Inamuddin - Biodiesel Technology and Applications-John Wiley & Sons (2021)

Biodiesel Technology
and Applications
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Biodiesel Technology
and Applications
Edited by
Inamuddin, Mohd Imran Ahamed,
Rajender Boddula
and Mashallah Rezakazemi
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Contents
Preface xvii
1 Biocatalytic Processes for Biodiesel Production 1
Ubaid Mehmood, Faizan Muneer, Muhammad Riaz,
Saba Sarfraz and Habibullah Nadeem
1.1 Introduction and Background 2
1.2 Importance of Biodiesel Over Conventional Diesel Fuel 3
1.3 Substrates for Biodiesel Production 4
1.4 Methods in Biodiesel Production 6
1.5 Types of Catalysts Involved in Biodiesel Production 7
1.5.1 Chemical Homogenous Catalysts 7
1.5.2 Solid Heterogeneous Catalysts 8
1.5.3 Biocatalysts 8
1.6 Factors Affecting Enzymatic Transesterification Reaction 8
1.6.1 Effect of Water in Enzyme Catalyzed
Transesterification 9
1.6.2 Effect of Bioreactor 10
1.6.3 Effect of Acyl Acceptor on Enzymatic Production
of Biodiesel 10
1.6.4 Effect of Temperature on Enzymatic Biodiesel
Production 14
1.6.5 Effect of Glycerol on Enzymatic Biodiesel Production 14
1.6.6 Effect of Solvent on Biodiesel Production 16
1.7 Lipases as Biocatalysts for Biodiesel Production 17
1.7.1 Mechanisms of Lipase Action 19
1.7.2 Efficient Lipase Sources for Biodiesel Producing
Biocatalyst 19
1.8 Comparative Analysis of Intracellular and Extracellular
Lipases for Biodiesel Production 21
1.9 Recombinant Lipases for Cost-Effective Biodiesel Production 26
1.10 Immobilization of Lipases for Better Biodiesel Production 28
v
vi Contents
1.11 Recent Strategies to Improve Biodiesel Production 31

1.11.1 Combination of Lipases 31
1.11.2 Microwave and Ultrasonic-Assisted Reaction 33
1.12 Lipase Catalyzed Reaction Modeling and Statistical
Approaches for Reaction Optimization 35
1.13 Conclusion and Summary 38
References 38
2 Application of Low-Frequency Ultrasound for Intensified
Biodiesel Production Process 59
Mohd Razealy Anuar, Mohamed Hussein Abdurahman,
Nor Irwin Basir and Ahmad Zuhairi Abdullah
2.1 Current Fossil Fuel Scenario 60
2.2 Biodiesel 60
2.3 Transesterification 61
2.4 Challenges for Improved Biodiesel Production 62
2.5 Homogeneous Catalyst for Biodiesel Production 63
2.6 Heterogeneous Catalyst for Biodiesel Production 64
2.7 Immiscibility of the Reactants 65
2.8 Ultrasound-Assisted Biodiesel Production Process 66
2.8.1 Fundamental Aspects of the Process 66
2.8.2 Homogeneously Catalyzed Ultrasound-Assisted
System 69
2.8.3 Heterogeneously Catalyzed Ultrasound-Assisted
System 72
2.8.3.1 Heterogeneously Acid Catalyzed System 72
2.8.3.2 Heterogeneous Based Catalyzed
Ultrasound-Assisted System 74
2.8.3.3 Influence of Reaction Parameters 78
2.9 Conclusions 79
Acknowledgement 80
References 80
3 Application of Catalysts in Biodiesel Production 85
Anilkumar R. Gupta and Virendra K. Rathod
3.1 Introduction 85
3.2 Homogeneous Catalysis for the Biodiesel Production 89
3.2.1 Homogeneous Acid Catalyst 89
3.2.2 Homogeneous-Base Catalyst 93
3.3 Heterogeneous Catalyst 96
3.3.1 Heterogeneous Acid Catalyst 97
3.3.2 Heterogeneous-Base Catalyst 106
Contents vii
3.4 Biocatalysts 115

3.5 Conclusion 119
References 124
4 Hydrogenolysis as a Means of Valorization
of Biodiesel-Derived Glycerol: A Review 137
Manjoro T.T., Adeniyi A. and Mbaya R.K.K.
4.1 Introduction 138
4.2 Ways of Valorization of Biodiesel-Derived Glycerol 139
4.2.1 Catalytic Conversion of Glycerol Into Value-Added
Commodities 140
4.2.1.1 Catalytic Oxidation of Glycerol 140
4.2.1.2 Catalytic Dehydration of Glycerol 143
4.2.1.3 Pyrolysis of Bioglycerol 144
4.2.1.4 Glycerol Transesterification 145
4.2.1.5 Glycerol Direct Carboxylation 146
4.3 Hydrogenolysis of Glycerol 147
4.3.1 Definition of Hydrogenolysis 147
4.3.2 Catalytic Hydrogenolysis of Glycerol 148
4.3.3 Product Spectrum from Hydrogenolysis of Glycerol 148
4.3.4 Hydrogenolysis of Glycerol to 1,2-PDO (Propylene
Glycol): Reaction Systems Overview 149
4.3.5 Catalyst Selection 151
4.3.6 Reaction Conditions That Influence the
Hydrogenolysis of Glycerol to 1,2-PDO 153
4.3.6.1 Effect of Reaction Temperature 153
4.3.6.2 Effect of H2 Pressure 154
4.3.6.3 Effect of Initial Water Concentration 155
4.3.6.4 Effect of Reaction Time 156
4.3.6.5 Effect of Catalyst Weight 156
4.3.6.6 Proposed Reaction Mechanisms for Glycerol
Hydrogenolysis to Produce 1,2-PDO 157
4.4 Conclusion 159
References 159
5 Current Status, Synthesis, and Characterization of Biodiesel 167
Akshay Garg, Gaurav Dwivedi, Prashant Baredar
and Siddharth Jain
5.2 Status of Biodiesel in India 169
5.3 Biodiesel Production in India 169
viii Contents
5.3.1 Feedstocks Popular in India 169

5.3.1.1 Jatropha (Jatropha curcas) Oil 171
5.3.1.2 Pongamia Oil 171
5.3.1.3 Mahua Oil 171
5.3.1.4 Neem Oil 171
5.3.1.5 Linseed Oil 171
5.3.1.6 Rubber Seed Oil 172
5.3.1.7 Tobacco Oil 172
5.3.1.8 Castor 172
5.3.1.9 Waste Cooking Oil 172
5.3.1.10 Algae Oil 172
5.3.2 Advantages of Non-Edible Oils 173
5.3.3 Modification Techniques 173
5.3.3.1 Blending 173
5.3.3.2 Micro-Emulsification 173
5.3.3.3 Cracking 174
5.3.3.4 Transesterification 174
5.3.4 Biodiesel Production Methodology 174
5.3.4.1 Catalytic Transesterification 174
5.3.4.2 Non-Catalytic Transesterification 178
5.3.5 Optimization Methodology for Biodiesel 179
5.3.5.1 Central Composite Design Technique 179
5.3.5.2 Box Behnken Technique 179
5.4 Properties of Biodiesel 180
5.5 Analytical Methods 181
5.5.1 Titration 181
5.5.2 Chromatic Methods 181
5.5.2.1 Gas Chromatography 183
5.5.2.2 High-Performance Liquid Chromatography 184
5.5.3 Spectroscopic Methods 184
5.5.3.1 Nuclear Magnetic Resonance Spectroscopy 184
5.5.3.2 Infrared Spectroscopy 185
5.5.4 Rancimat Method 185
5.5.5 Viscometry 186
5.6 Conclusion 186
References 187
6 Commercial Technologies for Biodiesel Production 195
Chikati Roick, Leonard Okonye, Nkazi Diankanua
and Gorimbo Joshua
Abbreviation 196
Contents ix

6.2 Biodiesel Production 197
6.3 Technologies Used for Biodiesel Production 198
6.3.1 Chemical Reaction (Transesterification) 199
6.3.2 Thermochemical Conversion 199
6.3.3 Biomechanical Conversion 201
6.3.4 Direct Combustion 201
6.4 Other Technologies in Use for Biodiesel Production 201
6.5 Feedstock Requirement 203
6.6 Some Problems Facing Commercialization of Biodiesel
in Africa 203
6.7 Case Studies/Current Status and Future Potential 204
6.8 Conclusions 207
Acknowledgments 208
References 208
7 A Global Scenario of Sustainable Technologies and Progress
in a Biodiesel Production 215
M. B. Kumbhar, P. E. Lokhande,, U. S. Chavan
and V.G. Salunkhe
7.2 Current Status of Feedstock for Biodiesel Production
Technology 218
7.3 Scenario of Biodiesel in Combustion Engine 222
7.4 Biodiesel Production Technologies 223
7.4.1 Direct Blending 223
7.4.2 Pyrolysis 224
7.4.3 Microemulsification 225
7.4.4 Transesterification 226
7.5 Microwave-Mediated Transesterification 227
7.6 Ultrasound-Mediated Transesterification 229
7.7 Catalysis in Biodiesel Production 230
7.7.1 Homogeneous Catalysts 230
7.7.2 Heterogeneous Catalysts 231
7.7.3 Heterogeneous Nanocatalysts 232
7.7.4 Supercritical Fluids 232
7.7.5 Biocatalysts 232
7.8 The Concept of Biorefinery 234
7.9 Summary and Outlook 236
7.10 Conclusion 237
References 237
x Contents
8 Biodiesel Production Technologies 241

Moina Athar and Sadaf Zaidi
8.2 Biodiesel Feedstocks 242
8.2.1 Selection of Feedstocks 243
8.3 Biodiesel Production Technologies 248
8.3.1 Pyrolysis 248
8.3.2 Dilution 249
8.3.3 Micro-Emulsion 249
8.3.4 Transesterification 249
8.3.4.1 Homogeneously Catalyzed
Transesterification Processes 250
8.3.4.2 Heterogeneously Catalyzed
Transesterification Processes 252
8.3.4.3 Enzymatic Catalyzed Transesterification
Processes 252
8.4 Intensification Techniques for Biodiesel Production 253
8.4.1 Supercritical Alcohol Method 253
8.4.2 Microwave Heating 253
8.4.3 Ultrasonic Irradiation 255
8.4.4 Co-Solvent Method 256
8.5 Other Techniques of Biodiesel Production 256
References 257
9 Methods for Biodiesel Production 267
M.Gul, M.A. Mujtaba, H.H. Masjuki, M.A. Kalam
and N.W.M. Zulkifli
9.1 Selection of Feedstock for Biodiesel 267
9.1.1 First-Generation Feedstock 268
9.1.2 Second-Generation Feedstock 268
9.1.3 Third-Generation Feedstock 269
9.2 Methods for Biodiesel Production 269
9.2.1 Dilution With Hydrocarbons Blending 269
9.2.2 Micro-Emulsion 269
9.2.3 Pyrolysis (Thermal Cracking) 270
9.2.4 Transesterification (Alcoholysis) 271
9.2.4.1 In Situ Transesterification
(Reactive Extraction) 271
9.2.4.2 Conventional Transesterification 272
9.2.4.3 Microwave/Ultrasound-Assisted
Transesterification 278
Contents xi
9.2.4.4 Variables Affecting Transesterification

Reaction 278
References 282
10 Non-Edible Feedstock for Biodiesel Production 285
Chikati Roick, Kabir Opeyemi Otun, Nkazi Diankanua
and Gorimbo Joshua
List of Abbreviations 286
10.2 Reports Relevant to Global Warming
and Renewable Energy 287
10.3 Biofuels as an Alternative Energy Source 288
10.3.1 First-Generation Biofuels 288
10.3.2 Second-Generation Biofuels 289
10.3.3 Third-Generation Biofuels 290
10.4 Benefits of Using Biodiesel 290
10.5 Technologies of Biodiesel Production From Non-Edible
Feedstock 291
10.6 Biodiesel Production by Transesterification 292
10.7 Non-Edible Feedstocks for Biodiesel Production 295
10.7.1 Non-Edible Vegetable Oils 296
10.7.2 Waste Cooking Oil 297
10.7.3 Algal Oil 298
10.7.4 Waste Animal Fat/Oil 299
10.8 Fuel Properties of Biodiesel Obtained From Non-Edible
Feedstock 299
10.9 Advantages of Non-Edible Feedstocks 302
10.10 Economic Importance of Biodiesel Production 302
10.11 Conclusions 303
Acknowledgments 303
References 304
11 Oleochemical Resources for Biodiesel Production 311
Gayathri R., Ranjitha J. and Vijayalakshmi Shankar
11.2 Definition of Oleochemicals 312
11.3 Oleochemical Types 313
11.4 Production of Biodiesel 315
11.5 Types of Feedstocks 317
11.5.1 Non-Edible Feedstocks 317
11.5.2 Non-Edible Vegetable Oil 317
xii Contents
11.5.3 Tall Oil 318

11.5.4 Waste Cooking Oils 318
11.5.5 Animal Fats 318
11.5.6 Chicken Fat 319
11.5.7 Lard 319
11.5.8 Tallow 320
11.5.9 Leather Industry Solid Waste Fat 321
11.5.10 Fish Oil 322
11.6 Uses of Oleochemicals 322
11.6.1 Polymer Applications 322
11.6.2 Application of Plant Oil as a Substitute
for Petro-Diesel 323
11.6.3 Used as Surfactants 323
11.6.4 Oleochemicals Used in Pesticide 324
11.6.5 Oleochemicals Used in Spray Adjuvants
and Solvents 324
11.7 Methyl Ester or Biodiesel Production 324
11.7.1 Palm Oil 326
11.7.2 Sunflower Oil 326
11.7.3 ME From AFW 327
11.8 Parameters Affecting the Yield of Biodiesel 327
11.8.1 Reaction Conditions 327
11.8.2 Catalyst 327
11.8.2.1 Alkali Catalyst 327
11.8.2.2 Acid Catalyst 329
11.8.2.3 Biocatalyst 329
11.8.2.4 Heterogeneous Catalyst 329
11.8.2.5 ME Conversion by Supercritical
Method 329
11.8.3 Properties of Feedstock 330
11.8.3.1 Composition of FA 330
11.8.3.2 FFA 330
11.8.3.3 Heat 330
11.8.3.4 Presence of Unwanted Materials 330
11.8.3.5 Titer 332
11.8.4 Characteristic of Feedstock 332
11.9 Optimization of Reactions Conditions for High Yield
and Quality of Biodiesel 332
11.9.1 Pre-Treatment of Feedstock 332
11.9.1.1 Elimination of Water 332
11.9.1.2 Elimination of Insoluble Impurities 332
Contents xiii
11.9.1.3 Elimination of Unsaponifiables 333

11.9.2 Characterization and Selection of Feedstocks 333
11.9.3 Selection of Reaction Conditions 333
11.10 Oil Recovery 333
11.10.1 Alkaline Flooding Method 333
11.10.2 Additives 334
11.11 Quality Improvement of Biodiesel 334
11.11.1 Additives for Improving Combustion Ability 334
11.11.2 Additives for Enhancing the Octane Number 334
11.11.3 Additives for Improving the Stability 334
11.11.4 Additives to Enhance Cold Flow Property 334
11.11.5 Additives to Enhance Lubricity 335
11.11.6 Additives to Enhance Cetane Number 335
11.12 Conclusion 335
Abbreviations 335
References 336
12 Overview on Different Reactors for Biodiesel Production 341
V. C. Akubude, K.F. Jaiyeoba, T.F Oyewusi, E.C. Abbah,
J.A. Oyedokun and V.C. Okafor
12.2 Biodiesel Production Reactors 342
12.2.1 Batch Reactor 343
12.2.2 Continuous Stirred Tank Reactor 344
12.2.3 Fixed Bed Reactor 346
12.2.4 Bubble Column Reactor 347
12.2.5 Reactive Distillation Column 349
12.2.6 Hybrid Catalytic Plasma Reactor 350
12.2.7 Microreactors Technology 350
12.2.8 Oscillatory Flow Reactors 353
12.2.9 Other Novel Reactors 353
12.3 Future Prospects 354
12.4 Conclusion 354
References 354
13 Patents on Biodiesel 361
Azira Abdul Razak, Mohamad Azuwa Mohamed
and Darfizzi Derawi
13.2 Generation of Biodiesel 362
13.3 Development of Catalyst 363
xiv Contents
13.3.1 Homogeneous Catalyst 364

13.3.2 Heterogeneous Catalyst 364
13.4 Method Producing Biodiesel 365
13.4.1 Pre-Treatment Process 365
13.4.2 Direct Use and Blending of Oils 366
13.4.3 Esterification of FFA 366
13.4.4 Transesterification of TAG 367
13.4.5 Pyrolysis 368
13.5 Reactor’s Technology for Biodiesel Production 369
13.5.1 Continuous Stirred Tank Reactor 370
13.5.2 Fixed Bed Reactor 370
13.5.3 Micro-Mixer Reactor 371
13.6 Conclusion 372
References 372
14 Reactions of Carboxylic Acids With an Alcohol Over
Acid Materials 377
J.E. Castanheiro
14.2 Zeolites 378
14.3 SO3H as Catalyst 379
14.4 Metal Oxides 380
14.5 Heteropolyacids 382
14.6 Other Materials 384
References 385
15 Biodiesel Production From Non-Edible and Waste
Lipid Sources 389
Opeoluwa O. Fasanya, Aishat A. Osigbesan
and Onoriode P. Avbenake
15.2 Non-Edible Plant-Based Oils 394
15.2.1 Jatropha curcas 394
15.2.2 Calophyllum inophyllum 397
15.2.3 Mesua ferrea 397
15.2.4 Jojoba Oil 398
15.2.5 Azadirachta indica 398
15.2.6 Rubber Seed Oil 399
15.2.7 Ricinus communis as Feedstock (Castor Oil) 402
15.2.8 Other Non-Edible Oils 403
Contents xv
15.3 Waste Animal Fats 404

15.4 Expired and Waste Cooking Oils 405
15.5 Algae/Microalgae 406
15.6 Insects as Biodiesel Feedstock 411
15.7 Deacidification 414
15.8 Other Technologies 414
15.9 Conclusion 415
References 415
16 Microalgae for Biodiesel Production 429
Charles Oluwaseun Adetunji, Victoria Olaide Adenigba,
Devarajan Thangadura and Mohd Imran Ahamed
16.2 Physicochemical Properties of Biodiesel From Microalgae 431
16.3 Genetic Engineering/Techniques Enhancing Biodiesel
Production 432
16.4 Nanotechnology in Microalgae Biodiesel Production 434
16.5 Specific Examples of Biodiesel Production From
Microalgae 434
16.6 Methodology Involved in the Extraction of Algae 438
16.6.1 Chemical Solvents Extraction 439
16.6.2 Extraction by Supercritical Carbon Dioxide 439
16.6.3 Extraction Using Biochemical Techniques 439
16.6.4 Extraction Involving Direct Transesterification 440
16.6.5 Extraction Using Transesterification Techniques 440
16.7 Conclusion and Future Recommendation to Knowledge 440
References 441
17 Biodiesel Production Methods and Feedstocks 447
Setareh Heidari and David A. Wood
17.2 Biofuel Classification in Terms of Origin and
Technological Conversion of Raw Materials 449
17.3 Techniques Capable of Producing Biodiesel
on Commercial Scales 451
17.3.1 Direct and Blending Methods With the Aim
of Biodiesel Generation 452
17.3.2 Microemulsion Methods 452
17.3.3 Pyrolysis Methods 453
17.3.4 Transesterification Methods 453
17.4 Influential Parameters on Biodiesel Production 454
xvi Contents
17.4.1 The Choice of Transesterification Catalysts 454

17.4.2 Effects of Catalyst Characteristics on Biodiesel
Production Efficiency 454
17.5 Biodiesel Markets and Economic Considerations 455
17.6 Challenges Confronting Biodiesel Uptake 456
17.7 Corrosion and Quality Monitoring Issues for Biodiesel 457
References 458
18 Application of Nanoparticles for the Enhanced Production
of Biodiesel 465
Muhammad Hilman Mustapha, Akhsan Kamil Azizi,
Wan Nur Aini Wan Mokhtar and Mohamad Azuwa Mohamed
18.2 Solid Nanoparticles 466
18.3 Nanobioparticles/Nanobiocatalyst 471
18.4 Magnetic Nanoparticles 473
18.5 How Nanoparticles Enhanced Biodiesel Production? 475
18.6 Conclusion 477
References 477
Index 481
Preface
Energy technologies have attracted great attention due to the fast develop-
ment of sustainable energy. Biodiesel technologies have been identified as
the sustainable route through which overdependence on fossil fuels can be
reduced. Biodiesel has played a key role in handling the growing challenge
of a global climate change policy. Biodiesel is defined as the monoalkyl
esters of vegetable oils or animal fats. Biodiesel is a cost-effective, renew-
able, and sustainable fuel that can be made from vegetable oils and ani-
mal fats. Compared to petroleum-based diesel, biodiesel would offer a
non-toxicity, biodegradability, improved air quality and positive impact
on the environment, energy security, safe-to-handle, store and transport,
and so on. Biodiesels have been used as a replacement of petroleum diesel
in transport vehicles, heavy-duty trucks, locomotives, heat oils, hydrogen
production, electricity generators, agriculture, mining, construction, and
forestry equipment.
This book describes a comprehensive overview, covering a broad range
of topics on biodiesel technologies and allied applications. Chapters cover
history, properties, resources, fabrication methods, parameters, formula-
tions, reactors, catalysis, transformations, analysis, in situ spectroscopies,
key issues and applications of biodiesel technology. It also includes bio-
diesel methods, extraction strategies, biowaste utilization, oleochemical
resources, non-edible feedstocks, heterogeneous catalysts, patents, and
case-studies. Progress, challenges, future directions, and state-of-the-art
biodiesel commercial technologies are discussed in detail. This book is
an invaluable resource guide for professionals, faculty, students, chemical
engineers, biotechnologists, and environmentalists in these research and
development areas. This book includes the eighteen chapters and the sum-
maries are given as follows.
Chapter 1 details the biocatalytic production of biodiesel. Microbial
enzymes such as lipases act as biocatalysts in the transesterification pro-
cess of biodiesel production. Suitable and cost-effective feedstocks or
xvii
xviii Preface
substrates for biodiesel production including their percentage yields are

discussed. Factors that affect the enzymatic transesterification reaction are
also explained.
Chapter 2 addresses ultrasonic energy which can increase the interface
area while creating a thermal effect in heterogeneous biodiesel production
process to result in higher biodiesel yield. Fundamental understanding of
the improved reactant-catalyst interaction, the nature of the thermal effect,
favorable process behaviors, reaction kinetic, as well as the effect on bio-
diesel quality is particularly addressed.
Chapter 3 is about the study of different types of catalysts used for
biodiesel production. The classification of catalysts, advantages, and lim-
itations, along with their mechanism, is explained. The heterogeneous
catalysts’ synthetic methods and immobilization of biocatalyst are also dis-
cussed in detail.
Chapter 4 discusses various methods used to produce value-added
chemicals from biodiesel-derived glycerol. The main focus being is given
to hydrogenolysis as a transformative process to selectively produce 1,2-
propanediol and the advancements in biodiesel technologies. Furthermore,
knowledge gaps are highlighted based on extensive literature research on
the subject.
Chapter 5 discusses various techniques of synthesizing biodiesel and
review of various existing analytical technologies for characterization of
biodiesel. The chapter focuses on the current status of biodiesel in India,
i.e., using non-edible sources and future feasibility of developing new
methods of characterization to reduce the cost of biodiesel production.
Chapter 6 examines various established technologies available for the
production of biodiesel, viz., chemical reaction, direct combustion, ther-
mochemical conversion, and biomechanical conversion. Each technology
is apportioned to a certain type of feedstock. Case studies, current sta-
tus, and future potential of commercialization of biodiesel production in
Africa are also discussed.
There is a huge demand for sustainable biofuel production in coming
decades. The key challenges for biodiesel production are high FFA with the
desired level of yield, stability, optimized and flexible production, commer-
cialization of feedstock and environmentally friendly cycle. The collective
effort and commitment of research survey regard feedstocks and commer-
cialization of technology around the globe towards sustainable energy are
expressed in terms of accelerating the biofuel economy in Chapter 7.
Chapter 8 provides an overview of the available feedstocks, pro-
duction methods, and the benefits and constraints of using homoge-
neous, heterogeneous, and enzymatic catalysts for biodiesel. Some latest
Preface xix
intensification techniques to manage mass transfer restrictions of oil and

alcohol phases along with some production cost reduction measures are
also highlighted.
Chapter 9 discusses different types of feedstocks used for synthesizing
biodiesel and feedstock selection criteria. Moreover, all biodiesel produc-
tion methods (i.e., dilution with hydrocarbons blending, micro-emulsion,
pyrolysis, and transesterification) are also described in detail with their
advantages and disadvantages. The major focus is given to the various
transesterification methods. Production methods also include experimen-
tal setup layouts, all process parameters, reaction conditions, the latest
advancement in reaction processes, and their effects on biodiesel yield.
Chapter 10 reviews the potential use of non-edible feedstocks in the
production of biodiesel. Special attention is given to the types of feedstocks
available and their production pathways to biodiesel. The state-of-the-art
technology, the properties of the fuel produced, and the environmental
concerns of biofuels are also discussed.
Chapter 11 discusses the various types of oleochemicals and their usage.
Optimization and production of biodiesel derived from oleochemicals
and their properties are also discussed. The primary focus is given for the
advantage of oleochemicals to be used as a potential feedstock for biodiesel
production from the available literature.
Chapter 12 provides details about the different configurations of reac-
tors used in biodiesel production. There are two types, namely, batch and
continuous reactors. Recently, other improved configurations like micro-
reactors have emerged. This chapter also discusses the merits and demerits
of these reactors.
Chapter 13 highlights and discusses the international patents on bio-
diesel applications. This chapter reviews the recent patents on the generation
of biodiesel which depends on the feedstock used, catalysts development,
the latest method for biodiesel production, and reactor technology for the
biodiesel production.
Chapter 14 overviews different reactions between a carboxylic acid
(fatty acids) and alcohol (methanol and ethanol) over heterogeneous cata-
lysts, an important step in biodiesel production. The nature of solid materi-
als, like zeolites, heteropolyacids, materials with sulfonic groups, inorganic
mixed oxides, and clays towards biodiesel production is discussed.
Chapter 15 sheds light on inedible feedstock that could be utilized for
biodiesel production. Plant-based and non-plant feedstock are discussed.
The waste lipid sources which are unfit for consumption are also high-
lighted. The chemical composition, economic viability, and sustainability
of some of these feedstocks are equally explored.
xx Preface
Chapter 16 provides detailed information on the fabrication of biodiesel

from microalgae. Specific information on the physical properties, amount
of biodiesel production, and level of transesterification of biodiesel are dis-
cussed. The application of photobioreactors for the production of biodiesel
with the special consideration of several factors such as flow rate, tempera-
ture, light intensity, CO2 concentration, and time is highlighted. Several
techniques for the extraction of biodiesel such as supercritical CO2, physi-
cochemical, direct transesterification, chemical solvents, and biochemical
respectively are highlighted.
Chapter 17 discusses the biofuel classification in terms of origin and
technological conversion of raw materials. Techniques capable of produc-
ing biodiesel on commercial scales are also presented. Furthermore, influ-
ential parameters and their roles in biodiesel production are elaborately
covered. Finally, challenges and limitations confronting biodiesel uptake
are presented.
Chapter 18 mainly explicates the application of nanoparticle catalysis
for the high production of biodiesel. In particular, various types of catalyst
nanoparticles with different synthesis strategy and their roles in enhancing
the biodiesel production are discussed.
Inamuddin, Mohd Imran Ahamed, Rajender Boddula

and Mashallah Rezakazemi
1
Biocatalytic Processes for
Biodiesel Production
Ubaid Mehmood1, Faizan Muneer2, Muhammad Riaz3, Saba Sarfraz4
and Habibullah Nadeem2*
College of Chemistry, Chemical Engineering and Biotechnology,

1
Donghua University, China

2
Department of Bioinformatics and Biotechnology, Government College University
Faisalabad, Pakistan
3
Department of Food Sciences, University College of Agriculture, Bahauddin
Zakariya University, Multan, Pakistan
4
Department of Chemistry, Government College Women University Faisalabad,
Faisalabad, Pakistan
Abstract
Enzymes such as microbial lipases can be effectively used as biocatalysts for bio-
diesel production in a sustainable manner. Biocatalytic processes to produce bio-
diesel or biofuel is the need of time to reduce the emission of greenhouse gases
produced from conventional diesel or fossil fuels. Lipases with excellent biochem-
ical and physiological properties are most commonly used to catalyze the trans-
esterification process for biodiesel production. Lipases obtained from microbes
such as bacteria and fungi produce 70%–95% ethanol and methanol. Biodiesel is
usually composed of fatty acid alkyl esters which are mono-alkyl esters of either
fatty acid methyl esters or fatty acid ethyl esters depending upon the alcohol (acyl
acceptor) being used in the reaction. Factors such as bioreactor type, acyl accep-
tor, temperature, and glycerol can affect the enzymatic transesterification reaction.
Recombinant enzymes such as recombinant lipases can be employed to obtain
higher percentage of biodiesel due to their high specificity and biocatalytic activity
for different substrates used for biodiesel production.
Keywords: Lipases, biodiesel, biocatalysis, biofuels, Novozyme, free fatty acids,
ethyl acceptors
*Corresponding author: habibullah@gcuf.edu.pk
Inamuddin, Mohd Imran Ahamed, Rajender Boddula, and Mashallah Rezakazemi (eds.) Biodiesel
Technology and Applications, (1–58) © 2021 Scrivener Publishing LLC
1
2 Biodiesel Technology and Applications
1.1 Introduction and Background

Biofuels are crucial for the conservation of our natural environment and
the climate. Biofuel such as bioethanol can be used for energy generation
purposes which are currently being produced by fossil fuels such as petrol,
diesel, and kerosene oil [1]. Being non-renewable energy sources, fossil fuels
will not only deplete from the planet earth but will also leave a long-term
impact on the globe both in terms of economy and climate change. Apart
from being limited natural fuel reserves, there are countless reasons available
that justify the need of natural and eco-friendly energy sources such as bio-
fuels. Transportation, power generation, and house hold appliances use fuels
directly or indirectly and for that purpose we are almost dependent on fossil
fuels [2]. If efficient and robust methods and technologies are not worked
out, we might come to a permanent stand still condition in the future when
all our natural fossil fuel reserves will be vanished. The use of fossil fuel pro-
duces gases such as carbon dioxide (CO2), carbon monoxide (CO), sulfur
oxides (SOx), and nitrogen oxides (NOx) which are unhealthy for human
beings causing health issues such as asthma, skin diseases, and even cancers
[3]. These by-products of fuel consumption affect not only human but also
animals and plants on a broader view. Plant production and growth rates are
highly effected by the changing environmental and climatic conditions due
to heavy use of fossil fuels and their derivatives such as plastics [4].
Vehicular CO2 emission in the past decade was 20%, and it is estimated
that by 2030, it will reach up to 80%. Liquide biofuels got prominence with
the automobile industry. Peanut oil was used to make biofuel, i.e., biodiesel by
Rudolph Diesel in 1898. Henri Ford who was the founder of Ford Company
an automobile industry was also convinced by the idea of using biofuels in
his automobile. During World War-II, Germany used biomass-based fuels for
their machines which is the evidence of its use back in 1940s. The utilization
of biofuels was presented, but after two major oil crises, first was in 1973 and
second in 1978, and brought back its importance to public again. Biofuels that
are produced using a large number of biomass sources are a sustainable solu-
tion for the environment and biosphere conservation. Being renewable energy
resources and eco-friendly to the environment and life on earth, these are
highly desirable products produced from renewable biomass substrates [5].
Currently, biofuels from various agricultural sources such as soybean oil,
rapeseed oil, recycled waste oils, and waste plant residues are being studied.
Depending on the feedstock type, processing technology and their devel-
opmental level, biofuels can be classified into first-, second-, and third-
generation biofuels. Biofuels produced directly from edible feedstock such
Biocatalytic Processes 3
as crops, sugars, and edible oil using conventional techniques are considered
as first-generation biofuels [6]. Non-edible feedstock such as waste crop res-
idues like lignocelluloses and waste vegetable oils are required to produce
second-generation biofuels which are comparatively economical and more
sustainable as there is no food versus fuel competition. Highly advanced
methods are used to produce second-generation biofuels which has certainly
less flaws and ultimately improved to get greater yield [7]. We are currently in
the phase of second-generation biofuels. Most of the processing techniques
for second-generation biofuel production are not available at commercial
level. One must think that the land dedicated for edible feedstock/crops will
be compromised if we start cultivating non-edible crops in that land. Marginal
lands can be used for the cultivation of grasses and other plants that are not
a food for human or nor a fodder for animals on a larger scale. These plants
or marginal grasses can be used for the production of second-generation bio-
fuels. There have been a lot of research investigations to produce biodiesel
using non-edible plant oils such as keranja oil, Jatropha curcas oil, tobacco oil,
Calophyllum inophyllum oil, and castor oil [8]. Jatropha is an effective source
of biodiesel production because of 30%–50% oil contents in its seeds [9]. The
actual precursors of most of the second-generation biodiesel production are
waste oils either in the form of waste cooking or industrial oils or animal fats.
The utilization of these waste materials as feed stock helps in managing and
disposing of waste material, which is one of the biggest problem for earth, for
the benefit of environment [10]. In order to comprehend different biofuels,
we can categorize them into four types which include biodiesel, bioalcohol
(biomethanol, bioethanol, biobutanol), biogas, and biohydrogen. The most
widely used biofuels are liquid biofuels such as biodiesel and bioethanol.
Biofuels can be blended with other petro-based fuels in order to manage and
enhance quality and quantity of fuel. Biofuel production includes chemical,
thermal, and enzymatic methods. Among all methods, the most effective way
to produce biofuels is through enzymes or biocatalysts [11]. Enzymes are
becoming the focus of research to produce biofuels because of their advan-
tages over other biofuel production techniques [12]. In this chapter, we dis-
cuss biodiesel production using biocatalytic processes and methods where
different microbial enzymes (obtained from microorganisms) are used.
1.2 Importance of Biodiesel Over Conventional

Diesel Fuel
Chemically, biodiesel is composed of fatty acid alkyl esters (FAAEs) which
are mono-alkyl esters of either fatty acid methyl esters (FAME) or fatty
acid ethyl esters (FAEE) depending upon the alcohol (acyl acceptor) being
used in the reaction [10]. Rudolf Diesel, the inventor of diesel engine, first
used biodiesel in 1900 but that was highly viscous so that engine could
not run effectively for a longer time [13]. Biodiesel is very suitable alter-
native to diesel fuel because of its remarkable properties and advantages,
i.e., biodiesel carries 4.5 times greater energy than fossil fuel [14] and sim-
ilar in chemical structure and energy content to conventional diesel [15].
It reduces approximately 85% carcinogenic compounds emission that is
why it is very less toxic than conventional diesel fuel, free of sulfur, free of
polycyclic aromatic hydrocarbons and metals, biodegradable, high cetane
number (CN), and flash point [16]. It has the potential to reduce pollutants
and emission of greenhouse gases [17] and is 66% more efficient lubri-
cating agent than petro-diesel, which enhances life and performance of
engine [18]. Blending of biodiesel with petro-diesel fuel that can affect
important properties of fuel such as flash point, CN, kinematic viscosity,
and lubricity is enhanced. It also decreases exhaust emissions and heat of
combustion [19]. The largest biodiesel producer is EU (European Union)
and biodiesel accounts 80% of the overall transport fuel in EU [20–22].
Biodiesel produced from different resources will have different composi-
tion and properties, but it must fulfill the standards and requirements of
international standards of American society for testing materials and EU
standards for biodiesel. Biodiesel has lots of applications such as it can be
used as a fuel for aviation purposes [20], for electricity production using
generators [21, 22] and in diesel fueled marine engines, because of its non-
toxic and biodegradable properties environmental impacts on engines can
be reduced. Alcohol type, quality of substrate that is to be converted, cata-
lyst used, temperature of the reaction, and alcohol-to-oil molar ratio deter-
mine the performance of biodiesel production [23–25].
1.3 Substrates for Biodiesel Production

Biodiesel feedstock accounts for 60%–80% of the total cost; therefore,
appropriate feedstock is required for economically valuable production
of biodiesel [26]. In order to obtain economically beneficial and sustain-
able biodiesel, feedstock must be easily available, cheap, and sustainable.
Feedstock is selected on the basis of biodiesel production that must be
compatible to chemical composition and properties of feedstock to be
used, percentage per dry biomass, agricultural potential, yield per hect-
are, and geographical region of that feedstock [27]. For example, soybean
oil, palm oil, coconut oil, and rapeseed oil are mainly used as feedstock in
US, tropical countries like Indonesia, coastal areas, and European coun-
tries, respectively. Cultivation and climate conditions of the feedstock pro-
duction area are also considered for its selection [28]. Depending on the
nature, there are two types of feedstock for biodiesel production. First is the
lipid raw material and second includes alcohol feedstock. Lipid sources can
be divided into three categories, i.e., oils derived from plant sources (edible
and non-edible oils), waste oils (waste cooking oils, industrial wastewater,
lard, yellow grease, and animal fats), and oils from oleaginous microorgan-
isms such as bacteria, fungi, and microalgae [29]. Properties of biodiesel
like cold filter plugging point and oxidation stability are determined from
the feedstock used for production. Feedstock properties like moisture con-
tent, impurities, content, and composition of free fatty acids (FFAs) affect
the performance of engine [27, 28]. Composition of fats and oils including
monoglycerides, diglycerides, and triglycerides are used for biodiesel pro-
duction. Utilization of edible plant oils as feedstock is an expensive way for
biodiesel production that leads to imbalance in food market and indus-
try. It is also associated with some environmental problems like disruption
of vital soil resources and deforestation due to mass propagation [29]. In
order to solve problems linked with edible plant oils, the best alternate is
the production of second-generation biodiesel which is produced by using
non-edible (inedible) feedstock which are more favorable than edible oils
due to reduction in cost and waste pollution, lower aromatic, sulfur con-
tents, and high calorific value [8]. Inedible oils involve inedible plant oils,
industrial waste, cooking oils, animal fats, and microalgal oils. Inedible oil
producing plants have certain remarkable features that make them favor-
able to use, for example, they can be managed to grow in arid and semi-arid
conditions and they do not require fertilizers and moisture for growth [24].
Repeated use of fried vegetable oils at high temperature leads to the
production of waste cooking oils. Moreover, chemical composition of
waste cooking oil is totally dependent on the oil from which it is derived.
Hydrogenation, oxidation, and polymerization are the main chemical
reactions that lead to production of very toxic and detrimental compounds
for consumption. Fatty acid content of these oils lies in the range of 0.5%
to 15% which is very much higher than refined oil having fatty acid con-
tent less than 0.5%. The waste cooking oil is known as yellow grease if the
fatty acid content is less than 15% and it is called low value brown grease
if the fatty acid content is higher than 15% [28]. Animal waste products
like lard, tallow, animal fat, poultry fat, fish oil, and pork fat are also very
effective feedstock for biodiesel production [30, 31]. Animal-based bio-
diesel is a good lubricating agent and has high percentage of saturated
fats which decreases sedimentation risk and low temperature fluidity.
Moreover, it increases oxidative stability and cold filter plugging point of

biodiesel which are the characteristics of good quality biodiesel. Utilizing
these waste materials is an effective solution to encounter waste disposal.
Apart from all these mentioned advantages of non-edible or waste oils,
there are also some shortcomings or disadvantages, for example, low oil
yield, higher carbon residue, unsaturated fatty acid content, and low vola-
tility [29]. In some cases, large plantation land for inedible oils is required
compared to edible ones, e.g., Pongamia pinnata and Jatropha has 2–50
folds less oil yield per hectare than palm oil so that is why they require
much area to meet the demand [31]. Because of the drawbacks associated
with second-generation biodiesel, scientists are looking for more efficient
methods for biodiesel production. Biodiesel production using oleaginous
microorganisms like bacteria, algae, microalgae, and fungi are considered
as the future of biodiesel production that can meet global biodiesel demand
for transportation fuels and other energy consuming applications [32].
Microbial oils are better than other plant oils because of their short life
cycle and rapid growth, less requirement of space, labor, and easier scaling
[33–35]. Microalgae as a feedstock is very effective because of its enormous
advantages like they have high oil yield, can grow in salty and waste waters,
use of non-arable land, and growth in 24 hours so multiple harvesting in a
year is possible. If we give land area for microalgal growth then according
to an estimate, only 2% of the US cropping land is enough for meeting
1/3 demand of US transportation fuels and less than 5% land is required
to completely replace all transportation fuels [36–38]. Moreover, dry algal
biomass can accumulate more than 80% oil without water and they have
a capacity to produce oil yield 250 times greater than soybean water free
oil [35]. Some examples of microalgae used for biodiesel production are
Botryococcus sp., Cylindrotheca sp., Schizochytrium sp., Chlorella sp., and
Nitzschia sp.
1.4 Methods in Biodiesel Production

There can be many ways for biodiesel production but esterification and
transesterification are the two most widely used methods. Esterification is
the reaction of FFAs and alcohol to make FAAEs and water is released, while
transesterification is the reaction of triglycerides or triacylglycerols (TAGs)
with alcohol to make FAAE and glycerol is produced as by-product [9].
Transesterification is slower than esterification process because of its multi-
ple steps or reactions. It is a three-step process to convert TAGs into FAAE.
In the first step, TAG reacts with one molecule of alcohol to produce one
molecule of FAAE and diacylglycerol (DAG). In second step, DAG further

reacts again with one molecule of alcohol to produce one molecule of FAAE
and monoacylglycerol and in the last step monoacylglycerol is converted
into one molecule of glycerol and FAAE after reacting with an alcohol mole-
cule. In each of these three steps, FAAEs are produced and in total one mol-
ecule of TAG and three molecules of alcohol are consumed to produce three
molecules of FAAE and one molecule of glycerol [6–10]. Transesterification
is a reversible reaction, and in order to make the reaction go forward to
produce more biodiesel, we have to supply alcohol in large excess so that the
reaction equilibrium shifts toward the product [36, 37].
1.5 Types of Catalysts Involved in Biodiesel

Production
Biodiesel production process is carried by either catalytic or non-catalytic
methods. Non-catalytic methods include use of alcohols or supercriti-
cal fluids or ionic liquids in the reaction system to produce biodiesel but
mostly catalytic methods have been used for last 2 or 3 decades because of
their advantages over non-catalytic methods [38]. Catalytic methods can
be categorized into chemical homogenous catalysts, solid heterogenous
catalysts, and biocatalysts.
1.5.1 Chemical Homogenous Catalysts

Chemical homogenous catalysts include combination of base and acid
catalysts. NaOH, KOH, and methoxides are the base catalysts while HCl
and H2SO4 are the acid catalysts [39]. Acid catalysts are mostly used to
overcome the problem of FFAs in the reaction system but the rate of trans
esterification by acid catalyst is slower than alkaline or base catalysts [8].
Chemical catalytic processes either alkaline or acid catalysis both have sev-
eral disadvantages. Alkaline catalysis provides high conversion of triacyl
glycerol into the alkyl esters in a very short time but it has many draw-
backs. Alkaline catalysis is very prone to FFA concentration (>2.5%) in the
reaction system because high FFA concentration results in saponification
reaction producing soaps and leads to loss in enzymatic activity and makes
difficult to separate transesterification by-product, i.e., glycerol from bio-
diesel. Hence, biodiesel yield decreases. Moreover, it needs high energy
requirement [40]. To counter FFA problem, acid catalysts are used, e.g.,
sulfuric acid but it also causes some technical problems regarding separa-
tion and purification of glycerol. Moreover, acid catalysis is a slow process
compared to alkaline process. Reactors, pipelines, and other equipment are

badly affected by acid catalysts because of their corrosive nature that can
increase the cost of biodiesel production [41].
1.5.2 Solid Heterogeneous Catalysts

Solid heterogeneous catalysts include acid heterogenous catalysts and base
heterogenous catalysts. Solid acid heterogenous catalysts include hetero-
polyacid catalysts (HPAs), mineral salts, acids, and cationic exchange res-
ins. Among these, titanium oxide, sulfonic ion exchange resin, tin oxide,
sulfonated carbon-based catalysts, zirconium oxide, zeolites, and sulfonic
modified mesostructured silica are the main acid heterogeneous catalysts.
Solid base heterogeneous catalysts have been categorized as mixed metal
oxides, supported alkaline earth metals, single metal oxides, and nano-
oxides. Among these, the most studied are magnesium oxide, calcium
oxide, and strontium oxide [44, 45].
1.5.3 Biocatalysts
Biocatalysts include enzymes especially lipases which are very popular in bio-
diesel production [43]. Enzymatic biodiesel production method diminishes
problems associated with alkali and acid catalyzed methods. Use of enzyme
catalysts has several economic and environmental advantages over chemi-
cal biodiesel production processes. Advantages of enzyme catalysis include
production of pure and high market value glycerol, minor, or no waste water
generation that is why treatment of waste water is not required, mild reaction
conditions are required, no soap formation because enzymes can esterify low
quality feedstock having high concentration of FFA that is why this method
is insensitive to feedstock concentration. Enzymatic biodiesel production is
simple so energy consumption is very low, enzymes can be reused because of
their easy separation from the reaction mixture, and overall chance of con-
tamination is lower than other transesterification methods [13].
1.6 Factors Affecting Enzymatic Transesterification

Reaction
There are a lot of factors effecting enzymatic transesterification reaction
such as source of enzyme, its type, preparation method, applying tech-
nique, its dosage, activity, and life time. Apart from these enzymes related
factors, there are also some other factors which affect transesterification
reaction, e.g., feedstock type and its quality, type of alcohol as acyl accep-
tor, reaction pH, presence or absence of solvent, type of solvent, reaction
temperature, alcohol-to-oil molar ratio [46].
1.6.1 Effect of Water in Enzyme Catalyzed Transesterification

Presence of water is not only required for chemically catalyzed biodiesel
production but also very much required for enzymatic biodiesel produc-
tion. It helps in maintaining enzyme structural confirmation and stabil-
ity so it directly affects activity of enzyme. Oil-water interface is required
for enzyme-substrate complex to proceed and water helps to increase this
interfacial area [44]. So, without water, transesterification is not possible
and absence of water can lead to permanent or temporal changes in protein
(enzyme) structure. If water content is minimal, then increase in water con-
centration moves the reaction equilibrium toward more hydrolysis. Thus, it
enhances reaction rate by providing greater stability to enzyme [45]. Excess
of water content also has some negative effects on the reaction as well as on
enzyme. Excess water content can be accumulated in the reaction medium
and within enzyme active site, that leads to decrease the reaction rate as
well as its alkyl ester yield [46]. So, concentration of water should be opti-
mally perfect in order to gain maximum benefit from it. Every enzyme has
its specific water content requirement, i.e., optimal water requirement, at
which that particular enzyme performs its best [47, 48]. Optimal water con-
tent not only provides great support, flexibility, and stability to the enzyme
but also maximizes transesterification yield by diluting methanol that has
an inhibitory effect on enzyme. Factors that determine optimal water con-
tent include feedstock and type of solvent used, enzyme, and its immo-
bilization technique used [48]. Chaudhary et al. [49] studied the effect of
water content in lipase catalyzed transesterification. At low water activity
(aw = 0.33), synthetic activity of enzyme was increased and at high water
activity (aw = 0.96) enzyme became more hydrolytically active. They tested
various enzymes/lipases at different water activity to check transesterifica-
tion rates. The lipase from Aspergillus niger was found more prominent to
give maximum transesterification rate of 0.341 mmolmin−1 mg−1 at aw = 0.75.
Measuring water content as weight percentage is a better choice and more
convenient to use than water activity (aw), measured by Karl-Fischer method
[50]. Maximum methyl ester yield was at water concentration of 10-15%
while increasing water content from 0% to 40% to study the effect of water
in conversion of salad oil into methyl ester. But after much increased water
concentration, methyl ester yield became very low. So, for maximum trans-
esterification yield, optimum water concentration is required.
1.6.2 Effect of Bioreactor

