Biodiesel Production E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Fachliteratur
- Sprache: Englisch
An incisive discussion of biofuel production from an economically informed technical perspective that addresses sustainability and commercialization together In Biodiesel Production: Feedstocks, Catalysts and Technologies, renowned chemists Drs Rokhum, Halder, Ngaosuwan and Assabumrungrat present an up-to-date account of the most recent developments, challenges, and trends in biodiesel production. The book addresses select feedstocks, including edible and non-edible oils, waste cooking oil, microalgae, and animal fats, and highlights their advantages and disadvantages from a variety of perspectives. It also discusses several catalysts used in each of their methods of preparation, as well as their synthesis, reactivity, recycling techniques, and stability. The contributions explore recently developed technologies for sustainable production of biodiesel and provides robust treatments of their sustainability, commercialization, and their prospects for future biodiesel production. * A thorough introduction to the various catalysts used in the preparation of biodiesel and their characteristics * Comprehensive explorations of biofuel production from technical and economic perspectives, with complete treatments of their sustainability and commercialization * Practical discussions of the development of new strategies for sustainable and economically viable biodiesel production * In-depth examinations of biodiesel feedstocks, catalysts, and technologies Perfect for academic researchers and industrial scientists working in fields that involve biofuels, bioenergy, catalysis, and materials science, Biodiesel Production: Feedstocks, Catalysts and Technologies will also earn a place in the libraries of bioenergy regulators.
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Table of Contents
Cover
Title Page
Copyright Page
Preface
List of Contributors
An Overview of Biodiesel Production
Part 1: Biodiesel Feedstocks
1 Advances in Production of Biodiesel from Vegetable Oils and Animal Fats
1.1 Introduction
1.2 History of the Use of Vegetable Oil in Biodiesel
1.3 Feedstocks for Biodiesel Production
1.4 Basics of the Transesterification Reaction
1.5 Variables Affecting Transesterification Reaction
1.6 Alkaline‐Catalyzed Transesterification
1.7 Acid‐Catalyzed Transesterification
1.8 Enzymatic‐Catalyzed Transesterification
1.9 Fuel Properties and Quality Specifications for Biodiesel
1.10 Conclusion
References
2 Green Technologies in Valorization of Waste Cooking Oil to Biodiesel
2.1 Introduction
2.2 Importance of Valorization
2.3 Purification and Characterization
2.4 Transesterification: A Comprehensive Look
2.5 Conversion Techniques
2.6 Economics and Environmental Impact
2.7 Conclusion and Perspectives
References
3 Non‐edible Oils for Biodiesel Production
3.1 Introduction
3.2 Vegetable Non‐edible Oils
3.3 Future Perspectives of Non‐edible Oils: Oils from Waste
3.4 Conclusion
Acknowledgments
References
4 Algal Oil as a Low‐Cost Feedstock for Biodiesel Production
4.1 Introduction
4.2 Lipid and Biosynthesis of Lipid in Microalgae
4.3 Optimization of Lipid Production in Microalgae
4.4 Conclusion
References
Part 2: Different Catalysts Used in Biodiesel Production
5 Homogeneous Catalysts Used in Biodiesel Production
5.1 Introduction
5.2 Transesterification in Biodiesel Synthesis
5.3 Homogeneous Catalyst in Biodiesel Synthesis
5.4 Properties of Biodiesel Produced by Homogeneous Acid and Base‐Catalyzed Reactions
5.5 Relevance of Homogeneous Acid and Base Catalysts in Biodiesel Synthesis
5.6 Conclusion
References
6 Application of Metal Oxides Catalyst in Production of Biodiesel
6.1 Basic Metal Oxide
6.2 Acid Metal Oxide
6.3 Deactivation of Metal Oxide
References
7 Supported Metal/Metal Oxide Catalysts in Biodiesel Production
7.1 Introduction
7.2 Supported Catalyst
7.3 Metals and Metal Oxide Supported on Alumina
7.4 Metals and Metal Oxide Supported on Zeolite
7.5 Metals and Metal Oxide Supported on ZnO
7.6 Metals and Metal Oxide Supported on Silica
7.7 Metals and Metal Oxide Supported on Biochar
7.8 Metals and Metal Oxide Supported on Metal Organic Frameworks
7.9 Metal/Metal Oxide Supported on Magnetic Nanoparticles
7.10 Summary
References
8 Mixed Metal Oxide Catalysts in Biodiesel Production
8.1 Introduction
8.2 Previous Research
8.3 State of the Art
8.4 Discussion
8.5 Conclusion
8.6 Symbols and Nomenclature
References
9 Nanocatalysts in Biodiesel Production
9.1 Introduction
9.2 Transesterification of Vegetable Oils
9.3 Conventional Catalysts Used in Biodiesel Production: Advantages and Limitations
9.4 Role of Nanotechnology in Biodiesel Production
9.5 Different Nanocatalysts in Biodiesel Production
9.6 Conclusion
Acknowledgment
References
10 Sustainable Production of Biodiesel Using Ion‐Exchange Resin Catalysts
10.1 Introduction
10.2 Features of Ion‐Exchange Resin Catalysts
10.3 Cation‐Exchange Resin Catalyst
10.4 Anion‐Exchange Resin Catalysts
10.5 Summary
References
11 Advances in Bifunctional Solid Catalysts for Biodiesel Production
11.1 Introduction
11.2 Application of Solid Bifunctional Catalyst in Biodiesel Production
11.3 Summary and Concluding Remarks
Acknowledgment
References
12 Application of Catalysts Derived from Renewable Resources in Production of Biodiesel
12.1 Introduction
12.2 Potential Renewable Resources for Production of Biodiesel Catalysts
12.3 Advantages, Disadvantages, and Challenges of These Types of Catalyst for Biodiesel Production
Acknowledgment
References
13 Biodiesel Production Using Ionic Liquid‐Based Catalysts
13.1 Introduction
13.2 Mechanism of IL‐Catalyzed Biodiesel Production
13.3 Acidic and Basic Ionic Liquids (AILs/BILs) as Catalyst in Biodiesel Production
13.4 Supported Ionic Liquids in Biodiesel Production
13.5 IL Lipase Cocatalysts
13.6 Optimization and Novel Biodiesel Production Technologies Using ILs
13.7 Recyclability of the Ionic Liquids on Biodiesel Production
13.8 Kinetics of IL‐Catalyzed Biodiesel Production
13.9 Techno‐Economic Analysis and Environmental Impact Analysis of Biodiesel Production Using Ionic Liquid as Catalyst
13.10 Conclusion
References
14 Metal–Organic Frameworks (MOFs) as Versatile Catalysts for Biodiesel Synthesis
14.1 Introduction
14.2 Biodiesel Synthesis Over MOF Catalysts
14.3 Conclusion
References
Part 3: Technologies, By‐product Valorization and Prospects of Biodiesel Production
15 Upstream Strategies (Waste Oil Feedstocks, Nonedible Oils, and Unicellular Oil Feedstocks like Microalgae)
15.1 Introduction
15.2 Biodiesel Feedstocks
15.3 Composition of Oils and Fats
15.4 Methods for Oil Extraction
15.5 Purification of Oils and Fats
15.6 Production of Biodiesel
15.7 Future Prospects
References
16 Mainstream Strategies for Biodiesel Production
16.1 Introduction
16.2 Mainstream Strategies and Technology for Biodiesel Production
16.3 Future Prospects and Challenges
Acknowledgment
References
17 Downstream Strategies for Separation, Washing, Purification, and Alcohol Recovery in Biodiesel Production
17.1 Introduction
17.2 Glycerol Separation and Refining
17.3 Membrane Reactors
17.4 Methanol Recovery
17.5 Additization
17.6 Conclusion
References
18 Heterogeneous Catalytic Routes for Bio‐glycerol‐Based Acrylic Acid Synthesis
18.1 Introduction
18.2 Acrylic Acid Synthesis from Propylene
18.3 Acrylic Acid Synthesis from Glycerol
18.4 Conclusion
Acknowledgments
References
19 Sustainability, Commercialization, and Future Prospects of Biodiesel Production
19.1 Introduction
19.2 Biodiesel as a Promising Renewable Energy Carrier
19.3 Overview of the Biodiesel Production Process
19.4 Evolution in the Feedstocks Used for the Sustainable Production of Biodiesel
19.5 First‐Generation Biodiesel and the Challenges in Its Sustainability
19.6 Development of Second‐Generation Biodiesel to Address the Sustainability
19.7 Algae‐Based Biodiesel
19.8 Waste Oils, Grease, and Animal Fats in Biodiesel Production
19.9 Technical Impact by the Biodiesel Usage
19.10 Socioeconomic Impacts
19.11 Toxicological Impact
19.12 Sustainability Challenges in the Biodiesel Production and Use
19.13 Concluding Remarks
References
20 Advanced Practices in Biodiesel Production
20.1 Introduction
20.2 Mechanism of Transesterification
20.3 Advanced Biodiesel Production Technologies
20.4 Conclusion
20.5 Future Perspectives
References
Index
End User License Agreement
List of Tables
Chapter 1
Table 1.1 Main feedstocks of biodiesel.
