstone preferred

Sandstone preferred

Sandstone or Carbonate

Sandstone or Carbonate

Sandstone or Carbonate

Formation type

Reservoir characteristics

Table 6.1 Criterion considered for designing of EOR process (Nabilou 2016)

>20

>10

NC

NC

Good vertical K

Wide range

Thin unless dipping

Thin unless dipping

>200–2540

>50

>10–800

>10–450

NC

NC

NC

NC

Net Average thickness (ft) permeability (md)

>4500 to 1500

>11,500 to 3500

9000 to 3250

>1800

>2500

>4000

>6000

Depth (ft)

NC (continued)

>100–115

>200–140

>200–30

NC

NC

NC

NC

Temperature (f)

6.1 Screening and Performance Evaluation of Surfactants 33

>7–11

Surface miring

a NC—Non-critical factor

Gravity (API)

Zero cold flow

Viscosity (CP)

Oil properties

EOR method

Table 6.1 (continued)

NC

Composition

>

Oil saturation

Tar sand

Formation type

Reservoir characteristics

>10

NC

Net Average thickness (ft) permeability (md) NC

Depth (ft)

NC

Temperature (f)

34 6 Applications of Natural Surfactants in EOR

6.1 Screening and Performance Evaluation of Surfactants

35

Improvement in overall oil recovery factor The overall oil recovery factor is administrated majorly by two factors, i.e. capillary number (N c ) and mobility ratio (M). By raising the capillary number and decreasing the mobility ratio, oil recovery can be increased. Capillary number (N c ) The capillary number can be defined as the ratio of viscous drag (viscous force) to interfacial force and denoted as (N c ) as shown in Eq. (6.4). It has been observed that the greater the value of Nc , greater is the recovery of oil which is achievable by lowering the IFT or enhancing the superficial velocity. But high injection pressure is not feasible to increase the N c . The factor mainly responsible to reduce the IFT and to recover more and more oil is the high capillary number (Ding and Kantzas 2007). However, an increase in viscosity of the displacing fluid also increases the capillary number to some extent. NC =

kp V iscous force μ×ϑ = = σ σL Interfacial force

(6.4)

where μ = displacing fluid viscosity, ϑ = superficial velocity, σ = IFT between the oil and aqueous solution, k = effective permeability to the crude oil, p = pressure gradient through distance L. L Mobility Ratio (M) Mobility ratio can be defined as the ratio of mobility of the surfactant solution (displacing fluid) to the mobility of crude oil (displacing fluid) and is depicted in Eq. (6.5). Several factors like the viscosity of displacing and the displaced fluid and the permeability of the reservoir rock system govern the mobility ratio. M =

λdisplacing λdisplaced

(6.5)

where λ = μkii , λ = mobility, k = effective permeability, μ = fluid viscosity, i = oil, water or gas. M > 1 signifies the greater mobility of displacing fluid than the mobility of the oil that results in an unwanted phenomenon like fingering and early breakthrough of injected slugs depicted in Fig. 6.1a. Greater mobility leads to lowering of areal

36

6 Applications of Natural Surfactants in EOR

Fig. 6.1 Schematic diagram depicting the enhancement in displacement efficiency at low mobility ratio (Moghadasi et al. 2018)

sweep efficiency as the amount of slug injected after breakthrough does not result in additional oil recoveries. Thus, M ≤ 1 is generally desirable as it permits the even movement of the flood front that enhances the areal sweep efficiency as shown in Fig. 6.1b.