In order to maximize production and benefit of product we need to per-
form optimized laboratory experimental procedure at a large industrial
scale, so, bioreactors are used in this regard. But results should be equiva-
lent to laboratory procedure [45]. There are some complications like pro-
duction should be cost effective and in good quality. Carefully planned
methodologies and objectives should be designed for effectively large-scale
production. This also includes bioreactor parameters like fluid flow per-
formance and unexpected environmental variation. In case of industrial
transesterification process, the main hurdle is multiphasic nature of lipase
catalyzed synthesis and hydrolysis because this does not allow the bioreac-
tor equivalent to laboratory experiment. Many types of bioreactors such as
fluid beds, recirculation membrane reactors, expanding beds, static mixers,
batch stirred tank reactors (STRs), and packed bed reactors (PBRs) have
been used for enzymatic biodiesel production [51, 52]. One of the leading
differences between STRs and PBRs is presence of enzyme at specific loca-
tion in reactor, e.g., in STRs it is dispersed in the reaction mixture but in
PBRS it is fixed in a column. STRs are the simplest type of bioreactors con-
taining just reactor and propeller that stirs reaction mixture mechanically.
Batch operated STR need to be empty, clean, and again add reactants for
the reaction in order to start new batch process and this is main reason of
batch process to produce less yield of the product. Solution of this problem
is to use STRs with continuous mode. This does not require to remove
enzyme and ingredients to start another cycle. There is a filter attached at
the reactor outlet that preserves enzyme in the reactor [52]. PBRs can also
be used in both batch and continuous mode but later is more advantageous
because of its low labor cost, stable and automated controlled operating
conditions, high efficiency, protects enzyme from shearing stress, continu-
ous glycerol removal, and ease of maintenance [53–55]. Currently, most of
the bioreactors are used in batch mode with STRs but a lot of research has
been done on PBRs usage and its optimization for enzymatic biodiesel pro-
duction to find this PBR method is better than batch mode STR [56–59].
1.6.3 Effect of Acyl Acceptor on Enzymatic Production

of Biodiesel
Alcohols are mostly used as an acyl acceptor for biodiesel production. To
get maximum economical profit at industrial scale, acyl acceptor (alcohol)
should be cheap and readily available and that is why ethanol and especially
methanol are widely used for this purpose. Usually, three moles of alcohol
are required for each mole of oil and in order to keep the reaction moving
forward [56]. By increasing alcohol concentration, yield also increases but
up to a certain limit [57]. Methanol as an acyl acceptor is frequently used for
biodiesel production [58] because it is less expensive, has low chain length,
more volatile, and more reactive, and gives high yield than other alcohols
[55]. A lot of research has been done utilizing methanol as acyl acceptor to
convert various types of oils such as soybean oil, jatropha oil, and canola
oil, in the presence of free or immobilized lipase 96.4% yield of FAME was
obtained from microalgal oil using methanol as acyl acceptor in the pres-
ence of Candida rugosa lipase immobilized on bio-silica polymer [59, 60].
Different alcohols with different substrates may result in different yield so
alcohol-substrate combination should be kept in mind for maximum output.
Excess of methanol causes inhibitory effect in the reaction because it changes
the stability and configuration of biocatalyst/lipase that can leads to partial or
complete inactivation of lipase [60–62]. Moreover, it also causes hindrance
in separation of glycerol [61, 62]. Methanol inhibition was observed with
Novozym® 435 lipase in transesterification of waste oils [63], microalgae
oils, and various vegetable oils [64–67]. Inhibitory effect was also observed
with some other lipases such as lipases obtained from Rhizopus oryzae and
Burkholderia glumae [65]. Addition of alcohol in each step should be done
after considering type of substrate and enzyme to determine alcohol sub-
strate molar ratio [66]. This method of sequential addition of alcohol in reac-
tion system was first performed by [67]. 98% biodiesel yield was obtained
utilizing T. lanuginosus lipase to convert soybean oil using stepwise addition
of methanol [68]. Inhibition of lipases such as C. rugosa lipase, P. cepacia
lipase, R. oryzae lipase, and P. fluorescens lipase was prevented using step-
wise addition of methanol and 90% yield was also obtained by converting
waste cooking oil into biodiesel [69]. Methanolysis of olive oil increases by
34% using stepwise addition of methanol compared to batch methanolysis
[70]. Transesterification of waste cooking oil using Novozym 435 was also
reported to yield 93% and 96% conversion for continuous and batch process
and lipase did not lose its activity even after 20 cycles [50]. Three-step addi-
tion of methanol resulted in 97% conversion of plant oil with 0.25- to 0.4-h
intervals. But this method of stepwise addition requires low level mainte-
nance of methanol concentration so it cannot be effectively used for indus-
trial scale. Alcohols as an acyl acceptor other than methanol include high
chain primary alcohols, secondary, branched, and linear chain alcohols such
as ethanol, isopropanol, t-butanol, and octanol [71].
Choice and selection of appropriate alcohol is important as it can
influence some biodiesel properties like lubricity and cold flow proper-
ties [75, 76]. Moreover, high chain alcohols cause less lipase inhibition
and produce high yield than methanol because lipase show more affin-
ity toward higher chain alcohols than lower chain [12]. The most widely
used alcohol as an acyl acceptor after methanol is ethanol as it is less
inhibitory, less toxic, and derived from renewable resources [73] unlike
methanol which is derived from coal and natural gas. There is minor
difference between characteristics of fuels obtained after methanol and
ethanol, i.e., FAME and FAEE, respectively. As FAEE has large viscosity
and lower pour and cloud points [74, 75]. Hernandez-Martin and Otero
[76] showed that, Novozym 435 catalyzed transesterification of sun-
flower oil, that was performed using methanol and ethanol separately
to check which acyl acceptor would perform better. Methanol-mediated
transesterification showed more lipase inhibition than ethanol contain-
ing reaction. Moreover, ethanol transesterification reaction was faster
than methanol reaction. Acyl acceptors other than alcohols can also be
used as an alternative such as methyl acetate, ethyl acetate, and dimethyl
carbonate (DMC). Methyl acetate was utilized as an acyl acceptor for
transesterification of soybean oil catalyzed by Novozym 435. In addition,
92% methyl ester yield was obtained [77]. Similarly, >90% ethyl ester
yield was obtained when utilizing ethyl acetate as an acyl acceptor for
transesterification catalyzed by Novozym 435 [78].
Use of DMC resulted in over 90% yield even after 10 times reuse of
Novozym 435 lipase to convert Chorella sp. KR-1–derived triglyceride
[79]. But use of methyl acetate and ethyl acetate is cost expensive and
also make the product difficult to separate. Another strategy can be used
to reduce methanol inhibition problem, i.e., use of solvents in the reac-
tion mixture [80]. Use of solvents is beneficial for various reasons such
as it increases solubility of alcohol and glycerol that results in preven-
tion of lipase denaturation [81]. It increases the rate of reaction because
it improves mass transfer rate. Use of solvents do not allow to form new
separate phase that hinders enzyme activity because it dissolves most part
of alcohol that makes a separate phase if remained undissolved. Moreover,
it reduces viscosity and stabilizes lipase [45, 55]. Enzyme stabilization is
associated with the presence of water molecules and their activity sur-
rounding the lipase structure. So, use of polar, less hydrophobic solvents
is not a good idea because that can lead to distortion of enzyme con-
firmation [82]. A higher yield of FAME was obtained from microalgae
lipids catalyzed by intracellular lipase when non-polar n-hexane solvent
was used as compared to polar tert-butanol solvent [83]. Organic solvents
such as hexane, petroleum ether, tert-butanol, n-heptane, and ionic liq-
uids are widely used for lipase catalyzed transesterification purpose [88].
Sometimes, it also happens that use of solvents becomes necessary in
transesterification reaction if short chain alcohols are being used as an

acyl acceptor in order to completely dissolve alcohol and produce max-
imum output but for the same reaction conditions solvent-free reaction
system can be used if higher chain alcohols are used as an acyl acceptor.
Iso et al. [85], immobilized P. fluorescence lipase catalyzed transesterifica-
tion was performed using methanol and ethanol as an acyl acceptor. They
also provided 1,4-dioxane solvent to the reaction to carry out effective
transesterification reaction. But when they used propanol and butanol as
an acyl acceptor, they did not provide any solvent to the reaction because
addition of solvents was not necessary required for transesterification.
Without solvent reaction worked and appropriate result was obtained.
Similar type of findings was also observed in another experiment that
in which hexane as solvent was used for methanolysis of various oils or
substrates like rapeseed oil, soybean oil, recycled restaurant grease, and
tallow. That reaction was catalyzed by C. antartica lipase (SP 435) and
M. miehei lipase (lipozyme IM 60) [53]. Solvents stabilized the lipase activity
shown by Li et al. [86], where lipase AK did not loss its activity. 1,4-dioxane
was used as solvent and gave higher yields. Presence of t-butanol as sol-
vent also resulted in the improvement of methyl ester yield [84].
Effects of various solvents like benzene, tetrahydrofuran, chloroform,
and 1-4 dioxane were investigated using different enzymes such as P. cepa-
cia (Lipase PS), C. rugosa (Lipase AY), M. javanicus (Lipase M), P. fluo-
rescens (Lipase AK), and R. niveus (Newlase F) by [85]. Use of solvents
definitely increases the reaction rate and solubility of alcohol which is ben-
eficial but it is not economical and environment friendly because to sepa-
rate organic solvent from reaction mixture a solvent recovery unit is also
required that increases the cost of recovery. Its flammability and toxicity
is another concerning factor [87]. Choice of lipase according to alcohol
is also important as some lipases show more resistance toward different
alcohols. Yang et al. [88] found that Photobaterium lipolyticum lipase was
more tolerant to methanol inhibition than C. antartica lipase B (Novozym
435) when transesterification was performed using one step methanol
addition. Similarly, Pseudomonas lipases were found to be more alcohol
tolerant compared to lipases from R. miehei and T. lanuginosus. That is why
pseudomonas lipases have higher methanol-to-oil molar ratio. Out of nine
lipases, only Pseudomonas cepacia lipase showed high ester yield from soy-
bean oil with 8.2:1 methanol-to-oil molar ratio [93, 94]. A recent and novel
approach of countering methanol inhibition is addition of silica gel in the
reaction system. Silica gel absorbs methanol and keeps its concentration
level below to prevent lipase inhibition. But presence of silica gel makes
separation of products difficult.
1.6.4 Effect of Temperature on Enzymatic Biodiesel Production

Use of enzyme in any chemical reaction makes the reaction less energy
intensive, but, like every other chemical reaction, increase in temperature
enhances reaction speed and rate. Similarly, in case of enzymatic biodiesel
production, increase in temperature increases enzyme activity, reaction
speed, its rate, and production yield [45]. When Lipozyme TL IM lipase
was used to transesterify crude palm oil using methanol then the resulting
FAME yield was 96.15% and 85.86% at 40°C and 30°C, respectively [95,
96]. But this effect is limited to certain extent because beyond enzyme opti-
mum temperature, enzyme structure becomes unstable and that leads to
enzyme denaturation and reaction becomes slower and yield also decreases.
Novozym 435 catalyzed biodiesel production from microalgal lipids, there
was 19% decrease in product yield when temperature went from 45°C to
55°C, i.e., higher than optimum temperature [97, 98]. Enzyme tempera-
ture should remain below the boiling point of alcohols being used in the
reaction system to avoid evaporation of alcohol. In case of methanol and
ethanol-mediated transesterification, reaction temperature is 65°C and
78°C, respectively [8]. Free bacterial lipases are considered thermally sta-
ble but if they get immobilized thermal stability increases [45]. Optimum
enzyme temperature is influenced by lipase thermal stability, type of sol-
vent, alcohol-to-oil molar ratio, and lipase immobilization. Every enzyme
has different optimum temperature depending on the source and type
of enzyme. Normally, lipases have optimum temperature range that is
20°C–70°C. Optimum temperature for C.antartica lipase is 40°C [99, 100].
1.6.5 Effect of Glycerol on Enzymatic Biodiesel Production

Glycerol is another product obtained along with TAG in transesterification
reaction for biodiesel production when alcohols are used as an acyl acceptor.
Like methanol inhibition effect, glycerol also hinders enzymatic transester-
ification. Production of glycerol cause reversal of reaction equilibrium and
thus opposes biodiesel production. Glycerol insolubility in the reaction sys-
tem makes it to accumulate in the system and increases the viscosity of the
reaction mixture. Not only it just increases viscosity but because of its hydro-
philic nature, it surrounds the lipase and hence prevents substrate to interact
with enzyme and binding at enzyme catalytic site. This effect is more promi-
nent when enzyme is in immobilized state. These things all together impacts
negatively on the transesterification reaction [93]. According to a research
study, rapeseed oil was transesterified using ethanol as an acyl acceptor with
different immobilized enzymes such as Novozym 435, Lipozyme TL HC
(immobilized on polymeric resin) and Lipozyme TL IM (immobilized on

silica). Among all reactions, glycerol became more accumulated and hin-
dered reaction when silica was used for immobilization purpose because it
had large number of micropores that helped in accumulation [94].
A lot of methods have been devised to overcome and tolerate glycerol
inhibition problem such as continuous removal of glycerol, use of solvents,
and use of acyl acceptors other than alcohols. Biodiesel production in PBR
is effective for continuous production and also to tolerate glycerol inhibi-
tion because it allows continuous removal of glycerol from it [95]. Bélafi-
Bakó [96] showed that 97% conversion yield was obtained by methanolysis
due to continuous removal of glycerol. Use of solvents is another strategy
to resolve glycerol inhibition problem. Solvents, for example, tert-butanol
and ionic liquids dissolve glycerol and thus reduce the glycerol inhibition
problem. Moreover, lipases also perform better in the presence of solvents
[97]. Azócar et al. [4] inferred that inhibition effect was eliminated when
tert-butanol was used as solvent to convert soybean oil into biodiesel pro-
duction in a continuous way because it is an excellent solvent for methanol
and glycerol to dissolve in it and, thus, reduces inhibitory effects of both
methanol and glycerol. These methods have shown promising work but
these are not as good for industrial scale production.
There is another novel method in which instead of alcohols other
compounds like methyl acetate, ethyl acetate, and DMC are in use. Use
of methyl acetate or ethyl acetate does not produce glycerol as a product
along with the main product instead it leads to produce triacetylglyc-
erol that does not inhibit any enzymatic or reaction activity and further
downstream processes are not halted [98]. According to Zhang et al. [99],
transesterification of palm oil was done using Novozyme 435 as catalyst
and DMC as acyl acceptor with reaction conditions were 10:1 DMC to oil
ratio, 55°C reaction temperature and 20% lipase in a solvent-free system.
In addition, 90.5% conversion yield, i.e., FAME was obtained, and after
eight reaction cycles, no reduction in enzyme activity and loss of yield was
observed. It was just because glycerol was not produced instead glycerol
dicarbonate was formed because of DMC as acyl acceptor for the reaction.
After discussing all negativity about glycerol, it seems glycerol does not
have any positive effect but it’s not true. Glycerol if purified absolutely from
the transesterification, as mostly huge biodiesel producing companies do,
has vast number of uses in diverse industrial fields. Moreover, 99.7% puri-
fied glycerol can be used as a raw material for various types of fields such as
paints, toiletries, animal feed, emulsifiers, pharmaceuticals, textiles, drugs,
tobacco, cosmetics, toothpaste, leather, plasticizers, paper, food, and for
different chemicals production [100, 101].
1.6.6 Effect of Solvent on Biodiesel Production

One of the major problems in enzymatic biodiesel production is enzyme
inhibition by short chain alcohols such as methanol and ethanol that are
used in the reaction. These alcohols’ insolubility in the reaction system
denatures the enzyme and hence reduces yield of biodiesel. So, solvent
application plays its role in this regard. Organic solvents are used to solubi-
lize these excessive alcohols so that enzyme denaturation can be prevented.
Hence, it stabilizes the enzyme. Solubility of oils and alcohols become
increased due to presence of organic solvents, this provides the required
environment for substrate to interact with enzyme at its active site. Organic
solvents also reduce viscosity of the reaction mixture and enhances mass
transfer toward the enzyme that leads to improved reaction rate [101].
Organic solvents also eliminate the need of stepwise addition of alcohol.
All these things in combination increase production of biodiesel. Organic sol-
vents that are commonly used include tert-butanol, petroleum ether, hexane,
and n-heptane [102]. Some other organic solvents that are used are 2-butanol,
cyclohexane, isooctane, acetone, 1,4-dioxane, and chloroform. While consid-
ering nature of organic solvents, hydrophobic organic solvents are majorly
used. Hydrophobicity of the organic solvents helps in accumulating water
molecules around enzyme which is important for enzyme structural stability
[103]. Polar or hydrophilic solvents work opposite to hydrophobic organic
solvents by playing role in distortion of enzymatic structure. But solvent with
little polarity can be beneficial to dissolve oil and alcohol. For example, hydro-
philic 1,4-dioxane and tert-butanol have produced some good results by pro-
ducing high enzymatic transesterification yield [104]. Tert-butanol, having
moderate polarity, eliminates glycerol and methanol inhibition problem for
enzyme because it can dissolve both in itself. This makes the enzyme more
stable and active and then ultimately produce better reaction yield [105]. Tert-
butanol is the most common solvent that proved its effectiveness in various
cases. According to Royon et al. [84], cottonseed oil was transesterified in the
presence of Candida antartica lipase. Methanol was found to be the cause of
enzyme inhibition in the reaction but when tert-butanol was used as solvent,
reaction yield goes up to 97% with minimal enzyme inhibition. Similarly,
in another research experiment, tert-butanol was tested for its effectiveness
when rapeseed oil was used as substrate for biodiesel production. In sol-
vent-free system, methyl ester yield was 10% but after utilizing tert-butanol
yield was 75%. But under optimum conditions having Lipozyme TL IM and
Novozyme 435 both in the reaction system, biodiesel yield reached 95% and
the reaction was so stable that enzymes did not lose their activity even after
200 cycles. Reaction was favored and well supported by tert-butanol [86].
Use of solvents provide many benefits but they also come with some
disadvantages such as organic solvents do not completely dissolve glycerol,
by-product of the reaction, that causes the enzyme to lose its activity and
become unstable. Use of solvents also make the process very costly because
there is a need of extra purification step to separate out solvent and product
from the reaction mixture. Organic solvents are mostly toxic and highly
flammable so there are also environmental and health concerns while
using them [11]. In order to tackle problems of conventional organic sol-
vents, researchers have suggested some alternatives. Diesel oil was found
to be an interesting alternative but the most recent, beneficial, and popular
alternatives are super critical carbon dioxide (SC-CO2) and ionic liquids
(ILs). Researchers have also confirmed the positive effect of using SC-CO2
and ILs in the enzymatic transesterification [106, 107].
1.7 Lipases as Biocatalysts for Biodiesel Production

Transesterification of oils for biodiesel production is done using either
chemical or enzymatic catalyst [108]. An enzymatic catalyst is used at first
place due to their normal reaction conditions, reusability, easy products
separation, and production of high-quality product. There is less energy
consumption in enzyme catalysis as it occurs at a low temperature as
compared to chemical catalysis requiring high energy consumption [109,
110]. Further, enzymatic catalysis is environment-friendly as there is no
wastewater production and produces pure biodiesel as compared to chem-
ical catalysis [107]. Among enzymatic catalysts, lipase with excellent bio-
chemical and physiological properties is most commonly used to catalyze
the transesterification process. Lipases play their role in several industrial
processes like alcoholysis, acidolysis, amynolysis, and hydrolysis reactions
but their leading role in biodiesel production is considered very important
[108–111]. The use of lipase in biodiesel production is proved to be bene-
ficial due to its characteristics like high efficiency, convert FFAs completely
into methyl/ethyl esters, reaction specificity, require low temperature, min-
imum energy consumption, and fewer side products [109]. Lipases belong
to class “hydrolases” as they carry out hydrolyses of triglycerides produc-
ing glycerol and fatty acids from it in an oil-water interface [110]. A general
reaction for biodiesel production using lipase is as follows:
lipase
Triglycerides + 3 Alcohol 3 Fatty acid methyl ester + Glycerol
(biodiesel) (by-product)
Lipases work on specific substrates and carry out catalysis of hetero-

geneous reactions in water-soluble as well as insoluble systems. Further,
lipases have the properties like chemo-specificity, region-specificity, and
stereo-specificity [111]. When classification is made based on region-
specificity, there come three classes of lipases: 1) non-specific lipases, 2) 1,3-
specific lipases, and 3) fatty acid-specific lipases. Non-specific lipases have
ability to attach with all the possible positions of triglycerides to give FFAs
and glycerol. The intermediates of the reaction, diglycerides, and mono-
glycerides do not accumulate in the reaction as they are instantly hydro-
lysed into fatty acids and glycerol [112]. 1,3-specific lipases are specific for
the 1 and 3 positions of triglycerides and remove fatty acids from these
positions. 1,3-specific lipases carry out the conversion of triglyceride to
diglycerides much faster than diglyceride to monoglyceride [113]. Fatty
acid-specific lipases carry out hydrolysis of a specific type of esters which
have double bonded long chains of fatty acids in cis position between C-9
and C-1. Hydrolysis of esters with unsaturated fatty acids occur slowly and
such class of lipases is not much common [114]. All the hydrolytic enzymes
including lipases have common folding pattern involve in a hydrolytic
activity called α/β hydrolase fold which is made up of a β sheet of eight
strands (one of which is antiparallel while remaining seven strands are
parallel) connected by α helices. Histidine residue, catalytic acid residue
and Nucleophilic residue are present in α/β hydrolase fold. Pentapeptide
sequence (Gly-X-Ser-X-Gly) which is a highly conserved in most of the
lipases involved in the construction of ‘nucleophilic elbow’ which is a typ-
ical β-turn-α motif having active nucleophilic serine residue between a β
strand and an α-helix. Catalytic triad made up of amino acids like his-
tidine, serine, and aspartic acid or glutamic acid build the active site of
lipases. The same catalytic triad is seen in serine proteases predicting com-
mon catalytic mechanism in them. Amphiphilic α helix peptide sequence
forms a lid or flap which covers the active site of lipase and has a struc-
tural variability depending upon the lipase source organism. Changes in
the structure of the lid are responsible for the activation/inactivation of
lipases [114]. Changes in the conformation of lipase structure as well as the
quality and quantity of interface being used in the reaction are responsible
for the activation of lipase. When the lipase enzyme meets the oil/water
interface there occur some changes in lipase structure that results in its
activation. For the activation of lipase first, the lid opens to uncover the
active site of lipase upon its contact with the ordered interface [115]. Due
to this restructuring of lipase, electrophilic region is created around serine
residue present in active site, lid hydrophilic side which was exposed in
native form now partly buried inside the polar cavity and hydrophobic side
of lid completely exposed, thus creating a non-polar surface around the

active site for efficient attachment of lipid interface with it [115].
1.7.1 Mechanisms of Lipase Action

Lipases interact with ester bonds of their substrate like acylglycerols to
catalyze the reactions of hydrolysis, synthesis, and transesterification.
Triglycerides, which are insoluble and long chained fatty acids, are precisely
catalyzed by lipases [113]. Lipase carries out triglyceride oil transesterifica-
tion with methanol in three reversible steps with the first step for conversion
of triglycerides to diglycerides followed by the second step of diglycerides to
monoglycerides conversion, and finally, monoglycerides convert into glyc-
erol molecules. Here, each conversion step produces one FAME molecule;
hence, a total of three FAME molecule are produced from one triglycer-
ide [116]. Two models are mainly under discussion to describe the kinet-
ics mechanism for esterification reactions, Michaelis-Menten kinetics and
Ping Pong Bi Bi model. Lipase catalyzed esterification mainly elaborated by
Ping Pong Bi Bi mechanism which is a bi-substrate reaction that releases
two products. It involves following steps: 1) acyl-donor donate their acyl
group to the enzyme resulting in the formation of acyl-enzyme complex,
2) release of the water molecule as a product, 3) binding of acyl acceptor
with the enzyme complex, and 4) release of ester [117, 118]. Many research-
ers made some modifications in this model depending upon inhibiting
factors [118]. The catalytic activity begins with the transient tetrahedral
intermediate formation with a negatively charged carbonyl oxygen atom.
The reaction between the hydroxyl group oxygen present in nucleophilic
serine residue of lipase enzyme and activated carbonyl carbon of the sub-
strate involved building this transient tetrahedral intermediate. The inter-
mediate thus formed is stabilized by its interaction with two peptide NH
groups. After that nucleophilic hydroxyl group of water react with the car-
bonyl carbon of acyl-enzyme complex resulting in the formation of acyl
product and enzyme is released for further catalysis [119].
1.7.2 Efficient Lipase Sources for Biodiesel Producing

Biocatalyst
Lipases can be obtained from plants, animals, and microorganisms and
based on that lipases can be classified on it as plant, animal, and micro-
bial lipases depending on their origin respectively. Lipases from different
sources with different structure has different properties and catalytic activ-
ities. We can use this to counter lipase problems in biodiesel production
like lipase cost and methanol inhibition. We need to optimize reaction

conditions according to chosen substrate and lipase from specific source
[107]. Microbial lipases are widely used at industrial and commercial
level as biocatalysts for biodiesel production because microbial lipases are
more stable and can be produced in bulk amount from microorganism
[23]. Microbial lipases can be manipulated genetically with ease, seasonal
changes have nothing to do with lipase production, and rapid growth of
microbes makes them the ideal candidates as lipase source [120, 121]. Use
of microbial lipase is increasing day after day and currently 5% of the world
enzyme market is being shared with microbial lipases [121]. Microbial
lipase weighs around 30–50 kDa and their optimum pH to work at is 7.5.
Based on temperature tolerance, microbial lipases can be categorized as
mesophilic and thermophilic lipases. Mesophilic lipases normally work at
35°C–50°C and they become denature above 70°C while thermophilic or
thermostable lipases normally work at 60°C–80°C, but some also work at
100°C under specific conditions [122, 123]. According to Hotta et al. [123],
lipases from Pyrobaculum calidifonti (hyperthermophilic archae) showed
its activity at 90°C. Similarly, thermostable lipases from Caldanaerobacter
subterraneus and Thermoanaerobacter thermohydrosulfuricus (highly ther-
mophilic bacteria) performed well in the range of 40°C–90°C. They not
only performed well at high temperatures but also were resistant toward
organics solvents [124]. Lipase producing microorganisms can be iso-
lated from soil, waste water, marine water, and industrial wastes. Isolates
of Mucor, Sclerotina, Candida, and Aspergillus strains have been reported,
which were isolated from soil. Similarly, various strains of microbes such
as P. alcaligenes, Bacillus acidophilus, Enterobacter intermedium, P. flu-
orescens, and Geotrichum asteroids are also reported as lipase producing
strains when isolated from vegetable oil processing plants [141]. Screening
of microbes is done by checking their lipolytic. Generally, lipases are
screened using batch cultures having agar as substrate but this is time con-
suming. So, the two mostly used methods for lipase production are solid
state fermentation and using submerged culture [142]. Purified form of
lipases is used in biochemical reaction to get maximum benefit from it, so
purification is required. Purification of lipase requires several techniques
including ammonium sulfate precipitation or ultrafiltration and after that
more sensitive and advanced techniques are utilized like gel filtration, ion
exchange chromatography, and affinity chromatography [143]. Moreover,
some other novel techniques can also be applied to purify lipases such as
immunopurification, column chromatography, hydrophobic interaction
chromatography, and membrane process. Generally, the strategy used for
purification lipases starts with the removal of lipase producing cells from
their growth culture to get extracellular lipases after fermentation. Then,

the extract without cells is concentrated by organic solvents, ultrafiltration,
and precipitation using ammonium sulfate. Ammonium sulfate precipi-
tation is used in the first stages of purification and it crudely separate out
things from mixture. After that advanced techniques of chromatography
are used to finely purify lipases [144]. According to Javed et al. [112],
diverse data from various research work suggested that purification had
been done from 2.4 to 500 folds with an increase in yield from 10.3% to
36%. Effective production and purification strategies of lipases are being
designed to get maximum yield at a very small expense. Among microbial
lipases, the most commonly used lipase sources are bacteria, fungi, yeast,
and algae; see Table 1.1 for some bacterial lipases and Table 1.2. for fungal
lipases that are used for biodiesel production [46]. Some of the commer-
cially available enzymes for biodiesel production are enlisted in Table 1.3.
1.8 Comparative Analysis of Intracellular and

Extracellular Lipases for Biodiesel Production
Transesterification reaction for biodiesel production is done with both
extracellular and intracellular lipases. Preference for their use is depen-
dent upon either we want simple upstream processes as in case of intra-
cellular lipase or high enzymatic conversion as in case of extracellular
lipase. But either we use intracellular lipase or extracellular lipase there is
no need for some downstream processes including separation and recy-
cling. Further, both immobilized lipase (extracellular) and immobilized
whole-cell lipase (intracellular) are proved to have highly efficient when
compared with free lipase used for transesterification [165]. Some exper-
imental studies for both intracellular and extracellular lipases are given
in Table 1.5. Intracellular lipases are the enzymes present inside the cells
or linked to the walls of cells producing it known as whole-cell biocat-
alysts. They are not purified or separated from their cells and used as a
whole-cell for transesterification (whole-cell biocatalyst) or immobilized
(whole-cell immobilization) [55]. Rhizopus and Aspergillus which are fila-
mentous fungi are most widely used as whole-cell biocatalyst for transes-
terification process [166]. As the main issue related to biodiesel production
at large scale is cost and the use of intracellular lipase for transesterifica-
tion resolves this problem like the use of intracellular lipase is considered
cost-effective because of the elimination of costly processes of lipase isola-
tion and purification before immobilization which are required in case of
extracellular lipase [167]. Intracellular lipase producing cells or whole-cell
Table 1.1 Some of the commonly used bacterial lipases for biodiesel production.
Acyl
Enzyme Immobilized on Substrate acceptor Yield Reference
Burkholderia Hydrophobic Jatropha oil Methanol 95% [125]

cepacia silica monolith
Lipase
Hybrid matrix of Jatropha Ethanol 100% [126]

alginate and curcas L.
κ-carrageenan oil
κ-carrageenan Palm oil Methanol 100% [127]
Modified Jatropha oil Methanol 94% [128]

attapulgite
SiO2-PVA Babassu oil Ethanol 100 % [129, 130]
SiO2-PVA Babassu oil Ethanol 100% [131]
Nb2O5 Babassu oil Ethanol 74.1% [132]
Pseudomonas Epoxy-acrylic Waste Ethanol 46–47% [133]

cepacia resin vegetable
Lipase oil
Phyllosilicate sol- restaurant Methanol 98% [134]

gel matrix grease and
Ethanol
Fe3O4 nanoparticle Soybean oil Methanol >88% [135]

biocomposite
Accurel Madhuca Ethanol 96% [136]

indica
Protein-coated Soybean oil Ethanol 98.93% [137]

microcrystals
Celite Jatropha oil Ethanol 98% [89]
Pseudomonas Octyl-silica resin Babassu oil Ethanol 97.5% [85]

fluorescence
Hydrophobic Soybean oil Methanol 65% [138]
sol-gel
Porous kaolinite Triolein Methanol 90% [139]

particles and
Ethanol
Asymmetric Triolein Methanol 80% [140]

membrane
Table 1.2 Some of the commonly used fungal lipases for biodiesel production.
Acyl
Enzyme Immobilized on Substrate acceptor Yield Reference
Candida Activated textile Waste cooking Methanol 91.08% [157]
antartica cloth oil
Lipase
Polyurethane foam Soybean oil Ethanol 81% [158]
Acrylic resin Sunflower oil Ethyl acetate 92.7% [78]
Soybean oil Methanol 83.31% [95]
Candida Microporous bio Scenedesmus Methanol 96.4% [59]
rugosa silica-polymer quadricauda
Lipase microalgal
oil
Poly(styrene- Soybean oil Methanol 86% [159]
methacrylic
acid)
microsphere
within an activated Palm oil Methanol 70% [160]
carbon as
support
Thermomyces Olive pomace Pomace oil Methanol 93% [161]
lanuginosus
Phyllosilicate sol-gel Grease Ethanol 80-90% [162]
Lipase
matrix
Mesoporous poly- Oleic acid Methanol 90% [163]
hydroxybutyrate and
particles (PHB) Ethanol
Toyopearl Babassu oil Ethanol 86.6% [164]
AF-amino-650M
resin
biocatalysts are directly employed for immobilization without separation

and purification steps for lipase enzymes [55]. Porous biomass support
particles (BSPs) are mostly used for whole-cell immobilization. BSPs was
developed by Atkinson et al. [168] and used by many scientists and each
scientist provide an efficient way of immobilization on it giving out a high
yield of biodiesel. A study to check the lipolytic activities of Bacillus species
using intracellular as well as extracellular lipase showed higher intracellu-
lar lipase activity than extracellular lipase activity [169]. Reported whole-
cell biocatalysts are Aspergillus oryzae, Burkholderia cepacia, filamentous
fungus Rhizopus chinensis, R. oryzae, and Enterococcus faecium [170–174].
Aspergillus oryzae used as whole-cell biocatalyst exhibited 98.1% relative
Table 1.3 Some examples commercial lipases commonly used for biodiesel
production.
Reaction
Enzyme Substrate Acyl acceptor yield Reference
Novozyme Chlorella sp. Dimethyl carbonate 90% [145]
435 KR-1 and methanol
mixture
Sunflower oil Methanol, Absolute >90% [146]
ethanol,
1-propanol
Oleic acid Ethanol, n-propanol, >90% [147]
and n-butanol
Crude Methanol 94% [148]
soybean oil
Soybean oil Ethyl acetate 63.3 % [149]
Soybean oil Ethanol [150]
Lipozyme Soybean oil Methanol >90% [151]
TL IM
Crude palm Methanol 96.15% [90]
oil
Waste Methanol 92.8% [152]
cooking oil
Palm oil Oleyl alcohol 79.54% [153]
Corn oil Methanol 92% [154]
Lipozyme Crude Monoacylglycerol 90% [155]
RM IM rapeseed
oil
Sunflower oil Methanol >80% [82]
Castor oil Ethanol 98% [3]
Soybean oil Ethanol >88% [156]
deodorizer
distillate
stability after the fourth batch and produced more than 97% FAME in 32
hours. Extracellular lipases are the purified form mainly fungal and bacte-
rial cells for their use in transesterification process.
Extracellular lipases are separated from broth containing lipase produc-
ing cells and after purification used as a catalyst in biodiesel production
processes [55]. The way to purify extracellular lipases depends upon its
structure and source organism [80]. Mostly extracellular lipases are used
in the immobilized form for transesterification than as free lipases because
of the low conversion rate and costly process [11]. Literature is full of
different methods as well as materials used for immobilization of extra-
cellular lipases. Main methods for immobilization involve cross linking,
carrier binding and entrapment while the most commonly used materi-
als for immobilization include silica, magnetic particles, and nanofibers
or nanoparticles for carrier binding, alginate beads, gels, and silicon poly-
mers for entrapment and glutaraldehyde for cross-linking [47]. The use
of a suitable solvent in case of extracellular lipase is a key factor for high
yield in transesterification as the use of unrelated solvent or absence of
solvent results in very low yield [102, 165]. The use of extracellular lipase
is also adapted because the use of intracellular lipase results in difficul-
ties of extraction and purification of the final product [171]. Extracellular
lipases are obtained from Candida guilliermondii, Burkholderia glumae,
Pseudomonas aeruginosa, and Yarrowia lipolytica [176–179]. Table 1.4
indicated a comparison between intracellular and extracellular lipases.
Table 1.4 Comparison between intracellular and extracellular lipase.

Intracellular lipase Extracellular lipase
Present inside the cell or linked to its Separated from cells producing it
walls (cell bound lipase)
No need of isolation and purification Complex isolation and purification
steps are required before using it for
biodiesel production
Low conversion rate High conversion rate
Not analyzed by direct sampling Analyzed by direct sampling
Direct immobilization of lipase Purification is required before
producing cells (whole-cell immobilization
immobilization
Biodiesel production is cost-effective Biodiesel production is costly
1.9 Recombinant Lipases for Cost-Effective Biodiesel

Production
In order to produce economically feasible and cost-effective enzymatic
biodiesel production, various methods have been used. For example,
improvement in purification procedures, use of better bioreactors, var-
ious immobilization techniques, use of easy to handle solvents and solu-
tion, finding novel organisms that can produce more stable and effective
lipases. These genetic manipulations enable recombinant organism
to overexpress active lipases. A lot of work has been done to produce
recombinant lipases from recombinant organisms by deriving desired
gene from another specie or organism to meet our demands. According
to Huang et al. [173], a good conversion of microalgal oil into FAME and
FAEE was obtained (<90%) when recombinant lipase from Rhizomucor
miehei was expressed in Pichia pastoris, in the presence of methanol and
ethanol as acyl acceptor, respectively. That recombinant lipase enzyme
was called Lipase GH2 and it was used as free enzyme for catalysis.
Aspergillus oryzea has been used majorly for lipase expression as manip-
ulating organism. Adachi et al. [174] created thermostable and solvent
tolerant whole-cell biocatalysts that worked as robust biocatalyst for bio-
diesel production. Geobacilus thermocatenulatus was used as a source
organism from which thermostable lipase (BTL2) gene was obtained and
then introduced into Aspergillus oryzea (r-BTL). Immobilized whole-
cell r-BTL was then used to convert palm oil into FAME production and
the resultant yield obtained was 100%. Whole-cell biocatalyst tolerated
40-50°C temperature and 30% (v/v) solvents such as methanol, DMC, and
acetone. These results proved the thermostability and solvent tolerance
of Aspergillus oryzea (r-BTL). Lipase from B68 strain of Pseudomonas
fluorescence (lipB68) was transformed into E. coli BL21 which resulted in
92% yield upon transesterification. The amazing thing about this exper-
iment was use of that novel psychrophilic lipase (lipB68) that catalyzed
reaction at 20°C and energy consumption became reduced in the reaction
system [175]. So, use of psychrophilic lipase for biodiesel production can
become more useful in the future. In many research experiments, recom-
binant lipases have performed better than commercially used lipases. For
example, according to Yan et al. [176], recombinant Pichia pastoris strain
was developed that used to overexpress Thermomyces anuginosus lipase.
When this strain was used as a whole-cell biocatalyst, it efficiently con-
verted waste cooking oil into FAME with 82% yield within 84 h. After
comparing this recombinant strain performance with commercial lipase
Lipozyme TLIM, it was found that the earlier one outperformed the
later one. In another research, lipase LIP2 coding gene was cloned from
Candida rugosa and expressed in Pichia pestoris after changing some
codons of that gene by side directed mutagenesis to make it more useful
and active. So, then that recombinant Candida rugose gave better results
when results of commercial C.rugosa lipase and recombinant LIP4 were
compared because recombinant LIP2 lipase was tolerating temperature
30°C–50°C and work even at 70°C [177]. A lot of research has been done
in utilizing recombinant lipases and found better results. Tables 1.5 and
1.6 showed some examples of recombinant whole-cell lipases with and
without immobilization.
Table 1.5 Some research investigations using recombinant whole-cell biocatalyst

after immobilization.
Expressing lipase Acyl
source Immobilized on Substrate acceptor Yield Reference
Fusarium Biomass support Aqueous Methanol 96.1% [178]
heterosporum particles plant oil
emulsion
Soybean oil Methanol 98% [179]
Thermomyces Protein-coated Palm olein Ethanol 89.9% [180]

lanuginosus microcrystals
Crude palm 82.1%
oil
Palm fatty 75.5%

acid
distillate
Geobacillus Reticulated Palm oil Methanol ~100% [174]

thermocatenulatus polyurethane
(BTL2) foam BSPs
Proteus mirabilis hydrophobic Canola oil Methanol 76% [181]

Immobead
350 oxirane
functionalized
beads
Staphylococcus poly Olive oil Methanol 90% [182]

haemolyticus L62 (methacrylate-
co-divinyl
benzene) resin
1.10 Immobilization of Lipases for Better Biodiesel

Production
Immobilization is the physical binding of enzymes to a solid support in
such a way that when the substrate passes over the enzyme support it
converted into their product [189]. The vast use of Enzyme immobiliza-
tion technique at industrial scale is because it results in enzyme stabiliza-
tion and prolonged enzyme–substrate contact which results in reduction
of purification steps. Further, it lowers the reaction cost by making the
reaction contamination free and enabling recycling of the enzyme [190].
As the cost of industrial production of lipase enzyme is one of the main
obstacle in its industrial application, so it can be eliminated through
lipase immobilization [191]. Industrial processes/reactions can be made
continuous with little protein using immobilized lipases because of their
easy separation from reaction system containing products, by-products,
residual substrates, and medium [192]. In transesterifications is the
Table 1.6 Some other experiments using recombinant whole catalyst without
immobilization.
Expressing lipase
source Substrate Acyl acceptor Yield Reference
Serratia marcescens Waste grease Methanol 97% [183]
YXJ-1002
Rhizomucor miehei Soybean oil Methanol >95% [184]
and Penicillium
cyclopium
Fusarium Soybean oil Methanol 95% [185]
heterosporum
Rhizomucor miehei Soybean oil Methanol 83.14% [186]
(RML)
Microalgal Methanol >90% [187]
oil
Thermomyces Waste Methanol 82% [176]
lanuginosus (Tll) cooking
oil
Rhizopus oryzae Soybean oil Methanol 71% [188]
IFO4697
main process involves in biodiesel production using lipase enzyme, the

use of immobilized enzyme (extracellular) and immobilized whole-cell
(intracellular enzyme) both reported highly efficient as compared to the
use of free enzymes. Bayramoglu et al. [59] set two reaction setups, one
with free enzyme and other using immobilized enzyme, and then reac-
tion comparison was measured using gas chromatography-mass spec-
trophotometry (GC-MS) by noticing FAME components. They Candida
rugosa lipase was immobilized on microporous bio-silica polymer. Both
enzymes then further used for transesterification of Scenedesmus quadri-
cauda microalgal oil using methanol in the presence of n-hexane solvent.
Reaction setup having immobilized lipase produced 96.4% yield as com-
pared to free lipase that produced 85.7% yield. Moreover, immobilized
lipase was very much stable as it just lost 17% of its activity after six
cycles. Kalantari et al. [193] used Pseudomonas cepacia lipase, immobi-
lized on mixture of mesoporous and nanoporous silica coated composite
particles, for transesterification of soybean oil into FAME using metha-
nol. Immobilization effect retains 55% enzymatic stability after five con-
secutive cycles compared to free lipase reaction. Shah et al. [194] showed
that three enzymes were selected initially and then Chromobacterium
viscosum was further chosen because of its better results. Celite 545 was
used as immobilization material applied to enzyme. Transesterification of
Jatropha oil using ethanol was conducted with and without immobilized
lipase. After immobilization, reaction yield increased from 62% to 71%
and then after further addition of water and immobilization, it reached
to 92%. Moreover, in another study [85], triolein transesterification was
conducted using methanol, ethanol, and immobilized Pseudomonas flu-
orescens in the presence of 1,4-dioxane solvent. Reaction yield for both
free and immobilized lipase reaction setups was same, i.e., 90%. But the
stability provided by immobilization, loss of lipase activity was mini-
mal in immobilized reaction setup than other. Reaction time was 10h
for immobilized as compared to 25h reaction time in free lipase system.
Further, when we use water free media, free enzyme molecules tend to
clump together and decreasing the surface area. Enzyme immobilization
inhibit clump formation and increase the surface area of the biocatalyst
[195]. Kumari et al. [97] carried out transesterification of jatropha oil
with Enterobacter aerogenes lipase immobilized on surface and reported
high yield (94%) of biodiesel production and noticed that lipase activity
reduced in little extent even after repeated use. Enzyme properties like
resistance to proteolytic digestion and denaturants, temperature pro-
file, pH-dependence, thermostability, and kinetics are mainly affected
by enzyme immobilization. The chief issues for enzyme immobilization
are preference for the selection of immobilization techniques and sup-

port matrices that permit both rapid enzyme activity and enzyme sta-
bility under the constraints imposed by the substrate medium [89, 196].
Some examples of different investigations regarding biodiesel produc-
tion methods using whole-cell immobilized biocatalysts are given in
Table 1.7.
Table 1.7 Investigation of immobilized whole-cell biocatalysts to produce

biodiesel.
Lipase cell Immobilized Acyl
factory on Substrate acceptor Yield Reference
Rhizopus Biomass Soybean oil Methanol 70%– [197]
oryzae cells support 83%
particles
Mucor Poly-Urethane Sardine Methanol NA [198]
circinelloides Foam (Sardinella
lemuru) oil
Mucor polyurethane Babassu oil Ethanol 98.1% [199]
circinelloides support
URM 4182
Rhizopus biomass Oleic acid Methanol 90% [200]
oryzae support
IFO4697 particles Soybean oil Methanol 72%
Rhizopus biomass Jatropha Methanol 90% [201]

oryzae support curcas oil
(ROL) particles
Soybean oil Methanol 90% [202]
Rhizopus Calcium waste Methanol 84% [203]
oryzae 262 alginate cooking oil
beads (sunflower
oil)
Rhizopus biomass Cottonseed Methanol 27.9% [204]
oryzae support oil
ATCC particles
34612
Pseudomonas Sodium Jatropha oil Methanol 72% [205]
fluorescens alginate
MTCC 103
Aspergillus Biomass Palm oil Methanol >90% [104]
niger support
particles
1.11 Recent Strategies to Improve Biodiesel

Production
1.11.1 Combination of Lipases
Lipases from different sources or organisms possess different properties.
Just like no ideal gas really exists, similarly, there is no ideal lipase that
will be considered as absolutely perfect. Just one lipase cannot have all
properties that are ideally required for optimal biodiesel production. But
researchers are trying to find the best among the lot. Novel sources pro-
vide different features of lipase that can be good for biodiesel production.
Some lipases are good at tolerating high temperatures, some may work at
low temperature, some provide a good temperature range, some may have
good catalytic activity, and some may have good hydrolytic activity. Raw
material or substrate that is used for biodiesel production is very diverse in
nature. Feedstock is mainly comprised of FFA, triglycerides, diglycerides,
or monoglycerides, so it is difficult for one lipase to tackle all these things
with best possibility. Likewise, every lipase has different alcohol inhibition
capacity to tolerate it. So, all in all, these things make it very difficult for one
lipase to be perfectly suitable to give best results. So, researchers have come
with an idea to use combination of enzymes/lipases. One may be best at
providing specific feature and other may be good at giving another specific
feature and so on. This way combination of enzymes will provide many
features that will be good for biodiesel production. A lot of combination of
enzymes have been studied recently for biodiesel production. According
to Li et al. [206], combined use of Lipozyme TL IM and Novozym 435
lipase resulted in 96.38% conversion of stilingia oil into FAME. Reaction
conditions were methanol-to-oil molar ratio (6.1:4), temperature 20°C
along with the use of co-solvent consisting of acetonitrile and t-butanol.
At these conditions even after 30 cycles, there was no loss in lipase activity.
Similarly, many investigations have been done and some of them are given
in Table 1.8.
Another way of using compound lipases is cloning and expression of
two or more different lipase coding genes from different organism in a host
organism. But cloning and effective expression of lipases from host organism
is a difficult and cumbersome process, but it has also provided better results.
For example, according to Guan et al. [184], Pichia pestoris was selected as
a host organism to express two lipase coding genes cloned from two dif-
ferent organisms, one of them was R. miehei (source of 1,3-specific lipase)
and the other was Penicillium cyclopium (source of non-specific lipase).
Table 1.8 Some examples to produce biodiesel using combination of lipases.