Table 1.2 Homogeneous catalysts and reaction conditions used for alkaline t...
Table 1.3 Biodiesel specifications according to ASTM D6751 and EN 14214 sta...
Chapter 2
Table 2.1 Feedstock for biodiesel classified according to type.
Table 2.2 Traditional catalyzed conversions using acids, bases, enzymes, or...
Table 2.3 Modern approaches in biodiesel production from nonedible/waste fe...
Chapter 3
Table 3.1 Non‐edible oils
Table 3.2 Fatty acids composition of non‐edible oils and relative biodiesel...
Chapter 4
Table 4.1 Comparison of oil yield between microalgae and oil crops.
Table 4.2 Different species of microalgae with their total lipid content [1...
Chapter 5
Table 5.1 Homogeneous acid‐catalyzed biodiesel synthesis.
Table 5.2 Homogeneous base‐catalyzed biodiesel synthesis.
Table 5.3 Properties of biodiesel produced from homogeneous acid and base c...
Chapter 6
Table 6.1 Catalytic performance of CaO.
Table 6.2 Catalytic performance of multimetal oxides.
Table 6.3 Catalytic performance of metal oxides.
Chapter 7
Table 7.1 Synthesis of biodiesel using different catalyst and supported cat...
Chapter 8
Table 8.1 Summary of some previous developments in mixed metal oxide catalys...
Table 8.2 Summary of some recent developments in mixed metal oxide catalyst...
Table 8.3 Summary of how certain metals/metal oxides can influence catalyst...
Table 8.4 Kinetic data from recent studies.
Table 8.5 Symbols and abbreviations used throughout this chapter.
Chapter 9
Table 9.1 Different metal‐based nanocatalysts used in the production of bio...
Chapter 10
Table 10.1 Physical properties of cation‐exchange resins.
Table 10.2 Phase conditions of methanol/triglyceride mixtures.
Table 10.3 Steady‐state triglyceride conversions during continuous biodiese...
Table 10.4 Physical properties of anion‐exchange resins.
Chapter 11
Table 11.1 Solid acid–base bifunctional catalyst used for biodiesel/FAME p...
Table 11.2 Different Brønsted–Lewis acid bifunctional solid catalyst used f...
Table 11.3 Different biowaste‐derived solid bifunctional catalysts for biod...
Chapter 12
Table 12.1 Summary of the production of biodiesel using catalysts from diff...
Table 12.2 Summary of the production of biodiesel using catalysts from diff...
Table 12.3 Summary of the production of biodiesel using catalysts from diff...
Table 12.4 Summary of the production of biodiesel using catalysts from diff...
Chapter 13
Table 13.1 Acidic and basic ionic liquids in biodiesel production.
Table 13.2 Supported ionic liquids in biodiesel production.
Table 13.3 IL lipase co‐catalysts in biodiesel production.
Table 13.4 Novel technologies of biodiesel production and optimization usin...
Table 13.5 Reusability of ILs in biodiesel production.
Chapter 14
Table 14.1 The transesterification results over different catalysts.
Chapter 15
Table 15.1 Oil content, total acid number (TAN) in different types of feeds...
Chapter 16
Table 16.1 Overview of intensified reactors for biodiesel production.
Chapter 20
Table 20.1 Synthesis of biodiesel using ultrasonic techniques.
Table 20.2 Yield of biodiesel using cosolvent techniques.
Table 20.3 Yield of biodiesel by the process of reactive distillation.
List of Illustrations
Chapter 1
Figure 1.1 General reaction for transesterification of vegetable oil.
Chapter 2
Figure 2.1 Catalyzed conversion of triglyceride and FFA into esters using me...
Figure 2.2 Dissociation of alkali and saponification with FFA.
Figure 2.3 Hydrolysis of triglyceride leading to FFA formation.
Chapter 3
Figure 3.1 Locations of potential cultivation areas for non‐edible oils.
Chapter 4
Figure 4.1 Ultrastructure of microalgae.
Figure 4.2 Lipid biosynthesis in microalgae.
Chapter 5
Scheme 5.1 Transesterification of vegetable oil (triglyceride) to biodiesel ...
Scheme 5.2 Mechanism of acid‐catalyzed reaction of triglyceride.
Scheme 5.3 Mechanism of base‐catalyzed reaction of triglyceride.
Scheme 5.4 Esterification of free fatty acid.
Scheme 5.5 Mechanism of acid‐catalyzed esterification of free fatty acid to ...
Figure 5.1 Representation of biodiesel production process using homogeneous ...
Chapter 6
Figure 6.1 Transesterification process for biodiesel production.
Figure 6.2 Potential materials for alkaline earth metal oxide synthesis.
Figure 6.3 Transesterification mechanism catalyzed by basic metal oxide.
Figure 6.4 Schematic of SO
4
2–
/Fe–Al–TiO
2
catalyst synthesis.
Figure 6.5 Preparation of SO
3
H@ZnO–TiO
2
–ICG.
Figure 6.6 Transesterification mechanism catalyzed by acid catalyst.
Chapter 7
Scheme 7.1 Proposed mechanism for CaO/Al
2
O
3
‐catalyzed synthesis of biodiesel...
Figure 7.1 TEM images of (a) ZnO/zeolite and (b) PbO/zeolite.
Figure 7.2 Biochar supporting different metal and metal oxides.