6.2 Thermal Stability and Compatibility with Reservoir Conditions Thermal stability and compatibility of the surfactants with the reservoir rock and fluid are amongst the important parameters for the screening of their application in the chemical EOR. The injected surfactant solution should be compatible with the reservoir formation fluid, as an incompatible injected fluid can cause undesirable precipitation in the formation, leading to pore blockage, as well as, surfactant separation, which will reduce the effectiveness of the injected surfactant slug. Testing the surfactant solution for turbidity on mixing with the formation water, at reservoir

6.2 Thermal Stability and Compatibility with Reservoir Conditions

37

Fig. 6.2 Thermal stability and compatibility test of surfactants (Sagir et al. 2020)

temperature, is an easy way of determining the compatibility of surfactant solution with the reservoir formation fluid. The turbidity test can result in one of the four scenarios, as shown in Fig. 6.2, where a clear solution represents the surfactant solution being compatible with the formation fluid, whereas, an incompatible surfactant solution will lead to a turbid solution, or surfactant separation, or surfactant precipitation. The incompatibility of the surfactant solution can be owing to few reasons, such as cloud point of cationic non-ionic, and anionic surfactants, cleaving of polar head and non-polar tail of surfactant and so on. Phase behaviour study helps to estimate the generation of microemulsion and salinity effects on microemulsion. For a salinity test, the concentration of salt is varied by keeping the concentration of surfactant and oil–water concentration constant. A typical salinity scan and formation of different microemulsions are depicted in Fig. 6.3. Phase behaviour study for various surfactant slugs and crude oil is amongst the main investigations piloted for the efficient chemical EOR process.

38

6 Applications of Natural Surfactants in EOR

Fig. 6.3 Phase behaviour study, salinity increases from left to right (Sagir et al. 2020)

6.3 Oil Mobilization and Recovery In the reservoir system, the trapped oil is present in the porous media through capillary forces and the presence of high IFT at oil–water interface. To recover this oil, chemicals like surfactant, polymer and alkali in various combinations like surfactantpolymer (SP), alkali-surfactant-polymer (ASP) are injected to form a microemulsion system (Gbadamosi et al. 2019). The microemulsion thus formed when this oil comes in contact with the slug produces very low IFT, which increases the capillary number that effectively mobilizes the trapped oil bank. The surfactant-polymer slugs have high viscosity that improves the macroscopic sweep efficiency that helps to push the oil bank in the forward direction and facilitating the effective recovery of oil.

6.4 Adsorption of Surfactant onto the Reservoir Rock Surface Adsorption of surfactant molecules onto the reservoir rock causes an alteration of the wetting state of the surface. The wetting nature of a reservoir is usually intermediate to oil-wet, and the rock mineralogy, composition of crude oil and brine and temperature and pressure conditions of the reservoir play an important role in changing the wettability of the reservoir after the migration of crude oil (Sohal et al., 2016). The mechanism of wettability alteration of the original water-wet reservoir to oil wetting

6.4 Adsorption of Surfactant onto the Reservoir Rock Surface

39

nature has been related to the adhesion of polar components of crude oil (Rahbar et al. 2012). After the migration of crude oil into reservoir pores, there exists a layer of brine between crude oil and rock surface, which prevents the contact of crude oil and rock surface (Hiorth et al. 2010). The rupture of the brine layer can occur due to the presence of attractive forces such as charge transfer, van der Waals forces and hydrogen bonding between crude oil and rock surface (Hirasaki 1991). Thus, these forces lead to the adsorption of crude oil components on the rock surface, and cause the oil-wetting state of the reservoir rock. The state of reservoir rock surface before surfactant flooding can be seen in the schematic diagram depicted in Fig. 6.4. When the surfactant is injected into the reservoir, the surfactant molecules interact with the adsorbed components of the crude oil like naphthenic acid, asphaltenes and resins. These adsorbed components of crude oil, which were responsible for the oil wetting state of the surface, can have either hydrophilic interaction or hydrophobic interaction with the injected surfactant molecules. Hydrophilic interaction leads to the formation of ion pair between the hydrophilic head of the surfactant and adsorbed crude oil (Hou et al. 2015). Whereas, the bonding of the carbon chain of surfactant molecules with the adsorbed crude oil components leads to hydrophobic interaction between crude oil and surfactant molecules (Standnes and Austad 2000). With the movement of the flood front, the crude oil components bonded with the surfactant molecules are desorbed into the bulk of the aqueous phase and gets produced. The surface, free from the crude oil components, is then occupied by surfactant molecules (Fig. 6.4). This can also be seen in the schematic diagram where at low surfactant concentration, there is a partial replacement of adsorbed crude oil components with surfactant molecules. With an increase in surfactant concentration, most of the adsorbed crude oil is desorbed and trapped in the surfactant micelles. The increase in the surface charge is due to the dominance of negative charge by negative ions and hydroxyl

Fig. 6.4 Schematic of preferential adsorption of surfactant on oil-aged sandstone rock with wettability alteration (Saxena et al., 2019a, b)

40

6 Applications of Natural Surfactants in EOR

groups. Thus, surfactant molecules adsorbed on the rock surface prevent further interaction of crude oil and rock surface and change the wettability of rock to water wet.