Combination of Acyl
lipases Immobilized on Substrate acceptor Yield Reference
Thermomyces Lewatit VP OC 1600 Soybean oil Ethanol 90% [207]
lanuginosus
lipase and TLL immobilized on Palm oil Ethanol 80% [208]
Rhizomucor acrylic resin, RML
miehei lipase. immobilized on
anion-exchange
resin
Pseudomonas Accurel PE-100 Used palm oil Ethanol >67% [209]
fluorescens microporous
and Candida polypropylene
rugosa powder
Immobilized macroporous Soybean oil Methanol 98% [210]
Pseudomonas polypropylene
fluorescens
lipase
followed by
immobilized
Pseudomonas
cepacia lipase
Combined use Lipozyme TL IM waste cooking Methanol 99% [211]
of Lipozyme immobilized on sunflower
TL IM and acrylic resin and oil
Novozym 435 Novozym 435
immobilized on
microporous resin
Novozym 435 RML immobilized on Soybean oil Ethanol 80% [212]
(CALB) and an anion-exchange
Canola oil Methanol >95% [213]
Lipozyme resin, and CALB
RM-IM immobilized on a
(RML) macroporous resin
Combination microporous Triolein Ethanol 96% [214]
of Rhizopus polypropylene
arrhizus lipase Accurel MP1000
and Candida
antarctica
lipase B
Candida rugosa Macroporous acrylic Acid oil, Methanol 91% [215]
lipase resin product of
followed by vegetable
Novozym 435 oil
Extract containing these two lipases when applied for biodiesel produc-
tion to transesterify soybean oil at 30°C with 4:1 alcohol-to-oil molar ratio
resulted in 99.7% yield after 24 h. In another research, a special recom-
binant Aspergillus oryzae whole-cell biocatalyst was created that used to
co-express two different lipases genes, one of these two lipases was derived
from Fusarium heterosporum (FHL) and the other one was mono and dia-
cyl glycerol lipase B. Use of that whole-cell recombinant Aspergillus ory-
zae biocatalyst resulted in 98% methyl ester yield [179]. According to Yan
et al. [216], recombinant Pichia pestoris was developed that displayed two
lipases, i.e., T. lanuginosus lipase (TLL) and C. antarctica lipase B (CALB)
from different sources on its surface. This whole-cell biocatalyst co-express-
ing both lipases produced 95.4% biodiesel yield under optimum conditions.
Apart from ILs advantages, there is a problem with the biodiesel recovery
because during continuous biodiesel removal reaction moves backward
and affects the resultant yield. So, to avoid this problem SC-CO2 has been
suggested along with ILs. SC-CO2 is very effective in recovering biodiesel
because ester molecules have good solubility in it. IL-SC-CO2 combina-
tion not only provides easy recovery but also prevent glycerol inhibition
effect. SC-CO2 saturated with (substrate) oil is introduced into the reaction
system and this creates two phases because of immiscibility in each other.
SC-CO2 can diffuse through IL (ionic liquid) phase bringing substrate with
it, reaches the enzyme active site and makes the reaction easily possible.
After enzyme activity when biodiesel is formed, biodiesel esters become
soluble in SC-CO2 phase, So, in this way, biodiesel becomes separate from
ILs. Glycerol (by-product of the reaction) does not dissolve into SC-CO2 so
it makes another separate layer and then glycerol can be easily taken out in
pure form. SC-CO2 containing biodiesel is then processed to recover bio-
diesel from it by depressurization [217, 218]. In this way, two phase system
due to IL-SC-CO2 combination enable to recover biodiesel in good qual-
ity. IL-SC-CO2 combination system was first used to extract naphthalene
using [bmim] [PF6] as IL [219]. Enzymatic biodiesel was produced with
IL-SC-CO2 system by transesterification of triolein using Novozyme 435 as
biocatalyst and methanol as acyl acceptor. In IL-SC-CO2 system, 12 differ-
ent ILs were used and there were two different temperature conditions, i.e.,
60°C and 85°C. After 6 h, the resultant biodiesel yield obtained was more
than 98% that made this reaction a successful one [220].
1.11.2 Microwave and Ultrasonic-Assisted Reaction

Microwave employment in the chemical or biochemical reaction is very
clean, economic, fast and energy efficient method. Use of microwave is
very helpful in substrate preparation, extraction, and biodiesel production.

Microwave irradiation assists the reaction by providing direct energy to
the reactants, and hence, the loss of energy becomes minimal. This fea-
ture makes it economic than using other conventional methods of heating
to make the reaction possible [221]. Easy energy transfers and use makes
the enzyme to perform better and its easy separation leads to cost reduc-
tion. So, this environment friendly method provides energy efficient, faster
and cost-effective reaction. There have some research investigations been
done to analyze how effective it would be to use microwave. Macauba oil
transesterification was performed using Novozyme 435 and Lipozyme IM
in the presence of ethanol as acyl acceptor. Activities of these enzymes
were checked and compared in the presence and absence of microwave.
Before microwave assistance enzymatic activity values of Novozyme 435
and Lipozyme IM were 0.09 and 0.08, respectively. But after microwave
presence activity value were 0.6 and 0.4, respectively. Results were clear
that microwave assistance enhanced enzymatic activity about one order of
magnitude [222, 223]. In another experiment, soybean oil and sunflower
oil was transesterified using Novozyme 435 and ethanol to oil molar ratio
was 3:1. Resultant ester yield was more than 99% within just 3 h when reac-
tion system was accompanied with microwave while conventional heating
produced yield about 57% with the same reactions conditions as provided
in case of microwave reaction system for biodiesel production. So, micro-
wave-assisted reaction produced better and faster biodiesel yield compared
to conventional heating reaction system [224, 225].
According to Zhang et al. [224], microwave and deep eutectic solvents
assisted transesterification of yellow horn seed oil using Novozyme 435
resulted in 95% conversion yield. Ultrasonication is another advancement
in effective biodiesel production. Just like microwave, ultrasonic assistance
increases the reaction rate and ultimately makes the transesterification
cost effective [225]. Increase in reaction rate is linked with enhancement
in mass transfer and good energy input. Ultrasonication also increases the
surface area for the reactant to work efficiently. Moreover, it also boosts the
enzymatic catalytic activity and efficiency which provides optimum results
even when catalyst is in low quantity [226, 227]. Sometimes, ultrasoni-
cation when combined with other method it produces better results and
effective rapid transesterification. According to Yu et al. [227], transester-
ification of soybean oil in the presence of methanol and Novozyme 435 as
biocatalyst produced good results when ultrasonic irradiation applied on
the reactants. When ultrasonic irradiation with vibration (UIV) applied
then conversion of soybean oil into FAME produced 96% yield in just
4 h and Novozyme 435 did not lose any activity after five cycles. But in
the absence of UIV, comparable results were obtained after 12 h. Results

proved that presence of UIV in the enzymatic transesterification reaction
gave faster and better yields with no loss in enzyme activity. In another
research, Novozyme 435 was utilized to catalyze transesterification of
waste cooking oil in an ultrasound-assisted environment. The resultant
biodiesel yield was 75.19% in just 2 h. It was also found that ultrasound
along with little agitation/vibration made the reaction more efficient [228].
Just like microwave, ultrasonication is also taking attention of researchers
to produce better and cost-efficient biodiesel.
Researchers have produced some good results in the past couple of years
using ultrasonication method. Ultrasound-assisted transesterification of
soybean oil using ethanol and Novozyme 435 resulted in ~78 % yield in
just 1 h. this method of assistance has the potential to become alternative to
the alkali catalyzed or conventional enzymatic biodiesel production [229].
In another experiment, sunflower oil and methanol were used for biodiesel
production in the presence of Lipozyme TL-IM under ultrasound-assisted
system. Results indicated that ultrasound assistance suppresses the much
needed requirement of using methanol, making the reaction fast and
clean [230]. Conventional transesterification using bath process technique
requires a lot of time because phase separation and recovery of glycerol
and biodiesel is a time-consuming process. Use of ultrasound and micro-
wave is very helpful in this regard and it has been proved that ultrasound
and microwave assistance make the reaction rapid and cost efficient.
1.12 Lipase Catalyzed Reaction Modeling

and Statistical Approaches for Reaction
Optimization
A lot of methods have been tried for the modelling of lipase catalyzed
reactions to fully understand reaction mechanism. Need of better catalyst
with great substrate specificity, immobilization, whole-cell catalyst, and
manipulation of lipase, all these methods have been applied with various
techniques to get better results [231]. But all these methods have been
used by hit and trial method to check feasibility. Apart from dealing with
lipases, there are many more parameters to set optimally to achieve max-
imum output. These parameters include temperature, pH, water content,
alcohol-to-oil molar ratio, and bioreactor choice. All reaction conditions
using various combination of parameters with diverse conditions have
been used but it is not actually we need because hit and trial method
leads to expensive experimentation. In this era of science and technology,
in silico experimentation is in great demand and it can apply to each and

every field. Optimization of biochemical processes is one of key things to
produce cost effective results. In order to optimize a reaction, there are
various parameters that are dealt with but normally optimization accounts
for changing just one parameter at a time by keeping others constant and
similarly one by one all parameters are optimized. This technique is called
one variable at a time technique. The major limitation of this technique
is that it does not show interactive results of parameters. So, it does not
produce results based on all parameters effects at the same time on the
process.
Process modeling, simulation, and statistical approaches are the best
way to tackle this problem. Modeling and simulation of the processes are
the base of in silico experimentation that provides similar environmental
conditions of the processes just like real system without so much invest-
ment. This not only provides process mechanism information but also
gives support for process development. Reaction optimization is difficult
to achieve and it requires a lot of efforts and financial support. While opti-
mization, high efficiency of one of many parameters sometimes reduces
the demand of some other parameter and reaction product may not alter
so much. For example, according to Tufvesson et al. [232], if enzyme has
excellent catalytic activity then this minimizes the need of enzyme specific
activity and similarly, if enzyme catalytic activity is fair enough to product
healthy amount of product then ultimately need of efficient downstream
processes will be reduced. So, all in all optimization of chemical processes
is difficult and tedious to achieve. That is why in silico experimentation is
helpful in process of optimization and handling.
Modeling and simulation of any process gives idea to the researchers
what they actually need regarding system conditions, type of catalyst with
respect to their mechanism kinetics and energetics from ping pong bi bi
mechanism, type of substrate, and various parameters setup. This greatly
prevents hit and trial approach and makes the process cost effective. There
are two basic approaches in process modeling: (a) empirical approach deal
with design of experiments and (b) statistical approach that gives relation
between process outcome and parameters [232]. Parameter estimation is
a key thing to avoid false outcome in process modeling and more chances
of error in estimation leads to wrong direction. Yu et al. [231] observed
that, optimal experimental design was developed for the improvement of
process estimation in biodiesel production process catalyzed by Novozym.
Simulation demonstrated the reduction in producing errors while estimat-
ing parameters through optimal experimental design. Response surface
methodology (RSM) is a collection of various mathematical and statistical
techniques that is used when there are multiple variables influencing the
reaction response at the same time. RSM is used for improvement, devel-
opment, and especially optimization of chemical and biochemical reac-
tions. RSM creates a mathematical model that can be used to predict what
can be the response of the process under certain variable conditions. That
is why it is called RSM.
A lot of research has been done using RSM to optimized chemical
reactions. For example, protease production in a bioreactor taken from
Bacillus mojavensis and statistically optimization of media [233] and
lipase catalyzed esterification reactions [234]. RSM is widely used for
optimization but it can also be used to determine kinetic constants and
enzyme stability. Kinetic constants for protease derived from Bacillus
mojavensis was determined using RSM [235]. According to Rana et al.,
kinetic and stability of b-1,3-glucanase from Trichoderma harzianum
and alcohol dehydrogenase was investigated using RSM [236]. RSM for
optimization is carried out in 3 stages, (a) independent variable and their
level is determined, (b) experimental design is selected then model equa-
tion is predicted and verified, and (c) different response plots are obtained
and optimum points are determined [237]. The most common and suc-
cessfully implemented design used in RSM is central composite rotatable
design (CCRD) for the optimization of reactions [238, 239]. Like every
other thing, RSM surely has advantages as well as disadvantages (Table
1.8). Like other chemical processes, optimization of enzymatic catalyzed
biodiesel production process has been widely investigated using RSM
statistical approach [241].
According to Sheih et al. [241], conversion of soybean oil into biodiesel
was catalyzed using lipase from Rhizomucor miehei (Lipozyme IM-77) in
the presence of methanol which was being investigated in this experiment.
RSM was implemented with having 5-level-5-factor CCRD. Through this
design and RSM, effect of time, methanol-to-oil molar ratio, temperature,
water content, etc., were measured and evaluated. Under optimal condi-
tions that were temperature of 36.5°C, reaction time of 6 h, water content
of 5.8%, and substrate molar ratio of 3.4:1, resulted in 92.2% conversion
yield when analysis was done using ridge max analysis. In another experi-
ment, optimization was done in pretreatment step to lower the concentra-
tion of FFA of Mahua oil that would halt the downstream processes and
ultimately biodiesel production. CCRD was again used to check the effects
of acid and methanol concentration and reaction time in reducing the pro-
duction of FFA. After pretreatment, Mahua oil was catalyzed through alka-
line catalyst, and then, the resultant biodiesel produced was according to
American and European standards [242].
1.13 Conclusion and Summary

Currently, the use of fossil fuels is on its verge because of the dependency
of our transportation and main industries on it. If its usage goes with even
at the same pace, there are great chances of its shortage due to depletion in
reservoirs in very near future. So, there is a strict need to divert toward alter-
nate sources like biofuels which not only overcome the shortage of fuel but
also environment-friendly. Biodiesel is the most widely used biofuel due to
its vast use from direct fuel to a lubricating agent. The production and use
of biodiesel are restricted to limited countries but there is a need to broaden
its use worldwide. The barriers which constrain its worldwide use are mainly
related to biodiesel production cost which can be reduced with optimization
of the production process by selection of preferable feedstock, reaction con-
ditions, type of catalyst used, enzymes for catalysis, and many other factors.
Researchers are making their full effort to construct a cost-effective bio-
diesel production process. Oils extracted from various sources are used as a
substrate or feedstock for biodiesel production, but microbial oil extracted
from microalgae is used at first place due to low cost, easy, and quick pro-
duction when compared with plant and animal oils. However, biodiesel
produced using animal oil act as a good lubricating agent along with good
oxidative stability. Biocatalysis involving enzymatic biodiesel production
via lipase enzyme is considered a low-price process as compared to other
ways. Lipase enzyme is preferably used as biocatalysis because of its easy
separation and reusability.
There are many factors like acyl receptors, water, and temperature that
have a serious impact on enzymatic transesterification and great research
have been done for to optimization of these factors to make the process
easy and affordable. Lipases from a broad range of sources immobilized
by different techniques on a variety of supports have their own resulting
impact in biodiesel production process. However, the use of whole-cell
immobilization or combination of lipase with optimized reaction condi-
tions like temperature, time of reaction, and pH makes the process indus-
trially favorable. Still, there exists a space for improvement to make the
biodiesel production process affordable and easy to conduct.
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2
Application of Low-Frequency
Ultrasound for Intensified
Biodiesel Production Process
Mohd Razealy Anuar, Mohamed Hussein Abdurahman, Nor Irwin Basir
and Ahmad Zuhairi Abdullah*
School of Chemical Engineering, Universiti Sains Malaysia,

Engineering Campus, Nibong Tebal, Penang, Malaysia
Abstract
Biodiesel is an energy source that is mostly derived from plant-based oils through
a transesterification and esterification reactions with alcohols. Due to the immis-
cibility of the reactants, the reaction is only limited to the interface and vigorous
mechanical stirring is often needed to homogenize the reactants. To achieve high
yields (>90%) in about 2 h, temperatures between 50°C and 65°C in the presence
of 0.5 to 3.0 wt. % of catalyst are usually required. The use of ultrasonic energy as
the source of mixing has become a great interest as it can increase the interface
area leading to higher biodiesel yield. During ultrasonication, the cavitation bub-
bles will be formed and subsequently collapse asymmetrically once the critical
sizes are reached. The boundary of the reacting phases will be disrupted by the
micro jets that result from these collapses. It will also result in a temperature rise
at the locality of the phase boundary. The use of ultrasonic energy in conjunction
with a heterogeneous catalyst can lead to shorter reaction times of 10–40 min with
two to three times lower amount of catalyst needed as compared to those expected
in normal mechanically stirred reactor. Thus, the process will require shorter reac-
tion time, lower catalyst amount and lower energy input to result in high methyl
ester yield.
Keywords: Biodiesel, ultrasound, mass transfer, immiscible reactant,

transesterification, process intensification, catalyst
*Corresponding author: chzuhairi@usm.my (https://orcid.org/0000-0001-6394-2917)
59
2.1 Current Fossil Fuel Scenario

Recently, the increasing demand on the unsustainable fossil fuels is a
challenging topic to be addressed. With the current rate of crude oil
consumption, the conventional energy sources could be depleted not
even 50 years down the line [1]. The high usage of such fuels to gen-
erate energy has also caused associated environmental effects such as
global warming [2], greenhouse gas emissions, and acid rain [3] and
other environmental pollutions such as particulate matters [4]. It is
also reported that carbon monoxide (CO), carbon dioxide (CO2), sul-
fur oxides (SOx), and nitrogen oxides (NOx) that result from fossil fuels
combustion are the key culprits for global warming [1]. It was antic-
ipated that the world’s overall energy consumption and thus the CO2
emissions to the atmosphere could show 60% increase in 2018 as com-
pared to 2008. Furthermore, oil and gas prices had also been increasing
in the recent years [5].
Due to the above-mentioned issues, the necessity of finding the envi-
ronmental-benign alternatives to fossil fuels to address the future energy
demand is a worthwhile effort [6, 7]. Alternatives to replace fossil fuels are
such as biofuels, wind, and solar energy [2]. The dependence of transpor-
tation sector on fossil fuels was about 96% of the current energy consumed
in the sector [5]. The current scenario of soaring fossil fuel prices and their
finite reserves therefore justify the quest for biofuels as the fifth energy
sources.
2.2 Biodiesel
Recently, methyl esters of fatty acids in vegetable oils, also known as
biodiesel, have been demonstrated to be effectively used to power die-
sel engines at certain blend ratios [8, 9]. Biodiesel fuel is a result of the
alcohol transesterification of triglycerides in vegetable oils or animal fats.
Alternatively, free fatty acids in those triglycerides can also be esterified
to yield methyl esters. This fuel has been demonstrated to show potentials
as a renewable fuel source based on several favorable specifications [6].
It consists of monoalkyl esters and produced through a reaction between
the triglycerides and a monohydric alcohol [10]. Biodiesel as a fuel prom-
ises the advantages of (1) minimum dependence on fossil, (2) renewability,
(3) positive energy balance, (4) better emission quality, (5) non-toxic, (6)
agricultural surplus as feedstock, and (7) better safety in handling [11].
Ultrasound-Assisted Biodiesel Production 61
The properties of biodiesel in strongly influenced by the characteristics

of feedstock as well as the production system used. There are several meth-
ods of biodiesel production reported such as homogeneous acid-mediated
process [12], supercritical fluid process [3], enzymatic process [13], and
homogenous base catalyzed process [14]. Base catalysts are usually more
favorable than acid catalysts or enzymes [15]. Research efforts toward
future use of heterogeneous catalysts for this conversion are also actively
investigated [16, 17].
2.3 Transesterification
Biodiesel is commonly produced by the catalytic reaction between tri-
glycerides (oils or fats) with simple alcohols (i.e., methanol, ethanol,
propanol and butanol). Glycerol is co-produced as the side-product.
The transesterification process is as schematically shown in Figure 2.1.
Stoichiometrically, the reaction involved 3 moles of alcohol and 1 mole
of triglyceride to yield 3 moles of methyl esters (biodiesel) and 1 mole of
glycerol. However, due to the reversible nature of this reaction, in prac-
tice, excess of alcohol is used to push the equilibrium toward favorable side
to achieve higher ester yield [9]. In this reaction, diglycerides and mono-
glycerides are undesired products that should be minimized for the sake of
better FAME yield.
Esters are the desired products of the transesterification reactions. At
the end of the reaction, glycerol is removed by centrifugation or settling
O O
CH2 O C Rx CH2 O C Rx
O CH2 O H CH2 O H
CH2 O C R1 O CH2 O H R1COOCH3
O CH2 O C Rx CH2 O H
CH2 O C R2 + 3 CH3OH CH2 O H + R2COOCH3
O CH2 O H
CH2 O H
CH2 O C R3 O O CH2 O H R3COOCH3
CH2 O C Rx CH2 O C Rx
O
Note : x=1, 2 or 3
CH2 O C Rx CH2 O H
Triglycerides Methanol Diglycerides Monoglycerides Glycerol Methyl esters

(Biodiesel)
Figure 2.1 Transesterification of triglycerides for the production of biodiesel.

for subsequent purification. Purified glycerol can be used in many con-

ventional applications (pharmaceutical, cosmetic, and food industries).
Newly developed applications for glycerol are also found in the fields of
animal feed, surfactants, polymers, lubricants, etc. [18, 19]. Glycerol recov-
ery is also crucial because of its several applications in different industrial
processes.
2.4 Challenges for Improved Biodiesel Production

Conventional biodiesel production processes are still more expensive as
compared to those of fossil diesel. The cost of the biodiesel as compared
to diesel does not make it favorable alternative to fossil fuels. One of the
important issues which can directly reduce the cost is the reduction in
the production costs. These expenses are such as the heating, labor work,
mixing, and raw material use. On the other hand, generally, biodiesel is
produced from various vegetable oils that have undergone extensive puri-
fication processes. These oils are relatively costly and at the same time more
suitable for edible purposes. There has been heated debate on the fuel ver-
sus food dilemma across the globe [20].
Homogeneous catalyst has many environmental impacts due to produc-
tion of wastewater during the separation process. Alcohol and oil are also
immiscible and the reaction only takes place in the interface of the reac-
tants. Thus, the production of biodiesel requires a rather long reaction time
and excess of catalyst to assure high yields. These conditions can increase
the overall biodiesel production costs. Therefore, as an ultimate objective,
alternative method to decrease the process costs and time should be iden-
tified. Long reaction time will directly and indirectly affect the produc-
tion cost of biodiesel while affecting it quality at the same time. Effective
transesterification process usually occurs at temperatures higher than
60°C. Lower temperatures often result in poor reaction rates while higher
temperatures will require a pressurized reactor considering the methanol
boiling point of 64.8°C. Thus, reduction in the reaction time can cause less
time of energy consumption for heating the system. This highlights the
importance of finding technologies which are less costly and less energy
consumption. Time reduction can also reduce the labor work for produc-
tion of the same amount of biodiesel.
Biodiesel also needs to fulfill the strict requirements of ASTM D6751-17
or EN 14212:2008 standards to be used as fuel. The consistent compliance
is an uphill task. In order to produce biodiesel that consistently meet the
technical standards, strict quality control measures for the feedstock and
the catalyst should be implemented. However, the severity of the produc-

tion process should be reduced bearing in mind the low stability of the
triglycerides used in the production process [21]. This technology should
also have the feasibility to be scaled up. Thus, the reaction rates and opti-
mized operating conditions are also of great concerns in this study.
2.5 Homogeneous Catalyst for Biodiesel Production

Biodiesel production process is usually catalyzed by enzymes, acidic or
basic catalysts. Sulfuric acid and hydrochloric acids are conventionally
used for the acid catalyzed processes. These catalysts are often used for
oils feedstock with high water and free fatty acid (FFA) contents. Acid-
catalyzed biodiesel production processes normally need longer reaction
time and higher alcohol to oil ratio [17]. As such, the production costs are
usually higher in this case. As such, biodiesel is more commonly produced
now from refined/edible type oils (with lower FFA and water contents)
in the presence of an alkaline catalyst. This reaction is relatively higher
to make this option more favorable. However, the difficulty of alkali-
catalyzed esterification of non-edible oils is excessive soap formation which
inhibits the effective separation of ester and glycerin. This phenomenon is
attributed to the residual amounts of FFA that present in the oil, particu-
larly in the case of non-edible/not refined oils [16]. For an alkali-catalyzed
transesterification process, the glycerides and alcohol must be substantially
anhydrous. In the presence of water, the undesired saponification reaction
between the catalysts with FFA will produce metal salts of the fatty acids
(soaps) [21].
There is also certain environmental impact associated with the catalyst
amount used. Excessive amounts will result in large amount of soap which
is undesirable as far as product separation and biodiesel quality are con-
cerned. Besides, the remaining catalyst can end up in the product leading to
increased biodiesel pH other biodiesel quality parameters such as ash con-
tent [2]. The typical catalyst used for the production of biodiesel is homo-
geneous base catalysts such as KOH and NaOH. This process can produce
high methyl ester yield under atmospheric pressure and temperature of
50°C–65°C which is usually carried out in 1–4 h [6]. In order to improve
the biodiesel quality to meet certain intentional standards, downstream
purification of the methyl ester is required prior to its use as biodiesel. This
could be achieved by removing impurities such as catalyst and glycerol
by hot water washing. It should be noted that such further purification
processes generate enormous amounts of wastewater [15]. Thus, replacing
conventional homogeneous catalysts with environmentally friendly het-

erogeneous catalysts seems to be essential for the benefit of lower produc-
tion costs and environmental considerations.
2.6 Heterogeneous Catalyst for Biodiesel Production

Due to environmental concerns, the interest in biodiesel production is cur-
rently been directed toward heterogeneous process. This approach allows
catalyst removal after the reaction without extensive downstream purifica-
tion processes. Other advantages are in the reusability potential of the cat-
alyst and the less corrosive character of heterogeneous catalysts [22]. They
can also be formulated to exhibit better activity, selectivity and stability
[13]. Solid catalyst can also be divided into two groups, i.e., acid catalysts
and base catalysts. It has been reported that acidic heterogeneous catalysts
usually show weak activity and react at relatively higher temperature with
longer reaction time as compared to basic heterogeneous catalysts [23].
Various types of heterogeneous catalysts for transesterification process
have been reported by several researchers. Alkaline and alkaline-earth
metal compounds were recently used in biodiesel production to replace
conventional homogenous catalysts [5]. Alkaline and alkaline-earth metals
supported on other materials such as alumina and silica can be consid-
ered as potential catalysts for the transesterification reaction. Zeolites are
another group of catalysts studied for the transesterification process [24].
Clay minerals such as hydrotalic, chrysotile, and sepiolite are considered to
be the next group. These minerals belong to the group of modest or weakly
basic catalysts.
In the recent years, heterogeneous base catalysts are gaining popularity
for biodiesel production due to their benefits. Yet, there are still a lot more
to understand about the natures of these catalysts. Clarifying the nature of
the interaction between the support and the catalytically active component
in the process is still worthy of further investigation. In this new process,
the catalyst is expected to promote the transesterification reaction without
experiencing catalyst loss. Yet, it is known that solid base catalysts can be
easily poisoned by water or carbon dioxide. Poisoning is a phenomenon
responsible for loss of catalytic activity that stems from strong chemisorp-
tion of certain substances on the active sites in the reaction system. When
solid bases are used in liquid phase organic reactions, the reaction rate
may decrease due to the diffusion of reactants and products. One of the
main drawbacks of heterogeneous catalysts is lower catalytic activity as
compared to that of homogeneous ones such as KOH [6]. Consequently,
higher reaction temperature and pressure than those in homogeneous pro-

cesses are required with an excess of methanol. This will certainly result in
higher production costs. Therefore, more research endeavor is required to
make this technology more economically interesting and environmentally
favorable.
2.7 Immiscibility of the Reactants

Alcohol and triglycerides as the reactants in the transesterification process
are mutually immiscible. This reaction is therefore a mass transfer-limited
one due to their immiscibility [25]. The rate of the reaction is very much
dependent on the mixing ability of the reactants providing a better contact
or interface area. The reason for poor rates of reaction of transesterification
process is the mass transfer limitations between the reactants that often
create immiscible phases in the reactor [26]. To overcome this problem,
researchers have recently introduced new methods to make rigorous mix-
ing in the system. One of the techniques is the use of cavitation which
results in conditions characterized by local intense turbulence. These effects
are capable of improving the rates of chemical reactions which are limited
by mass transfer resistances by increasing the interfacial area between the
two phases [27].
Ultrasonic irradiation is one of the approaches that have attracted much
attention in this respect to overcome the poor immiscibility of the reac-
tants [28, 29]. Ultrasound is defined as any sound pressure with a fre-
quency above the upper limit of hearing by human. As a matter of fact,
the upper limit varies depending on individual. However, about 20 kHz
has been established as the upper limit for healthy, young adults. As such,
this level usually serves as a lower limit for the definition of an ultrasound.
Figure 2.2 shows the approximate frequency ranges of sounds with rough
guide of some sources of the sound and common applications [30].
Sonochemical reacting system is an innovative approach in which ultra-
sonic wave is used to create an oxidative environment by means of cavi-
tation bubbles that are formed during the rarefaction period of the high
frequency sound. The creation, propagation, and implosion of cavitation
bubbles caused by the sonic waves will cause high local temperature and
pressure rises. These rises are considered the responsible mechanism for
the acceleration of chemical reactions in a sonochemical system. This
leads to the increase in the reaction rate and shortened the time required
for complete reaction or to reach equilibrium [31]. In an aqueous system,
three different regions have been postulated for the reaction to occur, i.e.,
20 kHz
Infrasonic Sonic Utrasonic Hypersonic
Hz
0 10 102 103 104 105 106 107 108 109 1010
Human hearing Plastic welding

Cleaning
Aircraft
Earthquake Dog Sonochemistry
Violin Bat Chemical analysis

Medical diagnostic
Dolphin Non-destructive testing
Figure 2.2 Approximate frequency ranges of sound with rough guide of some sources or
applications.
(i) the bulk solution, (ii) the interface between the bulk solution and the
cavitation bubbles, and (iii) the gaseous interiors of cavitation bubbles [32].
2.8 Ultrasound-Assisted Biodiesel Production Process

2.8.1 Fundamental Aspects of the Process
Lately, the potential of ultrasonic energy in biodiesel production process
has attracted the attention of many researchers [2, 27]. Because of the
poor immiscibility of a liquid-liquid heterogeneous system, the interaction
between alcohol and oil is just limited to the interface of the two phases
[9]. Vigorous mechanical stirring is conventionally used to homogenize
the reactants to enhance the interfacial area between the two phases [5].
In a conventional stirring method to achieve high yields (>90%), a tem-
perature of 50°C–65°C in presence of catalyst 0.5%–3.0% and the reaction
should also be extended to 2 h or more [6]. Kalva et al. [9] concluded that
the rate of reaction was influenced by the interfacial contact between the
two reacting phases. In addition, the creation of alcohol anions would ini-
tiate the methyl ester formation reaction.
The use of ultrasonic energy as the source of mixing has become a great
interest by two different ways. It will intensively create a virtually homoge-
neous mixture and at the same time, it can create heating effect to increase
the biodiesel production yield. The application of ultrasound in biodiesel
production process can be done in several options. It can be directly used
to mix the immiscible reactants while they are fed into a continuously flow
reactor as marked as Option 1 in Figure 2.3. This approach is highly effec-

tive as direct contact between the ultrasonic transducer with the reacting
mixture is allowed. Then, the desired effects of the ultrasonication are
passed directly to the reacting mixture. Ultrasonic cavitation will also
result in a localized temperature increase in the phase boundary leading to
enhanced reaction rate. However, it also causes unnecessary stress to the
ultrasonic system as high temperature could disrupt its normal operation.
In addition, metal transducer might also not so stable to the prolonged
exposure to acidic condition at high temperature. This is especially true in
the case of acidic catalysts used to process high FFA content feedstock [33].
Alternatively, ultrasonic processor can also be used to create micro-
droplets (~50 microns in diameter) of the alcohol and pre-mix them with
the oil to create a homogeneous dispersion to be fed into the reactor as given
in Option 2 in Figure 2.3. Ultrasonic irradiation has been demonstrated to
Ultrasonicator
Oil Methanol
Option 1
Ultrasonicator
Product
Separation
Option 2
Product
Separation
Figure 2.3 Different options of ultrasound application for biodiesel production.

be beneficial in accelerating an immiscible reaction system through the

generation of cavitation bubbles [2]. The disruption of the phase boundary
will then result from the asymmetric collapses of the cavitation bubbles to
create micro jets of the liquid. In turn, this will lead to the mixing effect
of the system, especially at the interphase. Consequently, the stable emul-
sion mixture is created to allow accelerated reaction rate in the reactor. It
has been reported that the use ultrasound in conjunction with homoge-
neous catalyst in the biodiesel process can lead to a shorter reaction times
of 10–40 min with two to three times lower amount of catalyst needed as
compared to those in normal mechanical stirring reactor [34].
The main principle of ultrasound that leads to an efficient mixing of
different viscosity reactants is the creation of cavitation bubbles at the
interfacial area between molecules of reactants [35]. The molecules would
experience a significant vibration which causes the weakening of the
attraction force to create gap between liquid. At an ultrasonic wave of >20
kHz, microscopic and macroscopic bubbles will be formed, and they are
beneficial in enhancing the mass transfer limitation [36]. The increased
vibration of the bubbles at the boundary layer eventually produces acoustic
cavitation that increases the mixing rate of the liquid reactants [37, 38].
The cavitation bubbles would then collapse due to vigorous breakdown
when exceeding the limitation point. This might generate localized pressure
increase to as high as 2,000 atm with the internal temperature approaching
5,000 K, thus initiating the transesterification and esterification reactions
[39]. The intense internal heat and pressure generation would extensively
provide severe mechanical agitation enticing a homogeneous mixing
between oil and alcohol. Thus, the immiscibility and emulsification lim-
itation would be minimized. Overall, the principle of ultrasound acoustic
cavitation bubbles is summarized in Figure 2.4.
Kalva et al. [9] concluded the desired effects of ultrasound-assisted bio-
diesel production system based on chemical and physical phenomena.
The chemical reaction would be accelerated by transient implosive of the
bubbles collapse and a homogenize mixture would formed due to radial
motion of the bubbles that can generate micro-turbulence. The collapse of
the bubbles can cause transient implosive that would eventually produce
H+ and OH− ions that will sequentially accelerate the chemical reaction.
Ultimately, the production of biodiesel will technically and economically
undergo a massive improvement with the intensification of ultrasound
irradiation processing with advanced catalytic system. With recent studies
on various types of catalytic system based on the use of ultrasound, a bio-
diesel process with an accelerated reaction rate is foreseeable in the near
future [36, 40].
Ultrasonication -Shockwaves
>20kHz -Microjets
-4,000++ K hot spots
-1,000++ atm
Emulsified
mixture
Bubble Bubble Critical Bubble Bubble

Formation Growth Size Implosion
Transesterification
reaction
Alcohol
Triglyceride Fatty acid methyl esters
Figure 2.4 Principle of ultrasound-induced acoustic cavitation bubbles.
2.8.2 Homogeneously Catalyzed Ultrasound-Assisted System

Studies on ultrasound-assisted biodiesel production process started with
the application of homogeneous catalysis system. Both acid and base
homogeneous catalysts have been used in previous works that are tabulated
in Table 2.1. Sulfuric acid is the most often used acid homogeneous catalyst
in homogeneous biodiesel production [46]. It is highly active during the
reaction and gives FAME results of up to 99% [41, 42]. In conventional
mechanical stirring method, acid homogeneous catalyst is 4,000 times
slower than base homogeneous catalyst [47]. However, it is highly bene-
ficial in achieving high FAME yield production from high FFA feedstock.
Acid catalyst is capable of handling FFA and triglycerides by conducting
simultaneous esterification and transesterification reactions [46]. Thus,
high FAME yield with high purity product is expected to be produced.
This is main attributed to milder reaction conditions needed to achieve
significantly high reaction rates. However, the resistance of the ultrasonic
transducer that has prolonged direct contact with the acidic medium could
be the drawback of the ultrasound-assisted process.
Mostly, basic homogeneous catalytic processes were carried out by
using alkaline metal hydroxides [42, 44]. The transesterification reaction
could occur at a sufficiently fast rate and the FAME yield might achieve
nearly 100% [42]. Alkaline earth metal hydroxides are also available at
low cost. However, they are also sensitive to the presence of FFA in feed-
stock. Saponification reaction would take place and impedes the formation
70
Table 2.1 Performance of ultrasound-assisted homogeneous biodiesel production systems.

Reaction
conditions
Alcohol to oil Time Frequency Biodiesel
Catalyst Feedstock ratio T (°C) Wcat (%) (min) (kHz) yield (%) Reference
Sulfuric acid, Soybean oil 9:1 (Methanol) 60 1 60 24 90 [41]
H2SO4
Sulfuric acid, FFA from 3:1–9:1 25 1 90 40 98 [42]
H2SO4 Oreochromis (Methanol)
niloticus
p-toluenesulfonic Rapeseed oil 3.3:1 45 1 180 20 12 [43]
acid (Methanol)
Biodiesel Technology and Applications
Pottasium Silybum 4:1–12:1 30–80 0.25–2 5–70 40 96 [44]

hydroxide, marianum (methanol
KOH oil and
ethanol)
Pottasium Soybean oil 9:1 60 1 60 24 99 [41]
hydroxide,
KOH
(Continued)
Table 2.1 Performance of ultrasound-assisted homogeneous biodiesel production systems. (Continued)
Reaction
conditions
Alcohol to oil Time Frequency Biodiesel
Catalyst Feedstock ratio T (°C) Wcat (%) (min) (kHz) yield (%) Reference
Sodium Soybean oil 3:1–9:1 29 1 30 40 100 [42]
hydroxide, (Methanol)
NaOH
NaOCH3 Peanut oil 3:1-9:1 25 1 60 20 90 [28]
(Methanol)
C2H5ONa Fish oil 6:1 (ethanol) 20–60 1 30 20 >98 [45]
Ultrasound-Assisted Biodiesel Production
71
of ester. Thus, the activity of the catalyst might decrease and poor reac-
tion yield will result. Besides alkaline earth metal hydroxides, some other
catalysts have also been reported as base homogeneous catalysts such as
NaOCH3 and C2H5ONa [28, 45]. The use of these catalysts usually showed
tremendous reaction yields of up to 98%.
Unfortunately, the use of homogeneous catalyst has many drawbacks
especially with regards to the product quality problem and environmen-
tal concerns. It also requires an additional complicated product separation
unit to obtain high purity product. To avoid such problem, another alter-
native has been explored in which heterogeneous catalysts would be the
best candidates to replace the role of homogeneous catalysts in biodiesel
production.
2.8.3 Heterogeneously Catalyzed Ultrasound-Assisted System

2.8.3.1 Heterogeneously Acid Catalyzed System
Some works focusing investigating the potential of solid acid catalyst in
an ultrasound-assisted biodiesel production are tabulated in Table 2.2.
Heteropolyacid, i.e., tungstophosporic acid (TPA) was used by Badday
et al. [33, 37, 48] to create acidic sites in different kinds of support includ-
ing gamma alumina, cesium, and activated carbon. The use of 25% TPA
loading in gamma alumina resulted in the FAME yield of about 64.3%.
After the reaction conditions were mathematically optimized (60% ultra-
sonic amplitude at 20 kHz, a methanol:oil ratio of 19:1, 65oC, 60 min), the
FAME yield successfully increased to 84%. Higher TPA loadings (above
25%) reduced the FAME yield and it was attributed to partial blockage of
catalytic pores by the acidic component that eventually reduced the acces-
sibility of reactants into pore sites. Small leaching of TPA was unfortunately
reported owing to the partial dissolution of the catalyst in the polar sub-
stances in the mixture and it was accelerated by the ultrasonic effect during
the reaction. Significantly higher yield was reported by Maneechakr et al.
[49] with higher ratio of alcohol to oil.
Next, a heteropolyacid-doped cesium (Cs) was used in the ultrasound-as-
sisted biodiesel production [37]. The effect of different Cs exchange levels
was investigated with the highest FAME yield obtained of about 81.3%. The
reaction was reported to be insensitive to the addition of FFA as the acid
sites in the catalyst dominantly converted FFA directly to FAME. However,
high content of FFA caused the reduction of FAME yield as water that was
produced from the esterification of FFA could also allow acid hydrolysis
Table 2.2 Ultrasound-assisted biodiesel production processes catalyzed by heterogeneous acid catalyst.
Reaction
conditions
Alcohol to Time Frequency Biodiesel
Catalyst Feedstock oil ratio T (°C) Wcat (%) (min) (kHz) yield (%) Reference
Heteropoly acid Jathropa oil 20:1 56 4 40–60 20 87.33 [33]
supported
on activated
carbon
Heteropoly acid Jathropa oil 5:1–25:1 65 2.5–4.5 10–50 20 64.3-84 [48]
supported on
alumina
Caesium doped Jathropa oil 5:1–25:1 65 2.5–4.5 10–50 20 81.3 [37]

heteropoly acid
Sulfonated carbon Waste cooking 20:1–40:1 50-150 5–15 2–14 25 90.8 [49]
oil
Tungstated Oleaginous 30:1–60:1 40-60 2–4 20 22.5 71% [50]

zirconia (WO3/ scenedesmus
ZrO2) sp.
73
of the ester. High porosity also caused the catalyst to become unstable and
eventually deactivated the catalyst.
Maneechakr et al. [49] attempted the use of carbon as the support for
acid heterogeneous catalyst in an ultrasound-assisted biodiesel produc-
tion. The carbon was previously sulfonated by contacting with H2SO4 and
it resulted in FAME yields of up to 90.8% under optimum conditions. The
sulfonated catalyst was very active, and it showed low activation energy
of 11.64 kJ/mol. However, the catalyst showed a significant reduction in
FAME yield after being used in successive reactions (12 cycles) without
regeneration with H2SO4. The reduction might due to the deactivation
caused by the deposition of polymerized products and appreciable acid
loss that might occur during the reaction. The disappearance of Na and K
elements after the fourth cycle was also reported. A successful work toward
activity improvement of phosphotangestic acid as the active catalytic com-
ponent has been demonstrated by Nikseresht et al. [51].
Guldhe et al. [50] highlighted the role of tungstated zirconia in produc-
ing biodiesel from Oleaginous scenedesmus sp oil. The extraction of lipid
was carried out in a single step together with transesterification to bio-
diesel under ultrasound system. In such system, ultrasonic effect was used
to extract lipid and a catalyst was used for converting lipid to FAME. The
use of acid catalyst often subjects to some difficulties in which the acid
strength could affect the activity of the catalyst and it was unlikely to cre-
ate a uniform porous catalyst [46]. As such, another alternative especially
basic heterogeneous catalyst is worth investigation for use to replace acidic
heterogeneous catalyst for biodiesel production.
2.8.3.2 Heterogeneous-Based Catalyzed Ultrasound-Assisted System

Recent biodiesel research works utilizing ultrasound-assisted systems cat-
alyzed by various heterogeneous base catalysts are tabulated in Table 2.3.
In their works, Mootabadi et al. [52] and Chen et al. [54] highlighted the
effectiveness of oxides of alkaline earth metals in converting palm oil to
biodiesel. CaO showed the highest activity with yields of up to 95% in 1 h.
Clearly, the alcohol to oil ratio requirement was lower than those com-
monly reported for acid-catalyzed biodiesel production.
Heterogeneous base catalysts have also shown their applicability for bio-
diesel production with a wide range of feedstock. These include rarely found
feedstock such as Silybum marianum oil [55] and sesame oil (Sesamum
indicum L.) [56]. Malani et al. [40] even investigated mixed non-edible oil.
In the study on biodiesel production from Silybum marianum oil, a series
of TiO2 doped C4H4O6HK catalysts differed by the catalyst preparation
Table 2.3 Performance of ultrasound-assisted heterogeneous base-catalyzed processes for biodiesel production.
Reaction condition
CaO, SrO, BaO Palm oil 3:1-15:1 65 3 60 20 95.0 [52]
Calcium Used cooking 6:1–14:1 45–65 0.5–1.25 0–40 20 93.5 [53]

diglyceroxide oil
CaO Palm oil 3:1–15:1 60 3–10 60–180 20 92.7 [54]
TiO2 doped with Silybum 8:1–18:1 40–70 1–9 10-40 40 90.1 [55]
C4H4O6HK marianum
oil
Commercial Waste 4:1–8:1 30–60 1–4 0–120 50 92.0 [20]
potassium cooking oil
and sodium
phosphate
Barium hydroxide Sesame 4.5:1–7.5:1 25–35 1–2 20–40 20 98.6 [56]
(Sesamum
indicum
L.) oil
(Continued)
75
76
Table 2.3 Performance of ultrasound-assisted heterogeneous base-catalyzed processes for biodiesel production. (Continued)
Reaction condition
Coal fly ash Used cooking 4:1–12:1 70 3–11 0.5–2.5 20 95.6 [57]
oil
Magnetic Jatropha and 5:1–7:1 48–8 1–9 20–100 20–25 Soybean: [58]
soybean oil 97.9
(Na2SiO3@
Fe3O4/C) Jathropa:
94.7
procedure were investigated [55]. In this study, TiO2 impregnated with

potassium bitartrate and calcined for 6 h at a temperature of 600°C showed
the highest activity by producing 90.1% of biodiesel yield. Barium hydrox-
ide was used in a similar reaction system to convert sesame oil into bio-
diesel [56]. In the optimization study performed using an artificial neural
network (ANN) approach, it was found that the catalyst loading was the
most influential parameter that significantly determined the FAME yield.
The maximum FAME yield recorded was 98.6%.
Pukale et al. [20] and Gupta et al. [53] investigated the production of
biodiesel with waste cooking oil as the feedstock and catalyzed by com-
mercial PO4 and calcium diglyceroxide, respectively. By using various
commercial PO4 catalysts doped with alkaline metals like potassium and
sodium, waste cooking oil was successfully converted to biodiesel with
K3PO4 demonstrated the best catalytic performance. The high catalytic
activity was retained until the fourth cycle and it only started to drop in the
fifth to the eighth cycles, observed as the gradual reduction in the FAME
yield to 65%. They also demonstrated significant leaching of the catalyst
during the reaction. Meanwhile, the use of calcium diglyceroxide was also
beneficial in biodiesel production with a maximum yield was 93.5% using
an ultrasound-assisted system [53]. However, the catalyst also experienced
a severe leaching problem and the FAME yield sharply reduced to 50.5% in
the third cycle. This might due to the partial solubility of calcium diglycer-
oxide in glycerol-methanol mixture in the successive reaction cycles.
Heterogeneous base catalysts have also been prepared using coal fly
ash as reported by Xiang et al. [57]. With nowadays requirement for the
advanced catalysis system for biodiesel production, such a material could
potentially conduct good transesterification reaction with low quality
feedstock such as used cooking oil. Coal fly ash possibly contains some
amount of silicon dioxide, calcium oxide and magnesium oxide. The opti-
mal FAME yield could achieve 95.57% under the right process conditions.
Excellent reusability potential was also demonstrated by the catalyst in
which it could withstand up to eight reaction cycles under ultrasonic con-
dition with only minimal reduction in the catalytic activity.
Zhang et al. [58] came up with a unique heterogeneous catalysis sys-
tem by combining ultrasound with magnetic stirring. Ultrasound served
to create emulsified mixture between the reactants while the conven-
tional stirring’s role was to ensure the emulsified mixture was distributed
to the whole reacting volume. The removal of the catalyst was achieved
by means of magnetic method. Soybean oil and Jathropa curcas oils were
tested and both feedstocks demonstrated high FAME yields of 97.9% and
94.7%, respectively. The combination of magnetic stirring and ultrasound
successfully improved the catalytic activity and prevented the reduction in

the catalytic activity after several successive reaction cycles.
2.8.3.3 Influence of Reaction Parameters