Figure 7.3 SEM analysis of (a) biochar, (b) 5 % of Ca loaded, (c, e, f) 10% ...
Figure 7.4 FTIR spectrum of supported catalyst recovered at the end of third...
Figure 7.5 (a) Cage type meso MOFs, (b) channel type meso MFOs, (c) chiral m...
Figure 7.6 Strongly acidic site in Zr‐doped hydrated MOF (Ha is involved in ...
Figure 7.7 TEM images of Au@Fe
3
O
4
nanoparticles showing quasispherical Fe
3
O
4
Chapter 8
Figure 8.1 Transesterification and esterification reactions.
Figure 8.2 Summary of catalyst types currently being researched.
Figure 8.3 A summary showing the diverse uses for MMO catalysts.
Figure 8.4 Diagram of surface structures for acidic, basic, and bifunctional...
Chapter 9
Figure 9.1 Different feedstock used in FAME HVO biodiesel production.
Figure 9.2 Year‐wise global production of biodiesel (FAME and HVO).
Figure 9.3 Schematic representation of overall biodiesel production process....
Figure 9.4 The general chemical reaction showing transesterification of trig...
Figure 9.5 The different conventional catalysts used in biodiesel production...
Figure 9.6 Schematic illustration of different nanocatalysts used in biodies...
Chapter 10
Figure 10.1 Comparison of esterification behavior of free fatty acids (FFA) ...
Figure 10.2 Variation of water concentration in effluent from column packed ...
Figure 10.3 Time courses of concentrations of (a) free fatty acids and (b) f...
Figure 10.4 Phase conditions of each reaction system: (a) two‐phase system w...
Figure 10.5 Photographs of phase conditions of methanol/triglyceride mixture...
Figure 10.6 Comparison of transesterification behavior of triglyceride (TG) ...
Figure 10.7 Comparison of catalytic activity for triglyceride transesterific...
Chapter 11
Scheme 11.1 Biodiesel production via transesterification and esterification....
Figure 11.1 CO
2
‐TPD profile for pure ZrO
2
(a), modified catalyst with Mg/Zr ...
Figure 11.2 Sonochemical setup for CaO dispersion on MCM‐41.
Figure 11.3 EDX analysis of sono‐enhanced CaO‐dispersed over Zr‐doped MCM‐41...
Figure 11.4 Schematic representation of the synthesis of lysine/HPA catalyst...
Figure 11.5 TEM micrographs (a–e) and SAED pattern (f) of SO
4
/Fe–Al–TiO
2
....
Figure 11.6 SEM micrographs of SO
4
/kaolin.
Figure 11.7 FESEM micrographs of (a) RHC/K2O‐20%/Ni‐1%, (b) RHC/K2O‐20%/Ni‐5...
Chapter 12
Figure 12.1 Process for transformation of animal sources as natural catalyst...
Figure 12.2 Production pathways for various plants‐derived alkali catalysts....
Chapter 14
Figure 14.1 Common examples of (a) metal clusters (secondary building units)...
Figure 14.2 Tunable active sites present in metal–organic frameworks: (a) me...
Scheme 14.1 Schematic representation of creation of missing linker defects i...
Scheme 14.2 (a) General esterification of carboxylic acids and (b) transeste...
Figure 14.3 (a) Structure of ZIF‐8 MOF, (b) secondary building unit (SBU)‐Zn...
Scheme 14.3 Transesterification of tributyrin with methanol.
Figure 14.4 Synthesis of functional DMOF‐1 catalysts through “click chemistr...
Scheme 14.4 Schematic representation of mechanism for the esterification of ...
Figure 14.5 (a) Secondary building units (SBU) corresponding to UiO‐66(Zr), ...
Figure 14.6 (a) Representation of synergistic active centers within the stru...
Figure 14.7 (a) Schematic representation of formation of NENU‐3a {Cu
12
(BTC)
8
Chapter 15
Figure 15.1 Steps in production of advanced biodiesel from waste cooking oil...
Figure 15.2 Global share of feedstocks.
Figure 15.3 Biodiesel production by countries.
Chapter 16
Figure 16.1 Rotating reactor‐assisted biodiesel production system (a) spinni...
Figure 16.2 Tubular flow reactor (a) packed bed reactor, (b) oscillatory flo...
Figure 16.3 Continuous microwave‐assisted biodiesel production system (a), s...
Figure 16.4 Schematic diagram of hybridized reactive distillation.
Figure 16.5 Schematic diagram of separated membrane reactor.
Figure 16.6 Schematic cross‐sectional view of the centrifuge contactor react...
Figure 16.7 Integration of different intensification techniques for biodiese...
Chapter 17
Figure 17.1 General scheme of flow processes for wet and dry washing.
Figure 17.2 Scheme of membrane separation unit for biodiesel purification.
Chapter 18
Scheme 18.1 Commercial synthesis of acrylic acid via propylene oxidation.
Figure 18.1 Renewable energy sources and biomass valorization to fuels and c...
Figure 18.2 Glycerol is a by‐product from biodiesel synthesis.
Figure 18.3 Conversion of glycerol to acrylic acid via different routes.
Figure 18.4 The reaction mechanism of glycerol dehydration over (a) Brønsted...
Figure 18.5 Concept of sustainable biomass processing.
Figure 18.6 Glycerol oxydehydration to acrylic acid in one‐bed catalytic sys...
Figure 18.7 Reaction mechanisms for (a) dehydration of glycerol into acrolei...
Chapter 19
Chart 19.1 Popularity of biodiesel (Google trends).
Figure 19.1 Viscosity implied by intermolecular forces in vegetable oil.
Figure 19.2 Representative process in the transesterification of vegetable/a...
Figure 19.3 Catalysts developed for the transesterification.
Figure 19.4 Generational evolution in biodiesel feedstock towards sustainabi...
Figure 19.5 Pros and cons of first‐generation biodiesel.
Figure 19.6 Single‐stage vs double‐stage transesterification of nonedible oi...
Chapter 20
Figure 20.1 Overall reaction of transesterification process.
Figure 20.2 Biodiesel separation using membrane process..
Figure 20.3 Biodiesel production using microwave heating.
Figure 20.4 Formation of ultrasonic sound and formation and growth of bubble...