References F.F. Craig, The Reservoir Engineering Aspects of Waterflooding, vol. 3. (HL Doherty Memorial Fund of AIME, New York, 1980) (Third Printing) M. Ding, A. Kantzas, Capillary number correlations for gas-liquid systems. J. Canad. Petrol. Technol. 46(02) (2007) A.O. Gbadamosi, R. Junin, M.A. Manan, A. Agi, A.S. Yusuff, An overview of chemical enhanced oil recovery: recent advances and prospects. Int. Nano Lett. 9(3), 171–202 (2019) D.W. Green, G.P. Willhite, Enhanced Oil Recovery, vol. 6. (Henry L. Doherty Memorial Fund of AIME, Society of Petroleum Engineers, Richardson, TX, 1998) A. Hiorth, L.M. Cathles, M.V. Madland, The impact of pore water chemistry on carbonate surface charge and oil wettability. Transp. Porous Media 85(1), 1–21 (2010) G.J. Hirasaki, Wettability: fundamentals and surface forces. SPE Form. Eval. 6(02), 217–226 (1991) B.-F. Hou, Y.-F. Wang, Y. Huang, Mechanistic study of wettability alteration of oil-wet sandstone surface using different surfactants. Appl. Surf. Sci. 330, 56–64 (2015) R. Moghadasi, A. Rostami, A. Hemmati-Sarapardeh, Chapter Three—Enhanced oil recovery using CO2 , in Fundamentals of Enhanced Oil and Gas Recovery from Conventional and Unconventional Reservoirs, ed. by A. Bahadori. (Gulf Professional Publishing, 2018) A. Nabilou, Best method for enhanced oil recovery from Sarvak reservoir and analyse sensitive parameters. Master Thesis, Technico Lisboa, Portugal, 2016 N. Pal, N. Saxena, A. Mandal, Studies on the physicochemical properties of synthesized tailor-made gemini surfactants for application in enhanced oil recovery. J. Mol. Liq. 258, 211–224 (2018) M. Rahbar, A. Roosta, S. Ayatollahi, M.H. Ghatee, Prediction of three-dimensional (3-d) adhesion maps, using the stability of the thin wetting film during the wettability alteration process. Energy Fuels 26(4), 2182–2190 (2012) M. Sagir, M. Mushtaq, M.S. Tahir, M.B. Tahir, A.R. Shaik, Surfactants for Enhanced Oil Recovery Applications. (Springer, Cham, 2020) N. Saxena, A. Goswami, P.K. Dhodapkar, M.C. Nihalani, A. Mandal, Bio-based surfactant for enhanced oil recovery: interfacial properties, emulsification and rock-fluid interactions. J. Petrol. Sci. Eng. 176, 299–311 (2019a) N. Saxena, A. Kumar, A. Mandal, Adsorption analysis of natural anionic surfactant for enhanced oil recovery: the role of mineralogy, salinity, alkalinity and nanoparticles. J. Petrol. Sci. Eng. 173, 1264–1283 (2019b) M.A. Sohal, G. Thyne, E.G. Søgaard, Review of recovery mechanisms of ionically modified waterflood in carbonate reservoirs. Energy Fuels 30(3), 1904–1914 (2016) D.C. Standnes, T. Austad, Wettability alteration in chalk: 2. Mechanism for wettability alteration from oil-wet to water-wet using surfactants. J. Petrol. Sci. Eng. 28(3), 123–143 (2000)