In an ultrasound-assisted system, the FAME yield can be influenced by a
few reaction parameters such as the ratio of alcohol to oil, reaction time,
reaction temperature, catalyst amount, and ultrasonic amplitude. These
parameters should be taken into consideration to run the reaction at its
optimum conditions to obtain highest possible FAME yield. Based on
mechanism of transesterification reaction, alkoxide ion produced from
alcohol is required to initiate the reaction. Lower alcohols (methanol, eth-
anol, etc.) are usually preferred for biodiesel production [59]. The alcohol
amount used should be stoichiometrically higher than oil to push the equi-
librium forward to form more FAME as the oil transesterification reaction
is in fact a reversible reaction [20, 53]. In excess alcohol condition, ade-
quate production of alkoxide ion is ensured and high reaction rate will
be achieved [55]. However, higher amount of alcohol might significantly
dilute the product leading to an initiation of reversed reaction to decrease
the FAME yield [20]. In this respect, intensified reaction with the use of
ultrasound could lower the alcohol to oil requirement to the benefit of the
high biodiesel yield.
Reaction temperature is another important factor influencing biodiesel
production. In an ultrasound-assisted system, only low reaction tempera-
ture is needed as the cavitation effect will also produce internal heating
effect during the reaction. An increase in the reaction temperature would
facilitate the solubility and miscibility of oil in alcohol and increase the dif-
fusivity of three-phase reaction mixture (oil, alcohol, and catalyst) [20, 53,
55]. Besides, it also increases the kinetic energy of molecules that will sig-
nificantly increase the collision between reactant molecules hence increas-
ing the reaction yield [53]. However, higher reaction temperature also
leads to the supersaturated formation of vaporized alcohol bubbles [20].
It causes cushioning of the collapse of bubbles resulting in low implosion
intensity and eventually decreases the mass transfer [53, 60].
Basically, ultrasound-assisted system effectively increases the rate of
biodiesel production through cavitation effect; hence, only short reaction
time is needed to achieve high reaction yield. Additional time is needed to
ensure the reversible reaction can achieve its equilibrium. In the first 10
min, the reaction was observed to start with slow reaction rate due to inad-
equate agitation effect and reactant mixture was not homogeneously mixed
yet [55]. Thus, sufficient time was required to complete the conversion
of triglycerides to yield FAME. However, the reaction needed is usually

significantly shorter than that required by conventionally stirred reactor
system.
In a biodiesel production reactor system, the amount of catalyst used in
biodiesel production should be correctly determined. The ideal amount of
catalyst might result in high FAME yield and minimizes wastage of pricy
catalyst. At the same time, it contributed to lower impurity level that could
be possibly introduced into the biodiesel product. Takase et al. [44] high-
lighted that less amount of catalyst would beneficially increase the FAME
yield while excess of catalyst might cause more saponification reaction to
occur to form excessive formation of soap. In addition, higher amount
of catalyst often leads to the formation of viscous reactant mixture that
requires higher energy to provide adequate stirring effect. Besides, it might
also give a negative impact of energy dissipation due to scattering on sound
wave [53]. With the intensified reaction rate made possible with the use
of ultrasound, same level of biodiesel yield will be achievable with signifi-
cantly less amount of catalyst. The impact will be significant on the per-
spectives of process economy, safety, and product quality.
2.9 Conclusions
Biodiesel is the most potential biofuel to replace petroleum diesel.
Chemically, it is made up of fatty acid methyl esters that are derived mainly
from many vegetable oils through either a transesterification or an esteri-
fication reaction with alcohols, particularly methanol. Slow reaction bio-
diesel production process is associated with rather small interfacial area
between the two immiscible reactants. Heterogeneous catalysts are greener
alternatives to conventionally homogeneous ones but they are often sub-
ject to low specific surface area for sufficient interaction with reactants and
poor internal mass transfer, leading to poor rate of reaction. Ultrasound-
assisted biodiesel production can be potentially used to enhance the
transesterification and/or esterification reactions with aid of advanced het-
erogeneous catalytic system. With the cavitation effect provided by ultra-
sonic irradiation, the emulsification and mass transfer limitation between
the two immiscibility reactants could be effectively minimized. Improved
internal mass transfer and hot spots generated during the ultrasonication
will allow high methyl ester to be made possible under milder process
conditions. Hence, the transesterification reaction might reach its equilib-
rium in shorter reaction time while lower catalyst loading and alcohol to
oil ratio are needed. Many aspects of this new process are yet to be fully
investigated such as behavior of the ultrasonic-mediated process, the roles

of ultrasound on the reactants and the catalysts, effects on biodiesel quality,
optimization of the reaction based on different aspects, and also the kinetic
modeling of the reaction. Influence of ultrasonication to the reaction in
terms of reaction temperature requirement, product separation and purifi-
cation, and methyl ester quality also deserves further research attention. It
is also necessary to evaluate the biodiesel quality parameters to make sure
that ultrasonic cavitations have no adverse effect on the biofuel quality to
make it not suitable engine use.
Acknowledgement
This oleochemical research work is made possible by a Fundamental
Research Grant Scheme (6071366) provided by the Ministry of Education
of Malaysia and a Research University grant (8014059) provided by
Universiti Sains Malaysia.
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3
Application of Catalysts in
Anilkumar R. Gupta and Virendra K. Rathod*
Department of Chemical Engineering, Institute of Chemical Technology,

Matunga (E), Mumbai, India
Abstract
Biodiesel has emerged as a potential substitute for petroleum diesel due to its supe-
riority in terms of renewable, biodegradable, and non-toxic nature. It can be pro-
duced from a wide range of feedstock using acid and base catalyst or biocatalyst.
Catalysts play a vital role in the economical production of biodiesel, as base cata-
lysts are only useful for high-quality feedstock, and low-quality feedstock requires
acid pretreatment followed by base catalysis. While using biocatalyst, simultane-
ous esterification and transesterification reaction can be carried out; however, its
high cost is of primary concern. Therefore, this chapter describes different cat-
alysts such as homogeneous acid (e.g., H2SO4 and H3PO4) and base (e.g., KOH
and NaOH) catalysts, heterogeneous acid (e.g., sulfated zirconia and alumina, and
cation-exchange resins), and base (metal oxide, hydrotalcite, etc.) catalyst, and
immobilized biocatalyst (immobilized lipase onto magnetic nanoparticles, resins,
etc.) with respect to their synthesis, mechanism, catalytic activity, effect on bio-
diesel yield or conversion, and their reusability.
Keywords: Biodiesel, heterogeneous catalyst, homogeneous catalyst, biocatalysis,

catalyst synthesis, transesterification, esterification
3.1 Introduction
Globally, energy demand is continuously increasing due to economic
growth and the rapid rise in the population [1]. The liquid fossil fuel is
*Corresponding author: vk.rathod@ictmumbai.edu.in
85
one of the primary sources used in transportation, agricultural, and indus-

trial sectors to meet their energy demand [2]. However, the burning of
fossil fuel emits harmful gases like carbon dioxide, nitrogen oxide, volatile
organic compounds, and hydrocarbons, which are responsible for global
climate change [3]. Apart from the environmental problem, it also impacts
the economic growth of major developing countries because of the depen-
dence on the import of crude oil. Being non-renewable is another disad-
vantage as it will be exhausted soon. Considering all these points, biofuel,
such as biodiesel, may be found as one of the alternatives to liquid fossil
fuel.
Biodiesel is monoalkyl esters of long-chain fatty acids produce using
edible or non-edible oils feedstock and alcohol (methanol or ethanol) or
esters (methyl acetate, ethyl acetate, and dimethyl carbonate) in the pres-
ence of a catalyst [4–6]. It can be used in the compression ignition (diesel)
engine (CIG) without any significant modification. Biodiesel appears as
an attractive biofuel because of renewable and biodegradable nature, free
from sulfur, aromatic compounds, and other harmful chemicals that harm
the environment [7]. It shows a high flash point and cetane number, better
lubricating properties, and similarities in physicochemical properties with
conventional petroleum diesel [6] and can be used as B100 (pure biodiesel)
or as a blend with petroleum diesel (B5–B20) in CIG [8].
Generally, edible vegetable oils such as sunflower oil, palm oil, soybean
oil, peanut oil, linseed oil, and coconut oil [9] have been used for the bio-
diesel production, but, due to continuous rise in the price and competing
with the food, raise the concern for the economic feasibility of biodiesel.
Non-edible oils (Jatropha curcas, Karanja, Neem, Madhuca indica, Rubber
seed oil, etc.), waste cooking oil (WCO), palm fatty acid distillate (PFAD)
[10], and animal fats (tallow, chicken fat, and a by-product of fish oil) [9]
can be the possible options to reduce the price and eliminate the competi-
tion with food. Furthermore, it also helps in solving waste disposal (animal
fats and waste oil) problems and reduction in the usage of arable land.
In recent times, microalgae become third-generation feedstock due to
the effective conversion of sunlight, water, and carbon dioxide into algal
biomass. The yield of algae oil per hector is 15 times higher than the second-
best oil, i.e., palm oil [11]. Therefore, there are different options available
to select the best available feedstock to reduce the cost and eliminate the
competition with food. The different feedstock used by the country has
been listed in Table 3.1 [12–14].
Biodiesel production can be carried out either by using a catalytic or
non-catalytic process. In the non-catalytic process, transesterification of
vegetable oil occurs well above the critical temperature of alcohol (513-K
Catalyst for Biodiesel 87
Table 3.1 Different biodiesel feedstock used by the respective country

in the world.
Country Biodiesel feedstock or raw material
Argentina Soybean, Sunflower, Crambe abyssinica, Jatropha
oil, Macrocarpa
Australia Waste cooking oil, Animal fat
Bangladesh Pongamia Pinnata, Rubber seed oil
Brazil Soybean oil, Palm oil, Caster oil
Canada Canola, Sunflower, Soybean
China Rapeseed oil, Waste cooking oil
Cuba Jatropha oil, Neem oil, Moringa oil
Europe Rapeseed oil, Sunflower oil
Finland Rapeseed oil, Animal fat
France Rapeseed oil, Sunflower oil
Germany Rapeseed oil
Ghana Palm oil, Coconut oil
Greece Sunflower oil, Cotton seed oil, Rapeseed oil
India Jatropha oil
Indonesia Palm oil
Ireland Animal tallow, Waste cooking oil
Italy Rapeseed oil
Japan Waste cooking oil
Kenya Castor oil
Malaysia Palm oil
Mali Jatropha oil
Mexico Animal fat, Waste cooking oil
Peru Palm oil, Jatropha oil
Philippine Coconut oil, Jatropha oil
(Continued)
Table 3.1 Different biodiesel feedstock used by the respective country

in the world. (Continued)
Country Biodiesel feedstock or raw material
Russia Rapeseed oil, Soybean oil, Sunflower oil
South Africa Canola oil, Sunflower oil, Soybean oil
South Korea Waste cooking oil
Spain Sunflower oil
Sweden Rapeseed oil
Tanzania Jatropha oil
Thailand Palm oil, Jatropha oil,
Turkey Sunflower oil, Rapeseed oil
USA Soybean oil
Zimbabwe Jatropha oil
methanol and 514-K ethanol) and pressure of 10–45 MPa [15]. This
process is not economically viable as energy consumption is too high
due to the requirement of high temperature and pressure. Therefore,
catalytic biodiesel synthesis is the most preferred process over the non-
catalytic process [16]. In the catalytic process, chemical catalysts or biocat-
alysts are used to transform the triglyceride (TG) molecule into fatty acid
alkyl esters (FAAEs).
The chemical catalysts exist in homogeneous (alkali and acid) and het-
erogeneous (solid base and acid) form. Traditionally, homogeneous cata-
lysts like sodium hydroxide (NaOH) and potassium hydroxide (KOH) are
used as it shows high catalytic activity for the transesterification of veg-
etable oil. However, it generates an ample amount of wastewater during
downstream processing, and being corrosive also enhances the cost due
to the requirement of costly corrosive resistance equipment [17]. The
use of heterogeneous catalysts is an alternative to overcome the problem
associated with a homogeneous catalyst with an advantage of recyclabil-
ity. The use of biocatalysts—free or immobilized form—is another option
for the transesterification process. It is beneficial over the chemical cat-
alyst in terms of producing high purity biodiesel, along with being envi-
ronment-friendly [18]. However, its higher cost is a significant obstacle
to employ on a commercial scale. The different catalytic methods used for
Homogeneous
Chemical
catalysis
Heterogeneous
Catalytic methods
Free enzyme
Biocatalysis
Immobilized enzyme
Figure 3.1 The different catalytic methods for the biodiesel production.
biodiesel production have been shown in Figure 3.1. This chapter concen-
trates on trends and current development in the field of catalysis for bio-
diesel production.
3.2 Homogeneous Catalysis for the Biodiesel

Production
In general, biodiesel is produced by using a homogeneous catalyst owing to
the number of benefits like faster reaction rate, high selectivity, ease of its
application, and optimization. The homogeneous catalysts are acids (sul-
furic acid, hydrochloric acid, phosphoric acid, aluminium chloride, zinc
chloride, etc.) and bases (sodium hydroxide, sodium methoxide, potas-
sium hydroxide, potassium methoxide, etc.). For scaling-up, the homo-
geneous catalyst is preferred as it requires milder reaction conditions.
However, the major drawback of the utilization of homogenous catalysts is
that it produces a vast amount of wastewater during the purification of the
crude biodiesel. However, studies have been carried out to solve this issue
by introducing newer technologies. Some of the selective homogeneous
catalysts used for biodiesel production with their reaction conditions have
been tabulated in Table 3.2.
3.2.1 Homogeneous Acid Catalyst

The low quality and non-edible feedstock content large amounts of free fatty
acids (FFAs) (5%–40%) [32] which are not suitable for the base-catalyzed
90
Table 3.2 List of some selective homogeneous catalyst used for biodiesel production with their reaction conditions.
Reaction conditions Yield/Conv.
Catalyst Feedstock a b c d (%) Ref.
KOH Madhuca indica oil 1.5 333 9:1 90 91.76 [19]
NaOH Waste oil 0.49 333 12.2:1 63 95.6 [20]
KOH Hempseed oil 1.2 316.4 6.4:1 98.5 [21]
NaOH Soybean oil 1.0 333 6:1 60 90.0 [22]
CH3ONa WCO assisted 0.75 MW power 6:1 3 97.9 [23]
750 W
KOH Soybean oil with US assisted 1 333 6:1 6 98.0 [24]
KOH WCO 1.2 338 6:1 60 93.2 [25]
KOH Karanja oil 1.25 333 9:1 120 88.7 [26]
KOH Fish oil 0.75 343 9:1 60 97.11 [27]

KOH WCO with micro reactor assisted 1.16 335.4 9.4:1 2 98.26 [28]
H2SO4 Mixed oil pretreatment 2.5 333 6:1 60 96.6 [29]
AlCl3 Canola oil with THF as co-solvent 5 383 24:1 1080 98.0 [30]
p-toluene sulfonic acid Corn oil with dimethyl ether as co-solvent 4 353 6:1 120 100.0 [31]
a, Catalyst loading (%); b, Temperature (K); c, Molar ratio; d, Reaction time (min).
transesterification reaction as it leads to soap formation as shown in Scheme

3.1. This formed soap not only reduces the biodiesel yield but also prevents
the separation of FAAEs and glycerin and thus affects the quality of the
biodiesel [33]. Therefore, acid catalysts sulfuric acid (H2SO4), hydrochloric
acid (HCl), phosphoric acid (H3PO4), and sulfonic acid have been used to
carry out esterification reaction (Scheme 3.2). Among all these homoge-
neous acid catalysts, sulfuric acid was reported to give a better result for
the conversion of FFAs to biodiesel [34].
In most of the cases, acid catalyst only used as a pre-treatment step to
reduce the FFAs content ~1% as acid-catalyzed transesterification reaction
is 4,000 times slower than the base and requires a large amount of alcohol
[9, 35, 36]. The reason for the slower reaction rate for the acid-catalyzed
transesterification reaction as compared to base-catalyzed transesterifi-
cation reaction has been revealed by Lotero et al. [37] through studying
both, i.e., acid and base-catalyzed mechanism. In the case of acid-catalyzed
transesterification mechanism (Scheme 3.3), the first protonation of the
carbonyl oxygen of TG molecule is taken place by Brønsted acid which is
the crucial step for the interaction between TG and catalyst. This initial
step increases the electrophilicity of the carbonyl carbon, which becomes
more susceptible to the nucleophilic attack of the alcohol. In the final step,
O O
R C OH + MOH R C OM + H2O
FFAs Base catalyst Soap Water

M = Na+, K+, etc.
Scheme 3.1 Soap formation in the presence of free fatty acids with the base catalyst.
H
O O OH OH
OH + R C OH R -H R
R C H C OH C OH
O O
Acid R' H R'
FFAs R'—OH
catalyst
Alcohol
H
H
O O OH H OH
OR' -H
R C R C OR' R C O R C O
-H2O
H O H
FAAEs O
R' R'
Scheme 3.2 General esterification reaction mechanism in the presence of an acid catalyst.
+
O OH
O O
O R1 O R1
H+
(i) R2 O R2 O
O R3 O R3
O O
+
OH OH + R
O O
O
O R1 O
(ii)
ROH R H 1
R2 O R2 O
O R3 O R3
O O
O
OH + R
O O O R1 OR
O H OH
(iii) R1 R2 O +
R2 O
O R3 O R3 +
O H
O
R1, R2, R3: Long chain fatty acid; R: Atkyl group of alcohol
Scheme 3.3 Acid-catalyzed transesterification of TG (i) Protonation of carbonyl oxygen

by acid catalyst; (ii) Alcohol (ROH) attacks on electrophilic carbon; (iii) Proton migration
and formation of product (FAAEs). This mechanism repeated two more times to give
finally three moles of product.
intermediate break down with the release of the product (FAAEs) and
regeneration of catalyst, i.e., H+ ion.
Whereas, the base-catalyzed transesterification reaction takes a more
direct pathway in which active species alkoxide ion (OR− act as a strong
nucleophile) generated initially and attacked to the carbonyl group to
transform TG to FAAEs. Thus, the difference in the formation of elec-
trophilic species in the case of an acid catalyst and nucleophilic species
for base catalyst is ultimately responsible for the acid and base-catalyzed
transesterification reaction rate.
Because of aforesaid reason, the feedstock with high FFAs is subjected
two-step process, i.e., esterification followed by transesterification. Bouaid
et al. [38] carried out the conversion of crude Jatropha oil into biodiesel,
where they employed the two-step process. In the first step, Jatropha oil
was subjected to esterification using acid catalyst H2SO4 to reduce the %
FFAs content from 9.48% to less than 1%, under the optimum condition
of molar ratio of 20:1, reaction temperature of 333 K, and 5 wt% H2SO4 in

60-min reaction time. In the second step, alkaline catalyzed transesterifi-
cation of Jatropha oil (FFAs < 1%) was performed and obtained more than
98% biodiesel yield.
In another study, crude algal oil (5.3 %FFAs) was converted into bio-
diesel using a similar approach, i.e., esterification followed by transester-
ification. In the beginning, acid (H2SO4) esterification was performed to
reduce the %FFAs from 5.3 to <1% with reaction parameter of 12:1 metha-
nol to oil molar ratio, reaction temperature of 333 K, 1 wt% of acid catalyst
(H2SO4), and agitation speed of 400 rpm in the reaction time of 90 min.
The esterified oil was then used for alkali (KOH) transesterification reac-
tion, where the maximum biodiesel yield of 83% was achieved in 20-min
reaction time [39].
Apart from Brønsted acid, homogeneous Lewis acid catalyst Aluminium
chloride (AlCl3) was also employed for the biodiesel production from
canola oil. The maximum conversion of 98% was achieved with optimized
conditions—methanol-to-canola oil molar ratio of 24:1, temperature
383 K, and reaction time of 1,080 min using THF as a co-solvent [30].
The acid catalysts are very sensitive to the water present in the feed-
stock as it deactivates the catalyst. It was investigated that a small portion
of water (0.1 wt%) in the raw material affects the yield of acid-catalyzed
biodiesel. When the water content becomes 5 wt%, it was observed that
acid-catalyzed transesterification of soybean oil was completely hindered
and esters conversion dropped drastically from 95.1% to 5.6% under the
similar reaction conditions—molar ratio of 6:1, reaction temperature of
333 K, and 3 wt% H2SO4 with reaction time of 5,760 min [40]. The acid-
catalyzed biodiesel synthesis has some disadvantages such as it generates
a large amount of acidic water during the neutralization process, corrode
the equipment, and slower reaction rate for the conversion of feedstock to
biodiesel. Therefore, the heterogeneous acid catalyst has been developed to
solve the problem associated with a homogeneous acid catalyst, which will
be discussed in Section 3.3.1.
3.2.2 Homogeneous-Base Catalyst

The alkali-based homogeneous catalysts are the most preferred catalysts
for commercial biodiesel production [34]. It includes alkali metal hydrox-
ides and alkali metal alkoxides. The metal alkoxides are the more reactive
catalyst in carrying out transesterification reaction as it readily dissociates
into CH3O− and metal ion (Na+ and K+). However, due to lower cost, alkali
hydroxides (NaOH and KOH) are preferred over alkoxides for industrial
biodiesel production [41]. NaOH has added an advantage over KOH due
to faster solubility in methanol and economically available [42]. The per-
formance of the alkali catalyst depends on the quality of the feedstock, e.g.,
feedstock with %FFAs <1 wt% and water content <0.5 wt% give higher
biodiesel yield. The homogeneous base-catalyzed transesterification reac-
tions require a relatively smaller amount of catalyst, lower temperature and
molar ratio, and shorter time to reach the completion of the reaction [43].
The general transesterification of TG with their mechanism has shown in
Scheme 3.4, and the process flow block diagram for base-catalyzed bio-
diesel production has been depicted in Figure 3.2.
The canola oil was transesterified with 3 wt% NaOH and gave 85% bio-
diesel yield with oil-to-methanol molar ratio of 6.5:1, reaction temperature
Mechanism:
(i) ROH + B RO +
+ BH
–
O O
O OR
O
O R1 O R1
(ii) R2 O + RO– R2 O
O R3 O R3
O O
O–
OR O O
O –
O R1 O
(iii) R2 O R1 OR + R2 O
O R3 O R3
O O
O O
O OH
+
(iv) R2 O + BH R2 O + B
O R3 O R3
O O
R1, R2, R3: Long chain fatty acid; R: Atkyl group of alcohol
Overall reaction:
B
Triglyceride + 3 ROH 3FAAEs + Glycerol
Scheme 3.4 Alkali catalyzed transesterification of TG (i) formation alkoxide ion (strong
nucleophile); (ii) attack of a nucleophile to the carbonyl carbon of TG to form tetrahedral
intermediate; (iii) break down of intermediate to form FAAE; (iv) regeneration of the
catalyst. This mechanism repeated two more times to give finally three moles of product.
Oil or pretreated oil + Catalyst + MeOH
MeOH
Transesterification
Separation Evaporation
Lower Phase Upper Phase

Crude Biodiesel
Purification Washing followed by

drying
Alkaline
Glycerol wastewater
Pure Biodiesel
Saponified
product
Figure 3.2 The block diagram for base-catalyzed biodiesel production.
of 70°C, and agitation speed of 550 rpm, in the reaction time of 120 min
[44]. In one more study, different concentrations of NaOH were used and
reported their respective rapeseed biodiesel yield. The maximum yield of
96% was found under mechanical stirring with 2 wt% NaOH in 15-min
reaction time [45]. Verma et al. [26] employed KOH for Karanja biodiesel
synthesis using both methanol and ethanol as an acyl acceptor. The highest
yield of 88.7% and 77% were obtained for methanolysis and ethanolysis,
respectively, at the reaction temperature of 333 K, the molar ratio of 9:1, and
catalyst loading of 1.25 wt% in 120-min reaction time. Maddikeri et al. [6]
investigated the potassium methoxide (KOCH3) catalyzed ultrasound-as-
sisted interesterification of WCO using methyl acetate as an acyl acceptor.
Under the optimal reaction conditions such as 12:1 WCO to methyl acetate
molar ratio, 313 K, and catalyst concentration of 1 wt%, biodiesel yield of
90% was obtained.
The main drawback of homogenous base-catalyzed transesterification
process is the requirement of high-quality pretreated feedstock as a pres-
ence of a small amount of water turn TG molecule into the soap as shown
in Scheme 3.5. The other disadvantages are energy-intensive purification
step and generation of a large amount of wastewater during the neutral-
ization of alkaline biodiesel. Hence, the researchers have been worked to
O
O O
O R1 OH
R2 O + 3MOH + 3H2O 3R OM + OH –
O R3 OH
O Base Water Soap Glycerol

TG Catalyst
+ +
M = Na, K, etc
Scheme 3.5 Soap formation in the presence of water and base catalyst.
develop a heterogeneous base catalyst to resolve the issues linked with

homogeneous catalyst and described in detail in Section 3.3.2.
3.3 Heterogeneous Catalyst

The process of conversion of feedstock to biodiesel can be improved by
introducing heterogeneous catalysts, as it minimizes the downstream pro-
cessing costs and generation of hazardous waste, which is linked with the
homogeneous catalysts [42]. Heterogeneous catalyst has added advantages
as ease of recovery, reusability, and promoting cost-effective greener pro-
cesses [46]. Heterogeneous catalysts can tolerate high FFAs and water con-
tent in the feedstock. These catalysts can be operated in harsh conditions
like high temperature and pressure.
The heterogeneous catalysts used for biodiesel production are metal
oxides, mixed metal oxides, supported acid and base catalysts, zeolites,
hydrotalcite (HT), and ion exchange resin, derived from waste sources,
renewable biomass, immobilized biocatalysts, etc. The main problem asso-
ciated with the use of heterogeneous catalysts is an increase in the mass
transfer resistance due to a further rise in the heterogeneity by forming
three phases (feedstock + alcohol + catalyst) [4]. An increase in the hetero-
geneity results in reduced interaction between TGs and alcohol molecules.
These mass transfer limitations can be reduced by introducing nanocatalyst
or solid support/carrier to provide a larger surface area for the interaction.
The supports are designed to carry out entrapment or anchoring of active
molecules on its surface or inside pores [47]. From the decade, a continu-
ous effort has been made to improve the properties of support materials.
The efficient catalytic process can be made by improving catalytic activity
and selectivity, which depends on the tailoring of the catalytic materials
and distribution of active sites [48]. The mesoporous support materials
offer such type of characteristics to improve the catalytic activity [47].
The heterogeneous catalysts for the FAAEs or biodiesel synthesis grouped

into acid and base catalysts.
3.3.1 Heterogeneous Acid Catalyst

Considering the obstacles allied with the usage of homogeneous acid cat-
alysts, there are many researchers who have been worked to develop het-
erogeneous acid catalysts as an alternative for biodiesel synthesis. These
catalysts are useful in the esterification of readily available low-quality feed-
stock. Also, it ables to carry out simultaneous esterification and transester-
ification of FFAs and TG molecules, respectively. The solid acid catalyst
shows high catalytic activity due to the presence of a variety of acidic sites
of different strength on its surfaces [49]. To date, different heterogeneous
acid catalysts, sulfated zirconia (SZ) and alumina, sulfated silica, tung-
stated zirconia [50], heteropolyacid (HPA)–derived catalyst [51], biomass
impregnated catalyst [52], H-form zeolites, cation-exchange resins [53],
etc., have been evaluated for the conversion of FFAs and TGs to biodiesel.
The SZ is a solid superacid catalyst and found a wide variety of appli-
cations in organic transformations like isomerization, alkylation, and
esterification reactions. The various methods have been evaluated for
the preparation of SZ such as impregnation of dried zirconium hydrox-
ide [Zr(OH)4] with H2SO4 or ammonium sulfate [(NH4)2SO4], co-
precipitation of Zr(OH)4 and sulfates, impregnation of crystalline zirco-
nium oxide (ZrO2) with H2SO4 or (NH4)2SO4 [54], using Zirconium oxy-
chloride octahydrate (ZrOCl2.8H2O) as a precursor to form Zr(OH)4, and
impregnating with chlorosulfonic acid (HSO3Cl) followed by calcination
as shown in Figure 3.3 [10].
It has been observed that SZ with low or medium sulfur content only
shows a tetragonal phase, whereas high sulfur content SZ shows minor
monoclinic phase along with primary tetragonal phase [55]. One of the
studies found that HClSO3 SZ contains three times more sulfur than H2SO4
SZ [56]. Zhang et al. [56] employed SZ as a superacid catalyst for one-
step synthesis of biodiesel from crude rice bran oil with 40% FFA and
reported yield above 92% for three consecutive cycles, under the reaction
conditions—molar ratio of 12:1, 6 wt% catalyst, 393 K, and 720 min of
reaction time. A similar super acid catalyst (SZ) was used to esterify the
PFAD into biodiesel. In this study, methanol to PFAD molar ratio of 8:1,
catalyst loading of 3.5 wt%, reaction temperature of 333 K, stirring speed
of 250 rpm, and molecular sieve of 5 wt% were used and obtained 91.5%
conversion in 150-min reaction time [10].
Synthesis of Zr(OH)4 precursor Synthesis of HCISO3-ZrO2
ZrOCl2.8H2O + Zr(OH)4 +
25% NH3 solution 0.5 M HCISO3
Hydrolysis at Stirred for 5 min
373 K pH 9-10
Mixture was heated to 393 K
Obtained solid was aged to remove solvent completely
for 720 min at 373 K
Washed with DI water Dried in oven at 393 K for 1440 min

till neutral pH
Absence of CI¯ detected

by AgNO3 test Calcined at 873 K for 180 min
Obtained Zr(OH)4 was dried

for 1440 min at 378 K HCISO3-ZrO2 catalyst obtained
Figure 3.3 The flow diagram of synthesis of SZ from zirconium oxychloride octahydrate
using chlorosulfonic acid.
The γ-alumina (Al2O3) intensively used for acid catalyst preparation due
to the high thermal stability and presence of Lewis acid sites on its surface
[57]. There have been various γ- Al2O3–derived heterogeneous acid cata-
lysts reported for the biodiesel synthesis. Vahid et al. [58] prepared alu-
mina supported SZ nanocatalyst by grinding ZrOCl2·8H2O and (NH4)2SO4
with different amount of aluminium sulfate [Al2(SO4)3·18H2O] followed
by calcination at 773 K for 600 min. The obtained catalyst was employed
for the conversion of WCO to biodiesel and reported the 93.5% yield in
93-min reaction time under the optimum parameters of 12.7:1 methanol
to WCO molar ratio, the temperature of 421.5 K, and catalyst loading (alu-
mina-supported SZ) of 2.9 wt%. Kashyap et al. [59] used γ-Al2O3 as a cata-
lyst for the interesterification of Karanja oil to produce biodiesel.
In another study, zirconia-alumina, the composite material, was synthe-
sized using the sol-gel method and then sulfated with wet impregnation
and hydrothermal method. In the wet impregnation method, Zr-Al2O3
impregnated with 1 N sulfuric acids followed by calcination at 823 K for
720 min, whereas, in the case of hydrothermal method, Zr-Al2O3 and
thiourea were fed to the steel reactor and autoclave to 453 K for 1,440 min.
The hydrothermally synthesized sulfated Zr-Al2O3 catalyst was used for
the Jatropha oil biodiesel production, and a maximum conversion of 96%
was obtained with reaction parameters of 20:1 methanol to oil molar ratio,
1.5 wt% catalyst, and reaction temperature of 383 K in 180-min reaction

time [60].
The mesoporous silica, such as SBA-15, can be used as catalysts sup-
port because of high surface area (400–900 m2/g) and high mechanical
and hydrothermal stability [61]. SBA-15 is synthesized with a coopera-
tive self-assembly process using Pluronic 123 as a template and tetraethyl
orthosilicate as a silica source under acidic conditions [62]. After comple-
tion of synthesis, the template is removed to form hexagonal pores with a
diameter of 5 to 30 nm [63]. The SZ supported on SBA-15 was synthesized
by dispersing SBA-15 into zirconium (IV) propoxide and hexane solution
followed by stirring until all the solvent get evaporated. The obtained solid
was dried and immersed in 0.5 N H2SO4 for 30 min. The sulfated product
was dried and subjected to calcination for 180 min. The obtained SZ sup-
ported on SBA-15 was used for the transesterification of palm oil. Under
the optimal conditions (catalyst loading of 5 wt%, molar ratio of 20:1,
473 K, and reaction time of 300 min) biodiesel yield reached more than
95% [64].
The sulfated titania-silica catalyst was synthesized by two steps pro-
cess. In the first step, titania-silica support was incorporated by the sol-gel
method, and in the second step, sulfuric acid was impregnated on support.
This catalyst was tested for the conversion of waste oil into biodiesel. The
maximum conversion was found to be 94.7% using a molar ratio of 20:1,
reaction temperature of 353 K, catalyst loading of 10 wt% in the reaction
time of 180 min [65]. For biodiesel production, esterification of palmitic
acid was carried out using two sulfonated catalyst—ZrO2-TiO2-SO3H and
ZrO2 -TiO2@SO24−. These catalysts were synthesized in two steps. In the
initial step, ZrO2-TiO2 nanorods were prepared by wet chemical precip-
itation method, whereas in the next step, nanorods were functionalized
2−
with an active group as depicted in Figure 3.4. The ZrO2 -TiO2@SO4 cata-
lyst exhibited high acidity and surface area and gave 95.3% biodiesel yield
while ZrO2-TiO2-SO3H showed lower acidity and surface area with 93.1%
biodiesel yield. However, ZrO2-TiO2-SO3H exhibited relatively high stabil-
ity even after five cycles [66].
Tungstated zirconia (WO3/ZrO2) was prepared by a simple impregna-
tion method where Zr(OH)4 was impregnated with ammonium metatung-
state hydrate [(NH4)6(H2W12O40).nH2O] followed by calcination at 1,073 K
for 240 min. The synthesized solid acid catalyst (WO3/ZrO2) was subjected
to in situ transesterifications of Scenedesmus sp. dried biomass under soni-
cation with molar ratio of 60:1, reaction temperature of 333 K, and catalyst
amount of 4 wt%. The maximum conversion of 71.37% was obtained in
20-min reaction time [67]. Peruzzolo et al. [68] synthesized heterogeneous
(a)
ZrO2
400 0C
pH=11 3h
TiO2 nanorods ZrOCl2·8H2O ZrO2–TiO2 nanorods

(b)
500 0C
H2SO4
5h SO42-
ZrO2-TiO2 nanorods ZrO2-TiO2@SO42- nanorods
C2H5
(c)
O
C2H5
OH SH 90 0C
O Si (CH3)3
OH
24h N2
O
OH
C2H5
ZrO2-TiO2 nanorods
OEt
Si (CH3)3
O SO3H
H2SO2 OEt
HCI OH
OH
ZrO2-TiO2-SO3H nanorods
Figure 3.4 Synthesis of (a) ZrO2-TiO2 nanorods, (b) ZrO 2 − TiO 2 @SO 24− nanorods, and
(c) ZrO2-TiO2-SO3H. (Adapted from Ref. [66] with permission from Elsevier Inc.).
acid catalysts in which tungsten species were supported on commercial

mesoporous silica. The two tungsten species—ammonium para tung-
state (NH4)10H2(W2O7)6 and sodium tungstate (Na2WO4)—were used for
incipient-wetness impregnation on mesoporous silica Cariact Q-15. For
the impregnation of (NH4)10H2(W2O7)6, the aqueous solution was used
whereas for Na2WO4, ammonia aqueous solution. Both these catalysts
were then employed for the esterification of palmitic acid. The ammonium
paratungstate impregnated catalyst gave 83.9% conversion. In comparison,

sodium tungstate impregnated catalyst gave 82.3% conversion under sim-
ilar reaction conditions, i.e., the temperature of 393 K, the molar ratio of
12:1, catalyst loading of 10 wt% in 360-min reaction time.
The heteropolyacid (HPA) belongs to the class of polyoxometalates and
generally soluble in the polar medium like water and methanol [51]. Hence,
it is required to impregnate on a solid support or modify to become hetero-
geneous in carrying out the transformation of feedstock to biodiesel. The
HPA was modified with surfactant (C16TA—cetyltrimethylammonium) to
get a heterogeneous catalyst with enhancing water tolerance capacity. The
obtained catalyst was then subjected to the esterification of palmitic acid
with methanol to give 94.7% conversion [69]. The HPA–phosphotungstic
acid (H3PW12O40) impregnated on mesoporous KIT-6 for biodiesel syn-
thesis from neem oil. For impregnation, dried support material KIT-6
was mixed with deionized (DI) water and stirred. The aqueous solution of
H3PW12O40 was added dropwise to support material under stirring in 360
min. After addition, the mixture was filtered and washed with DI water.
Then, the impregnated KIT-6 was dried and calcined at 573 K for 300 min.
The obtained catalyst was used for the transesterification of neem oil with
methanol, and under optimal reaction conditions, maximum conversion
of 90% was achieved [70]. de Oliveira’s group [71] also performed impreg-
nation of phosphomolybdic (H3PMo12O40) HPA on bentonite to carry out
esterification of the distillate of deodorization of palm oil. The maximum
conversion of 93.3% was found for the molar ratio of 30:1, catalyst loading
of 5 wt%, reaction temperature of 403 K, and reaction time of 120 min.
Waste biomass is an excellent choice for the synthesis of a low-cost het-
erogeneous acid catalyst. It can be synthesized using different techniques
like direct sulfonation or carbonization, followed by sulfonation [72]. The
direct sulfonation is a straightforward and most widely used process under
which sulfonation and carbonization of waste biomass are performed
using H2SO4 at a preset temperature and time. Savaliya and Dholakiya [73]
prepared the solid acid catalyst using sugarcane bagasse where in situ car-
bonization and sulfonation were carried with concentrated sulfuric acid.
The yield of bagasse derived catalyst was 25–35 wt% w.r.t. raw material.
Furthermore, the obtained catalyst was studied for the biodiesel pro-
duction from the soapstock oil, and the maximum conversion of 97.2%
was reported. Its reusability was also tested and recycled up to three con-
secutive cycles without hampering its activity. In another study, the direct
sulfonation of coconut meal residue was carried out for biodiesel synthe-
sis from waste palm oil. For the preparation of the catalyst, coconut meal
residue was mixed with concentrated sulfuric acid to bring out in-situ
incomplete carbonization. The prepared catalyst was used to transesterify

the waste palm oil into biodiesel. The maximum biodiesel yield of 92.7%
was achieved, and the catalyst recycled up to four batches with maintaining
high catalytic activity [74].
Guo et al. [75] investigated that directly sulfonated materials showed
reduced catalytic activity and low acid density and no recyclability. To
overcome this problem, phenol was used as an additive due to its ease of
sulfonation and enhancement of acid density. In the case of carbonization
followed by sulfonation process (Figure 3.5), different biomass such as
agricultural waste, lignin, bagasse, algae, and seed cake (DOWC, de-oiled
seed waste cake) was first carbonized to remove moisture and breakdown
the carbon-carbon bond followed by sulfonation [72]. The carbonization
can be carried out using different processes—pyrolysis, hydrothermal, sol-
vothermal, etc. The various biomasses used to derive solid acid catalysts
through different process conditions for biodiesel production have been
summarized in Table 3.3.
Zeolites are inorganic material—aluminosilicates occur naturally or can
be synthesized by varying Si/Al ratios [51]. Doyle et al. [88] prepared a
zeolite Y catalyst from kaolin and studied its catalytic activity in the ester-
ification of oleic acid. For the preparation of zeolite Y first NaY zeolite was
synthesized using kaolin clay then transformed into HY zeolite by cat-
ion exchange. The synthesized catalyst applied for the conversion of oleic
acid into biodiesel. The obtained conversion was 85% with molar ratio of
6:1, catalyst concentration of 5 wt%, and reaction temperature of 343 K
in 60-min reaction time. Patel and Narkhede [89] were synthesized the
zeolite derived catalyst in which HPA–12-tungstophosphoric acid (TPA)
was anchored to Zeolite Hβ. In the synthesis procedure, sodium zeolite β
with Si/Al ratio 10 was converted to NH+4 form via the conventional ion
COOH COOH
OH OH
O OH OH
O
HO3S SO3H
HOOC COOH H2SO4 (98%)
DOWC HOOC
COOH
Protein, HO
HO O O
carbohydrate HO3S
and lipid (trace) OH SO3H
HO OH
HO
HOOC SH
HOOC
Carbon source Activated Carbon Sulfonated Activated Carbon
Figure 3.5 Synthesis of sulfonated acid catalyst from the biomass (DOWC) using
carbonization followed by sulfonation route. (Adapted from Ref. [76] with permission
from Elsevier Inc.).
Table 3.3 Different biomass derived solid acid catalyst used for the biodiesel production.
Acid site density
Biomass a b c d Feedstock (mmol/g) Yield/Conv. (%) Ref.
Peanut shell 996 900 746 600 Cotton seed oil 6.85 90.20 [77]
Sugarcane bagasse 648 30 423 900 WCO 3.69 93.80 [78]
Coconut shell 695 240 373 900 Palm oil 3.21 88.15 [79]
Deoiled Jatropha 623 240 363 300 Jatropha curcas oil 2.24 99.13 [80]
curcas seed
Cassava stillage 873 180 433 120 WCO 1.60 94.30 [81]
residue 453 120 1.65 94.10
Deoiled Mesua ferrea 996 60 453 480 Oleic acid 2.01 42.00 [76]
L. seed
Hardwood 800 -- 423 1440 WCO 0.043 89.00 [82]
Vegetable oil asphalt 773–973 -- 483 600 Cotton seed oil 2.04 89.93 [83]
Deoiled Calophyllum 673 300 423 600 Calophyllum 2.8 36.40 [84]
inophyllum seed inophyllum oil
Catalyst for Biodiesel
(Continued)
103
104
Table 3.3 Different biomass derived solid acid catalyst used for the biodiesel production. (Continued)
Acid site density
Biomass a b c d Feedstock (mmol/g) Yield/Conv. (%) Ref.
De-alkaline lignin 533 1200 423 600 Jatropha and Soybean 5.05 92.20 [85]
673 120 423 600 blended oils 5.35 93.20
Sugarcane bagasse 723 300 423 300 PFAD -- 80.00 [86]
Wood waste 723 120 423 900 Canola oil 2.6 7.60 [87]
White wood bark 948 1.2 24.40
Wood shaving 1148 0.43 8.40

a, Carbonization temperature (K); b, Carbonization time (min); c, Sulfonation temperature (K); d, Sulfonation time (min).
exchange process. Then, calcination was carried out at 823 K for 360 min
to get Hβ zeolite. After the preparation of zeolite Hβ, the impregnation
of TPA was performed to obtain the acid supported catalyst. When the
synthesized catalyst was subjected to the esterification of oleic acid, the
highest conversion of 85% was obtained and retained its catalytic activity
even after four cycles.
The cation exchange resins are organic solid acid catalysts that show
quite high catalytic activity under mild reaction conditions. It also utilized
for industrial biodiesel production from the feedstock with high FFAs
content [53, 90, 91]. The most commonly used resin for the esterifica-
tion and transesterification reactions are sulfonic ion-exchange resin and
commercially available as Amberlyst resins (Amberlyst-15, Amberlyst-45,
Amberlyst-46, etc.), Nafion resins (Nafion NR50 and SAC-13), and EBD
resins (EBD-100, EBD-200, and EBD-300) [90]. These ion-exchange resins
are usually cross-linked polymer on which strong sulfonic acid groups are
bonded, and it acts as an active site for the esterification reaction [92].
Amberlyst-15 is one of the macroporous reticular polystyrene-based
sulfonic ion-exchange resins, generally used to esterify the feedstock
for the biodiesel production. For example, Amberlyst-15 (surface area
53 m2/g) used in the esterification of crude Macaúba oil with ethanol
in the temperature range 333–373 K. The maximum yield of 32.8% was
found with 72% conversion [93]. Hykkerud and Marchetti [94] applied
Amberlyst-15 Wet catalyst for the esterification of oleic acid with etha-
nol, and the highest yield of 53% was achieved in the reaction time of
300 min. Ilgen [95] investigated oleic acid esterification with methanol
using Amberlyst-46 (surface area 75 m2/g) catalyst. With optimal reaction
conditions, i.e., molar ratio of 3:1, catalyst loading of 15 wt%, reaction
temperature of 373 K, and the reaction time of 120 min, the extent of con-
version of 98.23% was attained. The Amberlyst-45 retained its catalytic
activity even after 10 cycles.
Nafion NR50 is a super acidic ion exchange resin made up of sulfonic
acid supported fluorinated polymers. In contrast, Nafion SAC-13 is a com-
posite material (sulfonic acid functionalized Nafion polymer on porous
silica) with high surface area (more than 200 m2/g) and high-temperature
stability (443 K). Both the acidic ion-exchange resins showed pronounced
catalytic performance in carrying out esterification and transesterification
reactions. For instance, López and co-worker [96] examined the trans-
esterification of triacetin using Nafion acid ion-exchange resins. They
investigated the swelling properties of Nafion NR50 and found methanol
enhances the higher degree of polymer swelling that results in increased
exposure of active sites of the catalyst. The Nafion NR50 showed a higher
initial reaction rate as compared to Nafion SAC-13 due to the presence of

more acid site density.
EBD resins are polymeric matrix made of styrene and divinylbenzene
co-polymers and functionalized with strong sulfonic acid. EBD-100 is a
microporous gelular resin and has a low quantity of divinylbenzene (5%–
8%), while the other two, i.e., EBD-200 and EBD-300 are macroporous
resins have a significant portion of divinylbenzene (12%–20%). Russbueldt
and Hoelderich [97] were used aforesaid acid ion-exchange resins for the
pretreatment of FFAs containing vegetable oils. The catalytic performance
of the microporous gelular resins EBD-100 was superior to the macropo-
rous resins—EBD-200 and EBD-300. The obtained result might be due to
dense gel matrix and poor methanol uptake of the macroporous materials,
while high swelling of low cross-linked EBD-100 in methanol. The main
problem associated with the use of EBD resins for the pretreatment is its
fast catalytic deactivation due to the presence of the low amount of salts as
a contaminant in the feedstock. However, deactivation of EBD resins can
be reversed by simply washing with hydrochloric acid [90].
Another, acid resins catalyst Purolite (polystyrene cross-linked with
divinylbenzene) D5081 and D5082 were used to esterify the oleic acid
with methanol at 338 K. It has been observed that both Purolite D5081
and D5082 showed highest oleic acid conversion for the similar catalyst
loading as compared to other tested sulfonic ion-exchange resins such as
Amberlyst-15, Amberlyst-35, and Nafion SAC-13. The reason might be
explained on the basis of ease of accessibility of the reactant molecule to
the active sites of the catalyst [98].
3.3.2 Heterogeneous-Base Catalyst

As mentioned, the drawbacks of homogeneous base catalysts in Section
3.2.2, the various heterogeneous base catalysts, have been investigated for
the transesterification of TGs. For example, alkaline and alkaline earth
metal carbonates (e.g., Na2CO3 and CaCO3), alkaline earth metal oxide
(e.g., CaO and MgO), mixed metal oxide (e.g., Ca-Zn mixed oxides), HT
(e.g., Al-Ca HT), supported and doped solid base catalyst (e.g., CaO or
MgO supported on silica), etc. [99–101].
The alkali and alkaline earth metal carbonate—sodium carbonate
(Na2CO3), potassium carbonate (K2CO3), calcium carbonate (CaCO3),
magnesium carbonate (MgCO3), etc.—have been attempted for the trans-
esterification of vegetable oil. In K2CO3 catalyzed transesterification of
Jatropha curcas oil, potassium carbonate reacted with methanol and gen-
erated potassium methoxide, which was measurably responsible for the
high biodiesel yield (ca. 98%) [102]. However, CaCO3 and MgCO3 were
not directly used to transesterify the feedstock as it has been less basic and
needs to transform into a more active catalyst, i.e., corresponding oxides
[99].
Alkaline earth metal oxides—MgO (magnesium oxide), CaO (calcium
oxide), SrO (strontium oxide), and BaO (barium oxide)—were extensively
studied as a solid base catalyst. These metal oxides show intense catalytic
activity in carrying out transesterification reaction due to the presence of
M2δ+–O2δ− ion pairs (Scheme 3.6) [103] and exhibit its effectiveness in the
order: MgO < CaO < SrO < BaO. Furthermore, Lee et al. [104] reported
that the basic strength of the metal oxides depends on the electronegativity
of the conjugated metal ion. The ionic radius of the Group II elements,
i.e., Mg2+, Ca2+, Sr2+, and Ba2+ in the periodic table, increases from top to
bottom due to which electronegativity decreases and that leads to decrease
the force of attraction on the electrons. Owing to this effect, the basic char-
acteristics of attached O2− enhances in alkaline earth metal oxides. Though
BaO is more effectively transesterified the feedstock, they are unsuitable
R–O– H+
2 + 2-
(i) ROH + M O
M O
O O–
O OR
O
O R1 O R1
– H
(ii) R2 O + R–O R2 O
O R3 O R3
O M O O
O
O OR O O
O R1 O–
(iii) R2 O R1 OR + R2 O
O R3 O R3
O O
O O
O– H+ OH
(iv) R2 O + R2 O +M O
O R3 M O O R3
O O
M-Ca2+, Mg2+, Sr2+, Ba2+
R1, R2, R3: Long chain fatty acid; R: Alkyl group of alcohol
Scheme 3.6 Alkaline earth metal oxides catalyzed transesterification of TG.