Guide
Cover Page
Title Page
Copyright Page
Preface
List of Contributors
An Overview of Biodiesel Production
Table of Contents
Begin Reading
Index
WILEY END USER LICENSE AGREEMENT
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Biodiesel Production: Feedstocks, Catalysts, and Technologies
Edited by
Dr. Samuel Lalthazuala Rokhum
National Institute of Technology Silchar
Department of Chemistry
NIT Road, Fakiratilla
Silchar, Assam
India
Prof. Gopinath Halder
National Institute of Technology Durgapur
Department of Chemical Engineering
National Institute Technology
Durgapur
India
Prof. Suttichai Assabumrungrat
Chulalongkorn University
Center of Excellence in Catalysis and Catalytic Reaction Engineering and Bio‐Circular‐Green‐economy Technology & Engineering Center (BCGeTEC)
Department of Chemical Engineering
Bangkok, Thailand
Assoc. Prof. Kanokwan Ngaosuwan
Rajamangala University of Technology Krungthep
Chemical Engineering Devision
Bangkok
Thailand
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Library of Congress Cataloging‐in‐Publication Data
Names: Rokhum, Samuel Lalthazuala, editor. | Halder, Gopinath, editor. | Assabumrungrat, Suttichai, editor. | Ngaosuwan, Kanokwan, editor.Title: Biodiesel production : feedstocks, catalysts, and technologies / [edited by] Prof. Samuel Lalthazuala Rokhum, National Institute of Technology Silchar, Department of Chemistry, NIT Road, Fakiratilla, Sichar, Assam, India, Prof. Gopinath Halder, Department of Chemical Engineering, National Institute Technology, Durgapur, India, Prof. Suttichai Assabumrungrat, Chulalongkorn University, Department of Chemical Engineering, Bangkok, Thailand, Dr. Kanokwan Ngaosuwan, Rajamangala University Technology Krungthep, Chemical Engineering Division, Krungthep, Bangkok, Thailand.Other titles: Biodiesel production (John Wiley & Sons)Description: Hoboken, NJ : Wiley, 2022. | Includes bibliographical references and index.Identifiers: LCCN 2021056412 (print) | LCCN 2021056413 (ebook) | ISBN 9781119771333 (cloth) | ISBN 9781119771340 (adobe pdf) | ISBN 9781119771357 (epub)Subjects: LCSH: Biodiesel fuels.Classification: LCC TP359.B46 B5634 2022 (print) | LCC TP359.B46 (ebook) | DDC 665/.37–dc23/eng/20220228LC record available at https://lccn.loc.gov/2021056412LC ebook record available at https://lccn.loc.gov/2021056413
Cover Design: WileyCover Image: © Julija Vidjajeva/Shutterstock
Preface
This book Biodiesel Production: Feedstocks, Catalysts, and Technologies includes the contribution of leading researchers in the fields of biodiesel, which will serve as a valuable source of information for scientists, researchers, graduate students, and professionals alike. It focusses on several aspects of biodiesel productions, technologies employed, and sustainability. It consists of 20 chapters, grouped together in three parts, in different technological aspects as follows.
The utilization of conventional and novel feedstocks for biodiesel production will be presented in Chapters 1–4.
Chapter 1 emphasizes on the conversion of several edible vegetable oils and animal fats to biodiesel. Different catalysts used and several factors that affect the overall biodiesel production are comprehensively discussed.
Chapter 2 provides the perspective of the biodiesel production from waste cooking oil via the conventional and modern technologies to bolster competitiveness of biodiesel with petrodiesel.
Chapter 3 addresses the state of the art and future perspectives of nonedible oils for biodiesel production. It provides several important aspects such as cultivation information, fatty acid composition, extraction, and conversion method for biodiesel production.
Chapter 4 proposes the important strategy of microalgae cultivation for the large‐scale optimization of lipid accumulation as a potential sustainable approach for biodiesel production.
In the next part, Chapters 5–14, the various types of homogeneous and heterogeneous catalysts for biodiesel production will be discussed.
Chapter 5 reviews the utilization of homogeneous catalysts for various feedstocks under optimum conditions to serve the growing demand of biodiesel as a cost‐effective production process.
Chapter 6 summarizes the development of metal oxide catalysts from various sources for biodiesel production. The reaction mechanistic pathways and causes of catalyst deactivation are discussed.
Chapter 7 focuses on the catalytic activity enhancement of metal oxides with particular focus on the role of supporters, their synthesis methods, and physicochemical properties to achieve eco‐friendly and economically viable processes of biodiesel production.
Chapter 8 highlights the development of new mixed metal oxides with a variety of novel acidic, basic, and bifunctional catalysts from various feedstocks for enhancing their catalytic performance. Their stability, catalyst regeneration techniques, and recommendation for full scale biodiesel production are also addressed.
Chapter 9 presents the outlook of using nanotechnology‐based catalysts for the development of more efficient, economically viable, durable, and stable nanocatalysts, targeting at achieving higher biodiesel quality and yields.
Chapter 10 reveals the advantages and issues of using ion‐exchange resins catalysts for both cation and anion exchange resins especially in continuous biodiesel production.
Chapter 11 discusses the solid bifunctional catalysts with acid–base and Lewis–Brønsted functionalities. The preparation methods, their characterization results, and the optimum condition for biodiesel production were addressed.
Chapter 12 proposes the green concept for biodiesel production using catalysts derived from renewable resources. Essential information on their preparation methods, physicochemical properties, and catalytic activities as well as the challenges are discussed.
Chapter 13 exploits the usage of the promising ionic liquid catalyst to replace homogeneously catalyzed biodiesel production concurrently with techno‐economic analysis, life cycle assessment, environmental impact assessment, and scale‐up technologies.
Chapter 14 demonstrates the effective acid/base metal–organic frameworks (MOFs) catalysts for both transesterification and esterification reactions to intensify biodiesel production based on their catalytic synergy.
The strategies in terms of upstream, mainstream, and downstream process to fulfill the economical and sustainable for biodiesel production will be addressed in Chapters 15–21.
Chapter 15 scrutinizes the strategies for upstream biodiesel production dealing with the advanced feedstocks like waste cooking oil, waste animal fats, nonedible oils, or genetically engineered oils based on the appropriate catalyst, reaction conditions, and the following downstream processes.
Chapter 16 approaches the operating key parameters of mainstream strategies in terms of the novel reactor for biodiesel production based on the scientific and practical viewpoints to achieve efficiency and sustainable concept.
Chapter 17 discloses the downstream strategies to accomplish biodiesel standard as well as operating cost reduction using methanol recovery and glycerol by‐product refining. The integration of bioenergy systems to produce antioxidant additives for improving biodiesel quality is also encouraged.
Chapter 18 addresses the conversion of bio‐glycerol to value‐added chemicals especially acrylic acid to boost alternative sustainable routes for biodiesel production.
Chapter 19 introduces the sustainability in the production and use of biodiesel, which is mainly dependent on the types of feedstocks and government policy as the incentives of using biodiesel.
Chapter 20 discusses the advanced, sustainable technology with respect to the diversified feedstock and design of the novel efficient catalytic system for production of biodiesel and its commercialization.