Conclusions

The slump in the production rates from mature crude oil reservoirs and low frequency of green fields led to the evolving of enhanced oil recovery methods, especially through chemical injection. Conventional surfactants employed in oil and gas industries are generally costly, non-biodegradable and contaminate the groundwater. The amplified use of commercial surfactants for industrial and domestic purposes levies a serious concern about the environment as most of the constituents are dispersed in various compartments of the environment such as soil, water, sediment, etc. These synthetic chemicals pollute the aquatic flora and fauna, and cause much damage to the human race in the form of dermatitis, irritation, respiratory problems. On the other hand, natural surfactants are directly obtained from natural resources or are modified forms of natural resources that are biodegradable and economically feasible at the production as well as application end. The present book highlighted a new route to find a substitute for the commercial surfactants and analyse the potential of natural surfactants for application in enhanced oil recovery. For the application of surfactants in the chemical-enhanced oil recovery process, it is important to analyse the interfacial properties and colloidal properties of the surfactants like interfacial tension, wettability alteration and emulsifications. These properties are the chief parameters studied during the screening of EOR processes. A comparative study of oil recovery along with different petro-physical properties are represented in Table 1, which clearly indicates that natural surfactants have good potential for their application in the EOR process in the near future.

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2

41

Fu et al. (2016)

Organic alkali-surfactant-polymer (OASP) flooding

17.2% porosity, 105 mD permeability of core system, IFT 0.323 mN/m

Ethanolamine + SLPS 37.6% porosity, + HPAM 1350 mD permeability of sand pack system, IFT 0.07 mN/m

Acrylic acid (Acid) + Sodium carbonate (Alkali) + Polymeric surfactant (S) from castor oil

30.13% porosity, 968 mD permeability of sand pack system, IFT 0.07 mN/m

Surfactant (S)-polymer LAyL (S) + HPAM (P) flooding (P)

Weidong et al. (2017)

Acid–alkali-surfactant (AAS) flooding

29% porosity, 1 D permeability of sand pack system, IFT 0.009 mN/m

Surfactant (S)-polymer Alfoterra 23 (S) + (P) flooding Polyacrylamide (P)

Iglauer et al. (2010)

Elraies et al. (2010)

29% porosity, 1 D permeability of sand pack system, IFT 0.02 mN/m

Surfactant (S)-polymer Aerosol TR-70 (S) + (P) flooding Polyacrylamide (P)

Porous media/Fluid properties

Iglauer et al. (2010)

Injected slug

Injection type

Authors

0.5 (OASP)

1 (AAS)

2.5 (SP)

0.25 (S) + 1.2 (P)

0.25 (S) + 0.5 (P)

PV of injected slug

(continued)

21.7% of OOIP

20% of OOIP

23.96% of OOIP

37% of Sor after initial water flooding

15% of Sor after initial water flooding

Result/Remarks

Table 1 Comparison of recovery efficiency of the synthesized surfactants with commercial and natural synthesized surfactants from some selected literature

42 Conclusions

Surfactant (S)-polymer Mahua (S) + PHPA (P) flooding (P)

Saxena et al. (2019)

30.2% porosity, 0.5 (SP) 2.5 D permeability of sand pack system, IFT 0.009 mN/m

0.5 (ASP)

22.64% porosity, 134 mD permeability of core system, IFT 0.047 mN/m

NaOH (A) + Saponin (S) + PHPA (P)

Alkali-surfactant (S)-polymer (P) flooding

Nowrouzi et al. (2020)

PV of injected slug

14.9% porosity, 18 8.73 mD permeability (Imbibition) of core system, IFT 9 mN/m

Porous media/Fluid properties

Ziziphus surfactant

Core flooding (Imbibition test)

Shahri et al. (2012)

Injected slug

Injection type

Authors

Table 1 (continued)

28.29% of OOIP (or 58.72% of Sor after initial water flooding)

32.20% of OOIP

16% of OOIP

Result/Remarks

Conclusions 43

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© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 N. Saxena and A. Mandal, Natural Surfactants, SpringerBriefs in Applied Sciences and Technology, https://doi.org/10.1007/978-3-030-78548-2

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