for biodiesel synthesis owing to higher solubility in methanol and noxious

property [105].
Among all alkaline earth metal oxides, CaO are the most investigated
catalyst for the conversion of vegetable oil into biodiesel due to its avail-
ability, lower cost, and ease of handling. It can be derived from different
sources in the form of carbonates such as chalk, limestone, marble, and
protective shells of a living organism such as eggs and seashells [106, 107].
Generally, the calcium carbonate is calcined in the range of 1,073–1,273 K
to decompose into CaO as shown in Eq. 3.1 [108].
−1273 K
CaCO3 ←1073
 → CaO + CO2 (3.1)
To test the activity of seashell derived CaO, Buasri et al. [109] carried
out the decomposition of waste seashell at 1,273 K and obtained CaO sub-
jected to transesterification of palm oil. At the optimal reaction conditions,
the catalyst gave a maximum yield of 97.23%. A similar study was per-
formed by the Goli and Sahu [110] using waste chicken eggshell derived
CaO (7 wt%), and the maximum biodiesel yield of 93% was reported.
Different calcium oxide sources used for biodiesel production with their
yield have been shown in Table 3.4.
Many of the researchers have been attempted to improve the catalytic
activity of CaO through physical or chemical treatment. Calcination,
hydration, and dehydration (C-H-D) of CaO sources are one the physical
treatment method to increase the surface area and basic strength of the
catalysts [119]. For instance, Begum’s group [120] carried out C-H-D treat-
ment to eggshells and reported enhanced surface area (8.64 m2/g) and basic
strength (12.2<H_<15.0) as compared to commercial CaO (surface area,
3.0 m2/g; basic strength, 9.8<H-<12.2). The treated eggshells were applied
for the transesterification of waste frying oil, and the obtained result was
compared with commercial CaO. It has been observed that C-H-D treated
CaO gave 94.52% yield, while commercial CaO gave only a 67.57% yield
for the same reaction conditions. Similar treatment (C-H-D) was applied
to Polymedosa erosa seashells to obtain highly activated CaO nanocata-
lyst with diameter 66 nm and surface area 90.61 m2/g [121]. The obtained
nano-CaO was subjected to Jatropha biodiesel synthesis and the yield of
98.54% was achieved with reusability up to six cycles without significant
loss in catalytic activity.
Some studies also revealed that the catalytic activity of CaO could be
improved by treating with different chemicals. For example, Tang and
co-workers [122] used surface modifier octadecyltrichlorosilane to modify
Table 3.4 Recent examples of different sources of calcium oxide used for the biodiesel production.
Calcination Transesterification reaction
CaO sources temp. (K) Feedstock conditions Yield/Conv. (%) Ref.
Chicken Eggshell 1,173 Palm kernel oil Catalyst amount - 4 wt%, T - 328 97.10 [111]
K, M/O - 10:1, t - 60 min
Waste Eggshell 1,173 Eucalyptus oil Catalyst amount - 12 wt%, T - 70.50 [112]
328 K, M/O - 6:1, t - 90 min
Chicken Eggshell 1,123 WCO Catalyst amount - 3 wt%, T - 338 93.10 [113]
K, M/O - 12:1, t - 90 min
Waste venus 1,173 Palm oil Catalyst amount - 5 wt%, T - 338 97.00 [114]
clam K, M/O - 15:1, t - 360 min
Limestone 1,273 Pongamia oil Catalyst amount - 12 wt%, T - 97.28 [115]
338 K, M/O - 15:1, t - 180 min
Chicken manure 1,123 WCO Catalyst amount - 7.5 wt%, T - 90.00 [116]
338 K, M/O - 15:1, t - 240 min
Ostrich Eggshell 1,273 WCO Catalyst amount - 1.5 wt%, T - 96.00 [117]
Chicken Eggshell 338 K, M/O - 12:1, t - 120 min 94.00
Mussel shell 1,173 Camelina sativa oil Catalyst amount - 1 wt%, T - 338 95.00 [118]
Clam shell K, M/O - 12:1, t - 120 min 93.00
91.00
Oyster shell
109
the CaO surface and applied for biodiesel production. It has been observed
that the surface-modified CaO performed very well (93.5% yield) as com-
pared to commercial CaO (80.6% yield) in the transformation of soybean
oil into biodiesel even in the presence of a small quantity of water. Lukic
et al. [123] carried out mechanochemical treatment of CaO using glycerol
to transform calcium oxide (9.3<H_<10) into more basic catalyst calcium
diglyceroxide (11.0<H_<15.0).
The mixed metal oxides are referred to as those which have more
than one metal oxide. The primary reason behind the synthesis of mixed
metal oxides is to improve the basic strength, surface area, and mechan-
ical strength as compared to single metal oxides [124]. The single metal
oxide like CaO leached out during transesterification reaction due to weak
mechanical strength and form suspension in the reaction mixture. The
formed suspension creates a problem during downstream processing. Lee
et al. [125] prepared the mixed metal oxide (MgO-ZnO) by co-precipitation
method and compared its effectiveness with corresponding individual
metal oxide (MgO and ZnO) for transesterification of Jatropha oil with
methanol. They found that MgO-ZnO mixed metal oxide is more active
catalyst for the conversion of TG into biodiesel and gave 83% yield while
individual metal oxide gave 64% for MgO and 41% for ZnO.
Taufiq-Yap and co-workers [126] also synthesized the calcium-based
mixed metal oxides (CaMgO and CaZnO) using the co-precipitation
method. For the synthesis of the catalyst, they used corresponding metal
nitrate, i.e., Ca(NO3)2, Mg(NO3)2, and Zn(NO3)2 in basic solution. The cal-
cination of the precipitates was performed at 1,073 K for CaMgO and at
1,173 K for CaZnO. The obtained catalysts showed higher basic strength
and reusability (up to six cycles) for the biodiesel production from crude
Jatropha curcas oil as compared to single metal oxide (CaO). The enhanced
catalytic activity of mixed metal oxides may be due to the synergy effect of
the interaction of multi-metal ion which results in increase basic strength
[127].
Hydrotalcite (HT) is a layer double hydroxide that occurs naturally or
it can be synthesized in the lab, which belongs to the class of basic and
anionic clays having general formula M12−+x M 3x+ (OH2)x+ (Ax/n)n-.yH2O. In
this formula, M+2 is a divalent metal cation and M+3 is a trivalent metal
cation, whereas An- is n- valent anions (CO3−, SO24−, Cl−, NO3−), and the value
of x in between 0.25 and 0.33 [128, 129].
HT was synthesized for the biodiesel production using simple co-
precipitation of aqueous solution magnesium and aluminum nitrates in
basic medium (NaOH and Na2CO3) followed by calcination. The prepared
Mg-Al HT was used for the transesterification of soybean oil. The maximum
conversion of 90% was achieved with 5 wt% catalyst loading. However, the
reusability of the catalyst was very poor as it showed a sudden drop in
the conversion from 90.7% to 64% after the first cycle [130]. To enhance
the catalytic performance, Gandia and co-workers [131] first prepared the
Mg-Al HT and then rehydrated to get more basic and recyclable HT, as
shown in Figure 3.6. The obtained catalyst was applied for the transesterifi-
cation of sunflower oil and gave 96% conversion with 2 wt% catalyst.
Fatimah et al. [132] also tried to enhance the catalytic activity of HT
by increasing basic sites on the surface. It was reported that potassium
impregnation increases the basicity of the catalyst. Therefore, potassium
fluoride (KF) modified HT catalyst was synthesized for biodiesel produc-
tion. The synthesized catalyst with 30% KF loaded HT gave maximum bio-
diesel yield of 97%.
Catalyst support provides not only large surface area to which cat-
alyst particles can be anchored but also chemical stability. The different
catalyst support like alumina, silica, zinc oxide, magnetic nanoparticles
(MNPs), and activated carbon (AC) have been used to carry out biodiesel
production.
Aluminum oxide also known as alumina with the chemical formula
Al2O3 is structural materials exist in different transitional phases that
have significant industrial application. The most common usage is as cat-
alyst support owing to high thermal stability, inexpensive, and high spe-
cific surface area [133]. The alumina-supported potassium oxides (K2O/
Al2O3) have been synthesized for the biodiesel production. The different
potassium compounds such as KF, KI, KOH, KNO3, and K2CO3 have been
used to support on Al2O3 by incipient-wetness impregnation method.
Triglycerides + MeOH
CO32- Mg(OH)2
H2O [AI(OH)2]+
Calcination
Mixed Oxide Reconstructed Hydrotalcite
Mg-Al Hydrotalcite Mg2+(AI3+)Ox Mg2+ nAI3+m (OH)(2n+3m)•yH2O
Active OH¯
[Mg2+nAI3+m (OH)2(n+m)]m+[Ax-]m/x•yH2O Rehydration No-active OH¯
Biodiesel + Glycerol
Figure 3.6 Calcination and rehydration of Mg-Al hydrotalcite for the biodiesel
production. (Adapted from Ref. [131] with permission from Elsevier Inc.).
For example, Baz’s group [134] synthesized KF impregnated γ-Al2O3 to

transesterify the canola oil and reported maximum biodiesel yield of 97.7%
with 3 wt% catalyst loading. Similarly, Luengnaruemitchai and co-work-
ers [135] prepared KOH/Al2O3 catalyst by impregnation of Al2O3 by an
aqueous solution of KOH. The obtained catalyst was tested for the trans-
esterification of palm oil, where the maximum yield of 91.07% achieved
with 3 wt% catalyst loading. Among different potassium sources (KF, KI,
KOH, KNO3, and K2CO3) the best result obtained by KF loaded alumina,
i.e., KF/Al2O3 catalyst, giving 99.6% yield with 3 wt% catalyst loading. The
enhanced catalytic activity might be due to the formation of the K2O phase
and surface Al-O-K groups which results in increased basicity [136]. CaO/
Al2O3 catalyst also prepared by the impregnation technique using calcium
acetate as a precursor. The obtained catalyst was employed for palm oil
biodiesel production and achieved a maximum yield of 98.64% with 5.97
wt% catalyst [137].
Mesoporous silica such as SBA-15 and MCM-41 are most widely used
for the incorporation of the guest molecule. For example, Mota’s group
[138] used MCM-41 mesoporous material (surface area ~ 1,000 m2/g) as
a support for the synthesis of amine-functionalized basic catalysts for the
biodiesel production. For the functionalization, the activated MCM-41
[MCM-41 activated at 453 K to remove adsorbed water and expose silanol
groups (Si-O-H)] first functionalized with 3-chloro propyl triethoxy silane
to form chloro-functionalized MCM-41 (MCM-41-Cl). In the next step
nucleophilic substitution of MCM-41-Cl with guanidine-derived com-
pound (1,5,7-triazabicyclo [4,4,0] dec-5-ene) was carried out as shown in
Figure 3.7 and obtained catalyst labeled as MCM-41-guanidine. The pre-
pared catalyst was subjected to transesterification of soybean oil and it gave
N N
CI CI N
N
N
Si Si
~ 3.5 nm O OO O Si Si
O O N O OO O
O O
N / NaH / THF / reflux
HN
CI Si(OEt)3 /
PhCH3 / refux
MCM-41 MCM-41-CI MCM-41-guanidine
Figure 3.7 Functionalization of MCM-41 surface with guanidine derivative

(1,5,7-triazabicyclo [4,4,0] dec-5-ene). (Adapted from Ref. [138] with permission
from Elsevier Inc.).
99% biodiesel yield in 180 min. However, the major drawback of the cat-
alyst was its reusability, as it shows a drastic drop in biodiesel yield (26%)
during the third cycle. The loss of catalytic activity of MCM-41-guanidine
might be due to the neutralization of basic sites by FFA present in the oil.
Samart et al. [139] prepared the KI supported mesoporous silica by
incipient wetness impregnation method applied for the biodiesel produc-
tion from soybean oil. The highest yield of 90.09% was achieved with 15%
KI loading on mesoporous silica and 5 wt% catalyst amount in reaction
time of 480 min. Furthermore, the catalyst was tested for their reusabil-
ity and it was found that after the first cycle, the yield was just 60%. The
mixed metal oxide–loaded mesoporous silica catalyst was prepared by Xie
and Zhao [140] for the soybean biodiesel production. They used incipient
wetness impregnation method under which SBA-15 was impregnated with
an aqueous solution of Ca(NO3)2 and (NH4)6Mo7O24, precursors followed
by drying at 373 K and calcination at 823 K. The obtained CaO–MoO3–
SBA-15 catalyst employed to transesterify the soybean oil. The optimized
conversion of 83.2% was achieved with 6 wt% catalyst.
ZnO supported calcium oxide catalyst was made in two steps. In first
step, ZnO was prepared from zinc oxalate, and in the second step, it was
impregnated with an aqueous solution of calcium acetate followed by
calcination at 873 K. The prepared catalyst further activated by thermal
treatment at 1,073 K for 60 min and used for the transesterification of
ethyl butyrate with methanol where it gave more than 90% yield [141].
Moholkar and co-workers [142], synthesized ZnO supported KI catalyst,
by a wet impregnation method. For the preparation of catalyst, 35 % aque-
ous solution of KI was used to impregnate ZnO to give KI/ZnO catalyst.
The obtained catalyst was applied for the ultrasound-assisted transesterifi-
cation of soybean oil to produce biodiesel. The highest conversion of 94.5%
was reported, while after the fifth cycle conversion was reduced to 54.7%.
The supported catalyst is lacking in the reusability generally due to leach-
ing of active catalytic species from the support, therefore, Kawi’s group
[143] calcium-doped Ce-incorporated SBA-15 catalyst was synthesized
and compared with SBA-15 supported mixed metal oxide (CaO-CeO2). For
the Ca-doped catalyst synthesis, the first Ce-incorporated SBA-15 was pre-
pared by dissolving P123, Ce(NO3)3, and tetraethylorthosilicate in acidic
solution (2 N HCl) followed by calcination at 823 K. After Ce-SBA-15
synthesis, it was doped with calcium by using Ca(NO3)2 aqueous solution
and finally calcined at 923 K to get Ca-doped-Ce-SBA-15. Whereas, for
mixed metal-supported SBA-15 (CaO-CeO2/ABA-15) was synthesized
using impregnation of an aqueous solution of calcium and cerium nitrate
followed by calcination at 923 K. Both these catalysts were tested for the
transesterification of palm oil with methanol. Ca-doped-Ce-SBA-15 cata-

lyst gave 96.4% yield while CaO-CeO2/ABA-15 catalyst gave only 71.2%.
Also, calcium doped catalyst reused up to 15 cycles without significant loss
in catalytic activity. The higher catalytic activity and reusability are shown
by calcium doped catalysts due to strong interaction between active species
and support.
MNPs recently received much attention as a support material because
of high surface area, simple synthesis and functionalization, and low cost
[144]. The main advantage of MNPs supported catalysts is their ease of
recovery under the magnetic field as compared to other energy-intensive
and time-consuming separation processes such as centrifugation and filtra-
tion [145]. The MNPs can be synthesized using different magnetic elements
like Fe, Ni, and Co into their oxides. The functionalization of MNPs can be
carried out by modification of their surface so that the active functional
group can be attached. For example, Chiang et al. [146] were synthesized
the MNPs, i.e., Fe3O4 by co-precipitation method using Fe+2 and Fe+3 in 1:2
molar ratio in basic medium then coated with silica using tetraethyl ortho-
silicate to form Fe3O4@Silica. The formed core-shell structure was function-
alized with organic super base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)
in two steps. First trimethoxysilyl propoxymethyl oxirane was anchored
onto MNPs coated silica and in the second step, TBD was functionalized to
get final catalyst (TBD-Fe3O4@silica). The synthesized basic catalyst was
tested for the Fatty acid methyl ester formation from algae oil and the high-
est yield of 97.1% was reported. Liu et al. [147] synthesized CaO coated
MgFe2O4 MNPs for soybean biodiesel production and with 1 wt% catalyst
loading, the maximum yield of 98.3% was achieved in 180 min.
AC exhibits high surface area, decent thermal stability, and low-cost
which makes it advantageous to use as catalyst support [148]. The highly
porous AC can be prepared from its precursor in two ways: the first way is
the physical activation where precursor thermally treated at 1,073–1,173
K in the presence of CO2 or steam, and in a second way, chemical activa-
tion is carried out by treating precursor with acid or base in the tempera-
ture range 723–923 K [149]. The support of the functional group on AC
was generally carried by impregnation. For instance, Narowska and co-
workers [150] were prepared AC from the beech tree and impregnated
with a saturated aqueous solution of KOH to get KOH/AC catalyst. This
catalyst was employed for the corn oil biodiesel production and it gave 92%
yield with 0.75 wt% catalyst amount. Fadhil et al. [151] also synthesized the
AC supported KOH catalyst using the wet impregnation method. The AC
was prepared from the precursor—polyethylene terephthalate waste. The
KOH/AC catalyst showed high basic strength and high catalytic activity in
the transformation of WCO and waste fish oil (WFO) into biodiesel. The
WCO gave 92.66% yield while WFO gave 88.12% yield, also the catalyst
was reused up to five cycles. In another study, AC supported CaO was syn-
thesized by impregnation of an aqueous solution of calcium nitrate on AC
followed by calcination at 813 K. The CaO/AC catalyst successfully trans-
esterified the WCO into biodiesel and showed the yield of 77.32% with 5.5
wt% catalyst in 142 min [152].
3.4 Biocatalysts
Nowadays, biocatalysts have found significant applications in various
industrial processes due to their ability to carry out selectively chemical
transformation [52, 153]. The enzyme-catalyzed reactions are environment
friendly, required milder reaction conditions, and high-quality byproduct
(glycerol) [154]. These advantages lead to the utilization of the enzyme
as a biocatalyst for biodiesel production. Also, it aids in overcoming the
problem associated with chemical catalysis like the generation of a large
amount of acidic or basic wastewater. Owing to insensitive to FFAs and
water content, biocatalyst (lipase) can be used for the lower grade feed-
stock to carry out simultaneous esterification and transesterification [155].
However, one of the bottleneck for the utilization of enzyme as a bio-
catalyst is its high cost. Immobilization of enzymes can mitigate the cost
by improving stability and reusability along with catalytic activity [156].
Immobilization of enzymes has been carried out using the physical method
(adsorption and entrapment/encapsulation) and chemical method (cova-
lent attachment and cross-linking) as shown in Figure 3.8 [157].
Enzyme immobilization
methods
Physical Chemical
methods methods
Adsorption Entrapment Covalent Cross-linking

attachment
Gel/fiber Micro- MOFs Cross-linking to
entrapping encapsulation embedding support matrix CLEAs
Enzyme
Figure 3.8 Different methods for immobilization of enzymes. (Adapted from Ref. [157]
with permission from Elsevier Inc.).
Enzyme immobilization was carried out using the physical adsorption

method, in which solid support soaked in the enzyme solution prepared
in the buffer. During the soaking period, hydrophobic interaction, and salt
linkage happened which lead to adsorption [158]. For instance, Thakur
and co-workers [159] immobilized the extracellular lipase (isolated from
Pangong Lake followed by purification) on activated biochar prepared
from sugarcane bagasse. For the immobilization, activated biochar was
packed in the column, and then, lipase solution was loaded and elute recir-
culated. After one day, the immobilized column washed thrice with a phos-
phate buffer solution of pH 7 followed by drying. The immobilized lipase
used for the transesterification of bacterial oil and gave 92.23% yield. It was
reused and retained their 75% activity after the third cycle.
Another physical method, entrapment, was introduced for the immo-
bilization of lipase (from Pseudomonas cepacia) and utilized for biodiesel
synthesis from hybrid oil with high FFAs. In this technique, polyvinyl alco-
hol, sodium alginate, and lipase were mixed to get a clear solution and
added dropwise to CaB4O7 solution (prepared from H3BO3 and CaCl2)
to get bio-support catalyst. The transesterification of non-edible oil with
2-propanol was carried out in jacketed packed bed bioreactor which holds
a bio-support catalyst in a fixed position. The biodiesel yield of 84.58%
was reported and the catalyst retained their ca.70% activity with respect to
initial yield even after 10 cycles [160].
Encapsulation of enzyme was also reported for the physical immobili-
zation process under which lipase encapsulated in κ-carrageenan by co-
extrusion technique. Typically, lipase buffer solution of pH 7 (inner core)
and the κ-carrageenan aqueous solution of 3% w/v (outer shell) were coex-
truded from the coaxial needle at flow rate 5–50 ml/h and palm oil was
used as the continuous phase. After the encapsulation of lipase, it was hard-
ened in 2% KCl solution overnight, followed by drying. This encapsulated
lipase was tested for palm oil biodiesel production, where it gave 100%
conversion in 1440 min. The reusability of the biocatalyst was also exam-
ined and it was found that catalyst retained their 85% activity even after
the fifth cycle [161]. To further improve the activity of encapsulated lipase,
Nadar and Rathod [162] encapsulated ultrasound treated lipase within the
metal-organic framework as shown in Figure 3.9. This encapsulated lipase
shows the increased relative activity of 155% with high thermal stability.
Covalently immobilization of enzymes to the carrier is one of the
chemical methods, which provides strong interaction between carrier and
enzyme and thus the stability during biocatalytic processes. Lipase from
Rhizopus oryzae was immobilized on Fe3O4 MNPs with covalent linkage
using 3-aminopropyltriethylenesilane (APTES) and glutaraldehyde as a
Sonication
Horn
Zn2+ + N NH
10 min
Room
Temperature
Lipase Sono-chemical Highly Activated Lipase-MOF

(5 mg/mL) Treatment Lipase
Native Lipase Activated Lipase Lipase-MOF
Figure 3.9 Encapsulation of ultrasound treated lipase within metal-organic framework

(MOF). (Adapted from Ref. [162] with permission from Elsevier Inc.).
linker. Furthermore, lipase was immobilized non-covalently on Fe3O4 and

compared its activity for the conversion of Chlorella Vulgaris microalgae oil
into biodiesel. It has been observed that covalently immobilized lipase gave
the highest conversion of 69.8% as compared to non-covalently immobi-
lized lipase - lipase/Fe3O4 (54.14%) and lipase/Fe3O4 -APTES (ca. 60%).
The lower conversion in case physically adsorbed catalyst, i.e., lipase/Fe3O4,
may be due to insignificant change in conformation along with leakage of
lipase from bare Fe3O4. However, lipase/Fe3O4-APTES showed enhanced
conversion, as amine group of APTES causes dipole interaction between
enzyme and carrier with less steric hindrance results in better conversion
than adsorbed catalyst—lipase/Fe3O4 [163].
Lipase from Candida rugosa was covalently immobilized onto micro-
porous biosilica-polymer composite, as shown in Figure 3.10. The immobi-
lized and free lipase tested for the conversion of algal oil into biodiesel. The
obtained results indicate that immobilized lipase gave higher yield (96.4%)
as compared to free lipase (85.7%) and also showed thermal and broader
pH range stability. Additionally, immobilized biocatalyst performed very
well during reusability and only showed a 17% decreased in catalytic activ-
ity after six cycles [164].
Cross-linked enzyme aggregates (CLEA) is an effective and low-cost
approach for the enzyme immobilization. For instance, Badoei-dalfard’s
group [165] prepared active CLEA by the addition of glutaraldehyde to the
Km12 lipase solution (5 mg/ml, pH 7) under stirring. Then, it was cova-
lently attached to amine-functionalized Fe3O4 (prepared from APTES)
O Br
O
OH OH
OH OH
OH
Br
Br
Br Br
Br H2C O CI
Br Br O
Bromoacetyl 2-Chloroethyl acrylate
bromide
Biosilica surface Br-end functionalization
biosilica
NH2
O O
NH
Cl Cl Cl O
Cl
Cl
Cl
Br Br Br H2N Br Br Br
Br Br NH2 Br O O
Br
Ethylendiamine Glutaraldehyde
Biosilica-g-chloroethyl acrylate
Br Br Br Br Br
Br Br Br
Br Br
Lipase
Figure 3.10 Lipase from Candida rugosa immobilization onto micro-porous biosilica.
(Adapted from Ref. [164] with permission from Elsevier Inc.).
with the aid of glutaraldehyde and termed as mCLEA-lip. The immobilized

CLEA transesterified the WCO and gave 1.45-fold higher yield (71%) as
compared to free lipase (49%). Moreover, it showed high stability terms of
temperature, pH, and storage with nine times reusability. L62 lipase from
Staphylococcus haemolyticus was used for the synthesis of two immobilized
biocatalysts: i) H-L62 [hydrophobic adsorption and entrapment onto poly
(methacrylate-co-divinyl benzene) resin] and ii) HC-L62 [hydrophobic
adsorption and entrapment with covalent cross-link onto poly (methac-
rylate-co-divinyl benzene) resin] (Figure 3.11). H-L62 biocatalyst showed
higher olive oil conversion (90%) than the HC-L62 (80%). However, the
reusability of H-L62 was significantly reduced after the fifth cycle, whereas
HC-L62 reused for more than 10 cycles without significant loss in the
activity. The reduction in the activity of H-L62 might be due to leaching
of active catalyst (lipase L62), while HC-L62 retained its activity owing
to cross-linking among each other [166]. Some selected reports in recent
N C
N C
L62 lipase glutaraldehyde
adsorption/ cross-linking
entrapment
MA-DVB bead H-L62 HC-L62
Figure 3.11 L62 lipase immobilization using adsorption/entrapment and adsorption/

entrapment with cross-linking onto MA-DVB [poly (methacrylate-co-divinyl benzene)
resin]. (Adapted from Ref. [166] with permission from Elsevier Inc.).
years on different immobilization methods for biodiesel production are

tabulated in Table 3.5.
The different immobilization methods and their advantages and dis-
advantages are summarized in Table 3.6. There are several immobi-
lized enzyme available commercially for the biodiesel production such
as Novozym 435—Immobilized Candida Antarctica Lipase B (CALB)
on hydrophobic support acrylic resin, Lipozyme TL IM—Immobilized
Thermomyces lanuginosus lipase on silica gel support, and Lipozyme RM—
Immobilized Rhizomucor miehei lipase, on an anionic resin, etc. Lipozyme
TL IM is a regiospecific biocatalyst that preferentially catalyzed 1 and 3
position of TGs, whereas Novozym 435 is not shown preferential position
for catalyzation [178].
3.5 Conclusion
From the last decade, the price of petroleum diesel has been increased
tremendously. Hence, as an alternative, biodiesel production became a
subject of interest where numerous researches have been conducted for
the economical production of biodiesel. Biodiesel catalysis is one of the
areas which has been explored a lot with respect to each and every type
of catalyst (homogeneous, heterogeneous, and biocatalyst). Therefore,
this chapter reports detailed information regarding previous and recently
developed catalysts.
Through our analysis of this report, it has been observed that for the
higher conversion of feedstock into biodiesel, some of the catalysts required
high temperature or needed a high amount of catalyst or excess of alcohol,
120
Table 3.5 Some selected reports on different immobilization methods for biodiesel production.
Immobilization Yield/Conv.
methods Carrier Lipase Reaction conditions (%) Recycles Ref.
Adsorption silica aerogels Rhizopus oryzae Esterification: butanol/oleic acid 80 12 [167]
lipase - 1:1, T - 310 K, biocatalyst -
450 IU, t - 60 min
Adsorption Granular activated Candida Transesterification: Isobutanol/ 100 NA [168]
carbon (ACG-E) antarctica Palm oil - 6:1, biocatalyst - 50 (ACG–
and activated carbon lipase B mg, T - 313 K, stirring - 300 E), 82
cloth (ACC-E) rpm, t - 2400 min (ACC–
E)
Adsorption Polypropylene Pseudomonas Transesterification: Methanol/ 98 NA [169]
fluorescens Soybean oil - 8:1, biocatalyst
lipase - 600 mg, T - 303 K, water
content - 0.5 mg/g of catalyst,

t - 4,200 min
Adsorption hydrotalcite Lipozyme TL Transesterification: Methanol/ 92.8 2 [170]
WCO - 4:1, biocatalyst - 4
wt%, T - 303 K, stirring - 300
rpm, t - 6300 min
(Continued)
Table 3.5 Some selected reports on different immobilization methods for biodiesel production. (Continued)
Covalent epoxy-functionalized Candida Transesterification: Methanol/ 68 16 [171]
binding silica antarctica canola oil - 3:1, biocatalyst
(CALB) - 13 wt%, T - 323 K, stirring -
250 rpm, t - 5760 min
Thermomyces 45 16
lanuginosus
(TLL)
Rhizomucor Transesterification: Methanol/ 98 16
miehei (RML) canola oil - 6:1, biocatalyst
- 13 wt%, T - 323 K, stirring -
250 rpm, t - 5760 min
Cross-linking MNPs Candida Transesterification: Methanol/ 90 10 [172]
antarctica FFAs - 10:1, biocatalyst - 1
(CALB) wt%, T - 303 K, t - 180 min
Covalent Amberlite IRA-93 Rhizopus Transesterification: Methanol/ 90.5 7 [173]
binding oryzae lipase soybean oil - 4.8:1, biocatalyst
- 24 U/g oil, T - 310 K, water
content - 60 wt% stirring -
180 rpm, t - 2,880 min

(Continued)
121
122
Table 3.5 Some selected reports on different immobilization methods for biodiesel production. (Continued)
Entrapment silica aerogels Candida Transesterification: Methanol/ ~90 5 [174]
antartica, sunflower oil - 1:1, biocatalyst
Lipozyme ~ 6 LU mg −gel1, T - 313 K, t -
3,000 min
Entrapment Celite supported Candida Transesterification: Methanol/ 60 NA [175]
sol-gels antarctica, triolein - 1:1, biocatalyst - 1 g,
Novozym T - 313 K, t - 360 min
435
Covalent polyporous magnetic Candida Transesterification: Methanol/ 92.3 5 [176]

binding cellulose support antarctica oil - 1.6:1, biocatalyst - 15
lipase B wt%, MW - 400 W, T - 333 K,
t - 120 min
Table 3.6 Advantages and disadvantages of different immobilized methods.

(Adapted from Ref. [177] with permission from Elsevier Inc.).
Methods Advantages Disadvantages
Adsorption Preparing conditions are The interaction between the
mild and easy with low lipase and the carrier is
cost. The carrier can be weak, so the immobilized
regenerated for repeated lipase was sensitive to
use. pH, ionic strength, and
temperature, etc. The
adsorption capacity is small
and the protein might be
stripped off from the carrier.
Covalent The immobilized lipase The preparation conditions are
bond is rather stable because rigorous, so the lipase might
of the strong forces lose its activity during the
between the protein and immobilized process. Some
the carrier. coupling reagents are toxic.
Cross-linking The interaction between The cross-linking conditions
the lipase and the are intense and the
carrier is strong and the mechanical strength of the
immobilized lipase is immobilized lipase is low.
stable.
Entrapment The entrapment conditions This immobilized lipase
are moderate, and the always has the mass
immobilized method transfer restriction during
is applicable to a wide the catalytic process, so
range of carrier and the lipase is only effective
lipases. for low molecular weight
substrates.
whereas some of the solid catalysts were not stable and leached out during
the recycling process. There are also examples of many catalysts that have
been prepared or modified in such a way that its performance and catalytic
activity improved and gave higher biodiesel yield with the requirement of
lower temperature (<353 K), the molar ratio (4:1–6:1), and catalyst loading.
The heterogeneous catalysts, which are easy to prepare and exhibit high
performance under mild reaction conditions, can be considered econom-
ical for biodiesel production. Moreover, the selection of catalyst depends
on the types of biodiesel feedstock. Therefore, SZ, metal oxide from waste
sources, and AC-supported catalysts appear to be the most used catalysts.
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4
Hydrogenolysis as a Means of Valorization
of Biodiesel-Derived Glycerol: A Review
Manjoro T.T.*, Adeniyi A. and Mbaya R.K.K.
Department of Chemical, Metallurgical and Materials Engineering,

Tshwane University of Technology, Pretoria, South Africa
Abstract
The hydrogenolysis of glycerol to 1,2-propanediol is one of the most promis-
ing routes for producing value-added chemicals from glycerol, a by-product of
biodiesel manufacturing. This process will improve the economics of the bio-
diesel manufacturing process that is currently costly compared to conventional
diesel from petroleum. Successful full industrialization of such a process will
shift the dependency on petroleum-based chemicals, thereby promoting renew-
able and sustainable energy usage. The conversion of glycerol proceeds faster in
a basic medium compared to a neutral one, in a helium atmosphere as compared
to under a hydrogen atmosphere and temperature lower than 200°C. Rhenium
was seen as the most effective catalyst in the selective catalytic transformation
of glycerol to 1,2-DPO. However, matter organic non-glycerol, non-methanol
(MONG-NM) impurities, and sulfur compounds must be removed from the
feedstock because they are detrimental to catalyst performance. The reaction
time needs to be kept low as increase in the reaction time does not lead to higher
selectivity of 1,2-propanediol. The reaction mechanism still needs to be estab-
lished to facilitate an effective process optimization to improve the selectivity of
1,2-propanediol.
Keywords: Hydrogenolysis, biodiesel, glycerol valorization, 1,2-propanediol,

heterogeneous catalyst
*Corresponding author: tendaimanjoro038@gmail.com
137
4.1 Introduction
Climate change is one of the 21st century’s greatest challenges. The fourth
assessment report of the Intergovernmental Panel on Climate change
(IPCC) identified human everyday activity as one of the major causes
of global warming [1]. The business as usual approach adopted thus far
by some countries, apart from being unproductive, may lead to a disas-
trous transformation of planet earth, and recent scientific discoveries
emphasize the growing urgency to the issue of reducing greenhouse gas
emissions [2]. One of the ways for reducing global warming is through
the use of renewable and sustainable energy, thus moving away from the
combustion of fossil fuels. Biodiesel is one of the promising renewable,
liquid fuel, and energy sources which is poised to compete and to a large
extent replace petroleum-based diesel fuel. The challenge at the present
moment that is hindering a wider implementation of the biodiesel tech-
nology and its subsequent full-scale industrialization, thus competing
with the traditional petroleum-based (or Fischer-Tropsch–based) die-
sel fuel, is the high cost involved in the currently used manufacturing
process.
The development and distribution of suitable renewable energy technol-
ogies is of paramount importance for meeting the growing energy require-
ments for economic expansion and to improve human life in general. The
development and holistic propagation of renewable energy technologies
has been and still is being prioritized in the global village countries so as
to provide sustainable energy source options to meet demands. Significant
advances have been made, since the mid-1970s, in a number of tech-
nologies such as wind energy, solar systems, geothermal applications,
and the production of biogas, bio-ethanol, and biodiesel from biomass
feedstocks [4].
The full deployment of the biodiesel technology is being hampered
mainly by the high cost of production compared to the conventional die-
sel, which is petroleum-derived and is, therefore, dependent on the cur-
rent price of petroleum and the politics surrounding this. Research work is
currently progressing at appreciable pace to find means of overcoming the
economic barriers associated with the development and implementation of
advanced biodiesel-based energy technologies. Support from governments
is being provided in the form of subsidies as witnessed in Europe, some
Asian states, Brazil, the United States of America, and South Africa. All of
these countries are currently making significant funds available to meet
their policy targets as far as biodiesel technology deployment is concerned.
Hydrogenolysis as a Means of Valorization 139
O COR OH O
cat.
O COR + MeOH OH +
R OMe
O COR OH
vegetable oil glycerin fatty acid methy esters

(FAME)
Figure 4.1 Biodiesel production through transesterification process [4].
As one of the ways to reduce the cost of the overall biodiesel produc-
tion, finding ways to add value to the glycerol that is produced as the main
by-product in the biodiesel manufacturing process (Figure 4.1) should be
considered. Finding uses for glycerol as such or after converting it into
high-value-added products has been identified as one way to significantly
lower the cost of biodiesel production [5].
Intensive research efforts are currently expended to find economically
and environmentally viable ways to transform the glycerol into value-added
chemical products. Of these methods, hydrogenolysis is one of the utmost
promising catalytic routes of conversion of glycerol into value-added comod-
ities [6]. Unfortunately, most development work reported thus far displays
significant shortcomings, particularly with respect to the selectivity toward
the desired product, 1,2-propanediol. From the results discussed in the fol-
lowing sections, it may be concluded that there is a clear need to develop
processes characterized by an improved selectivity toward the desired prod-
uct, and higher conversion of the glycerol fed to the process, while maintain-
ing mild and environmentally benign reaction conditions.
A way this may be achieved is by synthesizing novel catalyst systems,
selective to the production of 1,2-propanediol (1,2-PDO) and thereafter
identifying the optimal reaction conditions for maximizing the reaction
yield. This review deliberates on recent investigative work relating to the
optimization of the process of producing 1,2-PDO, beginning with the
catalyst selection and the choice of the most suitable reaction parameters
for this reaction among other reaction pathways used for the valorization
of glycerol. Recent findings and conclusions from various researchers are
listed and critically reviewed.
4.2 Ways of Valorization of Biodiesel-Derived

Glycerol
The increasing demand for biodiesel is expected to lead to potentially
abundant quantities of crude glycerol on the market. As mentioned above,
glycerol valorization has much to offer in the cost reduction of biodiesel

production within the framework of an integrated biorefinery. To this
end, various chemical or biotechnological strategies have been developed
to yield value-added chemical products using crude glycerol as substrate
[7]. The vast majority of unprocessed glycerol is used as raw mate-
rial for the production of other valued chemicals, followed by its use in
animal feeds.
Orthodox catalysis and biotransformation are the two foremost routes
available for transforming raw glycerol to an array of valued chemicals [8].
In recent times, encouraging results have been obtained in processes for
crude glycerol transformation. As an example, the production of 1,3-pro-
panediol, docosahexaenoic acid-rich algae, poly (hydroxy alkanoates),
butanol, hydrogen, mono glycerides, lipids, citric acid, and syngas from
crude glycerol are promising [9].
However, several of the available technologies require further develop-
ment to optimize them toward being cost-effective and operationally feasi-
ble for incorporation into functional biorefineries.
4.2.1 Catalytic Conversion of Glycerol Into Value-Added

Commodities
The summary of work done so far on the catalytic conversion of glycerol, as
one of the main routes to transforming glycerol into great value commod-
ity chemicals, is shown in Figure 4.2. The work substantiated the claim that
the catalytic conversion of this by-product of biodiesel manufacturing into
a variety of products as a feasible and commercially attractive route.
4.2.1.1 Catalytic Oxidation of Glycerol

Over the years, various researchers found that precious metal catalysts that
include gold, silver, palladium, and platinum showed remarkable catalytic
activity in the partial oxidation of glycerol in the liquid phase [10–14]. In
the various studies, the effect of reaction parameters such as varying tem-
perature, the oxygen pressure, the glycerol concentration, and the synthe-
sis method used to prepare the catalysts was investigated.
Ketchie et al. [12] studied the effect of gold (Au) particle size ranging
from 5 to 42 nm supported on carbon in the oxidation of glycerol in the
aqueous phase. Oxidation of glycerol in the liquid phase was performed
at 59.85°C and a pH of 13.8. The results obtained showed that large par-
ticles (≥20 nm) were more selective to glyceric acid (83%) with the small
O OH HO OH
OH
HO O O O
HO OH
OH OH O
dihydroxyacetone glyceraldegyde tartronic acid hydroxyethanoic acid
oxidation HO O
catalyst OH O O
O HO OH
HO OH HO HO OH formic acid
O OH O O O O
glyceric acid hydroxypyruvic acid mesoxalic acid oxalic acid
OH HO OH
hydrogenolysis HO HO OH ROH
catalyst
1,2-propanediol 1,3-propanediol ethylene glycol R=C1-C3
O
dehydration O
OH
catalyst
acetol acrolein
pyrolysis, CnH2n+2 (C+H2)

CnH2n ROH (CO+H2)
gasification
alkane olefin alcohol syngas carbon + hydrogen
catalyst
OH
HO OH OH O O
O R OH
transesterification,HO HO O O O
esterification OH
O O
catalyst monoglycides α-monobenzoyl glycerol glycerol dimethacrylate
OH
O
etherification O O O
OH
catalyst OH O O
OH O O O
OH OH
monoethers diethers triether
oligomerization, OH
polymerization O OH polyglycerol methacrylates
Ci
catalyst j
glycerol 1-monoethers
O
carboxylation O
catalyst O OH
glycerol carbonate
Figure 4.2 Catalytic processes for the conversion of glycerol into useful value-added
chemicals [5].
particles having a lower selectivity, 69%, at 50% conversion of glycerol. This

was attributed to the higher formation rate of hydrogen peroxide (H2O2)
during the oxidation process. The presence of the peroxide promotes
the cleavage of the C-C bond and thus the formation of other products
other than glyceric acid (GLYA), namely, glycolic (GLYCA), lactic, oxalic
(OXALA), and tartronic (TARAC) acids.
The effect of the catalysts’ preparation method, for instance, sol immo-
bilization versus deposition precipitation and the activation method used,
i.e., chemical reduction versus calcination on Au/TiO2 catalysts for liquid
phase oxidation of glycerol, was studied by Dimitratos et al. [11]. Their
study showed that catalytic performance was dependent on the method of
preparation used for the different catalysts. Catalysts prepared and treated
by different methods were tested for activity at 50°C and 0.304-MPa oxy-
gen pressure. The results in Table 4.1 show the dependence of the selectiv-
ity obtained on the method of preparation. The conclusion may be drawn
that with this type of catalysts, the deposition precipitation method fol-
lowed by calcination gives the best results as regards the selectivity of the
formation of glyceric acid.
Glycerol oxidation over palladium (Pd), gold (Au), and platinum (Pt)
nanoparticles supported on carbon was probed by Carrettin et al. [10]. A
batch reactor was used at 60°C and air at 0.1 MPa pressure as oxidant.
At stated conditions, Pd/C and Pt/C gave some selectivity to glyceric acid
even though the main products were the undesirable by-products, CO2,
HCHO, and HCOOH. The C–C cleavage reactions were propelled by the
strong acidic cites given by the metals and the formation of C1 compounds
was eliminated by the adding basic sodium hydroxide (NaOH) to the
reaction vessel. The use of pure oxygen at a raised pressure of 0.3 MPa
significantly improved the catalytic activity of Pd/C and Pt/C catalysts.
Supported Au catalysts were completely inactive at the initial operating
conditions though for 1 wt.% Au/C, 100% selectivity was readily achieved
when the basic promoter aid was used at 0.3 MPa pure oxygen pressure.
Table 4.1 Glycerol oxidation using different catalysts preparation methods at

50°C [11].
S50–S90
Entry Samples GLYA GLYCA TARAC d (nm) HRTEM
1 1% Au/TiO2 (DP/calcined) 81 13 4 5
2 1% Au/TiO2 (DP/NaBH4) 55–62 28–26 17–12 2–5
3 1% Au/TiO2 (THPC) 55–52 15–15 25–28 2–3
4 1% Au/TiO2 (PVA) 52–69 13–17 24–10 4–5
5 1.5% Au/TiO2 (WGC) 64–60 23–23 11–12 4
6a 1% Au/ACb (PVA) 64–52 12–12 9–10 5
DP, deposition precipitation; THPC, Tetrakis hydroxypropyl phosphonium chloride; PVA,
poly-vinyl alcohol; WGC, World Gold Council; HRTEM, high-resolution transmission
electron microscopy; S50 and S90, selectivity at 50% and 90% glycerol conversion, respectively.
a
: From Ref. [15]; b: activated carbon.
The base added is assumed to facilitate the initial dehydrogenation via

H-abstraction of one of the primary OH groups of the glycerol. In this
way, the rate limiting step (initial dehydrogenation) of the process will be
overcome. Similar results have been obtained by several researchers for
gold and palladium supported catalysts used in the catalytic oxidation of
glycerol [13, 15–20].
Furthermore, Skrzyńska et al. [14] investigated the activity of Pd, Pt,
Au, and Ag supported on alumina with a loading of 0.95 wt.% Pt, 0.96
wt.% f Pd, 0.98 wt.% Au, and 1.13 wt.% Ag in the oxidation of crude glyc-
erol. Based on the initial rate of reaction, Au/Al2O3 was the most active
catalyst sample, though a comparison of selectivity and conversion after
1–2 h showed that Pd/Al2O3 was the most robust and unaffected catalyst
toward impurities in crude glycerol, whereas the gold-containing sam-
ples rapidly deactivated. A loss of less than 50% (relative to the compara-
ble reaction which used pure glycerol) and an almost constant selectivity
to glyceric acid of close to 80%–90% was observed with the palladium
catalysts. The other catalysts’ activities were greatly affected, with the
conversion being lowered by a factor of 4 and 10 for Pt and Au systems,
respectively, when using crude glycerol instead of pure glycerol as raw
material. In the case of the effect of specific impurities on conversion
and selectivity, the group found that matter organic non-glycerol and
non-methanol (MONG-NM) impurities as well as sulfur compounds
were the most detrimental to catalyst performance. Therefore, in agree-
ment to the findings by [21], these should be removed prior to the cata-
lytic reaction.
4.2.1.2 Catalytic Dehydration of Glycerol

Numerous solid and acidic catalysts that include phosphates, sulfates, zeo-
lites, and supported heteropoly acids have been tested in the dehydration
of glycerol in the gaseous phase to produce acrolein [22–24]. The highest
selectivities to acrolein obtained by these research groups range between
65% and 80%. Suprun et al. [25] reported that solid catalysts with Hammet
acidity (Ho) of between −10 and −16 were the ones more suitable for use
in the dehydration of glycerol to acrolein compared to those catalysts with
Ho between −2 and −6. Also, in their studies, Suprun et al. [25] found
out that mesoporous Al2O3–PO4 and TiO2–PO4 catalysts which have large
pores showed high activity but only restricted selectivity to acrolein, while
catalysts based on the zeolites SAPO-11 and SAPO-34 with considerably
smaller micropores (5–6 Å) were less active but more selective. On the
aspect of deactivation of the catalysts, they found out that the more acidic
SAPO catalysts demonstrated the greatest cocking effect, compared to the

supported phosphates, probably due to the smaller pore diameters of the
zeolites; deactivation of the SAPOs was, therefore, quicker. Due to the fact
that crude glycerol contains a significant amount of water, there is broad
agreement among the above-mentioned researchers that there is need for
a catalyst with high water tolerance because it will improve the economics
of raw glycerol conversion to acrolein by eliminating the drying stages in
the glycerol purification.
4.2.1.3 Pyrolysis of Bioglycerol

The pyrolysis of glycerol under different operating conditions, varying
temperature (650°C–800°C), varying carrier gas flow rate (30–70 ml/
min), different packing material (quartz, silicon carbide and sand), and
different particle size of the material was investigated by Valliyappan et
al. [26]. While varying flow rate at 800°C, they reported that increasing
the carrier gas flow reduced the yield of H2 owing to the reduced resi-
dence time in the reactor. Increasing the flow rate to 70 ml/min resulted
in a drastic increase of the yield of CO and hydrocarbons, suggesting that
these are the primary products of pyrolysis. The effect of temperature
on the pyrolysis of glycerol was explored at 50 ml/min of carrier gas and
these researchers reported an increase in CO/H2 production, amounting
to a rise from 71% to 93.5% with an increase in the temperature from
650°C to 800°C. This was accompanied by char formation. At the same
time, a decrease in liquid products production was observed. The results
listed above are similar to those reported by Fernández et al. [27] who
also investigated the pyrolysis of glycerol to produce syngas (CO/H2).
These effects were attributed to thermal cracking of glycerol at high
temperatures.
Analyzing the effect of packing material and particle size variation at
800°C and 50 L/min H2 flow, Valliyappan et al. [26] reported that decreas-
ing the particle size of material resulted in the increase of gaseous products
and char simultaneously with decrease in yield of liquid phase products.
Smaller particle size packing materials simulated plug flow behavior in the
reactor coupled with enhanced heat transfer and thereby increasing the
conversion of liquid to gas and char. Of the catalysts tested, silicon carbide
of particle diameter of 0.15 mm was reported to have the greatest gas prod-
uct percentage of 77.6% while quartz and sand recorded maximum gas
product percentages of 71.2% and 71.9% respectively.
Buffoni et al. [28] investigated the use of nickel catalysts in the steam
reforming of glycerol to produce hydrogen. Nickel supported on α-Al2O3
and ZrO2 or CeO2 modified catalysts were used in the investigation and the
results obtained by the researchers indicated that the minimum tempera-
ture to obtain hydrogen with high selectivity is 550°C. They also reported
that the stability and activity of the supported catalysts was enhanced by the
inclusion of CeO2 in the structure of the catalysts. Lower coke formation
and higher stability was reported and was attributed to the highest basic
character of Ni-Ceα supported catalyst that inhibited the lateral dehydra-
tion, rearrangement, and condensation reactions that could have led to the
formation of intermediate compounds in coke formation.
The results correspond to the findings of Iriondo et al. [84], who also
investigated the effect of incorporating ceria in the preparation of Ni-Al2O3
catalysts for use in glycerol steam reforming. They found that low ceria
loadings enhance the catalyst activity and improved the selectivity of H2 as
the main product. The stability of the catalysts was reported to have been
caused by nickel-ceria interactions in the surface of the alumina support.
Furthermore, an increase in the ceria load on the catalyst was reported to
be a cause of reduced capacity of the catalyst to convert intermediate oxy-
genated hydrocarbons (OHCs) into H2.
Iriondo et al. [29] investigated the effect of incorporating promoters in
the making of Ni catalysts supported on alumina for use in steam reform-
ing of glycerol and found out that lanthana (La2O3) modified Ni catalysts
produced only gaseous products. This phenomenon was reported to have
been caused by the reduction of the acidity of the alumina support thereby
favoring the conversion of OHCs into CH4, CO, CO2, and H2. There was
the formation of more OHCs when Pt catalyst was used instead of the Ni,
a result similar to the outcome of the work of Pompeo et al. [30] on the
use of platinum catalysts in steam reforming of glycerol to produce hydro-
gen. The use of bimetallic catalysts of nickel and platinum was reported
to promote methanation of glycerol rather than forming the desired and
expected steam reforming products.
4.2.1.4 Glycerol Transesterification