List of Contributors
Pratibha AgrawalDepartment of Applied Chemistry Laxminarayan Institute of Technology RTM Nagpur University, Nagpur Maharashtra, India
Weerinda AppamanaDepartment of Chemical and Materials Engineering, Faculty of Engineering Rajamangala University of Technology Thanyaburi, Pathum Thani, Thailand
Arumugam ArumugamDepartment of Chemical Engineering School of Chemical and Biotechnology Center for Bioenergy, SASTRA Deemed to Be University, Thanjavur, India
Suttichai AssabumrungratCenter of Excellence on Catalysis and Catalytic Reaction Engineering Department of Chemical Engineering Faculty of Engineering, Chulalongkorn University, Bangkok, ThailandBio‐Circular‐Green‐economy Technology & Engineering Center, BCGeTEC Department of Chemical Engineering Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand
Vasudeva Rao BakuruMaterials science and catalysis division Poornaprajna Institute of Scientific Research, Bangalore Rural, India
G. BaskarDepartment of Biotechnology, St. Joseph’s College of Engineering, Chennai, India
Bidangshri BasumataryDepartment of Chemistry, Bodoland University, Kokrajhar, Assam, India
Sanjay BasumataryDepartment of Chemistry, Bodoland University, Kokrajhar, Assam, India
Rahul BhagatDepartment of Biotechnology, Government Institute of Science, Aurangabad Maharashtra, India
Trinath BiswalDepartment of Chemistry, Veer Surendra Sai University of Technology, Burla. Sambalpur, Odisha. India
Bishwajit ChangmaiDepartment of Chemistry, National Institute of Technology Silchar Silchar, India
Narita ChanthonCenter of Excellence on Catalysis and Catalytic Reaction Engineering Department of Engineering, Faculty of Engineering, Chulalongkorn University Bangkok, Thailand
Michael Van Lal ChhandamaDepartment of Biotechnology, School of Sciences (Block‐I), JAIN (Deemed‐to‐be University), Bengaluru, Karnataka, India
Valeria D’AmbrosioIstituto di Ricerca Sulle Acque, Consiglio Nazionale delle Ricerche (IRSA‐CNR) Bari, Italy
Yosvany Díaz‐DomínguezFaculty of Chemical Engineering Universidad Tecnológica de la Habana Havana, Cuba
Marilyn Esclance DMelloMaterials science and catalysis division Poornaprajna Institute of Scientific Research, Bangalore Rural, India
Apiluck Eiad‐uaCollege of Nanotechnology, King Mongkut's Institute of Technology Ladkrabang, Bangkok, Thailand
Jabbar GardySchool of Chemical and Process Engineering, University of Leeds Leeds, UK
Gopinath HalderDepartment of Chemical Engineering National Institute of Technology Durgapur, India
Ali HassanpourSchool of Chemical and Process Engineering, University of Leeds, Leeds, UK
Balkis HazmiInstitute of Nanoscience and Nanotechnology (ION2)Universiti Putra Malaysia, Serdang Selangor, Malaysia
Kousuke HiromoriDepartment of Chemical Engineering Tohoku University, Sendai, Japan
Avinash P. IngleBiotechnology Centre, Department of Agricultural Botany, Dr. Panjabrao Deshmukh Agricultural University, Akola Maharashtra, India
Pavan Narayan KalbandeCatalysis and Inorganic Chemistry Division, CSIR‐National Chemical Laboratory, Pune, IndiaAcademy of Scientific and Innovative Research (AcSIR), CSIR‐National Chemical Laboratory, Pune, India
Suresh Babu KalidindiDepartment of Inorganic and Analytical Chemistry, School of Chemistry, Andhra University Visakhapatnam, India
Aleksandra SanderDepartment of Mechanical and Thermal Process Engineering, University of Zagreb Faculty of Chemical Engineering and Technology, Zagreb, Croatia
Bisheswar KarmakarDepartment of Chemical Engineering National Institute of Technology Durgapur, India
Rupam KatakiDepartment of Energy, Tezpur University Tezpur, Assam. India
Worapon KiatkittipongDepartment of Chemical Engineering Faculty of Engineering and Industrial Technology, Silpakorn University, Nakhon Pathom, ThailandHui LiSchool of Thermal Engineering, Shandong Jianzhu University, Jinan, PR China
Brandon LoweSchool of Chemical and Process Engineering, University of Leeds Leeds, UK
Mangesh P. MoharilBiotechnology Centre, Department of Agricultural Botany, Dr. Panjabrao Deshmukh Agricultural University, Akola Maharashtra, India
Biswajit NathDepartment of Chemistry, Bodoland University, Kokrajhar, Assam, IndiaDepartment of Chemistry, Science College Kokrajhar, Assam, India
Kanokwan NgaosuwanDivision of Chemical Engineering, Faculty of Engineering, Rajamangala University of Technology Krungthep, Bangkok, Thailand
Carlo PastoreIstituto di Ricerca Sulle Acque, Consiglio Nazionale delle Ricerche (IRSA‐CNR) Bari, Italy
Nattawat PetchsoongsakulCenter of Excellence on Catalysis and Catalytic Reaction Engineering Department of Engineering, Faculty of Engineering, Chulalongkorn University Bangkok, Thailand
Ana PetračićDepartment of Mechanical and Thermal Process Engineering, University of Zagreb Faculty of Chemical Engineering and Technology, Zagreb, Croatia
Ramón Piloto‐RodríguezFaculty of Chemical Engineering Universidad Tecnológica de la Habana Havana, Cuba
Armando T. QuitainFaculty of Advanced Science and Technology, Kumamoto University Kumamoto, JapanCenter for International Education Kumamoto University, Kumamoto, Japan
Umer RashidInstitute of Nanoscience and Nanotechnology (ION2), Universiti Putra Malaysia, Serdang Selangor, Malaysia
Samuel Lalthazuala RokhumHamid Yusuf Department of Chemistry University of Cambridge, Cambridge, UKDepartment of Chemistry, National Institute of Technology, Silchar, Assam, India
B. SangeethaDepartment of Biotechnology, St. Joseph’s College of Engineering, Chennai, India
Kumudini Belur SatyanDepartment of Biotechnology, School of Sciences (Block‐I), JAIN (Deemed‐to‐be University), Bengaluru, Karnataka, India
Shreshtha SaxenaBiotechnology Centre, Department of Agricultural Botany, Dr. Panjabrao Deshmukh Agricultural University, Akola Maharashtra, India
Enrico ScelsiIstituto di Ricerca Sulle Acque, Consiglio Nazionale delle Ricerche (IRSA‐CNR), Bari, Italy
Krushna Prasad ShadangiDepartment of Chemical Engineering, Veer Surendra Sai University of Technology, Burla. Sambalpur, Odisha. IndiaNaomi Shibasaki‐KitakawaDepartment of Chemical Engineering, Tohoku University, Sendai, Japan
Nittan SinghCatalysis and Inorganic Chemistry Division, CSIR‐National Chemical Laboratory, Pune, IndiaAcademy of Scientific and Innovative Research (AcSIR), CSIR‐National Chemical Laboratory, Pune, India
Atthapon SrifaDepartment of Chemical Engineering Faculty of Engineering, Mahidol University, Nakhon Pathom, Thailand
Putla SudarsanamCatalysis and Inorganic Chemistry Division, CSIR‐National Chemical Laboratory, Pune, IndiaAcademy of Scientific and Innovative Research (AcSIR), CSIR‐National Chemical Laboratory, Pune, India
Pothiappan VairaprakashDepartment of Chemistry, School of Chemical and Biotechnology, Center for Bioenergy, SASTRA Deemed to Be University, Thanjavur, India
Chhangte VanlalveniDepartment of Botany, Mizoram University, Aizawl, Mizoram, India
Andrew E.H. WheatleyHamid Yusuf Department of Chemistry University of Cambridge, Cambridge, UK
Doonyapong WongsawaengDepartment of Nuclear Engineering Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand
Kejun WuSchool of Chemical and Process Engineering, University of Leeds Leeds, UKSchool of Chemical and Biological Engineering, Zhejiang University Hangzhou, P.R. China
An Overview of Biodiesel Production
The advent of the industrial revolution had many benefits such as increases in wealth of the average masses, upgrade in living standards, and vast improvements in production of goods (both in quality and in quantity), which reduced prices drastically. Technological advancements also occurred in the transport sector, which enabled ease in travel, while the use of coal and petroleum skyrocketed: an example of this would be the 20‐fold increase in coal imports between 1550 and 1700 in Newcastle, England. Consequently, a proportional increase in mining of these fossilized reserves had to be done as far as from the early nineteenth century. Since then, the energy demand per capita has increased manifold to the point where current consumption trends cannot be supported without exhausting the remaining global reserves – alternative energy sources must be sought. Additionally, large areas of forest land had been cleared for fuelwood, which served as the primary energy source for cooking and heating in rural households. Widespread deforestation led to a rapid rise in global temperature since less trees are available for climate modulation. Also, upon using wood and other fossilized sources as fuel, huge amounts of particulate matter, smoke, and other noxious gases (NOXs, SOXs, CO, and CO2) are emitted, and thus their continued emission for the last few centuries has led to global warming, harmful impacts on terrestrial and aquatic life (through acid rain, aquatic pollution resulting in eutrophication), and changes in weather patterns, which has even impacted the overall health and life expectancy of humans (lung diseases caused by air pollution, water pollution leading to chronic diseases, etc.).