The main high commodity chemical yield from the transesterification of
glycerol is glycerol carbonate (GCL) which is used as a precursor and inter-
mediate in many chemical reactions such as polymerization and in the
coatings industry. Literature has documented research work that has been
performed on the transesterification of glycerol using basic catalysts. Liu et al.
[31] investigated the use of Mg/Al mixed oxide catalysts in the transesterifi-
cation of glycerol using dimethyl carbonate. They reported that while vary-
ing the Mg:Al ratio between 2 and 6, it was found that a ratio of 2:1 gave
the highest activity with 56% conversion of glycerol. This reduced to 42%
as the ratio increased, and 100% GCL selectivity when experiments were
done at 100°C and retention time of 90 min. This phenomenon was also
reported by Alvarez et al. [32] who observed the same trend and attributed
it to the increased surface basicity which depends on the metal ratio in the
catalyst. The effect of calcination temperature was also investigated between
the range 300°C to 700°C, and it was found that increasing the calcination
temperature increases the activity of all the catalysts, and notably, the high-
est activity of the Mg/Al = 2 was obtained when this system was calcined
at 600°C. The basicity is said to improve with calcination temperature due
to the formation of more weak −OH basic sites and O2− strong cites on the
catalysts. The less Al3+ Lewis acidic cites are available, the more the overall
catalyst basicity and thus the activity of the catalysts improves [31].
This result is consistent with the findings of Kumar et al. [33], Zheng et
al. [34], and Zheng et al. [35] who also investigated the use of mixed metal
oxides in the transesterification of glycerol. In comparison with other basic
catalytic materials used for this reaction, such as NaOH, CaO, and MgO
with glycerol conversion of 70%, 79%, and 50%, respectively, they demon-
strated that mixed metal oxides of Mg/Al = 2 is very much competitive
with a conversion of 66% and GLC selectivity of 100%. CaO and NaOH
fall short on the GLC selectivity with values of 81% and 70%, respectively,
when reactions were run for 2 h [35].
Apart from the use of metal oxides as basic catalysts in the transesteri-
fication of glycerol, Lanjekar and Rathod [36] reported the use of enzymes
to catalyze the reaction. They reported a high conversion of glycerol of
94.85% after running the reactions for 14 h at a temperature of 60°C.
Commercially, this route will turn to be expensive due to the long retention
times, expensive enzymes and the easiness to poisoning of the enzymes.
Algoufi and Hameed [37] reported the use of K-zeolite derived from coal
fly ash in the transesterification of glycerol. The reported data showed that
4 wt.% catalyst loading, reaction temperature of 75°C, and retention time
of 90 min yielded 100% conversion of glycerol and 96% GC selectivity.
4.2.1.5 Glycerol Direct Carboxylation

The high-value end product of catalytic glycerol carboxylation is glyc-
erol carbonate (glycerine carbonate or 4-hydroxymethyl-2-oxo-1,3-di-
oxolane). The same product is also obtained by the transesterification of
glycerol using organic carbonates [38]. Glycerol carbonate is a versatile
building block for a variety of advanced materials. Little is known to
have been reported on the direct carboxylation of glycerol using carbon
dioxide except the works of Aresta et al. [39] and Ezhova et al. [40] that
was reviewed by Sonnati et al. [38]. The work by these research groups is
consistent in that they all used high pressure CO2 in liquid phase (above
5.07 MPa) and high temperatures (over 180°C). The stringent reaction
conditions require specialized equipment and thus escalate the ultimate
production cost of glycerol carbonate. Notable is the research by Ezhova
et al. [40] who investigated the use of gaseous CO2 at lower tempera-
tures in the presence of rhodium complexes with phosphine ligands.
The group reported a conversion of only 0.24% of the glycerol, achieving
selectivity toward glycerol carbonate of 100% while operating at 5.07
MPa (4.05 MPa CO2 and 1.02 MPa H2), 140°C, and 17-h reaction time.
This result falls far lower than the maximum conversion reported by
Aresta et al. [39], who reported a conversion of 6.86% while operating
at 5 MPa, 180°C, and 15-h retention time in the presence of a tin oxide–
based heterogeneous catalyst. Reasons for the anomalies and discrepan-
cies in the results might be attributed to differences in catalytic activity
between the two systems and different operating conditions used by the
two research groups.
Having highlighted some advancements being made in other catalytic
routes for the conversion of glycerol to high value chemicals, the following
section focuses on the conversion of glycerol to 1,2-PDO via hydrogenoly-
sis using different reaction systems.
4.3 Hydrogenolysis of Glycerol

4.3.1 Definition of Hydrogenolysis
Hydrogenolysis is defined as the chemical reaction involving the cleav-
age of a C-C or C-X (X=heteroatom) bond of a hydrocarbon compound,
followed by the addition of hydrogen, forming two molecules as a result.
This process has widely been used in the crude oil refining industry for
a variety of processes. One example is the catalytic hydrodesulfurization
of sulfur-rich hydrocarbons obtained from petroleum feedstocks. The
hydrogenolysis of carbohydrate feedstocks has been extensively studied
and its history dates back to the 1930s [41].
In recent times, the process of hydrogenolysis has witnessed renewed
interest for the transformation and conversion of glycerol and carbohy-
drates feedstocks into value-added polyols that include propylene gly-
col, ethylene glycol, and propane diols, among other derived products
[42–48].
OH OH
OH 1-propanol C3H8
1,2-propanediol Propane
(1,2-PD)
H2 OH
HO OH 2-propanol
HO OH + + C2H6
OH Catalyst 1,3-propanediol Ethane
Glycerol (1,3-PD)
OH
Ethanol
CH4
HO OH Methane
Ethylene glycol CH3OH
(EG) Methanol
Dihydric alcohol Monobasic alcohol Alkane
Figure 4.3 Successive stages in the hydrogenolysis of glycerol [49].
4.3.2 Catalytic Hydrogenolysis of Glycerol

Catalytic hydrogenolysis of glycerol is a multistage chemical reaction, usu-
ally activated by supported heterogeneous transition metals together with
base metals as evident in the above cited publications. Figure 4.3 shows
the successive hydrogenolysis of glycerol (as a starting raw material) to a
variety of products at different stages of the reaction.
4.3.3 Product Spectrum from Hydrogenolysis of Glycerol

Several chemicals can be derived from glycerol via chemoselective hydrog-
enolysis of glycerol, including 1,2-PDO, 1,3-PDO, lactic acid, with a fur-
ther hydrogenolysis of the main products leading to the formation of
propanol and subsequently propane as secondary products [6, 50–53]. In
some instances, CO2, formic acid, and even methane were detected in the
product streams, owing to reaction conditions used that end up affecting
the truncation of reaction systems [44].
The main point raised from the observations of Guo et al. [44], was the
significant amounts of lower alcohols and hydrocarbons that are detected
in the product streams with elevated reaction temperature. Other aspects
that influence the product range are the catalysts used and the relative
acidity of the active sites, the reaction time and the pressure of the hydro-
gen in cases where hydrogen was introduced to the reaction mixture. In
some instances where hydrogen donors (methanol, 2 propanol, and formic
acid) were used as sources of the reactive hydrogen to the reaction mix-
ture, the effect of the different molecules, pumping rate, and concentration
have been studied to also help explain the phenomenon of hydrogenolysis

product range [43].
1,2-Propanediol, also known as propylene glycol, is a major commodity
chemical and has seen a 4% year on year market growth [42]. Propylene
glycol has several commercial applications, for example, as antifreeze,
coolant, solvent and extractant, de-icing agent, precursor in pharmaceu-
ticals, cosmetics, animal feed, and tobacco industries. It also plays a role
in the petroleum production, sugar refining, paper making, toiletries, liq-
uid detergent, alkyl resins, printing inks, plasticizers, and hydraulic break
fluids [6].
The vast array of uses and market growth for 1,2-PDO has thus influ-
enced the focus of this review to be centred on the production of propylene
glycol via the hydrogenolysis of glycerol.
4.3.4 Hydrogenolysis of Glycerol to 1,2-PDO (Propylene

Glycol): Reaction Systems Overview
Key claims have been made with some of the findings being patented
regarding the process systems that can be used in the conversion of glyc-
erol to propylene glycol. Below is an overview of both heterogeneous and
homogeneous catalyst systems that have been reported to aid in the che-
moselective conversion of glycerol to 1,2-PDO.
Dalai et al. [54] described a process for hydrogenolysis of glycerol to
produce propylene glycol as the major product, comprising contacting the
glycerol with hydrogen in the presence of a heterogeneous catalyst under
the following reaction conditions: 240°C, 4 MPa H2, 80% glycerol solution,
3% w/w catalyst on support, and 1,000 rpm mixing in a batch process. The
heterogeneous catalytic systems used by these researchers consisted of Cu,
Cr, Zn, and Zr obtained by co-precipitation and calcination. High selectiv-
ities for propylene glycol formation in the range of 90% were achieved. In
comparison, Stankowiak and Franke [55] reported a 97.5% selectivity of
1,2-PDO from the hydrogenolysis of glycerol, while using a heterogeneous
catalytic system based on metal oxides (20%–60% CuO, 30%–70% ZnO,
and 1%–10% MnO). In their process, 95% purity glycerol was reacted with
2.0 to 10.0 MPa H2 pressure at 180°C.
Using Rh(CO)2 acetylacetonate and tungstenic acid (H2WO4) as a homo-
geneous catalyst system for the hydrogenolysis of glycerol, Che [56] reported
a yield of 30% 1,2-PDO and 20% 1,3-PDO. This was achieved while oper-
ating at 200°C, 30 MPa of 1:2 (CO:H2) synthesis gas and 28.6% solution of
glycerol in 1-methyl-2-pyrolidinone solvent as optimal reaction condition.
150
Table 4.2 Heterogeneously catalyzed reactions without the use of solvents.
Reaction
temperature Glycerol 1,2-PDO
Catalyst system (°C) H2 pressure MPa conversion% selectivity% Source
Raney Cu 240 3 100 86 [57]
Cu and Zn 240– 270 15 99.4 84.4 [58]
Co, Cu, Mn, Mo, and inorganic 250 25 100 95.8 [59]
polyacid
Cu, Pd, Rh on ZnO and C 183 8 19 100 [60]
Cu Chromite 200 1.38 54.8 85 [42]
Ru/C and Cation exchange resin 120 4 15 53.4 [61, 62]
(Ambient 15) 8 12.9 55.4
Raney Ni and Phosphonium Salt 150 1 12 93 [63]

Cu/Al nanocatalysts 220 7 38 91 [64]
5% Ru/Al2O3 and 5%Pt/Al2O3 220 In Situ Generated 50 47.2 [65]
Raney Cu 205 Trickle-bed Reactor 100 94 [66]
(H2/Liquid: 375/0.05)
Ru/Pt 200 In Situ Generated 20.6 53.1 [67]
Similar results were also obtained in systems employing ruthenium, nickel,

palladium, or cobalt as the metal component instead of rhodium [57].
Adding titanium or molybdenum metal promoters with a group 8 metal in
the catalyst systems still did not significantly alter the composition of the
products [56]. Similarly, Drent and Jager [68] reported the hydrogenolysis
of glycerol in the presence of a homogeneous catalyst based on a platinum
group metal (PGM) or a compound of a PGM and methanesulfonic acid.
They achieved a selectivity of 21.8% toward 1,2-PDO from hydrogenolysis
of glycerol at 170°C and 2.0/4.0 (CO/H2) MPa. They suggested that further
optimization could possibly yield better results.
In addition to the findings highlighted above, a large number of other
publications demonstrated the supremacy of the heterogeneously cat-
alyzed hydrogenolysis of glycerol to produce propylene glycol. Table 4.2
summarizes results obtained by different researchers using heterogeneous
catalysts.
The major hindrances that severely dent the use of homogeneous cat-
alysts in this process are the use of toxic solvents (methanol and sulfur
containing acids) in the reaction systems and the problems related to the
catalysts recovery after the reaction completion. Coupled with the low
conversions and selectivity toward 1,2-PDO, the use as well as research
pertaining the use of homogeneous catalyst systems is limited to a few
publications.
Despite the publication of several investigation results by a number of
researchers, the heterogeneously catalyzed glycerol hydrogenolysis to 1,2-
PDO process still has several drawbacks, which prevent scaling up beyond
bench scale to the pilot plant level. Aspects of great concern include the
high operating H2 pressures (>1.03 MPa), high temperatures (> 300°C),
use of very dilute glycerol solution (10%–30%), poor catalyst reusability,
catalyst leaching coupled with low glycerol conversion, and/or low 1,2-
PDO selectivity. Also, another significant limitation is that of long reaction
times (>5 h in batch systems) presently required to achieve an acceptable
conversion of glycerol to 1,2-PDO, thus rendering the current methods
economically non-viable [5].
Having noted the above systems’ drawbacks in the conversion of glyc-
erol to 1,2-PDO, the following sections disclose recent research work find-
ings by different groups in quest of optimizing the process.
4.3.5 Catalyst Selection

The applicability of supported precious metal catalysts and/or nickel-
based systems in the hydrogenolysis of glycerol with relatively high
activity and selectivity toward 1,2-PDO has been reviewed critically by

various researchers [43, 69–71]. They went on to propose that further
work should be carried out using different catalysts based on ruthe-
nium or copper on various supports. Their proposals were derived from
the works of Montassier et al. [72] and Feng et al. [73] who investigated
the use of ruthenium (Ru) in the hydrogenolysis of glycerol to 1,2-PDO.
Their findings were compared with the results when other noble metal
catalysts (Pt, Pd, and Ni) were tested [72, 73]. They derived the conclu-
sion that supported Ru catalysts demonstrated the highest activity and
selectivity toward 1,2-PDO. Findings by Miyazawa et al. [53], Balaraju et
al. [74], and Lahr and Shanks [75] concurred with the outcomes of this
research work.
Furthermore, Checa et al. [76] performed work on the catalytic trans-
formation of glycerol using various metal systems supported on zinc
oxide (ZnO) to investigate the different activities toward the reaction
exhibited by these metals. The group performed their catalytic tests at
2.0 MPa hydrogen (H2) or helium (He) pressure, 180°C, and a run time
of 12 h under basic or neutral atmosphere. The results obtained led to
the conclusion that the conversion of glycerol proceeds faster in a basic
medium compared to a neutral one and in a He as compared to under
a H2 atmosphere. Of the metal systems tested, the highest conversions
were reported in the order of Pt > Rh > Pd > Au, consistent with the
findings of Auneau et al. [77] who investigated the effect of reaction
medium, with gold and palladium. They recorded zero in neutral phase
and 5% and 17% for rhenium and platinum, respectively. Under basic
conditions, the conversion levels were 100%, 97%, 32%, and 26% for Pt,
Rh, Pd, and Au, respectively. With regard to the selectivity toward 1,2-
PDO, there was minimum variation ranging between 14% for Au and Pd
whereas the values were 19% and 27% for Pt and Rh, respectively. These
figures however fall short of those reported by Vasiliadou et al. [78]
which were 40.5% glycerol conversion and 1,2-PDO selectivity of 60.5%
using Ru-based catalyst supported on ZrO2. Other results quoted that
dwell on the effectiveness of Ru in the selective catalytic transformation
of glycerol to 1,2-DPO include Huang et al. [50] who achieved 47.8%
selectivity while Dasari et al. [42] obtained a moderate 40.0% selectivity
toward 1,2-PDO.
Of late, copper (Cu)–based catalysts have since been reported to have
high selectivity toward 1,2-PDO in the selective hydrogenolysis of glycerol
owing to its ability to promote the cleavage of the C-O bonds in contrast
to C-C bonds. Bienholz et al. [69], Guo et al. [71], and Gandarias et al.
[43] concurred with respect to Cu catalyst systems activity toward glycerol
hydrogenolysis with all of them reporting the selectivity of 1,2-PDO rang-

ing from 70% up to 98% depending on the reaction conditions. It was
observed however, that, though the selectivity of the formation of 1,2-PDO
was very high, the conversion was very low, hovering below 30% for cat-
alysts with a Cu loading of 60% CuO, despite the system being operated
at an elevated temperature of 200°C and a pressure of 5 MPa [69]. High
conversions of 100% were only realized for gaseous reactions, elongated
reaction times up to 24 h and high catalyst weight loaded into reactors as
highlighted by Akiyama et al. [79] and Guo et al. [71].
The aspects of reusability of catalyst systems and ultimate trade-offs of
running the selective hydrogenolysis of glycerol to yield 1,2-PDO using
the front runner catalysts have not yet been explored, and thus, it becomes
inconclusive to declare the prime system that can solely be applied for the
hydrogenolysis of glycerol process. This uncertain and inconclusive sce-
nario leaves a knowledge gap for further investigations to be performed
around the hydrogenolysis of glycerol to 1,2-PDO and to optimize the pro-
cess thereof.
4.3.6 Reaction Conditions That Influence the Hydrogenolysis

of Glycerol to 1,2-PDO
Reaction conditions are the main drivers of all the transformations from
raw materials to desired products. In the case of the selective hydrogenoly-
sis of glycerol to 1,2-PDO, the combination of catalyst systems and physical
parameters (temperature, H2 pressure, catalyst loading, and reaction time)
influence the reaction pathway and thus the product mix obtained. This
section reviews some recent published investigations done in the quest
to ascertain optimal operating conditions for the production of 1,2-PDO
from the heterogeneously catalyzed hydrogenolysis of glycerol.
4.3.6.1 Effect of Reaction Temperature

Akiyama et al. [79] investigated the effect of reaction parameters using
Cu-based catalysts and found out that elevated temperatures (from 170°C
and above) lead to complete glycerol conversion but also subsequently lead
to decomposition of glycerol into lower alcohols (2-propanol, 1-propanol,
ethanol, methanol, and ethylene glycol) as the temperature is raised above
190°C as evident by the drop in selectivity of 1,2-PDO. This pattern is
clearly shown in Figure 4.4. Shinmi et al. [80] and Dasari et al. [42] also
found that selectivity toward 1,2-PDO drastically drops with excessive
reaction temperature above 200°C.
100 100
Glycerol Conversion (%) 95 95
Selectivity 1,2-PDO (%)

90 90
85 85
80 80
75 75
70 70
65 65
60 60
55 55
50 50
150 170 190 210 230 250
Reaction Temp (ºC)
Glycerol Conversion Selectivity 1,2-PDO
Figure 4.4 Effect of temperature on glycerol conversion and selectivity of 1,2-PDO [79].
Dasari et al. [42] found that there was a great influence of temperature
on the overall yield of propylene glycol (1,2-PDO) from the experimen-
tal reactions carried out while varying temperature from 150°C to 260°C
and at an operating hydrogen pressure of 1.38 MPa in the presence of a
copper chromite catalyst. The results obtained by this group showed that
as the temperature was increased from 150°C to 260°C, there was a uni-
form rise in the glycerol conversion from a low 7.2% to 87%. In the case
of yield and selectivity of 1,2-PDO, similar trends were observed where an
increase in the reaction temperature resulted in an increase in yield and
selectivity only up to 200°C. Further rise in temperature to 260°C resulted
in a decrease in the yield and the selectivity of 1,2-PDO as show in Figure
4.5 below. The further hydrogenolysis of the products obtained to lower
alcohols with excessive temperatures (above 200°C) was verified by the
detection of lower alcohols in the product stream and the drop in yield and
selectivity.
4.3.6.2 Effect of H2 Pressure

Regarding the effect of pressure on the process of hydrogenolysis of glyc-
erol to 1,2-PDO, Dasari et al. [42] reported that as the pressure was raised
from 0.34 to 2.07 MPa, the conversion of glycerol increased from 25%
to 65.3%, respectively, while the selectivity to 1,2-PDO improved from
36.4% to a maximum of 89.6%. In contrast, Shinmi et al. [80] reported an
increase in glycerol conversion from 25% to 79% with a pressure rise from
100
90
80
70
60
50
%
40
30
20
10
0
100 150 200 250 300
Reaction Temp (ºC)
% Conversion % Yield % Selectivity
Figure 4.5 Effect of varying temperature on conversion, yield, and selectivity of 1,2-PDO.
Reactions were performed using 80% glycerol solution at hydrogen pressure of 1.38 MPa
for 24 h [42].
2 to 8 MPa but found no significant change (between 40% and 43.5%) in

the selectivity with the variation of operating pressure. The discrepancy
could be explained due to the different nature of the catalytic systems used,
which exhibit different characteristics since Dasari et al. [42] used co-
precipitated copper chromite catalysts while the findings of Shinmi et al.
[80] were based on rhodium supported systems. The claim is supported
by Bolado et al. [70] who noted that different catalyst systems with vary-
ing physical and chemical properties also perform differently in these
chemical reactions, even though the other parameters are held constant
[57, 73, 72].
4.3.6.3 Effect of Initial Water Concentration

The effect of initial water content in the reaction mixture on the conver-
sion of glycerol and also on the selectivity to 1,2-PDO was investigated
by Ma and He [81], Dasari et al. [42], and Guo et al. [71]. Ma and He
[81] reported that there was almost no change in the glycerol conversion
but an increase in 1,2-PDO selectivity from 22.2% to 34.3%. According to
these authors, this resulted in changing the glycerol concentration from
10% to 40%, while using the Ru/Al2O3 catalyst system. Contrary to that,
when reactions were performed over Ru/Al2O3 + Re2(CO)10 conversion
of glycerol increased from 36.4% to 53.4% together with the 1,2-PDO
selectivity rising from 36.5% to 50,1%. Similar trends with regard to ini-
tial water content were also observed previously by Dasari et al. [42] who
achieved 85.0% as highest selectivity to 1,2-PDO at 20% initial water con-
tent. Dasari et al. [42] also witnessed a decline in selectivity, as they reduce
the water content to zero, to 71.9% when tests were performed using pure
glycerol.
In contrast to the decline reported by Dasari et al. [42], Guo et al.
[71] observed a maximum of 93.3% selectivity to 1,2-PDO correspond-
ing to 41.9% glycerol conversion while using pure glycerol. Dasari et al.
[42] further went on to suggest that it was advisable to exclude water
from the feedstock in an effort to drive the equilibrium toward the
products of hydrogenolysis since the reaction itself produces water as
a by-product.
4.3.6.4 Effect of Reaction Time

The increase in reaction time has a positive effect on the conversion levels
of glycerol but causes insignificant change to the selectivity toward 1,2-
PDO [71]. The same can be said for the findings of Nakagawa et al. [82]
where conversion of glycerol approached 90% after 50 h of residence time
though selectivity showed a rather decreasing trend from about 10% to
4.5% with increasing reaction time. It is thus wiser to limit the retention
time in the reactor so as to shorten the turnover time of the process for
there seems to be no considerable gain in 1,2-PDO selectivity as the main
product of choice in this instance.
4.3.6.5 Effect of Catalyst Weight

The work of Dasari et al. [42] was extended to investigating the effect of
varying the catalysts weight where they found that conversion of glyc-
erol increased with the rise in catalyst weight loaded into the reactor.
Initially, as the catalyst weight percentage is increased from 1% to 5%,
the conversion increased from 28.3% to 54.8%, whereas selectivity rose
from 63.3% to 85.0%. Further, catalyst weight percentage increase to 20%
levels resulted in a decline of the selectivity to 62% though the conversion
continued to rise to a peak 78.5%. Dasari et al. [42] attributed the fall
in selectivity with rising catalyst percentage to the availability of more
hydrogenolysis sites on the surplus catalysts that promoted excessive
hydrogenolysis of the formed 1,2-PDO to lower alcohols and gaseous
products.
4.3.6.6 Proposed Reaction Mechanisms for Glycerol Hydrogenolysis

to Produce 1,2-PDO
Glycerol hydrogenolysis is thought to proceed via a mechanism that
involves the dehydration of glycerol to acetol and 3-hydroxy-propanal pro-
moted by acid catalysis in the first stage, subsequently followed by hydro-
genation to the glycols by the metal catalysts used, as noted by Vasiliadou
et al. (2009). The scheme in Figure 4.6 shows the proposed reaction mech-
anism revealing products of over-hydrogenolysis, hydrolysis of propane
diols to 1-propanol, 2-propanol, ethanol, and methanol.
The scheme proposed by Vasiliadou et al. [78] is in sync to mech-
anisms also proposed by Furikado et al. [83] who found that there is
sequential hydrogenolysis of the propanediols formed to give either 1-
propanol and/or 2-propanol using supported Ru catalysts on carbon. To
further substantiate the reaction mechanism which suggests the forma-
tion of acetol as an intermediate product in the hydrogenolysis of glyc-
erol, Miyazawa et al. [62] investigated the hydration of acetol and reported
that there was 100% conversion of acetol at 8 MPa H2 pressure, 120°C
temperature and a reaction time of 10 h. Product composition is similar
to that mentioned above in the proposed reaction mechanism scheme of
Vasiliadou et al. [78] (Figure 4.6).
The work performed by Dasari et al. [42], Montassier et al. [72], and Lahr
and Shanks [75], together with those reported above, concurred with the
detection of trace amounts of acetol in the final product analysis, implying
that there was a stage at which it was produced in the system. To further sub-
stantiate their claim that acetol is an intermediate product in the proposed
+H2
CH3 C CH2 CH3 CH CH2 1-propanol
O OH OH OH
acetol 1.2-propanediol +H2
-H2O 2-propanol
-H2O
-H2O O +H2
CH2 CH CH2
C CH2 CH2 CH2 CH2 CH2 +H2
OH OH OH ethanol
H OH OH OH
methanol
3-hydroxypropionaldehyde 1.3-propanediol
+H2
ethylene glycol
ethanol
methane
Figure 4.6 The scheme for glycerol hydrogenolysis reaction mechanism [78].
reaction mechanism, the authors proceeded to perform the hydrogenolysis

of glycerol in a two-step process. In the first stage, the reaction was left to
proceed without hydrogen but in the presence of the metal catalysts tested for
hydrogenolysis of glycerol. The subsequent stage would then be performed
under hydrogen pressure with the resulting product selectivity showing that,
in the first stage, acetol was produced and, in the second stage, results showed
acetol depletion simultaneously with great yield of 1.2-PDO.
In contrast to the above-mentioned mechanism, there also exists another
mechanism proposed by Montassier et al. [57] shown in the Figure 4.7.
The mechanism that includes an initial dehydrogenation of glycerol is
said to lead to the formation of glyceric aldehyde in equilibrium with its eno-
lic tautomer. A nucleophilic reaction of water or an adsorbed OH function
(dehydroxylation) followed by the hydrogenation of the unsaturated alde-
hyde was proposed to be the explanation for the end product being 1,2-PDO.
Based on their results, multiple groups suggested otherwise that a differ-
ent mechanism was followed by the system [42, 72, 75, 78]. There seems to
be no evidence that supports the route proposed by Montassier et al. [57]
for the formation of 1,2-PDO from glycerol, owing to the lack of any trace
of the postulated intermediate compounds in the product mixture.
On the other hand, the mechanism suggested by Montassier et al. [72]
was shared by Maris and Davis [52] who proposed the very same route for
chemoselective hydrogenolysis of glycerol. These groups argued that the
path and selectivity toward certain products is dependent on the catalyst
Dehydrogenation Dehydroxylation by
of C-O H2O oradsorbedOH
Hydrogenation
O OHOH
C- C- CH2
H H “H O”
2 O OH OH OH
OH OH OH 2 H2
C- C= CH2 CH2- CH - CH3
CH2- CH - CH2
H
Glycerol Glyceraldehyde Propylene Glycol
“H2O”
H- O OH OH
C= C- CH2
H
Figure 4.7 Conversion of glycerol to 1,2-PDO, reaction mechanism [57].

type and, particularly, the surface properties of the catalyst used, thus
implying that any proposed mechanism that is fully supported by valid
results might be the actual pathway for the reaction.
4.4 Conclusion
The hydrogenolysis of glycerol to 1,2-propanediol is one of the most
promising routes for producing value-added chemicals from glycerol, a
by-product of biodiesel manufacturing. However, there is need to develop
processes characterized by an improved selectivity toward the desired
product, and higher conversion of the glycerol fed to the process, while
maintaining mild and environmentally benign reaction conditions.
There are other competing by-products which include glyceric acid but
there is a vast array of uses and increase in market growth for 1,2-PDO.
Advancements made in catalytic routes for the conversion of glycerol to
1,2-PDO via hydrogenolysis using different reaction systems was explored.
It was evident that organic non-glycerol and non-methanol (MONG-NM)
impurities as well as sulfur compounds were the most detrimental to cat-
alyst performance and should be removed prior to the catalytic reaction.
The results obtained led to the conclusion that the conversion of glycerol
proceeds faster in a basic medium compared to a neutral one and in a He
as compared to under a H2 atmosphere. The review pointed to the effec-
tiveness of rhenium in the selective catalytic transformation of glycerol
to 1,2-DPO and also to the fact that operating temperature must be kept
below 200°C. It is also very important to exclude water from the feedstock
in an effort to drive the equilibrium toward the products of hydrogenoly-
sis since the reaction itself produces water as a by-product. The retention
time in the reactor must be reduced so as to shorten the turnover time of
the process because higher reaction time do not lead to considerable gain
in 1,2-PDO selectivity as the main product of choice. Further investiga-
tions are still needed in order to establish the reaction mechanism for the
hydrogenolysis of glycerol to 1,2-PDO and so as to optimize the process.
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5
Current Status, Synthesis, and
Characterization of Biodiesel
Akshay Garg1, Gaurav Dwivedi2*, Prashant Baredar2 and Siddharth Jain1
Department of Mechanical Engineering, College of Engineering Roorkee,

1
Roorkee, India
2
Energy Center, Maulana Azad National Institute of Technology, Bhopal, India
Abstract
Biodiesel is an alkyl ester produced by transesterification of vegetable oils and ani-
mal fats. It can be used in the diesel engine without any changes in the existing tech-
nology of the engine. Biodiesel is proved as an environment-friendly fuel with low
emissions. Thus, this chapter focuses on the policies formulated by the Indian gov-
ernment to promote the production and commercialization of biodiesel in India.
Indian government is focusing mainly on the cultivation of non-edible sources on
agricultural waste lands. The chapter covers all the aspects of biodiesel feedstocks,
production techniques, and optimization techniques. The main emphasis is given
on the analytical methods to measure the biodiesel properties. The characterization
of biodiesel as a fuel is based on its properties. Thus, development various analytical
methods used in biodiesel analysis have been discussed in this chapter.
Keywords: Biodiesel, feedstocks, catalyst, optimization, analytical methods
5.1 Introduction
India is the second most populated country and one of the fastest-growing
economies in the world. Being a developing country, the energy consump-
tion is very high. Since past few decades, conventional fuels are fulfilling
this energy demand. Due to large consumption, these sources are depleting
at a high rate. This consumption is estimated to increase with an increase
*Corresponding author: gdiitr2005@gmail.com
167
in population in the near future. The utilization of fossil fuels to produce

energy contributes to the emission of greenhouse gases increasing global
warming in the environment. In 2017–2018, coal accounted for 70.69%
of the total energy generation and crude for 10.34% and natural gas for
8.7% [1]. In India, the amount of energy consumption is expected to rise
to 2280 BkWh by 2021–2022 and about 4,500 BkWh by 2031–2032 [2].
India’s crude oil reserves is about 0.92% of total crude oil production in
the world, while it consumes about 4.96% of total world consumption [1].
The crude price has been increasing rapidly in the past few years. This rise
Table 5.1 Consumption of crude oil in India (MT) [1, 4].

S. no. Year Native production Import Total % of import
1 1971 6.8 11.7 18.5 63
2 1981 10.5 16.2 26.7 61
3 1991 33.0 20.7 53.7 39
4 2001 32.0 57.9 89.9 64
5 2003–2004 33.4 90.4 123.8 73
6 2004–2005 33.98 100.0 133.98 75
7 2005–2006 32.19 105.0 137.19 77
8 2006–2007 33.99 120.0 153.99 78
9 2007–2008 36.68 148.0 184.68 80
10 2008–2009 33.51 132.78 166.28 80
11 2009–2010 33.69 159.26 192.95 82
12 2010–2011 37.68 163.60 201.28 81
13 2011–2012 38.09 171.73 209.82 82
14 2012–2013 37.86 184.80 222.66 83
15 2013–2014 37.79 189.24 227.03 83
16 2014–2015 37.46 189.43 226.90 83
17 2015–2016 36.4 202.85 239.79 84
18 2016–2017 36.01 213.93 249.94 85
19 2017–2018 35.68 220.43 256.12 86
Synthesis and Characterization of Biodiesel 169
in crude prices is severely affecting the developing countries like India.

Conventional oil meets about 95% of the demand for the transport sector
and has been steadily rising [3]. The demand for crude oil and its produc-
tion capacity (MT) of India is given in Table 5.1.
Table 5.1 indicates that large amount of crude oils is imported in India
for its domestic consumption.
In the present energy scenario, sustainable production of energy in an
effective manner is a huge concern, to mitigate the GHG emissions. Solar,
wind, biomass, and hydro are renewable. The government of India with the
help of policymakers is trying to balance the energy demand and environ-
mental protection with fossil fuels and other sources of energy.
5.2 Status of Biodiesel in India

In recent decades, the Indian Government is focusing on promotion of
biofuel production. The government agencies have introduced certain pol-
icies to encourage investment in this field.
The country has recognized biofuels as the most promising factor in fulfill-
ing the energy demand of the nation. Biofuels are non-toxic renewable fuels
and their production would lead to less import of crude oil and the global
concern of containment of carbon emissions. The transport sector plays the
major role in oil consumption and emissions. The government has intro-
duced various policies regarding vehicle emission standards. Thus, the use of
alternative fuels has become a priority to meet the standards to control air pol-
lution. Biofuels can meet energy demands in an environmentally and cost-
effective manner while reducing the dependency on the import of fossil fuels.
As per the Indian government policy of 2019, more attention is to be
given on the waste agricultural lands for the cultivating trees bearing
non-edible oil seeds for the biofuel production. The blend percentage of
biofuel in diesel is yet to be decided because of uncertainty in the availabil-
ity of biofuel. Utilization of the by-products of the biodiesel production
process is also promoted to maximize the use of waste [3].
5.3 Biodiesel Production in India

5.3.1 Feedstocks Popular in India
As per the Indian government policy, the study focuses on different feed-
stocks of biodiesel from the non-edible oils. The Fuel properties of differ-
ent oils are mentioned in Table 5.2.
170
Table 5.2 Fuel properties of oils [18, 21–36].

Density at Heating value Flash point Viscosity at 40°C Cetane Iodine Acid
Oil 15°C (MJ/Kg) (°C) (mm2/s) number number value
Diesel 820 43.8 70 3.5-5 45-55 220 0.07
Jatropha oil 916 38.96 211.7 37.28 46-55 97.9 11.89
Pongamia oil 933 35.992 222 39.9 32 90.7 4.73
Mahua oil 920 36.85 232 24.58 57 71 38
Neem oil 929 39.84 214 38.875 41 75.295
Linseed oil 924 39.3 241 26.24 34.6 188 1
Rubber seed oil 920 38.64 257 11.22 49.73 134.51 1.68
Tobacco oil 918 39.4 220 27.7 38.7 135 -

Castor oil 960 37.4 228 231.22 42.3 80.5 4.57
Waste cooking oil 937 - 235 50 52 - 21.84
Algal oil 860 41 102 21 59 119.1 0.45
5.3.1.1 Jatropha (Jatropha curcas) Oil

Jatropha includes 175 species and belongs to the Euphorbiaceae family. It
is a drought-resistant perennial, growing well in marginal areas, tropical
areas with rainfall of 1,000–1,500 mm per year [5]. It grows quickly and
produces seeds for 50 years and lives about 60 million years. The tree can
have a height ranging from 6 to 12 m with 2.5- to 3-cm length of seeds
[6]. One of the most recognized biodiesel production sources in India is
jatropha tree [4].
5.3.1.2 Pongamia Oil

Humid and subtropical environments are most suitable for pongamia tree
cultivation, with annual rainfall of 500 to 2,500 mm in its natural habitat.
Karanja is mainly found along the coasts and river banks in India [7]. A sin-
gle tree contributes about 8–24 kg of kernels. The maximum height of the
plant is 15–25 m. The pongamia trees are in abundance stage in india, but
in spite of that, pongamia oil has been proven potential oil in India [8, 9].
5.3.1.3 Mahua Oil

Mahua is a forest-based tree bearing non-edible oil sources with a pro-
duction potential of 60 MT per annum in India. Total oil content in the
kernel of mahua is 50% and about 34%–37% can be obtained by the small
expeller. Mahua trees are found in northern tropical parts of India with
a maximum height of 20 m [10]. In addition, 20- to 200-kg seeds can be
produced yearly from a single mahua plant [11].
5.3.1.4 Neem Oil

Since early times in India, neem has been used for protecting food from
pests, insects, and curing some diseases. Neem is grown all over India from
south to north spreading from tropical to subtropical regions. Neem plant
can possess maximum height of 18 m. Neem plant requires 120- to 140-cm
rain yearly for cultivation. Neem plant possess highest productivity after 15
years of plantation with oil content of 20%–30% [13].
5.3.1.5 Linseed Oil

Linseed oil (Linum usitatissimum) belongs to the family Linaceae and has
100 species. It is an herbaceous type crop containing 35–45 wt% oil. Its
height ranges from 0.3 to 1 m. Adequate moisture and cool temperature

is required during maturity of the plant which leads to an increase in oil
content and oil quality. Each branch of linseed tree consists of 1–10 seeds.
Madhya Pradesh and Uttar Pradesh produce about 70% of linseed oil in
India [14].
5.3.1.6 Rubber Seed Oil

Rubber tree (Hevea brasiliensis) belongs to Euphorbiaceous family. It
grows to a height of up to 34 m. The tree requires heavy rainfall and non-
frost climate condition for growth. The oil content in kernel of rubber seed
is 40%–50% and 50%–60% in seeds [15].
5.3.1.7 Tobacco Oil

Tobacco (Nicotiana tabacum) belongs to Solanaceae family. This plant is
mainly grown to produce cigarettes but due to the presence of the char-
acteristics similar to vegetable oils, this plant can be used for producing
biodiesel. It contains oil content of 35%–49% by weight [16].
5.3.1.8 Castor
Castor (Ricinus communis) belongs to the Eurphorbiaceae family. It is cul-
tivated in hot temperature in tropics and subtropic areas. About 1.8 MT
of castor oil is produced per year in all over the world. The height of the
castor tree can reach upto 3 m [17]. The oil content present in castor seeds
is 46%–55% [16].
5.3.1.9 Waste Cooking Oil

The WCO can be obtained from various sources. The waste oil produced
in restaurants, food processing industries, and fast food industries have
been found to degrade with usage time. Waste cooking oils are cheap and
possess poor food quality. WCO needs acidic pretreatment before using it
for biodiesel production to remove the unwanted residues [18, 19].
5.3.1.10 Algae Oil

Algal oils are found to be potential sources of biofuels to replace conven-
tional fuels to promote sustainability in the world. These are aquatic plants
which remove toxic components from water and can be used in producing
biodiesel. These plants take very less time for cultivation and consist of
50% oil by weight [20, 21].
5.3.2 Advantages of Non-Edible Oils

Non-edible oilseed crops have various advantages in concern of their
growth, feedstock, and adaptability which promote their use for biodiesel
production in India.
(1) Non-edible oil sources eliminate the need of fertile land as

they can be cultivated in waste agricultural land with low
fertility and low moisture demand.
(2) They eliminate the use of edible oils and food scarcity for
biodiesel production. Non-edible oils are harmful for human
consumption as there are many toxics present in these oils.
(3) During the conversion process, non-edible feedstocks pro-
duce useful by-products which can also be used power
generation.
(4) Non-edible oils are abundant and biodegradable. They possess
good fuel properties like high heat content, low sulfur content,
and lower aromatic content and are biodegradable [37, 38].
There are many problems faced during the direct use of oils as the fuel in
engines. Due to high viscosity of oils, overhauling of the engine takes place.
Thus, there is a need to perform some modification techniques to make the
oil ready to be used as a fuel in engine. Some commonly used methods are
mentioned in the following section.
5.3.3 Modification Techniques

5.3.3.1 Blending
Direct mixing of oil with diesel fuel to decrease the fuel viscosity and mak-
ing a blend is known as blending technique. Utilization of 100% oil is also
possible, some modifications are required in the engine fuel system [39,
40]. To prevent the modifications in the engine, the oil can be treated by
various techniques to decrease its viscosity.
5.3.3.2 Micro-Emulsification
Blending of oils with alcohols have been reported by many researchers
to decrease viscosity of oil as a fuel. Micro-emulsification improves spray
characteristics of fuel by explosive vaporization. All micro-emulsions with

higher alcohols like butanol, hexanol, and octanol remain within the range
limit of the properties of the fuel for diesel engines.
5.3.3.3 Cracking
Conversion of a substance into some useful form by application of pyrolysis
process is known as cracking. The pyrolysis can be performed on vegeta-
ble oils and animal fats to yield biodiesel with favorable fuel properties. The
pyrolysis process has been studied worldwide by various researchers from
more than a century, especially in the areas which lack in petroleum deposits.
5.3.3.4 Transesterification
Transesterification is the most commonly applied method to convert oil
into biodiesel of low viscosity. The produced biodiesel has the ability to run
the existing engine technology without any modifications. Triglyceride is
reacted with alcohol in the presence of a catalyst to produce alkyl ester and
glycerol as a by-product. This process results in a noticeable reduction of
viscosity of triglycerides [8, 9]. The method of transesterification is shown
in Figure 5.1.
5.3.4 Biodiesel Production Methodology

5.3.4.1 Catalytic Transesterification
The catalytic transesterification is classified into homogeneous catalytic
transesterification and heterogeneous catalytic transesterification.
Transesterification
Non Catalytic Catalytic
Super Critical
Homogeneous Heterogeneous
Methanol
Figure 5.1 Methods of transesterification [18–21].