In order to combat or gradually reverse the effects of such a global situation where arable land and potable water are scarce, alternative energy sources that have no or negligible environmental impacts must be sought. Thus, renewable energy research over the last few decades has been steadily increasing and is now capable of changing an entire country’s energy consumption trend. A good example is Brazil, which runs entirely on “sustainable” fuels, having produced 26.1% (a staggering 26.72 billion liters) of the global ethanol being used as fuel in 2017, and many countries have tried to replicate the so‐called “Brazilian ethanol model.” Among the wide variety of renewable energy sources available, feedstock for biofuels such as biodiesel and bioethanol are limited to a few varieties. Vegetable oils (edible or nonedible) cannot be directly used in engines due to their incompatible physicochemical properties. This had been tested by Dr. Rudolph Diesel who used peanut oil for his internal combustion (IC) engine and reported many problems in required performance when run for extended durations. Thus, such oils are converted into esters that are the main component of biodiesel, a fuel suitable for use in diesel engines with minor modifications. To convert vegetable oils as well as other potential feedstock such as microalgal lipids, animal fats and greases, waste oils, and other miscellaneous sources, various approaches may be used with different conversion efficiencies. The most efficient conversion process, however, is transesterification, which may or may not be coupled with an esterification pretreatment stage depending on the free fatty acid content of the oil.
For both esterification and transesterification, the reactants are the feedstock and an alcohol, which in the presence of a catalyst are converted into their esters, producing either water or glycerol as by‐products. Depending on the reaction conditions (based on the approach used), catalysts may not be required, although a multitude of catalysts have been developed and tested with varying degrees of efficiency. Such catalysts range from the simplest mineral acids, enzymes, or bases, which are added for achieving a homogeneous system and discarded with every use to simple heterogeneous catalysts that rely on solid metal oxides or the use of inert carbonaceous or siliceous biomass doped with the required catalytic groups (including transition metals) or enzymes, as well as nanocatalysts that have increased efficiency (when compared with inert microporous support‐based catalysts), while specially designed catalysts based on resin supports or metal organic frameworks have also been developed and can be very efficient but may be difficult to commercialize due to high development costs and unavoidable losses in each cycle of use. Strangely, processes such as supercritical fluid technology or superheated vapor technology can function reliably even without the use of catalysts, although the use of catalysts can augment the process, which may require a cost‐to‐benefit analysis before commercialization.
The process of biodiesel commercialization does not simply end at its production, since there are many stages that need to be considered for downstream processing as well as the consideration for treatment of hazardous materials generated (such as biodiesel wastewater that contains spent catalyst or leached ions) and the recovery of spent alcohol and the valorization of generated glycerol. Additionally, the produced fuel must have an acceptably long shelf life, and since biodiesel is prone to auto‐oxidation (it contains high oxygen content that helps in reducing pollution due to complete fuel combustion), such additives are essential for storage. Such processes generally increase the cost of available fuel, which has made it necessary to consider these hurdles that are yet to be overcome before the complete utilization of biodiesel is feasible as an environment‐friendly and affordable alternative to petrodiesel.
Editors: Samuel Lalthazuala Rokhum, Gopinath Halder, Kanokwan Ngaosuwan, Suttichai Assabumrungrat
Part 1Biodiesel Feedstocks
1Advances in Production of Biodiesel from Vegetable Oils and Animal Fats
Umer Rashid and Balkis Hazmi
Institute of Nanoscience and Nanotechnology (ION2), Universiti Putra Malaysia, Serdang, Selangor, Malaysia
1.1 Introduction
Currently, the energy requirements of the world are mainly met through fossil fuel resources, such as gasoline, petroleum‐based diesel, and natural gas. Such fossil‐derived resources are too limited to fulfill the future energy demands and meet the challenges of rapid human population growth coupled with technological developments [1]. Presently, research is progressively more directed toward exploration of alternative renewable fuels. Several types of biofuels, such as vegetable oil/animal fat (raw, processed, or used), methyl esters from vegetable oil/animal fat, and ethanol or liquid fuels from biomass (bioethanol and biomethanol), have been investigated as a replacement for gasoline and petrodiesel [2].
At present over 197.97 million metric tons of 10 major vegetable oils are produced worldwide [3]. Vegetable oils are commonly derived from various oilseed crops. In a vegetable oil, almost 90–95% is glycerides, which are basically esters of glycerol and fatty acids (FAs) [4]. The vegetable oils can be considered as a feasible alternative for diesel fuel as the heating value of vegetable oils is comparable to that of diesel fuel [5, 6]. However, the uses of vegetable oils in direct injection diesel engines are restricted due to some unfavorable physical properties, particularly the viscosity. The viscosity of vegetable oil is roughly 10 times higher than the diesel fuel. Therefore, the use of vegetable oil in direct injection diesel engines creates poor fuel atomization, incomplete combustion, and carbon deposition on the injector [7, 8].
Several techniques are employed to bring down the physical and thermal properties of vegetable oils close to mineral diesel, by which these oils and fats can be used in internal combustion engines as fuel. This mainly requires improvement in viscosity of the vegetable oil. The possible treatments employed to improve the oil viscosity includes dilution with a suitable solvent, microemulsification, pyrolysis, and transesterification [9, 10].
The uses of biodiesel (BD) as a renewable, biodegradable, nontoxic, and eco‐friendly neat diesel fuel or in blends with petroleum‐based fuels are fascinating [11, 12]. “Biodiesel,” termed as the monoalkyl esters of long‐chain FAs, is derived from vegetable oils or animal fats. Numerous types of conventional and nonconventional vegetable oils and animal fats including those of used oils from the frying industry, soybean oil, rapeseed oil, tallow, rubber seed oil, and palm oil have been investigated to produce BD [13–15]. The production of BD involves the conversion of vegetable oils/animal fats using methanol or ethanol and a catalyst to produce fatty acid methyl esters (FAMEs) and crude glycerin as by‐product through a process termed as “transesterification” [16].
The transesterification process is accomplished by reacting vegetable oil with alcohol in the presence of alkaline or acidic catalyst. A catalyst is typically used to accelerate the reaction rate and yield. The stoichiometric equation requires 1 mol of triglyceride and 3 mol of alcohol to form 3 mol of methyl ester and 1 mol of glycerol [17]. Since the reaction is reversible, excess alcohol is used to shift the reaction equilibrium to the product’s side. The most preferred catalysts are sulfuric, sulfonic, and hydrochloric acids as acidic catalysts and sodium hydroxide, sodium methoxide, and potassium hydroxide as alkaline catalysts [18]. The product, fatty esters, have improved viscosity and volatility relative to the triglycerides. A dense, liquid phase rich in glycerol is the coproduct of this process. The separated fatty esters have cetane number and heating value close to that of the conventional diesel. The transesterification process for converting vegetable oils to BD is shown in Figure 1.1.
The “R” groups are the FAs, which are usually 12–22 carbons in length. The large vegetable oil molecule is reduced to about one third of its original size, lowering the viscosity and making it like diesel fuel. The resulting fuel can work like diesel fuel in an engine. The by‐product “glycerin” produced in this process is valuable due to its diverse industrial applications [19].
Technically, BD is a fuel comprising of monoalkyl esters of long‐chain FAs derived from vegetable oils or animal fat, which meets current EN 14214 and ASTM D 6751 BD standards of Europe and the United States, respectively. These standards are frequently employed as references to evaluate and compare the properties of other fuels.
Presently, the BD is commonly produced using a base‐catalyzed transesterification reaction because it involves low temperature and pressure processing, high conversions, no intermediate steps, and lower costs of processing materials [20]. Alkoxides and hydroxides of potassium and sodium are often used as catalysts in the transesterification of refined oils and low FA greases and fats. However, acid esterification followed by transesterification of high free fatty acid (FFA) fats and oils is also applicable. The base catalysts have better efficiency than the acid catalysts [21]. The base‐catalyzed transesterification reaction can be carried out at lower temperature, yet at room temperature, with the base catalysts, whereas acid catalysis required higher temperature (100 °C) and longer reaction time. During the process, basic catalyst breaks the FAs from the glycerin one by one. When a methanol molecule contacts an FA molecule, it will bond and form BD molecule. The hydroxyl group from the catalyst alleviates the glycerol formation. The resulting product named as methyl esters (BD) has appreciably lower viscosity and increased volatility relative to the triglycerides present in vegetable oils [22–24].
Figure 1.1 General reaction for transesterification of vegetable oil.
The second usual method of producing BD involves the use of an acid as a substitute of a base catalyst. Any mineral acid can be employed to catalyze the process; the most used acids are sulfuric acid and sulfonic acid. Although yield is high, the acids, being corrosive, may cause damage to the equipment, and the reaction rate is also observed to be relatively low [9, 21]. Oil feedstocks containing more than 4% FFAs must pass through an acid esterification process to increase the BD yield [25]. Such feedstocks are filtered and preprocessed to remove water and contaminants and then fed to the acid esterification process. The catalyst (sulfuric acid) is dissolved in methanol and then mixed with the pretreated oil [26].
The alcohols employed in the transesterification are generally short‐chain alcohols such as methanol, ethanol, propanol, and butanol producing esters named as methyl‐, ethyl‐, propyl‐, and butyl‐esters, respectively [9, 10]. It is reported that when transesterification of soybean oil using methanol, ethanol, and butanol was performed, 96–98% of ester’s yield could be obtained after an hour of reaction [27]. Though utilizing different alcohols presents little differences with regard to the kinetic of reaction, the final yield of esters remains unchanged. Thus, assortment of the alcohol is based on cost and performance consideration. Generally, reaction temperature is set at near the boiling point of the alcohol used [28].
Due to the reality that many vegetable oils, including soybean, canola (rapeseed) oil, and rice bran oil, have a major number of FAs with double bonds, oxidative stability is a problem, particularly when storing BD for longer period of time [29, 30]. This problem becomes severe due to improper storage conditions, which may include exposure to air and/or light, temperatures above ambient, and presence of extraneous materials (contaminants) with catalytic effect on oxidation. Some additives such as antioxidants might control the oxidation.
Characterization of BD fuel properties and evaluation of its quality are the matters of great concern for the successful commercialization of this fuel. A high fuel value with no operational problems is a condition for market acceptance of BD. Accordingly, the analysis of BD and the monitoring of the transesterification reaction have been the subject of numerous publications [31, 32]. The constraints, which are used to define the quality of BD, can be divided in two groups [33]. One of them is also used for mineral diesel, and the second illustrates the composition and purity of fatty esters. The former includes, for example, density, viscosity, flash point, sulfur percentage, carbon residue, sulfated ash percentage, cetane number, and acid number. The latter comprises, for example, methanol, free glycerol, total glycerol, phosphorus contents, water, and esters content. Chromatography and spectroscopy are the mainly used analytical methods for BD analyses, but procedures based on physical properties are also available [34]. Furthermore, it is important to mention that in most chromatographic analyses, mainly gas chromatography (GC) has been applied to methyl and not to ethyl esters [29].
As the demand for vegetable oils for food has increased tremendously in recent years, hence, the contribution of nonedible oils such as jatropha, Moringa oleifera, rice bran oils, etc. can play an important role for BD production. In view of the limited petro‐oil resources and rapidly growing energy demands of the world, there is an extensive need to take immediate initiatives for exploring alternative energy sources to meet the domestic needs and reduce the dependence on imported fossil fuels. In view of the future perspectives of biofuels, the present book chapter was designed with the main purposes to assess the feasibility of BD production from multi‐feedstock vegetable oil sources.
1.2 History of the Use of Vegetable Oil in Biodiesel
The idea to use vegetable oils as fuels for diesel engines dates back to more than one hundred years. Historically, Rudolf Diesel, the inventor of diesel engine, at the Paris Exhibition in 1900, conducted engine tests, for the first time, on peanut oil [22, 35]. At that moment Diesel said, “The use of vegetable oils for engine fuels may seem insignificant today. However, such oils may in course of time be as important as petroleum and the coal tar products of the present time.” Today, over a century later, the scientific community is working to fulfill his dream by considering potential benefits of BD as an alternative fuel to petrodiesel for future uses.
1.3 Feedstocks for Biodiesel Production
All over the world, the usual lipid feedstocks for BD production are refined vegetable oils. In this group, the oil of choice varies with location according to availability; the most abundant lipid is generally the most common feedstock. The bases for this are not only the desire to have an ample supply of product fuel but also because of the inverse relation between supply and cost. Refined oils can be comparatively costly under the best of conditions, compared with petroleum products, and the choice of oil for BD production depends on local availability and corresponding affordability. The four oil crops clearly dominate the feedstock sources used for worldwide BD production. With a share of nearly 85%, rapeseed oil is by far leading the field, followed by sunflower seed oil, soybean oil, and palm oil [36]. Apart from the “great four” – rapeseed oil, sunflower seed oil, soybean oil, and palm oil in BD production – other edible plant oils have also successfully been transesterified to produce BD.