Table 5.3 Different parameters in biodiesel production from non-edible oils [18–21] and [27–42].
Methanol-
Type of Catalyst to-oil Reaction Temperature Biodiesel
Oil transesterification concentration ratio time (°C) yield (%) References
Jatropha Homogeneous 1% H2SO4 3:7 (v/v) 6h 65 21.2 [41]
Oil 1% NaOH 3:7 (v/v) 6h 50 90.1
Heterogeneous 5% Na2ZrO3 1:16 8h 65 99.9 [44]
Supercritical - 43:1 4 min 320 100 [45]
Pongamia Homogeneous 1.43% KOH 11.06:1 81.43 56.6 98.4 [27]
Oil min
Heterogeneous 3% CaO/ZnO 10:1 6 min 92.61 [46]
Supercritical - 43:1 90 min 300 81% [47]
Mahua Oil Homogeneous 1.24% H2SO4 0.32 1.26 h 60 [48]
0.7% KOH 0.25 30 min 60 98
Heterogeneous 8% ZnO/Mg 1:7 50 min 50 97 [49]
Synthesis and Characterization of Biodiesel
(Continued)
175
176
Table 5.3 Different parameters in biodiesel production from non-edible oils [18–21] and [27–42]. (Continued)
Methanol-
Neem Oil Homogeneous 0.08 H2SO4 1:8 1h 60 85 [51]
1% NaOH
Heterogeneous 6% eggshells 15:1 2h 65 97 [52]
Linseed Homogeneous 0.5% NaOH 9:1 40 min 60 95.99 [31]
Oil
Heterogeneous 0.98% CaO 9.41:1 60 min 30 98.77 [53]
Rubber Homogeneous 0.5% H2SO4 1:2 120 min 55 91.05 [55]
seed Oil
Heterogeneous 5% CaO 9:1 4h 65 97.84 [56]
Supercritical - 42:1 9 min 350 90.86 [57]
Tobacco Homogeneous 1% KOH 20:1 30 min 60 91 [58]
Oil
Heterogeneous
Supercritical - 43:1 90 min 303.4 92.8 [59]
(Continued)
Table 5.3 Different parameters in biodiesel production from non-edible oils [18–21] and [27–42]. (Continued)
Methanol-
Castor Oil Homogeneous 1% KOH 9:1 30 min 60 95 [36]
Heterogeneous 11% ZnO/Ni 1:8 60 min 55 95.2 [36]
Waste Homogeneous 1% H2SO4 3:7 (v/v) 3h 65 21.5 [18]
Cooking 1% NaOH 3:7 (v/v) 3h 50 90.6
Oil
Heterogeneous 10% RS-SO3H 20:1 6h 70 97.71 [61]
Algal Oil Homogeneous 3.36% H2SO4 8:1 60.44min 50 89.583 [63]
3.49% NaOH 8:1 73.63min 50 87.421
Heterogeneous 1.56% CaO. 3.2:10 125 min 50 88.89 [21]
Al2O3
Synthesis and Characterization of Biodiesel
177
Homogeneous catalysts are mainly used in commercial production

of biodiesel as they have high catalytic activity. Homogeneous catalysts
mainly include KOH, NaOH base catalyst during transesterification, and
HCL, H2SO4 as the acid catalyst during esterification. Esterification is a
pretreatment method performed in case of high FFA oils [42].
Heterogeneous are less active but are reusable. These catalysts have less
catalytic activity as compared to homogeneous catalysts and require high
temperature for complete transesterification [43]. The different parameters
of transesterification process are shown in Table 5.3.
5.3.4.2 Non-Catalytic Transesterification

Supercritical method is based on the process of transesterification in the
absence of any catalyst. This process includes the reaction of oils with alco-
hol at very high temperature, thus increasing high energy consumption
and high equipment cost [43].
Various researchers have produced biodiesel from homogeneous, het-
erogeneous catalyst, and supercritical method. This section focuses on the
advantages and disadvantages of the homogeneous catalyst, heterogeneous
catalysts, and supercritical method. The advantages and disadvantages of
different biodiesel process methods is shown in Table 5.4.
Table 5.4 Advantages and disadvantages of different processes [42, 43, 65–67].
Type Advantages Disadvantages
Homogeneous Low cost, good catalytic Pre-treatment required,
activity, the low low FFA required,
temperature required, the more wastewater
high reaction rate from purification,
saponification
Heterogeneous No pretreatment is required Low catalyst activity and
in case of high FFA, the reaction rate
catalyst is recyclable,
ecofriendly
Supercritical Catalyst is not required The high reaction
in reaction, no effect of temperature and pressure
water and FFA in oil, is required, excess alcohol
high biodiesel quality, the required amount in the
high reaction rate reaction, high equipment
cost.
5.3.5 Optimization Methodology for Biodiesel

5.3.5.1 Central Composite Design Technique
Response surface methodology is the most frequently used technique
to design the experiments and optimize the transesterification process.
Optimization is based upon the experimental data obtained by experimen-
tal values of transesterification.
RSM is used to build an empirical model based on statistical and math-
ematical techniques. Output variables depend upon input variables vari-
ables. Design-Expert software is used to develop a mathematical relation
between the response and independent variables and its optimization.
Central composite design (CCD) is a technique to perform RSM. Various
studies have been done using CCD as the optimization technique for bio-
diesel production. C.H. Ali et al. used five-level, four-factor CCD for opti-
mizing biodiesel production using WCO and obtained a yield of 85.8% at
reaction temperature of 44.2°C, methanol oil ratio (3.5:1), with an amount
of lipase 0.782 g with an incubation period of 24 h [68]. P. Goyal et al. used
five levels of four-factor CCD to optimize the yield of high FFA jatropha
oil. The yield of 98.3% was obtained. Fifty-four experiments for both ester-
ification and transesterification each were performed with increases run-
ning cost and time consumption [69]. T. Mathimani et al. [70] used eight
assays, four center points, and six axial points to predict the lipid content of
algae on input parameters as incubation days and pH. M. Balaji et al. used
CCD to optimize the biodiesel yield of Ceiba pentandra oil using three
center points. A biodiesel yield of 98.73% was obtained by the optimum
parameters of 2.68 wt% catalyst, 11.46 methanol-to-oil ratio and 106-min
reaction time [71].
5.3.5.2 Box Behnken Technique

Box Behnken design technique is another optimization technique of RSM.
Unlike CCD, BBD has a smaller number of experiments for the same num-
ber of independent variables for biodiesel production. BBD always have
three levels per factor, whereas CCD can have up to 5. Thus, it is less expen-
sive to run BBD as compared to CCD. Gaurav et al. used the BBD tech-
nique to optimize biodiesel production from Pongamia oil. The reaction
conditions of (11.06:1) methanol-to-oil ratio, KOH catalyst 1.43 (w/w%),
and 81.43 min at a reaction temperature of 56.6°C was found optimum to
obtain FAME yield of 98.4% [27]. V. Narula et al. [72] optimized the bio-
diesel yield of algae-jatropha oil blend using BBD technique and obtained
a FAME yield of 81.98% with (3:5) methanol/oil ratio, 0.9 wt% KOH
catalyst in 180 min at a reaction temperature of 50°C. R. Chamola et al.
optimized the biodiesel yield of microalgae using BBD and obtained satis-
factory results [63].
5.4 Properties of Biodiesel

Biodiesel properties mainly depend upon properties of feedstock used,
production process, and the storage technique. The physico-chemical
properties of the fuel characterize the biodiesel quality. It has better lubri-
cating properties than conventional diesel [73]. It is biodegradable, renew-
able, and non-toxic. The calorific value of biodiesel is about 29,442 (kJ/
kg). The density at 25°C was 874 and a very high flash point of 156°C as of
diesel is 60°C, thus making it safer to handle [74]. There are various other
properties on the basis of which the characterization of the quality of bio-
diesel as performed as fuel for CI engine.
Oxidation Stability: The presence of unsaturated fatty acids in alkyl
esters play major role in the oxidation stability. With an increase in unsat-
uration, the tendency of biodiesel to degrade and form insoluble products
also increases. Amount of water content in biodiesel contributes to an
increase in their oxidation. Metal contamination in biodiesel also results
in acceleration of free radical oxidation process; thus, metals have catalytic
behavior in oxidation [75].
Pour Point and Cloud Point: The key cold flow properties of the fuel are
cloud point and pour point. Pour point is the minimum temperature at which
the flow tendency of the fuel decreases. The fuel with a lower degree of unsat-
uration has poor pour points. Cloud point is the minimum temperature at
which the wax starts to crystallize and the fuel starts to solidify. This is the
minimum temperature until which the fuel can be used in an engine [76].
Flash Point: The lowest temperature at which the vapors of fuel ignite
when an ignition source is applied to it. It is inversely proportional to the
volatility of fuel. A higher flash point temperature is necessary for storage
of the fuel. The flashpoint of biodiesel is much higher than conventional
diesel that making it safer to handle.
Cetane Number: The measurement of ignition delay for a fuel is denoted
as its cetane number. A fuel with a high cetane number is considered as a
good fuel because of short ignition delay [76].
Kinematic Viscosity: It is the measurement of the magnitude of the
internal friction of the fluids. During the storage of biodiesel, the precip-
itation occurs, which leads to gum formation and increases the viscosity.
High viscosity decreases tendency of atomization of the fuel spray and thus
affecting the proper combustion of the fuel [77].
5.5 Analytical Methods

All the above-mentioned properties in (Section 5.4) can be measured by
the analytical methods. These properties are the standards to characterize
biodiesel and its blends as fuel. The quality control of biodiesel is necessary
as the presence of contaminants may lead to severe operational and envi-
ronmental hazards. The majorly used methods for monitoring biodiesel
production process and determination of biodiesel quality are chromato-
graphic and spectroscopic methods. The various biodiesel properties and
respective measuring apparatus is shown in Table 5.5.
5.5.1 Titration
Biodiesel consists of methyl esters of fatty acids and always a portion of free
fatty acids. The acidity of FFAs is very low but they act as acids during the
titration method for determining acid value. Thus, two methods, potentio-
metric titration method and the titration method with two indicators, were
introduced to find the acid number of the fuel [78]. The potentiometric
titration method was found more reliable, giving separate concentrations
of strong acids and weak free fatty acids simultaneously. A new study pro-
posed the use of coulometric titration for determining the acid number. This
method was found as good alternative to the volumetric method because
of its higher precision and no requirement of standard solutions for analy-
sis [79]. Water and LiCl are the major solution in the coulometric titration.
The method was based on constant-current coulometric titration integrated
with potentiometric detection. The method contributes in better accuracy in
determining acid number with reducing waste generation from the analysis.
5.5.2 Chromatic Methods

Monitoring transesterification reaction is a necessary task as all the prop-
erties and contaminants change in this reaction. The first chromatographic
analysis of oils was done by means of thin-layer chromatography (TLC)
using a silica gel. It was observed that about 80% of allyl ester yield was
obtained in 2 min [80]. The presence of alcohol does not interfere with
the estimation of yields by TLC. In another report, TLC with flame ion-
ization detection (TLC/FID) was used through a latroscan TH-10 analyzer
[81]. The FID was operated with hydrogen and air flows. The formation of
Table 5.5 Biodiesel properties and measuring apparatus [63, 97, 99–109].
Properties Methods Specifications
Oxidation Rancimat • Metrohm 892 Professional Rancimat
Stability • Determine stability according to
national and international standards:
AOCS Cd 12b-92 fats and oils
ISO 6886 vegetable oils and fats
2.4.28.2-93 Fat stability, CDM Japan
• Simultaneous analysis of up to eight
samples.
• User-friendly StabNet software for
instrument control.
• It can measure the oxidation stability
of biodiesel, vegetable oils, fats, and
food.
Karl Fischer • A digital meter for measuring
apparatus conductivity)
(modified) • The reaction vessel of 24 mm in
diameter coupled with 150 mm long
of quartz glass
• Proper piping to allow the air to pass
through.
Water Near-Infrared • The wavelength is measured one at a
spectroscopy time.
• The grating and slit combination is
used to select the wavelength to be
measured.
• The detector produces a spectrum
of a plot of transmittance against
frequency for analysis.
Acid value Titration • Important materials for titration-
pH indicator
Titrant
Equivalence point indicator
UV-VIS Spectra • Absorption spectroscopy in the
ultraviolet-visible spectral region.
• Uses light near-UV and near-infrared
ranges
(Continued)
Table 5.5 Biodiesel properties and measuring apparatus [63, 97, 99–109]. (Continued)
Properties Methods Specifications
Ester Gas • GC is equipped with a FID.
Content chromatography • Quantitative analysis is performed in
the presence of nitrogen as a carrier
gas.
• European standard EN14103: 2003 is
used for quantitative analysis.
FTIR Spectroscopy • Relies upon various frequencies of
light to produce a spectrum.
• An assembly of a beam splitter and
two strategic mirrors that act as an
interferometer.
• A laser beam is superimposed for the
operation of the instrument.
• Components in IR spectrometer-
Radiation source
Monochromator
Detector
Sample
(Na+K) Flame Atomic • Used to determine the concentrations
Absorption of Ca2+, Mg2+, Na+, and K+.
Spectroscopy • The concentration of elements greater
than 1 µg ml−1 in biological fluids.
Flash Point Pensky-Martens • Works on the standards ASTM D93,
closed cup ISO 2719, IP 34.
test apparatus • Automatic high-precision flash point
(D-93) testing
• It is used in petroleum, chemical, and
fragrance industries.
mono-, di-, and triglycerides during the reaction was also analyzed along
with the ester yield. Other chromatographic methods are as follows.
5.5.2.1 Gas Chromatography

Capillary gas chromatography (CGC) discussed the analysis of transes-
terified soyabean oil with a Spectra-physics SP100 gas chromatograph
equipped with FID and a 1.8 × 0.32 mm bonded SE-30 fused silica capil-
lary column [82]. Helium was used as a carrier gas. The results were favor-
ble with the actual and measured values of the content of biodiesel. Gas
chromatography works on the basis of ASTM 6584. The presence of glyc-

erol and glycerides in a fuel determines fuel quality as their presence can
damage engines and cause harmful emissions [83]. After this, an import-
ant method was developed performing trimethylsilylation of glycerol, and
mono, di followed by GC and triglycerides in vegetable oil methyl esters
using CGC [84]. A method of determination of different fatty acid profiles
of three different oils was studied by GC using a fused silica capillary col-
umn at the split ratio of 1:5 [85].
5.5.2.2 High-Performance Liquid Chromatography

The first HPLC method was used for determining the free glycerol content
in esters [86]. High-pressure liquid chromatography combined with pulsed
amperometric detection was used in the method to determine free glycerol
in methyl or ethyl esters (HPLC-PAD). HPLC-PAD was found attractive
because it is simple and fewer operations for analysis. This method was
capable of determining the glycerol and alcohol traces simultaneously. The
limit of detection was 1 lg/g with high accuracy. In another study, HPLC
analysis was performed on soyabean oil biodiesel. HPLC chromatogram
integrated with refractive index (RI) and ultraviolet (UV) detectors in
series was used for determining fatty acid composition [87]. The RI detec-
tor was found universal for all FAMEs, whereas UV detects the unsaturated
FAMEs consisting carbon-carbon double bonds. The FAME composition
and FAME yield at the time of transesterification of soybean oil was esti-
mated. As HPLC requires low temperature during analysis, the risk of
isomerization of double bonds is reduced during analysis [88].
5.5.3 Spectroscopic Methods

Emission of light is used in this method for the analysis. It is discriminated
by the wavelength of light and regions of the electromagnetic spectrum
produced. Transesterification is monitored for the analysis of biodiesel.
Some most commonly used methods of spectroscopy are nuclear magnetic
resonance spectroscopy and infrared spectroscopy [89]. The peaks charac-
terize the conversion of the triglyceride to the FAME yield.
5.5.3.1 Nuclear Magnetic Resonance Spectroscopy

NMR spectroscopy technique is used for the characterization of chemical
structures. NMR method is integrated with hydrogen signals. NMR has
been found to be able to determine the blending level with high accuracy.
A study reports that 1H NMR was used to characterize the palm biodiesel
and its blends. The amount of unreacted vegetable oil was detected due to
incomplete transesterification reaction [90]. Another study was performed
for the investigation of results obtained on transesterification of rapeseed
oil. The rate of transesterification was monitored [91]. The catalytic activ-
ity and reaction kinetics were determined in a study for different reaction
parameters [92]. Peak fitting and partial least squares regression (PLS-R)
were integrated with high-field NMR spectroscopy was used to monitor
the FAME concentration with variation in time. The PLS-R method was
found to be better than the peak fitting method. NMR was found much
accurate to determine the reaction kinetics.
5.5.3.2 Infrared Spectroscopy

Infrared spectroscopy is used to study the chemical bonds and the func-
tional groups in the molecules. This method is faster than GC, easy to
use, and can also measure the flashpoint [93]. In this study, spectra were
recorded with the help of a fiber-optic probe. Transesterification was mon-
itored with the help of infrared spectroscopy. In another study, NIR mea-
sured the cetane number of WCO and its biodiesel [94]. NIR absorption
was assumed to be linear with the concentration of organic materials. The
standard error of prediction of CN from WCO was 1.2 with an RPD (ratio
of performance to deviation) of 3.83. Mid- and near-infrared spectroscopy
were used for the prediction of the dynamic and kinematic viscosities of
biodiesel-diesel blends [95]. MIR and NIR were integrated with an FT-IR
spectroscopy machine. The fingerprint spectral region of 550–1,500 cm−1
was observed suitable for MIR spectroscopy and NIR spectroscopy chose
multiple regions which were 1,100–1,500, 1,600–1,700, and 1,800–2,200
nm. Results for both MIR and NIR spectroscopy were found acceptable,
NIR was found more accurate.
5.5.4 Rancimat Method

Rancimat test is performed to check the oxidative stability of biodiesel. The
apparatus is based on the EN14214 standard. It works on the basis of the
aging process. The temperature of the samples is increased and a continu-
ous stream of air is passed through it [100]. The effect of five antioxidants
was studied using the rancimat method to evaluate the oxidation stabil-
ity of fuel produced [96]. The conductivity was continuously measured
by passing a stream of pure air 10 L/h through the samples at 110°C. The
stream swept the volatile oxidation products and collected in an electrical
conductivity measuring vessel containing deionized water. But the testing

of this parameter is very costly thus a new method was developed. A Karl
Fischer (KF) apparatus was modified to measure the oxidation stability [97].
The working principle was based on Rancimat, i.e., a conductivity-based
determination of volatile degradation products and automatic plotting of
the conductivity against time. The results showed that tests performed with
modified Karl Fischer apparatus were in a good agreement with the values
on Rancimat. Modified Karl Fischer apparatus was of less cost and can be a
replacement of the Rancimat apparatus with slight modification.
5.5.5 Viscometry
The oils are highly viscous to use as a fuel in diesel engines. This is the
main reason for performing transesterification and decrease the viscosity
of the oils and produce biofuels. The viscosity differences of biodiesel from
different feedstocks characterize them. A study was reported by using vis-
cometry for the analysis of the products of transesterification, i.e., FAME
[98]. The FAME yield was investigated with respect to the viscosity curves
of the products. The viscometric analysis was performed for the binary
mixtures of soybean biodiesel/soybean oil. All the samples were tested at
40°C according to ASTM D445. The study showed that viscometry is a
promising analytical method for determining the amount of ester levels in
biodiesel. This is a simple and inexpensive technique.
5.6 Conclusion
The non-edible sources are the most promising feedstocks to meet the gov-
ernment targets of biofuel in India. The study has reported various produc-
tion and analytical methods of biodiesel. The fuel properties were reported
according to ASTM and European standards which are to be considered for
the commercialization of biodiesel in India. More focus is to be concerned
on monitoring the transesterification process and the analytical methods
to characterize biodiesel according to their properties. The monitoring of
transesterification process is mainly performed by the spectroscopy meth-
ods and are very much efficient, whereas chromatography methods are
used to estimate the biodiesel yield. Both the methods work on standards
and can analyze the fuel quality for operation in CI engine. Some modified
methods were developed which can contribute in decreasing the cost of
biodiesel analysis. Thus, the development of alternate analytical methods
is necessary which can be used in analyzing the process as well as the yield.
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6
Commercial Technologies for
Chikati Roick1, Leonard Okonye2, Nkazi Diankanua1 and Gorimbo Joshua2*
School of Chemical and Metallurgical Engineering, Faculty of Engineering and the

1
Built Environment, University of the Witwatersrand, Johannesburg, South Africa

2
Institute for the Development of Energy for African Sustainability (IDEAS),
University of South Africa’s College of Science, Engineering and Technology,
Florida, South Africa
Abstract
The commercial production of biodiesel and other biofuels is a pursuit central
to the modern fuel industry. The chapter reviews various established technolo-
gies that are available for producing of biodiesel. These include mainly thermo-
chemical conversion, biomechanical conversion, direct combustion, and chemical
reaction. These technologies are hardly comparable as they are used to process
different biomass feedstocks and developed to satisfy different aims. Extracting
fuels from renewable feedstocks is the only feasible option thus far to cut down
on fossil fuels utilization, which also has a positive effect on the global health. The
chapter looks at Africa as a case study, with its vast renewable energy sources, and
the continent is expectant to reap massive benefits, with the growing attractiveness
of biodiesel to replace conventional fuels. The anticipated benefits calls for eco-
nomically sound and innovative process technologies for commercial production
to meet the growing demand and compete with conventional petroleum products.
Currently, second-generation biodiesel production is not competitive in Africa
due to the associated high cost of production. To reduce the influence of biofuels
production on food security, more attention should be dedicated to the develop-
ment of modern second-generation biodiesel production technologies in Africa,
to their optimum potential.
Keywords: Biofuels, biomass to fuel, thermochemical conversion, gasification,
anaerobic digestion, fermentation, transesterification
*Corresponding author: joshuagorimbo@gmail.com
195
Abbreviation
Institute for the Development of Energy for African Sustainability (IDEAS)
greenhouse gases (GHG)
polycyclic aromatic hydrocarbons (PAHs)
Zimbabwe’s National Biodiesel Feedstock’s Production Program (ZNBFPP)
Biomass Energy Strategy (BEST)
International Energy Agency (IEA)
Fischer Tropsch Synthesis (FTS)
6.1 Introduction
Energy is a necessity for socio-economic growth, as it makes available vital
services for the enhancement of the quality of life, with a direct influence
on all aspects of development [1, 2]. In the wake of the continual surge
in the demand for energy, declining petroleum/fossil fuel production and
energy security issues, combined with adverse effects on the environment,
there is impetus to secure an unconventional and adequate, renewable
energy source, that is reasonably priced, dependable with lesser adverse
effect on the environment for energy services [3–9].
In addition to fossil fuels having a negative impact on our environment,
fossil fuels are reportedly depleting rapidly. As such, extracting fuels from
renewable feedstocks can be a better option to cut down on utilization of
fossil fuels, which also has a favorable effect on the global health. Several
research centers around the world viz a viz Institute for the Development
of Energy for African Sustainability (IDEAS) in South Africa, Exxonmobil,
BP USA continues to fund and conduct research on renewable energy
with emphasis on biofuels. This area of work is undoubtedly relevant with
a transformative potential to ease energy supplies and reduce emissions.
However, the use of food crop to produce the much-needed transportation
fuel may not be an ideal solution for the energy problem; hence, research
focuses on non-food-based biomass.
Alternative utilization of biomass as energy fountainhead to generate liq-
uid fuels (biodiesel) with vast environmental and socio-economic advan-
tages cannot be over emphasized [8, 10–12]. Biomass is defined as the plant
or animal material that can be used for energy production such as electric-
ity or heat. Biomass conversion to biodiesel is a favored choice for future
energy needs and sustainable socio-economic [1, 10]. Biodiesel is one of
the energy carrier derived from biomass, which can be utilized to pro-
vide energy for heating, electricity, as well as transportation. Undoubtedly,
Technologies for Biodiesel Production 197
sources of renewable energy can improve energy supply security [11, 12].
The conversion from biomass sources can be achieved through biochemi-
cal, physicochemical, and thermochemical processes. Biodiesel is unequiv-
ocally the favored pathway to supplant existing petroleum fuels, as it offers
a direct route to decarbonize the transport system and lessen the reliance
on fossil fuel and greenhouse gases (GHG) emission, with a positive con-
tribution to socio-economic development [13–15].
Africa, with vast renewable energy sources, is expectant to reap massive
benefits, with the growing attractiveness of biodiesel to replace conven-
tional fuels. There will be opportunities for rural development, employ-
ment, and economic growth [12, 13, 16]. The anticipated benefits calls for
technically innovative technologies for commercial production to meet the
growing demand and compete with conventional petroleum products [12].
Although development practitioners, resource owners, policy makers, and
other stakeholders want to cash in on the numerous advantages offered
by the technology, early projects did not hit the ground running due to
unforeseen challenges. Some of which include lack of proper regulatory
institutions, lack of appropriate agronomic knowledge, lack of “sustainable
agricultural systems”, investor caution, poor market development, improper
“natural resource management” ability, and the potential socio-economic,
food and social security, as well as environmental impacts [17–19].
Biodiesel offers the following advantages [6–8, 20–27]:
• biodegradability,
• sulfur-free,
• with lower level of polycyclic aromatic hydrocarbons (PAHs)
and n-PAHs emitted,
• enhanced performance, higher cetane number, and flash-
point than conventional diesel,
• reduced emmisions,
as well as improved energy security, some prospect of energy indepen-

dence, and improved socio-economic development [1–3, 15, 28].
6.2 Biodiesel Production

The production of biodiesel from renewable biomass resources is growing
rapidly in commercial significance. The biomass feedstock include but not
limited to vegetable oils, algae, water hyacinth, waste cooking oils, and animal
fats [2, 11, 12, 29–31]. Various conversion processes have been established
as technological routes for the commercialization of biodiesel [13]. The

starting material and the fuel production pathway determines the naming
of the biofuel produced, for example, one can have first-generation biofuel,
second-generation, etc. Usually, first-generation biodiesel can be reaped from
oily crops such as sunflower and or derived from waste oil, animal waste via
bio-chemical conversion pathway, while second-generation biodiesel is synthe-
sized from non-food crops via thermo-chemical pathway [6, 7, 13, 32–40]. A
number of first-generation technologies for biofuel production applicable in
Africa exist. Currently, second-generation biodiesel production is not com-
petitive in Africa due to the associated unfavorable capital expenditure. To
reduce the influence of biofuels production on food security, more attention
should be dedicated to establishment of state of the art second-generation bio-
diesel production technologies in Africa, to their optimum potential [1, 41].
6.3 Technologies Used for Biodiesel Production

Various established biomass to biodiesel pathways are documented [2,
8–10, 42, 43]. They include thermochemical conversion (gasification,
pyrolysis, or thermal cracking), biomechanical conversion (fermentation,
anaerobic digestion, etc.), direct combustion, chemical reaction (transes-
terification), ultrasound technology, membrane technology, reactive dis-
tillation technology, micro-emulsions, and blending [2]. The mostly used
technologies are presented in Figure 6.1.
(>700 °C), without combustion, controlled Syngas (CO, H2, CO2)

amount of oxygen and/or steam.
Thermochemical Pyrolysis Syngas, Bio-oil,

conversion above> 430 °C and under pressure. Charcoal
Hydrothermal liquefaction
250-550 °C and high pressures of 5-25 MPa Bio-oil
Anaerobic digestion Methane (CH4),

utilization of microorganisms,
in anoxigenic conditions Hydrogen (H2)
Biomechanical Fermentation Bio-ethanol, Acetone,
Biomass conversion substrate such as sugar. Some yeasts,
25-35 °C. Butanol
Photobiological hydrogen
production Hydrogen (H2)
uses microorganisms and sunlight to turn
H2O, and sometimes organic matter, into H2
Power generation
Direct Bio-oil
combustion °
Chemical reaction alcohol, ester molecule react in either Bio-oil

the presence of an acid or base
Figure 6.1 Four level flow chat for the production of fuel energy from biomass.
6.3.1 Chemical Reaction (Transesterification)

Transesterification reaction entails reacting an alcohol molecule with an
ester molecule acidic, basic medium, or biological enzyme usually lipases.
Basically, the reaction happens by swapping the organic moiety of an ester
with the one of the alcohol to form a new ester. Catalyzed transesterifica-
tion of triglyceride is the main technique used (first-generation production
technique for biofuel production [12, 38–45]. The catalysts can either be
acids, alkalis (carbonates, alkali metal oxides, and alkaline earth metals),
or enzymes (lipases) [12, 32, 45], with alkali catalysts given more prefer-
ence due to higher reactivity and moderate process conditions [12]. The
key downside of this process catalyst depletion and difficulty in separation,
leading to high cost of production [46].
The general equation for transesterification is given as follows:
Ester + alcohol ↔ ester + alcohol (6.1)
For instance, the transesterication of triglyceride with methanol goes as

follows:
Triglyceride + methanol ↔ glycerol + methyl esters (6.2)
6.3.2 Thermochemical Conversion

Thermochemical conversion can be classified as gasification, pyrolysis, and
liquefaction. This second-generation technology uses high temperature to
gasify or pyrolyse biomass and then trailed by the fuel synthesis. The gas
produced is then processed different liquid and gaseous fuels, after ade-
quate treatment and conditioning to syngas.
Gasification is a thermal process which takes place at elevated tem-
peratures (600°C to 1,000°C) in an oxidizing atmosphere. Oxidizing agent
making up the oxidizing atmosphere typically air and steam and, in some
cases, N2, CO2, O2, or a mixture of these are used. During gasification under
ideal conditions large polymeric moieties or molecules of biomass disin-
tegrate to yield lighter molecules and useful gases. The emergence minute
contaminants such as sulfide (H2S), carbonyl sulfide (COS), and hydrogen
cyanide (HCN) during the process is inevitable. Incomplete conversion of
biomass yields char and tar which in most cases contains trace elements
of both organic and inorganic origin in the feed such heavy metals mainly
mercury and arsenic.
All inclusive, gasification reaction in different atmosphere is given by

Equation 6.3, and this proceeds via multiple pathways. Equations 6.4–6.10
are side reactions feasible during the gasification process. Equations 6.6–
6.9 are observed when steam is added during the process.
Biomass + air + steam = methane + carbon monoxide + carbon dioxide
+ hydrogen + unreated steam + char + tar
CHxOy+ O2+ H2O CH4+ CO + CO2+ H2+ H2O + C (6.3)
2C + O2 2CO (6.4)
C + O2 CO2 (6.5)
C + 2H2 CH4 (6.6)
CO + H2O CO2+ H2 (6.7)
CH4+ H2O CO + 3H2 (6.8)
C + H2O CO + H2 (6.9)
C + CO2 2CO (6.10)
The product gas from biomass gasification is further processed

downstream for instances via Fischer Tropsch Synthesis (FTS) to yield
hydrocarbons.
(2n+1) H2 + n CO → Cn H(2n+2) + n H2O
where n takes the values of positive whole numbers. The FTS can be opti-
mized to yield more valued products.
Another thermochemical conversion process of significance is pyrolysis.
Pyrolysis (conventional, fast pyrolysis, or flash pyrolysis) by using catalyst
or heat in the lack of air or oxygen is used to reduce the crude oil’s viscosity,
leading to lower pour and flash point, viscosity, and comparatively higher
cetane number to conventional diesel [12, 27, 32, 47–51]. Hydrothermal
liquefaction is mostly applied to wet biomass and it entails using super-
critical fluids (H2O and CO2) to extract bio-liquid. Reaction conditions for
these processes are summarized in Figure 6.1.
6.3.3 Biomechanical Conversion

Anaerobic digestion, fermentation, and photobiological hydrogen produc-
tion are mature technologies that are already in use for the transformation
of the biomass and other carbon containing waste to useful products.
Anaerobic digestion involves processes such as methanogenesis, hydro-
lysis, acetogenesis, and acidogenesis. The general equation can be repre-
sented as follows:
organic matter → Carbon dioxide + methane
For example, glucose gets digested by anaerobic microorganisms as

follows:
C6H12O6 → 3CO2 + 3CH4
In the case of fermentation, sugars in biomass are broken down to

yield alcohol and carbon dioxide. For example, glucose is broken down as
follows:
C6H12O6 → 2 C2H5OH + 2CO2
Photobiological hydrogen production entails the use of sunlight and

microorganisms to convert sugars in biomasssunlight to turn water and,
sometimes, organic matter into hydrogen.
6.3.4 Direct Combustion

The process involves directly combusting biomass feedstock in surplus air
to heat the boiler to produce steam. Direct combustion is usually executed
inside a furnace or steam turbine. The operation is mostly applicable to
biomass with low percentage moisture.
6.4 Other Technologies in Use for Biodiesel

Production
Ultrasound technology as applied to biofuel synthesis has been studied and
developed. Mixing intensity is a key parameter a progressive transesterifi-
cation reaction [48]. This homogenization method has been successfully
employed for both batch and continuous biodiesel production processes
[12, 49, 50, 52]. The ultrasound technology presents a swift, innovative, and
cost-effective process with the advantage of fast separation and a reduced
temperature and reaction time to occur, and higher yields compared to
conventional processes [11, 12, 44, 49, 51–53].
Membrane technology: application of membrane reactors for synthe-
sis of bio-derived diesel is being developed commercially in Sub-Saharan
Africa. There is ongoing design, and optimization studies are being car-
ried out to improve the membrane (organic or inorganic in nature) reactor
for operations. Transesterification of lipids may possibly be fused with the
membrane reactor hybrid. If reaction followed by separation is integrated
as a unit operation, there will be reduction in the cost of separation and
recycle requirements, leading to higher conversions [12, 54–56].
Reactive distillation technology: Due to the controllability of the chem-
ical reaction used in producing biodiesel by chemical equilibrium, reac-
tive distillation technology can be successfully applied for production, as
several features of this technique have been explored to improve the yield.
The addition of an extra flash evaporator and a decanter will lead to better-
quality biodiesel from various feedstock types. The energy requirement of
the process lower (with roughly 45% savings) [12, 57–59].
The energy stored in biomass discussed in the above sections can be
extracted via various means as shown in Figure 6.1. There are many dif-
ferent types of process technologies used. These technologies are hardly
comparable as they are used to process different biomass feedstocks and
developed to satisfy different aims.
Figure 6.1 gives an overview of how energy is extracted from biomass
(especially lignocellulosic biomass). Biomass from lignocellulosic crops
comparatively need much effort to degrade than first-generation feed-
stocks such as sugarcane, corn, soy, palm, or grapeseed etc, so for these
second-generation feedstocks gasification seems to be the option favored
by researchers though research keeps focusing on improving the yield opti-
mizing the production process. Gasification as one of the thermochemical
conversions of any carbon containing material to synthesis gas (syngas) and
char. Gasification essentially converts carbonaceous materials into mixture of
CO, H2, and CO2 in varying ratios depending of feed source and conditions.
This process involves heating the biomass at elevated temperatures, without
combusting the feed that is tailoring the amounts of O2 and steam amounts.
The gasification of biomass reportedly shows a methodical and effective
way of producing heat, power, and hydrogen production as well as second-
generation biofuels. Attention should therefore be given to state-of-the-art
equipment or setups for biomass gasification, assessing the downstream pro-
cess of converting the syngas to fuel and electricity via Fischer Tropsch.
6.5 Feedstock Requirement

To successfully guarantee the sustenance of industries in biofuel synthesis,
furnishing enough cheap raw materials (biomass) should not impact on
food production. In Africa, possible suitable feedstocks being considered
include the following [1, 2, 12, 32, 60, 61].
Waste oil: waste oil is the major raw material used for biodiesel synthe-
sis by Southern Africa biodiesel plants (both small and medium scale);
however, inadequate supply and availability pose as a hurdle large-scale
synthesis of biodiesel.
Canola: The exceptional cold-flow properties and low triglyceride con-
tent saturation of canola oil makes it efficient feedstock biodiesel for bio-
diesel production. When crushed, it is possible to extract approximately
44% oil from the seed.
Sunflower and soybean: The seeds of sunflower and soybean (which is
widely cultivated in the Southern African region) yield approximately 30%
and 18% oil.
Jatropha: Jatropha was considered a bio-energy feedstock as oils can be
extracted from the seed, and processed to biodiesel.
Algae: Algae is seen as an alternative and sustainable energy source, with
potentially higher oil yield per hectare compared to vegetable oils. It can
be grown with the aid of waste materials (like sewage) to harvest oil for
biodiesel production.
Other feedstocks being considered include cotton seed, sunflower,
cashew nut, castor oil, pumpkin, rapeseed, sesame seeds, avocados, coco-
nut, soyabean, Canola, rubber seed, oil palm, neem, animal fat/waste,
olives, moringa, karanja, linseed, moringa, oleifera, and tobacco plants.
6.6 Some Problems Facing Commercialization

of Biodiesel in Africa
Food in contrast to fuel factor: The shift from food crops to energy crops
is the main concern to local farmers and the rural communities in Africa,
with most of the countries still in developmental stage. A rapid decline in
food crop production will lead to increase in price and starvation, in par-
ticular among the rural populations [2, 62, 63].
Land: To sustain a beneficial commercialized biodiesel production, vast
land is required for the cultivation of energy crops. Traditionally, land
ownership in Africa is essentially by heritage, usually in small portions,
as such vast land for energy crop cultivation can be acquired from com-
munity lands, which, in some cases, leads to dispute. Taking land from
socio-economically vulnerable communities/families will have a negative
impact on their livelihood [2, 64].
Finance: The initial cost for the acquisition of resources and infrastruc-
ture for production of biodiesel is high. The inadequate financial arrange-
ments as well as the lack of low interest rate credit facilities is a main
obstruction for the commercialization of biodiesel technology in many
African countries, as small-scale investments is not supported by the cap-
ital markets [2].
Policy hurdles: Lack of coordination among government, energy and sci-
ence ministries, and technology, financial institutions, and research groups
have contributed to the slow growth in biodiesel process development and
commercialization [2].
6.7 Case Studies/Current Status and Future Potential

The commercialization of biodiesel synthesis in Africa is projected to
provide, among other benefits, the opportunity for Africa to have a vari-
ety agricultural activity, energy sources, and contribute immensely to
socio-economic growth in a more sustainable way [3, 65]. Although
biodiesel technology development is nascent in Africa, the large-scale
advanced projects investment plans, limited the commencing of com-
mercial production in many countries in African countries, e.g., Nigeria,
Ghana, Senegal, Liberia, Zambia, Ethiopia, Tanzania, Kenya, and even
South Africa [2, 66, 67]. Other investments include Madagascar, Niger,
Ethiopia, D1 oils in Swaziland, Malawi, Mali, Uganda, Nigerian National
Petroleum Corporation, Angola, International Biofuels Crops in Liberia,
and the Dutch biodiesel equipment manufacturer in Senegal [2].
Biodiesel industry development in most African countries is in the early
stages, with South Africa being an exception (implementations of small to
medium scale) and Zimbabwe (with first ever commercial biodiesel plant
in Africa) [13, 68, 69].
A number of countries in the Southern region of Africa came up with
policies to empower biodiesel production—achieved via the direct fiscal
motivation for biodiesel production or penalties for use of conventional
fuels. Although many biodiesel production routes are fully established, they
are comparatively expensive than the conventional diesel synthesis route,
which makes it difficult for commercialization and widespread adoption of
the technology [13, 69]. Even though South Africa is the most advanced
nation technologically, tax exemptions and favorable leasing contracts in

neighboring countries attract private investments to these countries.
South Africa: Presently, South Africa has over 200 small-scale biodiesel
production capacity, from waste vegetable oils, and by 2007, South Africa
has implemented a 10% biodiesel blend in petroleum fuels sales at its fill-
ing stations, However, the key concern has been sustained availability of
feedstock, and refining it to specifications of petrochemical industries [2].
Rainbow Nation Renewable Fuels Ltd. (Coega, near Port Elizabeth)
made the first serious commercial investment into biodiesel production by
acquiring a license and erecting a 1.1 Mt per annum use Australian technol-
ogies (Desmet Ballestra). The crushing facility for soybean, it is expected to
produce and distribute roughly 228 ML biodiesel fuel. This Investment of
US $250 M created 350 full‐time jobs, 1,500 in construction and associated
industries, and roughly 5,000–10,000 in agricultural sector [70].
Zimbabwe: Zimbabwe’s National Biodiesel Feedstock’s Production
Program (ZNBFPP) targeted a 10% substitution of imported fossil fuel
daily consumption with biodiesel by the end of 2018 [15]. Zimbabwe’s $6
million biodiesel plant is capable of producing 100 million liters (Ml) of
biodiesel annually, if operated at full capacity, and has the capability to pro-
cess different feedstock, such as sunflower and soya, cotton seed, jatropha,
among others. Roughly $80 million a year is the expected annual savings in
foreign exchange from diesel import by this plant [3, 15].
Zambia: Zambia, with the aid of Marli Investment set up an $8 million
plant, which will utilize jatropha oil as the major raw material for biodiesel
synthesis. Another biodiesel plant capable of producing 60 Ml/year of bio-
diesel started operations in August 2007 [2].
Ghana: Anuanom Industrial Bio-Products and Biodiesel was capable of
producing about 360,000 t/a of biodiesel, but the construction was stalled.
However, Anuanom currently have two production plants, with a com-
bined capacity of 140,000 metric tonnes of jatropha oil. Ghana Energy
Commission targeted a 20% national biodiesel production by 2015, and
in partnership with South Africa-based BD-1Group, Ghana planned a
12,000-hectare project focused on J. curcas production [2, 11, 71, 72].
Other African countries with initiated projects include in place for the
development include the following:
Botswana: Biomass Energy Strategy (BEST) was launched to ensure that
the biomass derived energy is carried out in a social-economic and envi-
ronmentally sustainable way. BEST has the backing of German-EU Energy
Initiative [32].
Tanzania: Ministry of Energy and Minerals established a Biofuels Task
Force in conjunction with other government ministries and institutions.
The aim is to ensure a sustainable socio-economic, environmental, and

bioenergy development. Sun Biofuels originating from UK contributed 20
million dollars toward the production of J. curcas and processing plant for
biodiesel in Tanzania, with panned expansion to Burkina Faso, Malawi,
and Madagascar [11, 33, 34].
Kenya: The National Biofuels Committee established 14 years ago, to
increase energy supply security and diversify local energy sources via bio-
diesel supplements and reduce imported fossil fuels dependency [32].
Mozambique: In the course of 2006–2007, three important projects
were announced, with Canadian-based Energem Resources investing $4
million on its first plantation. Duelco renewable energy based in South
Africa is in partnership with Mozambique for a plantation that measures
60,000 hectares, while ESV-Bio Africa has a plantation that measures
11,000 hectare and they project to achieve 100,000 hectares. As per the
International Energy Agency (IEA), Mozambique is capable of producing
roughly 3,000,000 barrels/day of biomass derived oil from non-food feed-
stock [11, 73].
Angola—Angola has the largest non-forest agricultural lands in the
world (with over 80,000,000 hectares reserved land for biodiesel crops
growing). If developed, the country’s biodiesel daily export is estimated at
2.7 million barrels of oil [11, 74].
Coal Nuclear energy

Renewables Natural gas
Hydroelectricity Oil
100
90
80
70
60
50
40
30
20
10
North S. & Cent. Europe CIS Middle East Africa Asia Pacific 0
America America
Figure 6.2 Primary energy regional consumption by fuel 2018 in Percentage. BP

Statistical Review of World Energy 2019 (Outlook, 2019) [75].
Angola and Mozambique are collaboration with Petrobras, Brazil, to

develop soybean-based biodiesel, to aid biofuels supply to industries in
both countries [74].
Renewables are mainly consumed in Asia Pacific and Europe. Together,
these regions account for 70% of global consumption. From Figure 6.2,
Africa and Middle East reap less fuel from renewables in the energy mix.
Oil and natural gas remain the dominant fuel in most parts of the globe.
Global coal consumption is heavily concentrated in Asia Pacific while more
than two thirds of nuclear consumption is concentrated in North America
and Europe. Asia Pacific and South and Central America account for almost
60% of hydro. More than 90% of renewables are consumed in Asia Pacific,
Europe, and North America. Biofuels from renewables are now common
fuels components blended in petroleum derived fuels in many countries.
6.8 Conclusions
The chapter reviews various established technologies that are available
for producing of biodiesel. Extracting fuels from renewable feedstocks is
the only feasible option thus far to cut down on the utilization of fossil
fuels, which also has a positive effect on the global health. They include
thermochemical conversion, biomechanical conversion, direct combus-
tion, chemical reaction, ultrasound technology, membrane technology,
reactive distillation technology, and micro-emulsions. These technologies
are hardly comparable as they are used to process different biomass feed-
stocks and developed to satisfy different aims. The commercialization of
biodiesel synthesis in Africa is projected to provide, among other benefits,
the opportunity for Africa to broaden energy supply and diversify agricul-
tural activities and contribute immensely to socio-economic growth in a
more sustainable way. To reduce the influence of biofuels production on
food security, more attention should be dedicated to the development of
modern second-generation biodiesel production technologies in Africa, to
their optimum potential. Several research centers around the world con-
tinues to fund and conduct research on renewable energy with emphasis
on biofuels. This area of work is undoubtedly relevant with a transforma-
tive potential to ease energy supplies and reduce emissions. However, the
use of food crop to produce the much-needed transportation fuel may not
be an ideal solution for the energy problem; hence, research focuses on
non-food-based biomass.
Biodiesel industry development in African is still in infancy, except for
South Africa and Zimbabwe with Africa’s first ever commercial biodiesel
plant. Although a number of biodiesel synthesis routes are well developed,

the lack of cost competitiveness with conventional diesel fuel is the fore-
most difficulty for the commercialization and the widespread adoption of
the technology especially in Africa.
Acknowledgments
The authors are grateful for the financial support provided by the
University of South Africa (UNISA), University of the Witwatersrand,
National Research Foundation (NRF) of South Africa, and the Institute for
the Development of Energy for African Sustainability (IDEAS) research
unit at UNISA.
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7
A Global Scenario of Sustainable
Technologies and Progress in
a Biodiesel Production
M. B. Kumbhar1, P. E. Lokhande1,2*, U. S. Chavan2 and V.G. Salunkhe3
Department of Mechanical Engineering, Sinhgad Institute of Technology,

1
Lonavala, India
2
Department of Mechanical Engineering, Vishwakarma Institute of Technology,
Pune, India
3
Department of Mechanical Engineering, Annasaheb Dange College of Engg.
and Technology, Ashta, India
Abstract
Biodiesel is an alternative fuel source to replace the non-renewable crude oil and
their possible environmental pollution.The production of a biodiesel has currently
many challenges such as performance-based efficiency, environmental friendly
cycle, next generation–based, flexible and ease production technique, sustainabil-
ity, and commercialization. Feedstock has played crucial role to run the biodiesel
production to sustain the global market. This chapter gives latest development
as regards the feedstock research review that gives remarkable progressive fea-
ture of an existing feedstock which survives a long-term consistent availability
for biodiesel commercialization. Feedstock sources and combustion parameter are
strongly believed to improve the production method that gives exact ways to apply
the knowledge to produce a biodiesel from a catalyst-assisted biodiesel plant or a
biorefinery. The current scenario of technology and research areas in this alterna-
tive fuel are highlighted.
Keywords: Feedstock sources, combustion performance, biodiesel

commercialization
*Corresponding author: prasadlokhande2007@gmail.com
215
7.1 Introduction
The natural renewable source as an alternative fuel among these some
well-known sources is a biodiesel instead of current crude oil sources. It
is available in unlimited large amount in the world. This sustainable and
strong potential source reduces petroleum holding and pollutant emission
contributes to global warming [1]. There is wide application such as auto-
mobile, industrial, heating oil, and aviation. The use of biofuels in the avia-
tion sector can eliminate greenhouse gas emissions between 50% and 90%
compared to existing kerosene. Advanced biofuels have environmental
footprints associated with greenhouse gas emission savings between 80%
and 90% compared with fossil references. Many challenges stand to zero
and reverse the harm done to Mother Nature by mankind, and still, society
cannot simply end its energy demand. Therefore, it must continue to utilize
its current energy sources more efficiently while investing in renewable
sources. Numerous replacements like nuclear, solar, biofuel hydro, wind,
biofuel, and biodiesel are recommended, but still, they are in the stage of
research and development stage [2]. Several researchers are focus to syn-
thesize with low cost and in emerging commercial technologies. Biodiesel
consumes oxygen of 11% by weight which satisfies and fulfills the com-
bustion and thus improves the performance characteristics of engine [3].
Although the biodiesel industry has sustainable with tremendous global
growth rate, raw material or feedstock supplies have strongly recom-
mended as a natural brake and created a strain on margins for biodiesel
producers. Therefore, commercial technologies for biodiesel production
from biodiesel feedstock receive tremendous interest all over the globe.
There have many challenges as regards biodiesel commercial technologies
and environmental concerns that are enlisted as follows.
• Researchers focus to produce high free fatty acid (FFA) for

selected level of biodiesel yield as well as higher flash point,
remarkable biodegradability, excellent lubricity, with high
rate of combustion efficiency associated with petro-diesel
properties [1].
• Biodiesel production from alternative resources poses many
limitations. Unsteady crude oil prices, depletion of fossil-fuel
resources, and ecological measure are the main limitations
for searching an innovative fuel which satisfies and fulfills
the parameters such as eco-friendly, inexpensive, extensively
accessible, and technically suitable [2].
Progress in Biodiesel Production 217
• To ensure stability of biodiesel, it is degraded by numerous

influences like (i) long-term storage conditions, (ii) auto-
oxidation, (iii) thermal decomposition, (iv) biodegradation
with microbial progress, (v) water absorption, (vi) contami-
nation of metal, and (vii) nonappearance and occurrence of
additives. It is significant to advance such additives, which
may provide all these benefits to modify and utilize the
application of biodiesel for commercialization [3].
• A major common feedstock currently utilized in biodiesel
production is vegetable oils. Although biofuel from vegeta-
ble oils is debatable to a straight utilization in a quantity, of
times, it has called criminal against humanity due to social
activities in biofuels, and biodiesel is foremost the cause
behind global growth rate in food market supply. This con-
troversial factor of “food vs. fuel” war does not fulfill circum-
vented if cherished cultivated land is consumed for making
of non-edible oil crops [4, 5].
The mandatory and revolutionized elements are energy, soil, water,

nutrient, agrochemical board and crop safety, landscape and biodiversity
safeguarding, and energy harvesting, which are good agreement to green
sustainable ecological practices that would report biodiesel invention and
commercialization. This methodology integrates technology with eco-
nomic, social, and environmental disputes that will upsurge biodiesel profit
and improve the biorefineries that are accomplished of sustainable bio-
diesel production and additional remarkable chemicals. As early it is seen,
government strategies will be the powerful energy for advance growth rate
in biodiesel production. These strategies must embrace the great signifi-
cance social attentions like employments and favorable working environ-
ment, creating awareness about environments among peoples, etc. Later,
strong support between the governments and stakeholders is required to
grow and spread over effectively sustainability criteria in worldwide [6].
Researchers collaborating with the investing a greater role of conducting
the initial waste, i.e., unwanted resources to the commercial equality that
creates the complete procedure toward fulfilling a green environment.
Continuously usage of waste feedstock is anticipated in centuries to emerge
as to withstand the production of biodiesel firm and additionally extend
the gap among biodiesel cut point and the trade price. The researcher is
always learning, sharing, and connecting to fulfill the gap between loca-
tions and production technology and commercializing the source of a bio-
fuel for biodiesel production technology and commercializing the source
of a biofuel. Also, the European Union communal has continuously in

research for oil crops additional for petro-based chemicals eliminate the
dependence on imports [7]. Hence, the former opportunities left out to
the corporate economically though evading its provocative structures
applicable waste-oriented or non-edible oil feedstock increase on non-
agricultural space and efficient biodiesel production from these diverse
feedstock categories.
For 2018, the world’s biodiesel production is overviewed by the United
States production of 1,190.2 thousand barrels/day, followed by Brazil out-
put of 693.2 thousand barrels/day. Third, Germany has produced 75.8
thousand barrels/day, fourth, Argentina production of 70.6 thousand
barrels/day, and fifth, China that reported a production of 68 thousand
barrels/day [5]. Biodiesel has been one part of the social discussion and
critically innovated by environmental organization for a biodiesel produc-
tion innovation and technology. It globally support policies that capture
biodiesel from residue and waste materials and the self-introduction to the
market, i.e., synthetic fuels from renewable power [8]. These synthetic fuels
run the automobiles, aviation, and industrial sectors.
7.2 Current Status of Feedstock for Biodiesel