The choice of raw material used for BD production in a specific region mainly depends on the respective climatic conditions. Thus, rapeseed and sunflower oils are mainly used in the European Union [37], palm oil predominates in BD production in tropical countries [38, 39], and soybean oil [40] and animal fats are the major feedstocks in the United States. FA ester production has also been demonstrated from a variety of other feedstocks, including the oils of coconut [41], rice bran [42], Thespesia populnea[43], safflower [44], palm kernel [45], M. oleifera[46], Citrus reticulata (mandarin orange) [47], Jatropha curcas[48], Ethiopian mustard [13], Cynara cardunculus[49], Hibiscus esculentus[50], maize [51], Cyperus esculentus (Barminas et al. [52]), Prunus mahaleb[53], kapok [54], tobacco [55], milkweed [7], Yucca aloifolia[56], Oleum papaveris seminis[57], Pongamia[58], Brassica napus[59], Citrullus colocynthis[53], rubber seed oils [60], palm FA distillate [61], the animal fats, tallow [7, 62], lard [63], and waste oils [64, 65]. As such, any animal or plant lipid should be a ready substrate for the production of BD. Such features as supply, cost, storage properties, and engine performance will determine whether a particular potential feedstock is actually acceptable for commercial fuel production.
One way of reducing the production costs for BD fuels is the use of nonedible oils, which tend to be considerably cheaper than edible vegetable oils [66]. A number of plant oils contain substances that make them unsuitable for human consumption. In some cases, these substances can be removed by refining. For example, gossypol contained in cottonseeds can effectively be eliminated from the oil and the press cake to allow utilization as a cooking oil and animal feed, respectively [55]. Sometimes harmful ingredients can also be eliminated by breeding, as was the case with glucosinolates and erucic acid in rapeseed. In many cases, however, the removal of toxic components from the fatty material has not been accomplished or even attempted yet.
1.3.1 Generations of Biodiesel
BD production has proven to be sustainable because of the wide coverage of raw material availability, estimated at more than 350 types of oilseed crops worldwide. The feedstocks are generally easily accessible but vary depending on geographic location, weather conditions, land type, and agricultural practices in any country. In addition, the BD feedstocks portray 75% of total manufacturing cost; thus it is essential to choose appropriate feedstock to ensure the BD production feasibility. Typically, BD raw materials can be categorized as first‐generation, second‐generation, and third‐generation BD, accordingly to the material used for the BD synthesizing as shown in Table 1.1[15].
1.3.2 First‐Generation Biodiesel
First‐generation BD may be defined as edible oils from agricultural products such as palm oil, olive, sunflower, coconut, canola, rapeseed soybeans, etc. [71, 72]. Today, derived BD from edible oils has reached approximately more than 95% and has raised many issues, especially the competition between food supply and oil demand crisis, deforestation, and soil destruction for feedstock plantation purposes [73]. In the past decade, the price of edible oils has escalated, while the production demand for BD conversion is continuously increasing, resulting in edible‐based BD being less economically feasible [74]. Given these circumstances, the exploitation of first‐generation BD as a replacement for diesel fuel has put the world's stock of edibles in jeopardy.
Table 1.1 Main feedstocks of biodiesel.
Source: Adapted from [67–70].
First‐generation oil
Second‐generation oil
Third‐generation oil
Soybean Canola Palm Rapeseed Coconut Olive Sunflower Peanut Sesame Mahua Barley Wheat
Rubber seed Cotton seed Tobacco seed Karanja Jojoba oil Neem Moringa Jatropha Coffee ground Used cooking oil Tallow Fish oil Chicken fat Bitter almond oil
Nannochloropsis oculata
Chlamydomonas pitschmannii
Isochrysis
sp.
Chlorella vulgaris
Monoraphidium
sp.
1.3.3 Second‐Generation Biodiesel
Currently, BD derived from inedible oil has sparked scientists' interest in replacing reliance on edible oil‐based diesel. The inedible oil crops can be planted in wasteland or fallow areas without intensive agriculture, which can produce high oil yields [39]. Besides, waste oils and animal fats can be categorized as second‐generation BD. The use of waste as a BD feedstock may reduce the problem of waste disposal and the cost of BD production [75]. Both waste oils and animal fats are most likely to contain water and a slightly higher FFA value compared with virgin oils, which result in lower oil quality. Different types of raw materials will produce different quantities of yield and characteristics of the oil, so the selection of raw materials is very important because the cost of producing BD is very expensive.
1.3.4 Third‐Generation Biodiesel
Recently, the use of microalgae‐based BD has gained immense awareness and prospects for meeting the growing supply of BD feedstocks. The microalgae‐based BD has the advantage of growing at a faster rate under photoautotrophic condition and is able to produce high yield of oil than edible and nonedible crop oil [76]. Also in the future, microalgae may make a significant contribution to addressing the issue of food production versus BD production and reducing competition for farmland [77]. Moreover, a study discovered that the algae‐based BD has lower carbon footprint, which is beneficial to the ecosystem [67]. Nevertheless, it is important to study the production cost and energy output of algae‐based BD so that it is much more feasible and cost‐effective for mass production as an alternative to fossil fuel sources.
1.4 Basics of the Transesterification Reaction
The direct use of a vegetable oil in diesel engines is problematic because of its high viscosity (about 11–17 times higher than petrodiesel fuel), which reduces the fuel atomization leading to high engine deposits, thickening of lubricating oil, and lower volatilities that cause the formation of deposits in engines due to incomplete combustion [78, 79]. The extremely high flash points of vegetable oils and their tendency for thermal or oxidative polymerization aggravate the situation, leading to the formation of deposits on the injector nozzles, a gradual dilution and degradation of the lubricating oil, and the sticking of piston rings. As a consequence, long‐term operation on neat plant oils or on mixtures of plant oils and fossil diesel fuel inevitably results in engine breakdown [80].
Chemically, the vegetable oils/animal fats consist of triglyceride molecules of three long‐chain FAs that are ester bonded to a single glycerol molecule. These FAs differ by the length of carbon chains and by the number, orientation, and position of double bonds in these chains. Thus, BD refers to alkyl esters of long‐chain FAs, which are synthesized either by transesterification with alcohols or by esterification of FAs. The latter strategy aimed at modifying plant oils by various technologies to produce fuels that approximate the properties and performance of fossil diesel. Four methods to decrease the high viscosity of vegetable oils to enable their use in common diesel engines without operational problems such as engine deposits have been investigated: blending with petrodiesel, pyrolysis, microemulsification, and transesterification [81]. Transesterification is by far the most common method that leads to the products commonly known as BD, which are alkyl esters of vegetable oils or animal fats.
Pyrolysis denotes thermal decomposition reactions, usually brought about in the absence of oxygen. Pyrolysis of vegetable and fish oils, optionally in the presence of metallic salts as catalysts, was conducted as a means of producing emergency fuels during the Second World War, as various Chinese, Japanese, or Brazilian publications show [13]. In addition, the technology has occasionally found entry into the more recent literature as well [82, 83]. This treatment results in a mixture of alkanes, alkenes, alkadienes, aromatics, and carboxylic acids, which are similar to hydrocarbon‐based diesel fuels in many respects. The cetane number of plant oils is increased by pyrolysis, and the concentrations of sulfur, water, and sediment for the resulting products are acceptable. However, according to modern standards, the viscosity of the fuels is considered as too high, ash and carbon residue far exceed the values for fossil diesel, and the cold flow properties of pyrolyzed vegetable oils are poor [81]. Moreover, it is argued that the removal of oxygen during thermal decomposition eliminates one of the main ecological benefits of oxygenated fuels, namely, more complete combustion due to higher oxygen availability in the combustion chamber [22].