Production Technology
The biodiesel market growth rate is built on the availability of feedstock
sources for biodiesel production technology. A long-term strategy (bio-
fuels after 2050) can only be based on “high yield per hectare”. A primary
source to run the biodiesel plant or refineries is biodiesel feedstock.
Potential biodiesel feedstock and technology resources of the future are
currently leading for higher effectiveness, commercialization, and reducing
economic impediments. Therefore, biodiesel feedstock has some research
circumstances to sustain the biodiesel production, reduces pressure on
cropland, portfolio of feedstocks, green house emission (GHG) reduc-
tions, integrated models across agricultural, forestry, and energy markets,
and profitable for farmers and forest managers to produce data for recent
generation-wise feedstocks.
Also, conversion efficiency is an important parameter based on the cost
of biofuels production. Analysis of literature focused at modifying methods
used in feedstock production and conversion could modify feedstock avail-
ability and extract the quantity needed to achieve biofuels target, lowering
feedstock cost and making more utilization for other uses. A conceptual
framework of literature describes the relationship between consciousness

feedstocks for biofuels and the substantial market for each and every feed-
stock, including how higher yields for respective feedstocks (e.g., resulting
from investments in research) affect feedstock and biofuel economy. The
following focused current status of feedstock analysis reviews emerge as
priorities for future investigating efforts to sustain the biodiesel from these
feedstock or complex integration of a feedstock.
The most significant principle for biodiesel expansion is to discover
low price feedstock with higher amount of oil content. Transesterification
method for production of biodiesel from goat waste with substantial FFAs
is investigate with infrared radiation assisted reactor [1]. For biodiesel pro-
duction, investigators have considered several categories of homogeneous
and heterogeneous catalyzed transesterification reaction. These methods
can boost the quality of Fatty Acid Methyl Ester (FAME) implementation
for diesel engines without any variation [2]. The integrated production
plant of first-generation soybean biofuel and sugarcane ethanol concludes
negligible influences to the GHG emission drop and greater prices owing
to the low sulfur diesel. A biorefinery design gives region-wise biodiesel
production that provides us a lot of local opportunities [9]. Next rich
source of oil content in rubber seed with combination of 40%–48% shell
and 52%–60% kernel is consumed as a feedstock for biodiesel as per their
sustainability. Particle size and extraction time optimization parameters
are analyzed to production of a higher yield biodiesel. The characteristic
physico-chemical oil proves that it can be sustained as a possible cause for
biodiesel production [10]. Second-generation source as a Moringa oleif-
era oil and leaf as a valuable contribution causes for the biodiesel produc-
tion as well as antioxidant biodiesels additives. This Moringa oleifera is
a sustainable and natural source as an antioxidant as compared to tert-
butyl-hydroquinone (TBH) for biodiesel to provide low oxidation stability
and high induction period (IP) value [11]. The crude Moringa oleifera oil
considers as a higher FFA content and use for human utilization. As com-
pared to diesel fuel, cetane number of Moringa oil is approximately 67, and
among these resources, it is a maximum stated value for a biodiesel fuel.
In Moringa oleifera, oil contains antioxidant and low polyunsaturated fatty
acid which provides higher oxidation stability. The oil properties like oxi-
dative stability, kinematic viscosity, density, acid value, and iodine value of
synthesized Moringa oleifera methyl esters are in good settlement with the
EN and ASTM standard. Higher flash point marks Moringa oleifera methyl
esters to be intensely recommended as a non-flammable. Hence, Moringa
oleifera oil owns a major impending source to be used for production of
biodiesel as a feedstock. In India, it is stated that Moringa oleifera oil has
major impending for production of biodiesel and shows that high stability
to oxidative rancidity [12].
Sludge palm oil (SPO) is considered as a cheap substrate edible oil
(1 USD/Ton) for production of biodiesel. Conversion of SPO to biofuel is
an effective means of providing a cheap biodiesel production and waste
utilization. Generally, biodiesel is produced via a transesterification reac-
tion with the help of homogenous alkaline catalyst. This method has wide
range advantages such as high conversion, short reaction time, and low
catalyst use [15]. Palm oil mill effluent (POME) is a sustainable feedstock
for conversion biodiesel worthwhile of high volumes. Next criteria is its
huge quantities of freely available fatty acids (FFA), and water in POME
prevents trans/esterification reaction and harmfully disturbs present tech-
nology engaged in biodiesel production [16].
To boost the properties for sustaining the storage stability, research is
focused on availability of variable complex feedstock. The complex mix-
ing of Karanja and Coconut biofuel and their respective blends conserve
long-term storage. Also, good agreement with stability of biofuel upon
sustaining the storage, sunlight, and non-contact with air is found to be
the superior storage condition studied [17]. Rapeseed and soybean oils
have been considered as an alternative energy source in Europe and North
America, and the utilization of palm and jatropha oils for production of
biodiesel contributes to a new energy source in West Africa and South-East
Asia [18]. The second biggest traded commodity global is coffee, i.e., it is
a sustainable source for biodiesel. Instead of solvent extraction, esterifica-
tion, and transesterification (three-step process), direct transesterification
to biodiesel production from spent coffee grounds (SCGs) with favorable
reaction condition [19, 20].
Third-generation micro-algae are now promising the major resource of
production of biofuel in the global world. They are assessed as the non-
competitive, safer, and drastically growing organisms among those that
could be utilized for production of biodiesel. The potential to grow with-
out much care on waste nutrients and the better renewable source of bio-
diesel production as compared to other sources can affect food problems
as they are majorly considered as plants which are used for food [21]. A
primary standard process trained in microalgae culture, harvesting, and
processing, the existing study boons a summary of recent development
in area of algal biofuel. Impending resource of biofuels which is majorly
studied is algae. Algal fuels are striking to many investigators in the areas
of bioenergy and biodiesel. Investigation of dynamic algae species and its
revolution into alternative fuels and bioproducts is attractive in public and
private sector [22]. Lipid extracted from microorganisms, including algae,
yeasts, fungi, and bacteria, are defined as single-cell oil (SCO) which is the
best capable feedstock for biodiesel production due to their homogene-
ity in structure of fatty acid which is good agreement to vegetable oils. A
microbial base for lipid production has numerous benefits such as small
growth duration with advanced lipid productivity and poor in climate
change. The reports on biodiesel were evaluated from different oleaginous
yeast integrated with low-cost raw material for large-scale commercial
production so as to progress a worksheet for production of biodiesel. The
concluded constraints help to analyze fuel blends which diminish the risk
of noncompliance with the technical standard [23]. Advanced biodiesel
and biogas can be extracted from a numerous of feedstock; Norwegian
companies majorly produced bioethanol and biodiesel from lignocellu-
lose biomass [24]. Edible mustard oil from Cruciferae family is consid-
ered as oil and spice plant which is in lengthwise 0.2–1.5 m and white or
yellow flowering. Entire world, approximately, 10 types of mustard were
obtained from white and black species. It has showed that 96.695% of bio-
diesel yield was found from yellow mustard [25]. Soybean biodiesel and
linseed-derived blends determined an inclination of minimal emission
that constitutes nitrogen oxides as related to maximum diesel engine loads
[26]. A sustainable city and society waste cooking oil (WCO) is comfort-
ably accessible from household kitchens, restaurants, and cafeterias. The
pretreated acid WCO was laid open to transesterification with base cata-
lyzed to production of biodiesel. In total, 94% of a higher yield was gained
with 1:3 methanol to oil ratio, reaction temperature 60°C, and 1% cata-
lyst dose [27]. Sunflower and rapeseed oils are majorly utilized in Europe,
canola oil in Canada, soybean oil in the United States, and palm oil avail-
able in tropical countries. It is significant to footprint that the price of bio-
diesel production from the first-generation feedstock is 30% greater than
of petroleum-based diesel. Feedstock for second-generation biodiesel such
as lowcost non-edible sources, e.g., from karanja, pongamia, jatropha, as
well as microalgae, alters sources of microorganisms. Waste frying oil and
waste from slaughterhouses and rendering industry can be classified under
this category. Microalgae are considered as “micro sunlight-operated bio-
chemical company”. They are obtained as a third-generation potential
source of biodiesel production [14]. The seeds of different plants indig-
enous of tropical scale could be used for production of biodiesel, and it
determines the suitable properties that they show. Such plants could be
cultured in several tropical ecoregions with marginal costs, to provide bio-
diesel instead of carbon-based fuels [28].
Nanoadditive is a modern nanocommercial application on microalgae
biofuel enrichment and it has been classified according to different phases
from waste material production to end product insinuations: nanoadditives

for microalgae cultivation for the resolution of microalgae biomass trans-
formation into biofuels and nanoadditives for microalgae-biodiesel appli-
cations. Scientists are still discovering an invention which will improve the
higher yield microalgae biofuel from the beginning step to end product
and prime concerns toward a cost-effective fuel results [29]. The ligno-
cellulose ethanol market has been slower progress rate due to concerns of
intensive capital costs, high technological risk, and the low oil prices that
highlighted in poor economics for the biorefineries. Food and Agriculture
Society of the United Nations (UN) (2015) has calculated a total capacity
of 1703 million liters for second-generation ethanol by 2024, majorly in
USA and Europe (UNCTAD, 2015). Second-generation biodiesel (2G) that
consists of herbaceous crops, lignocellulose materials, hardwood, and soft-
wood is the intensive feedstocks used for the production of liquid ethanol
[30].
Koelreuteria paniculata (KP) that belongs to a family of Sapindaceae
is a recent second-generation non-edible seed oil which will enhance
production of biodiesel. Approximately, 1-hectare zone will grow up to
115,000-kg seeds and the productivity of biodiesel is near about 30,000
kg per hectare zone. KP species firstly belong to countries such as Japan,
China, and Korea. The concluded optimization transesterification param-
eters are catalyst concentration (0.32 g wt.%), oil-to-methanol ratio (6:1),
temperature (65°C), stirring rate (700 rpm), and time (80 min), and the
highest biodiesel yield of 95.2% was determined, which is satisfactory for
marketable technology. The physical-chemistry properties of the biofuel,
i.e., flash point, cloud point, pour point, and density, are acceptable to the
ASTM (D6751) and (EN14214) standards; biofuel good values are closer
to mineral diesel, to improve the performance of an engine application.
KP seeds are analyzed to be substitute and alternative source of biofuel for
generation of potential technology, which might be a crucial auxiliary for
petroleum and diesel [31].
7.3 Scenario of Biodiesel in Combustion Engine

Biodiesel revolution is helping several countries to overcome their depen-
dence on diesel. The adoption of biodiesel worldwide economy within the
shipping sector has fetched with a reliable and smooth fuel supply. It can
be used without any variation or minute moderation in diesel engines. It is
biodegradable and nontoxic and it produces fewer pollutants when burnt
completely. Biodiesel having acceptable source such as 11% oxygen by
weight can ensure total combustion and thereby results in upsurges in the
engine performance as well as it diminishes the exhausted gas emission as
associated to that of diesel.
Nevertheless, the certain limitations for marketable application of bio-
diesel such as higher viscosity cause injector coking, fuel filter plugging,
moving parts sticking, poor atomization, and fewer fuel injector precise
operations.
The real fact is that biodiesel is auto-oxidative and can easily affect its
other fuel properties such as flash point, cetane number, viscosity, and den-
sity [3, 32]. The analysis result shows that CO, HC, smoke, and CO2 reduc-
tion for biodiesel blend and NOx upsurges related to diesel are utilized in
the same engine. However, some analysis shows that NOx declines with
biodiesel. It exhibits feedstock quality, engine type, and running situations
that vary from one to another; later, the distinction of performance and
emission parameter is investigated [33].
Jatropha oil, Moringa oleifera, KP, and microalgae are foremost aspi-
rants for the commercialization of biodiesel production instead of diesel
fuel in combustion engines. The effective method to eliminate emissions
and refining engine performance is by supplementing nanoadditives with
emulsified fuels [34].
7.4 Biodiesel Production Technologies

There are also some little worth mentioning challenges such as environ-
mental parameters, feedstock sources, combustion-based parameter, and
convenient technology adopted with biodiesel production. Among these,
frequently stated are the rate of feedstock and the suitable optimization
technology for effective biodiesel production from several feedstock cat-
egories. The technologies, which enable us to utilize biofuel and fat feed-
stock types and to utilize fuel in diesel engines, are always defined as
straight utilizing or blending, microemulsion, pyrolysis, and transesteri-
fication. Transesterification is presently stated by several investigators as
utmost acceptable due to its improved quality of fuel produced [32]. All
these technologies are briefly explained with their applicability, benefits,
and limitation as follows.
7.4.1 Direct Blending

Direct utilization of vegetable oils is normally considered as non-
acceptable and unrealistic for direct and indirect diesel engines. The FFA
content, composition, high viscosity, and gum development due to oxida-

tion and polymerization at the time of storage and combustion, lubricat-
ing oil thickening, and carbon deposits are obvious problems. Inadequate
combustion and oil deterioration are the two simple limitation related to
the straight utilization of vegetable oils as biofuels [32].
7.4.2 Pyrolysis
Pyrolysis is considered as a chemical modification affected by the applica-
tion of heat in the occurrence of a catalyst and deficiency of air or oxygen,
in which result shows the splitting of bonds and establishment of several
tiny scale molecules. Three types of methodology for pyrolysis technique
are as follows: (1) conventional pyrolysis exhibits with temperature range of
550–900 K, (2) fast pyrolysis exhibits with temperature range of 850–1250
K, and (3) flash pyrolysis exhibits with temperature range of 1,050–1,300
K. Currently, acceptable number of pyrolysis reactors is utilized with 50%
to 70% yield range. These are categorized as a (1) circulating fluidized bed,
(2) bubbling fluidized bed, (3) ablative, (4) rotating cone, and (5) focused
solar reactor [35].
There are two in situ and ex situ onsite methods to produce a biodiesel
from pyrolysis technique (Figure 7.1). In situ catalytic pyrolysis, the ability
to splitting the reactions to cut downcast the substantial molecules exist-
ing in the pyrolysis goods foremost to the establishment of lighter and
min viscous bio-fuel. In situ catalytic process of biofuel vapors is also per-
formed in the same pyrolysis reactor, e.g., a fluidized bed reactor. Ex situ
In-situ catalytic pyrolysis Ex-situ catalytic pyrolysis
Biomass Gas Biomass Gas
Catalyst
Catalyst Reactor Reactor Packed
Bed
Char/Catalyst Bio-Oil Char Bio-Oil
Figure 7.1 Online two-way catalytic pyrolysis reaction process for conversion of biodiesel
with the help of zeolite catalysts [36].
catalytic process of biofuel can be implemented at the downstream of the

pyrolysis reactor in a distinct reactor such as a packed bed reactor sys-
tem. Combination of pyrolysis with their appropriate catalyst is a com-
mercialized technique for cost competitiveness of production of biofuel
[36]. Innovating these pyrolysis techniques for commercialization has
many challenges such as feasibility, potential catalyst, reduction of unde-
sired compounds, imprecise product quality, uncontrolled reaction, and
post-treatment of end products [37].
7.4.3 Microemulsification
Microemulsification method is also identified as a viscosity reduction. It is
carried out by blending of two immiscible liquids. Microemulsions exhibit
colloidal distribution of optically isotropic fuel which occurs as micro-
structures under symmetry. Surfactants are used for processing of micro-
emulsions that have substantial role to aquatic and terrestrial ecotoxicity
[35]. Microemulsification technique formation, stability, and phase behav-
ior have been proposed over the years. With the help of these theories, the
biodiesel properties for sustainability are improved.
Microemulsions steady blend of oil are consist of, an anisotropic, trans-
parent and thermodynamically. This steady blend of oil exists in water
Water/ Vegetable
Ethanol Oil
(Polar) (Non-Polar)
W/O O/W W/O/W O/W/O
I II
Surfactant/Co-surfactant
W/O: Water in Oil Emulsion

O/W: Oil in Water Emulsion
W/O/W: Water in Oil in Water Emulsion
IV O/W/O: Oil in Water in Oil Emulsion
MHBF MHBF: Microemulsion based hybrid Biofuel
Figure 7.2 W/O/W and O/W/O emulsion P. A. Winsor I-II and IV type emulsion [37].
(O/W) or water in oil (W/O) stabilized with the assistance of surface-

active agents (surfactants and/or co-surfactants). Figure 7.2 shows the
Winsor I-II (W/O, O/W), and IV types of microemulsions and W/O/W
and O/W/O type microemulsions; the applications of microemulsions
are medicinal/food/paint industries and biodiesel. The sustainability
analysis of microemulsions, exergy analysis, and its lengthy occurrence
effects upon engine are also a major factor considered for forthcoming
research work [37].
7.4.4 Transesterification
Transesterification reactions are always catalyzed by the mixture of
an acid or base catalyst. This method is also widely use to convert fats (tri-
glycerides) into production of biodiesel. Transesterification extracted vege-
table oil (biodiesel) was utilized to power heavy-duty vehicles before World
War II in South Africa.
Therefore, transesterification is an ease process to production of bio-
diesel extract from fat and oil feedstock sources. Transesterification is a
reversible method, which basically exhibits principally by mixing the reac-
tants with the help of heat and/or pressure. Transesterification reaction for
effective production of biodiesel is designated by simple and effective part-
ing of an ester and glycerol layer after the reaction time. Production of bio-
diesel via a transesterification reaction by mixture of homogenous alkaline
catalyst. This method has several benefits such as short reaction time, high
Biodiesel Methods
Blending Pyrolysis Micro-emulsion Transesterification
• Double layer formation • Side product formation • Significant injector • Cost effective method and gives
• Gum Formation • Lack of an effective needle sticking high conversion efficiency
• Carbon Deposits catalyst • Incomplete combustion • Improve the fuel characteristics
• Increase smoke, CO and • Expensive setup • Carbon deposits • Glycerol produced as by-product
HC emission • Eliminates environmental • Increase the lubricating can be used for medicinal pupose
• Ring sticking benefits oil viscosity • Biodiesel produced by this method
is miscible in any proportional with
the mineral diesel
• Can be employed to a variety of
feedstocks
Figure 7.3 Biodiesel production methods.

conversion, and low catalyst use [15]. Some of the advantages over other
biodiesel production methods are shown as Figure 7.3.
7.5 Microwave-Mediated Transesterification

Microwave irradiation process is a substitute to the traditional heating
system with minimum reaction time [13]. It has been widely acceptable for
a variation of applications such as organic synthesis reaction. The chemi-
cal reactions are augmented because of specific absorption of microwave
energy by polar molecules. Due to the blend of methanol, vegetable oil,
and potassium hydroxide that encloses both polar and ionic components,
rapid heating occurs upon microwave irradiation. The energy interrelates
regards to the reactant on a molecular level, actual effective heating is
achieved [38].
The uninterrupted microwave reactor constructed in this investigation
can generate about 19,000 L of biodiesel per day with approximate yield of
90% that is considered, as shown in Figure 7.4. Microwave irradiation pro-
cess and conducting reaction more capably, with less parting and reaction
times, eliminate the numbers of by-products and drop energy use. It shows
that microwave-mediated transesterification results are in close agreement
Line-Out
Product
reactor
Line•In
Biodiesel
Pump Pump
Glycerol
Jatropha•Oil CH3OH
Figure 7.4 Continuous microwave reactor [38].

Table 7.1 Biodiesel production from various feedstocks [13, 14].

Second- Fourth-
First-generation generation Third-generation generation
biofuel biofuel biofuel biofuel
Sources Sources Sources Sources
Edible oil: Non-edible oil: Oleaginous microbes Genetically
Soybean, Neem, Jatropha, microalgae, optimized
Coconut, Moringa, Algae, bacterium, yeast and feedstocks
Sunflower, Orange, Linseed, fungi algae to biofuels
Palestine, Mahua, Karanja
Corn, Rice or Pongamia
bran, Olive, Jojoba, Kusum,
Sesame seed, Cottonseed,
Palm, Pistachio, Rubber seed,
Rapeseed, Deccan hemp,
Peanut oil, Sea mango,
Safflower oil Waste cooking
oil, and Animal
source
Benefits Benefits Benefits Benefits
Renewable Renewable sources, Renewable sources, Renewable
sources, Environmental Environmental friendly, sources,
Environmental friendly, High lipid production, Capture large
friendly, Effective land Do not compete with amounts of
Easy conversion utilization, land utilization and carbon, with
into biofuel Do not compete food, genomically
with food crops High growth rate synthesized
tendencies microbes,
High yield
and lipid
containing
algae,
Economical
running
production
Limitations Limitations Limitations Limitations
Net energy losses, High cost, Insufficient biomass Advanced
Compete with Inefficiency, production to synthetic
food crops Unsustainability, commercialization, biology,
(food energy Land and water use Higher initial High initial
crime), competition investment cost for investment
Raising cost production
of food due
to food
competition,
Land scarcity
with appropriate production process and cost competitive to make bio-

diesel in global market (Table 7.1) [38].
7.6 Ultrasound-Mediated Transesterification

Ultrasonication-mediated transesterification is the process to convert
mechanical energy for blending and to carry out a reaction. It consumes
minimum energy consumption and efficiency of cavitations which is
reliant on transformation to FAME (99%) within minute and irradiation
frequency [13]. The ultrasonication process has major benefits that are
reduced process time, positive effect on transesterification process, and
saved energy in the biodiesel production [39].
The benefit of microwave and ultrasonication technologies is to syn-
thesize the reaction, and it directly drops costs in the biodiesel production
Table 7.2 Difference between conventional, microwave, and ultrasonic heating [40].
Conventional heating Microwave heating Ultrasonic heating
Thermal gradient Inverse thermal Limited thermal
(outside to inside) gradient (inside to gradient due to
outside) mixing
Conduction and Molecular level hot Microbubble formation
convection currents spots and collapse
(compression and
rarefaction cycles)
Longer processing Very short and instant Very short reaction
times heating times
No or low solvent No or low solvent Solvent saving possible
saving reactions possible
Product quality and Higher product quality Same as conventional
quantity can be and quantity possible heating
affected
Separation times are Very short separation Less than conventional
longer times heating
High energy Moderate to low Moderate to low
consumption consumption consumption
Simple process Very simple process Moderate complexity
configuration
process due to clear FAME [13]. Ultrasonic and microwaves together

improve extraction of oils/lipids by diffusive and disruptive mechanisms
and simultaneously transesterify the lipids/oils due to thermal/specific
non-thermal effects at molecular levels and increased mass/heat trans-
fer phenomena. Microwave and ultrasound-mediated transesterification
methods have several power steps at several frequencies [39].
Among these two technologies, microwave and ultrasonication technol-
ogies are differentiated on the basis of chemical and physical parameters as
shown in Table 7.2. The biodiesel reaction proficiency can be modified by
integrating intensification process effects and the green chemistry princi-
ples. Green chemistry is defined as chemical products and reduces the use
and generation of hazardous substances methods. Microwave-assisted bio-
fuel intermixes the reaction efficiency due to maximum product recovery
and minimum by-product formation and eliminates energy use [40]. The
difference between these two processes over conventional method is given
in Table 7.2.
7.7 Catalysis in Biodiesel Production

Catalysis is the procedure of modifying the growth rate of a chemical reac-
tion by mixing a substance known as a catalyst, which is not expended in
the catalyzed reaction and can carry out to act repeatedly. That is why, only
very negligible amounts of catalyst are essential to change the reaction rate
in furthermost processes.
Catalytic reactions are selected in environmentally friendly green chem-
istry due to the eliminated amount of waste generated. Few of the reported
chemical catalysis utilized for biodiesel production are mentioned in the
following.
7.7.1 Homogeneous Catalysts

A homogeneous catalyst is defined as the molecules that are isolated in
the similar phase (usually gaseous or liquid) as the reactant’s molecules.
There are two types of homogenous catalysis that are acid and base catal-
ysis. The evergreen first method from homogenous catalyst is used as an
acid catalyzed transesterification to biodiesel production (ethyl ester) from
palm oil utilizing ethanol and sulfuric acid. Traditionally, homogeneous
chemical catalysts have several benefits: effortless optimization of activ-
ity including high selectivity, reaction rate, turnover frequency, and cheap
and readily available. NaOH, KOH, CH3ONa, and CH3OK (potassium
methoxide): these are strong alkali catalysis that is utilized for production
of biodiesel. Therefore, alkali metal oxides are established to be extraener-
getic than hydroxides. Most regularly used organic sulfonic acid, sulfuric
acid, sulfonic acid, hydrochloric acid, and ferric sulfate are utilized for
homogenous catalytic transesterification process. There are some limita-
tions such as water content and minimum tolerable FFA, and the refine-
ment procedure is complex, used high energy which affects a considerable
upsurge in apparatus investment costs and safety and maintenance prob-
lem. Also, this method has FFA content in the feedstock and is highly sen-
sitive to water. Two-step transesterification homogenous catalysis method
is enhanced than one-step homogenous catalysis reaction since it needs a
minor alcohol, amount of catalyst, and reaction temperature but modified
an advanced translation rate [2, 14, 32, 42].
7.7.2 Heterogeneous Catalysts

A heterogeneous catalyst, where the molecules are not in the similar phase
as the reactants, which are naturally gases or liquids that are adsorbed onto
the surface of the solid catalyst. Heterogeneous catalysts are modifying
the transesterification method by reducing the large processing costs in
a homogeneous catalysis reaction and eliminate the growth of pollutants.
Heterogeneous catalysts enhance reusability, smooth recovery, and cost
reduction methods. These catalysts increase high FFA and moisture con-
tent. Low-cost and effective heterogeneous catalysts optimize the overall
production cost of biodiesel. Heterogeneous catalysts are acceptable inte-
gral in specific harsh situation like high pressure and temperature. These
catalysts are simple to regain from the reaction mixture, are enhance to
withstanding aqueous treatment methods, and modify the parameter
such as high activity, selectivity, and longer catalyst lifetimes [2, 14, 32,
42].
In various chemical reactions, the general catalysts are used such as
alkali metal compounds, alkali earth metal oxides, mixed metal oxides,
transition metal oxides, ion exchange resins, supported on alumina or zeo-
lite, waste material-based heterogeneous catalyst, carbon-based heteroge-
neous catalyst, and enzyme-based heterogeneous [2, 14, 32, 42].
Alkaline earth metal oxides catalysts include BeO, BaO MgO, CaO,
SrO, and RaO. Solid-base catalysts used in transesterification include CaO,
MgO, SrO, K2CO3/Al2O3 KNO3/Al2O3, KF/Al2O3, Li/CaO, KF/ZnO, basic
hydrotalcite of Mg/Al, Li/Al, anion exchange resins, and base zeolites. MgO,
CaO, and TiO2 catalysts at temperatures up to 200°C have higher poten-
tial biodiesel production, and it can achieved 95% yield. Heterogeneous
solid-base catalysts are widely used for industrial application due to its
oversimplification of purification processes and production [2, 14, 32, 42].
7.7.3 Heterogeneous Nanocatalysts

Nanocatalysis is one of the most promising subfields introduced in nano-
science. Higher growth rate of chemical reactions is achieved by altering
its size, chemical composition, dimensionality, and morphology of the
reaction center and by changing the kinetics using nanopatterning of the
reaction. Heterogeneous nanocatalysts to commercialize catalyst with
outstanding high stability, high activity, selectivity, and with a high yield
product is promising by altering the elemental composition, surface func-
tionality, and/or the number of atoms in the substance [2, 14, 32, 42].
7.7.4 Supercritical Fluids

Vegetable oil converted into biodiesel is via a transesterification reaction,
where the triglyceride is transformed to the methyl ester and glycerol. This
is often completed using methanol and acid or caustic catalysts, and it can
be attained by supercritical methanol without a catalyst. The supercriti-
cal fluid (SCF) method offers a several benefits that are fast reaction, easy
separation of the products, water content of feedstocks, allowing a greater
range, and it is also environmentally benign. A recent technology of pro-
duction of biodiesel was synthesized by a noncatalytic supercritical process
with higher yield at 96% within 10 min. It is simple fluids to continuous
biodiesel production [2, 14, 32, 42]. Table 7.4 describes the transesterifica-
tion process characteristics based on basic, acid, enzymatic, and supercrit-
ical transesterification.
7.7.5 Biocatalysts
Biocatalysts can play better role in the limitations of the chemical catalytic
system, free lipase, immobilized lipase, and lipase immobilized on MNPs.
Biocatalysts are produced by animals, microorganisms, and plants; these
are consist of biocatalysts for biodiesel production [13]. Biodegradability,
biocompatibility, and environmental applicable enzymes are playing bet-
ter role than homogeneous catalysts. Lipases have also a potential catalytic
method and stability in nonaqueous media. Conventional lipase consists
of immobilized lipase and lipase immobilized on MNPs. The immobilized
lipases should be available in batch and fixed bed processes with appropriate
Table 7.3 Comparison between homogeneous, heterogeneous catalysis,

supercritical alcohol use, and basic enzyme catalysis in terms of advantages
and disadvantages.
Example of
catalyst Advantage Disadvantage
Homogenous
Basic (NaOH, Low cost, speeds Incompatible with free fatty
KOH) of high reaction, acid formation of soap,
advantageous polluted separation effects
operating condition,
high activity.
Acid (H2SO4) No soap formation, Corrosion, polluted separation
catalyze the effects, long reaction time,
esterification of high reaction temperature.
free fatty acid and
the transesfication
of glycerides
simultaneously.
Heterogeneous
Basic (CaO, Recyclable, non- Incompatible with free fatty
CaCO3, corrosive, easy acid formation of soaps,
KOH-Al2O3, separation, better incompatible with water-
Al2O3-KI, selectivity, long formation of free fatty
Zeolite catalyst life cycle. acids, high molar ratio
ETS-10) of alcohol/oil required,
high temperature and
high pressure, diffusion
limitation, higher costs.
Acid (ZnO-I2, No soap formation, Low acid site concentration,
ZrO2-SO4-2, catalyze the low catalytic activity,
TiO2-SO4-2, esterification of free diffusional limitations due
solid catalyst fatty acid, and the to low microposity, high
based on transesterification cost.
carbon or of glycerides
carbohydrates) simultaneously,
recyclable.
(Continued)
Table 7.3 Comparison between homogeneous, heterogeneous catalysis,

supercritical alcohol use, and basic enzyme catalysis in terms of advantages
and disadvantages. (Continued)
Example of
catalyst Advantage Disadvantage
Supercritical
Without catalyst Very low reaction Drastic operating condition,
time, no limitation (high temperature, high
to transfer due pressure, high molar ratios)
to uniqueness of high operating cost.
phase, no catalyst to
recycle.
Enzymatic
Candida No parasitic reaction, Risk of denaturation of the
antarctica, easy separation, no enzyme, very slow.
Pseudomonas pollutant.
fluorescens
supports (magnetic nanoparticles) as these stabilize immobilization with

regard to covalent linkage in the amino acid residue (Table 7.3) [42].
7.8 The Concept of Biorefinery

The novel concept of “multi feeds-multi products” in combined methods
will make production of biodiesel as feasible and practicable. The sustain-
able methods of biomass are scalable for economy-based bioproducts and
bioenergy for potential market. Biorefinery principles highlighted few
basic concepts to be fulfilled: minimal environmental impacts, non-critical
feedstock, regeneration of biomass and biodiversity, readiness variations in
feedstock quality and operational flexibility, quantity, in acceptable man-
ner to the biodiesel production, and the ability to utilize the multi-feed
multi-products method. The biorefinery method easily addresses the exu-
berance causes as well as eliminates the logistics cost and other savings in
term of energy use [7]. Biorefinery policies that boost the remarkable bio-
diesel regain as well as technology of spent biomass should be developed to
make the fulfilled, low-cost, and energy-positive process [39]. Biorefinery is
a system which integrates biomass conversion processes and equipment to
Table 7.4 Comparison of various transesterification processes [41].
Process Basic Acid Enzymatic Supercritical
characteristics transesterification transesterification transesterification transesterification
Yield alkyl’s esters High (>94%) High (>94%) High (>90%) High (>95%)
Reaction Moderate (50–70°C) High (60–120°C) Low (30–60°C) High (200–280°C)
temperature
Alcohol-oil ratio Excess alcohol molar High excess alcohol Alcohol High excess alcohol
ratio (6–12 : 1). molar ratio stiochiometrically molar ratio
(10–166 : 1). ratio (3–4 : 1). (methanol : brute
oil) (40 : 1).
Reaction time Fat (4 h) Short (12 h) Short (28 h) Very short (7–15 h)
Catalyst Cheaper Cheaper Expensive Without catalyst
Energy High High Moderate Low
consumption
Product recovery Difficult Easy Easy Very easier
Environmental Using high quantity of The process is Ecological, no step Using high quantity
impacts water to wash corrosive; the acid washing with of water to wash
Progress in Biodiesel Production
catalyst is polluting. necessary.

235
produce biofuels, power, and value-added chemicals from biomass. The

biorefinery approach is related to current petroleum refinery, and it will
exhibit products from petroleum and multiple fuels.
7.9 Summary and Outlook

In 2020, there is major controversy as regards electric vehicles and biofuel
sustainability. Yet, there are much more limitations to run the entire vehi-
cles and system on electric. Nature is always surviving the energy sources
with their optimum utilization. If this attention is right, then yes there is
huge demand for biofuel production in coming decades. There is need to
commercialize the biodiesel plant or refineries widely.
The 2018 biodiesel production in a global world report gives progressive
future to commercialize the plant for production of biodiesel in a com-
ing decade. The key challenges for biodiesel production are high FFA with
desired level of yield, stability, optimized and flexible production, commer-
cialization of feedstock, and environmental friendly cycle. The worldwide
region where huge sources of biodiesel feedstock. The only limitation is to
construct a biodiesel plant is to complex integration or combine the vari-
ous feedstock sources of their region-wise and availability for production
of a biodiesel. It will solve major obstacles to resolve the commercialization
of a biodiesel plant with effective production for biodiesel economy.
There is generation-wise report for biodiesel feedstock that has been
reviewed. Feedstock optimization with their location are sustainable for
biodiesel refinery. Among the all resources, the major productions are that
is going on to produce a biofuel are soybean, Moringa oleifera, jatropha,
karanja, KP, and genetically optimized microalgae for feedstock. Additives
plays major role to boost the efficiency of a biofuel production for a commer-
cialization. Moringa oleifera is a strong potential to produce complex bio-
diesel feedstock with others resources because of its antioxidant properties.
Transesterification by heterogeneous nanocatalysts or biocatalyst is a
potential technique to carry out biofuel from biodiesel plant as per the
requirements. Catalytic pyrolysis and microwave-mediated transesterifi-
cation have strong potential to commercialize the biodiesel plant for bio-
diesel production. Biorefinery is a commercial process for biodiesel and
biogas production systems in order to demonstrate higher valuable prod-
ucts that could additionally modify economically and environmentally
sustainability of these biomethods.
The utilization of renewable sources in few countries has an autho-
rized funding. For the transport sector, accomplished Renewable Energy
Directive (2009/28/EC) is targeting 20% share of alternative energy con-

sumption in the year of 2020, European Policy Framework with a sub-
target of 10% renewables. The collective effort and commitment of research
survey as regards feedstocks and commercialization of technology around
the globe toward sustainable energy are expressed in terms of accelerating
the biofuel economy.
7.10 Conclusion
According to biodiesel production technology world, the latest develop-
ments in biodiesel are increasing day by day, and the current status of tech-
nology is discussed. The existing edible feedstocks have some limitation as
regards crime against humanity. Therefore, major role of feedstock sources
is to widely available in rich energy of non-edible sources for commer-
cializing production of biodiesel. Among these, well-known high FFA for
desired level of yield and stability of a biodiesel and sustainable advanced
generation-based feedstock fulfill the criteria for a biodiesel production.
As per availability of a number of multiple feedstock grow up the plant or
a biorefinery for biodiesel production. Catalytic pyrolysis and microwave-
mediated transesterification develops desirable characterized biodiesel for
revolutionize the commercialization market. The summarized extracted
results shows that the evolutionary future to sustain the biodiesel for future
of a fuel to run the global world.
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8
Biodiesel Production Technologies
Moina Athar1* and Sadaf Zaidi2
1
Department of Petroleum Studies, Z H College of Engineering and Technology,
Aligarh Muslim University, Aligarh, India
2
Department of Post Harvest Engineering and Technology, Faculty of
Agricultural Sciences, Aligarh Muslim University, Aligarh, India
Abstract
During the past few years, biodiesel has emerged as a potential renewable source
that could replace current petro-diesel. It is a less polluting, biodegradable, and
non-toxic that can be simply produced by a transesterification reaction. Vegetable
oils, animal fats, waste oil, and microbial oils are the main feedstocks for the pro-
duction of biodiesel. The current commercial use of edible and refined oils for
the production of biodiesel is not feasible and uneconomical due to the high cost
of feedstock and priority as a food source. However, non-edible oils which are
low-grade and low cost can be a better option but the presence of a high amount
of free fatty acids (FFAs) in these oils has been the main problem for their use as
potential feedstocks. This chapter is focused to give an overview of the various
feedstocks for the production of biodiesel especially non-edible oils. The benefits
and constraints of using homogeneous, heterogeneous, and enzymatic catalysts
for transesterification of vegetable oil containing a high amount of FFA are dis-
cussed in detail. Toward the end of this chapter, a few of the latest intensification
techniques for biodiesel production that are capable to manage the mass transfer
restrictions of oil and alcohol phases such as supercritical alcohol method, micro-
wave heating, ultrasonic irradiation, and co-solvent method are discussed. Some
other techniques that reduce the biodiesel production cost like in situ transesteri-
fication, membrane reactor, reactive distillation, static mixers, micro-channel, and
oscillatory flow have also been discussed briefly.
Keywords: Biodiesel feed stock, production methods, catalyst, microwave
heating, ultrasonic irradiation, co-solvent method, in situ method, static mixture
*Corresponding author: mathar.pe@amu.ac.in
241
8.1 Introduction
Present crises of fossil fuels, hike in crude oil prices, increased environmen-
tal pollution, and environmental awareness have changed the world’s focus
on the use of alternative fuels [1]. Biodiesel is one of the most eco-friendly,
renewable, and promising alternative for diesel engine [2, 3]. Chemically
biodiesel is defined as mono-alkyl esters of long-chain fatty acids (FAs)
present in vegetable oils or animal fats [4–9] which on combustion pro-
duces fewer pollutants like sulfur, carbon dioxide, particulate matters, car-
bon monoxide, smoke, and unburned hydrocarbons emissions. Complete
combustion takes place due to excess oxygen present in biodiesel which
also reduces emission [10, 11]. It can be mixed with petrodiesel in any
proportion and can be used in the present diesel engine with no or very
few engine modifications. The mixtures are represented by acronyms like
B20, which signifies a mixture of 20% biodiesel with petro diesel [12, 13].
Biodiesel provides fuel efficiency, torque, and horsepower similar to stan-
dard diesel fuel [14].
8.2 Biodiesel Feedstocks

Great varieties of feedstocks can be used for biodiesel production. More
than 350 oil containing seeds have the potential for biodiesel production
[15]. These feedstocks include both edible and non-edible type of vegetable
oils, fats of animals, different waste oils, and microbial oils. Table 8.1 shows
Table 8.1 Various types of oil and their sources for the production of biodiesel.
Type of oil Source of oil
Vegetable oils Edible Soya bean, mustard, rice bran, sunflower,
cottonseed, olive, peanut, sesame, palm, etc.
Non-edible Jatropha, mahua, jojoba, neem, karanja, milk
bush, rubber seed, nagchampa, castor,
petroleum nut, silk cotton tree, tung, etc.
Animal fat Chicken fat, beef tallow, fish oil, pork lard
Waste oil Waste frying oil, pit oil
Microbial oil Fungi, microalgae (chlorellavulg), algae
(cyanobacteria)
Biodiesel Production Technologies 243
3% 2% 1%
7%
Cost of oil
Cost of chemical
12%
Depreciation cost
Direct labour cost

Energy cost
75%
General overhead
cost
Figure 8.1 Cost breakup for biodiesel production [7, 21–23].
the various types of oils and their sources that can be used for the produc-
tion of biodiesel [16–19].
The availability of this vast range of feedstock is one of the major rea-
sons for producing biodiesel [5, 8, 20]. Low production cost and large pro-
duction scale are the two main demands which should be fulfilled by any
of the feedstocks. The feedstocks present in any region or area depend-
ing on the geographical locations, regional climate, conditions of soil, and
adopted agricultural methods of that country [15]. It was established from
various studies that biodiesel feedstock alone contributes to 75% of the
total production cost as depicted in Figure 8.1. Hence, the selection of low-
cost feedstock is essential for economical biodiesel production. Figure 8.2
shows the various feedstocks used for the production of biodiesel.
8.2.1 Selection of Feedstocks

Triglycerides are the basic component of all types of oils used for biodiesel
production. Chemically, they are esters of FAs with glycerol and contain
several different types of FAs. As the chemical and physical properties of
different FAs differ with each other, so they also affect the various prop-
erties of the associated oils and fats. Table 8.2 presents the quantities of
FA presents in selected fats and oils. At present, edible oils comprise more
than 95% of the main feedstocks for biodiesel production worldwide [16].
However, the utilization of edible oils for biodiesel production is uneco-
nomical and impractical because of its high cost and its priority use as food
sources. Thus, low quality [high free FA (FFA)] and low-cost non-edible
oil that is not being used in human nutrition could be an option. Plants
for non-edible oil seeds are easily grown in lands that are not appropriate
Soyabean
y Sunflower Mustard
Rice bran Cotton seed Palm seeds
Jatropha Jajoba j
Karanja
Mahua Neem Rubber seeds
Animal fat Waste frying oil Algal oil
Figure 8.2 Various types of feedstock for biodiesel production.
for edible oil crops with much lower costs [24]. Growing of these plants
can also reduce the amount of CO2 in the atmosphere [25]. Apart from all
the above-mentioned advantages, the presence of a high amount of FFA,
which leads to high production cost, is the major drawback associated with
these low-grade non-edible oils [26].
Jatropha is among the most prospective non-edible source for the pro-
duction of biodiesel in Central and South America, South-East Asia, Africa,
and India. Presently, it is the main feedstock of biodiesel in developing
countries like India, where its yearly production is around 15,000 t [27].
Jatropha can be cultivated anywhere like on saline and sandy soil, waste-
lands, in different climatic conditions, with low or high rainfall without
Table 8.2 Fatty acid profile of fats and oils [34].
C(12:0) C(14:0) C(16:0) C(16:1) C(18:0) C(18:1) C(18:2) C(18:3) C(20:1) C(22:1)
Lauric Myristic Palmitic Palmitoleic Stearic Oleic Linoleic Linolenic Gadoleic Erucic
Feedstock acid acid acid acid acid acid acid acid acid acid Unknowns
Algae – 0.6 6.9 0.2 3.0 75.2 12.4 1.2 – – Remaining
amount
Babassu 48.8 17.2 9.7 – 4.0 14.2 1.8 – – – Remaining
amount
Beef Tallow 0.2 2.9 24.3 2.1 22.8 40.2 3.3 0.7 0.6 – Remaining
amount
Borage – – 9.3 – 3.8 17.1 38.7 26.1 – 2.5 Remaining
amount
Camelina Oil – – 5.0 – 2.2 17.7 18.0 37.9 9.8 4.5 Remaining
amount
Canola Oil – – 3.8 0.3 1.9 63.9 19.0 9.7 – – Remaining
amount
Castor – – 0.9 – 1.1 93.4 4.0 0.6 – – Remaining
amount
Choice white – 1.3 21.6 2.8 9.0 50.4 12.2 1.0 0.5 0.3 Remaining
grease amount
Coconut 49.2 18.5 9.1 – 2.7 6.5 1.7 – – – Remaining

amount
245
(Continued)
Table 8.2 Fatty acid profile of fats and oils [34]. (Continued)
246
C(12:0) C(14:0) C(16:0) C(16:1) C(18:0) C(18:1) C(18:2) C(18:3) C(20:1) C(22:1)
Coffee – – 11.0 0.5 3.4 70.0 12.7 0.8 0.1 – Remaining
amount
Corn – – 12.1 0.1 1.8 27.2 56.2 1.3 – – Remaining
amount
Cuphea – 4.7 18.2 – 3.5 46.9 22.8 2.3 – – Remaining
Viscosissima amount
Evening – – 6.0 – 1.8 6.6 76.3 9.0 – – Remaining
Primrose amount
Hemp – – 5.2 – 2.4 13.1 57.1 20.0 – – Remaining
amount
Jatropha – – 12.7 0.7 5.5 39.1 41.6 0.2 – – Remaining
amount
Linseed – – 4.4 – 3.8 20.7 15.9 54.6 – – Remaining
amount
Mustard – – 2.6 0.2 1.2 20.6 20.6 13.3 10.7 25.6 Remaining
amount
Neem – – 14.9 0.1 20.6 43.9 17.9 0.4 – – Remaining
amount
(Continued)
Table 8.2 Fatty acid profile of fats and oils [34]. (Continued)
C(12:0) C(14:0) C(16:0) C(16:1) C(18:0) C(18:1) C(18:2) C(18:3) C(20:1) C(22:1)
Palm 0.2 0.5 43.4 0.1 4.6 41.9 8.6 0.3 – – Remaining
amount
Perilla Seed – – 5.3 0.1 2.2 16.6 13.7 62.1 – – Remaining
amount
Poultry Fat 0.1 1.0 19.6 3.2 7.5 36.8 28.4 2.0 – 0.4 Remaining
amount
Rice Bran – 0.3 12.5 – 2.1 47.5 35.4 1.1 – – Remaining
amount
Soybean – – 9.4 – 4.1 22.0 55.3 8.9 – – Remaining
amount
Sunflower – – 4.2 – 3.3 63.6 27.6 0.2 – – Remaining
amount
Used cooking 0.1 0.1 11.8 0.4 4.4 25.3 49.5 7.1 – 0.3 Remaining
oil amount
Yellow Grease 0.1 0.5 14.3 1.1 8.0 35.6 35.0 4.0 – 0.2 Remaining
amount
247
much care and with minimal efforts. The life cycle of the Jatropha plant is
30–40 years, which eliminates its yearly plantation. Although the oil con-
tent of Jatropha depends on the type of species as 40%–60% of oil is present
in its seeds and 46%–58% is present in kernels [28]. It is a potential alter-
native to petro-diesel as it has equivalent properties to diesel, like calorific
value, cetane number, and does not require any engine modification [27,
29]. While, its toxicity is a serious problem for the people and animals [30].
Among all the new generation non-edible feedstocks, microalgae are
being considered to be the most potential one. Microalgae produce oil in
the presence of water, sunlight, and carbon dioxide in a more efficient way
than crop plants. As different types of algae contain different amounts of oil
so among all the species only a few that contain higher amounts of oil are
appropriate for the synthesis of biodiesel. The oil content of some microal-
gae exceeded significantly the oil yield of some of the best oil-producing
crops [31, 32]. Moreover, it can be easily grown anywhere, like in sewage
or salty water, and no fertile land is needed and most of all its processing
needed less energy than it provides [33].
8.3 Biodiesel Production Technologies

Polyunsaturated character, viscous, and low volatile vegetable oils are not
suitable for diesel engines for direct use [35]. Refinement of these oils is
needed to transform them into quality fuel. The principal methods which
enable oils and fats to be used in diesel engines are usually direct use by
dilution, micro-emulsion, pyrolysis, and transesterification.
8.3.1 Pyrolysis
Pyrolysis is defined as chemical change after applying heat without air or
oxygen or by using catalyst resulted in chemical bond breakage and pro-
duction of different small molecules. The changes during pyrolysis take
place at a reaction temperature range from 400°C to 600°C using different
vegetable or animal oils, naturally accruing FAs or esters of FAs. Process
of thermal breakage of triglycerides yields aromatics, alkenes, alkanes,
alkadines, and carboxylic acids, which are fuel components for the die-
sel engine; however, some undesirable components are also produced
due to the absence of air during this process [35–37]. Low heating value,
incomplete volatility, and instability of the product are some unwanted
properties that often limit the use of biodiesel produced through pyrolysis
[38, 39].
8.3.2 Dilution
The direct use of vegetable oil in an existing diesel engine is limited by its
high viscosity, carbon deposits, FFA contents, gum formation by oxidation
and polymerization processes, etc. In such situations, dilution of vegetable
oils with diesel fuel, solvents, or ethanol is recommended which reduces
its viscosity and density [40]. The use of pure oil in an existing petrodiesel
engine is not feasible; instead, a mixture of 20% oil and 80% petro-diesel is
recommended [41].
8.3.3 Micro-Emulsion
It is another effort toward the viscosity reduction of vegetable oils. The pro-
cess of biodiesel microemulsion is carried out by the use of petro-diesel,
alcohol, vegetable oil, surfactant, and cetane improvers in appropriate pro-
portions. Some low molecular weight alcohols like methanol and ethanol
are used as additives for viscosity reduction; high molecular weight alcohols
can be utilized as surfactants whereas alkyl nitrates are compounds that are
used for improving the cetane number [42]. Micro-emulsion reduces the
viscosity, improves cetane rating, and introduces excellent spray quality in
the biodiesel.
8.3.4 Transesterification
Transesterification is the reaction of oil and alcohol with or without a cat-
alyst to produce esters (biodiesel) and glycerol as a product (Figure 8.3).
Since the reaction involved is reversible, an extra volume of alcohol is
needed to support the forward reaction and to shift the equilibrium to the
product’s side [43]. The transesterification reaction is completed in three
steps in which the triglyceride conversion to diglycerides is the first step,
followed by the subsequent diglycerides conversion into monoglycerides
and then to glycerol, producing one ester molecule from each glyceride at
each step (Figure 8.4) [44].
CH2 OCOR1 CH2OH R1COOCH3

Catalyst
CH OCOR2 + 3CH3OH CHOH + R2COOCH3
CH2 OCOR3 CH2OH R3COOCH3
Triglyceride Methanol Glycerol Methyl esters
Figure 8.3 General transesterification reaction.

Triglyceride + R1OH Diglyceride + RCOOR1
Diglyceride + R1OH Monoglyceride + RCOOR1
Monoglyceride + R1OH Glyceride + RCOOR1
Figure 8.4 General mechanism of the transesterification reaction.
The transesterification reaction is carried out in the presence of acidic,

basic, or enzymatic catalysts. It can be homogeneously or heterogeneously
catalyzed, based upon the catalyst solubility in the reactants. The reaction
can be in a single step (by acid or base catalyst) or two steps (acid/base),
based on the amount of FFA content of the oil.
8.3.4.1 Homogeneously Catalyzed Transesterification Processes

Homogeneous catalysts can be basic or acidic type and their selection
mainly depends upon the FFA and water content of the oil.
8.3.4.1.1 Alkaline Catalyst

The alkaline catalysts are used for oils containing a low percentage of FFA
(less than 5 wt.%) [45]. Thus, the most common homogeneous alkaline
catalysts that have been used and successfully commercialized for pro-
duction of biodiesel are potassium hydroxide (KOH), sodium hydrox-
ide (NaOH), and sodium methoxide (CH3ONa) [3, 5, 43, 46–48]. Mostly
sodium hydroxide and potassium hydroxide are used by biodiesel cata-
lysts. Although the conversions in the presence of sodium and potassium
methoxides are better, they are not very frequently used as they are costly.
Transesterification by the alkaline catalyst is the fastest and economical
method compared to other catalytic methods. It is 4,000 times faster than
the acid catalyst of the same amount and achieves a high yield of biodiesel
with high purity in less reaction time (30–60 min) [15]. Therefore, it is
preferred over the other biodiesel production catalyst.
8.3.4.1.2 Acidic Catalyst

Despite many associated problems like the slower rate of reaction, a higher
volume of alcohol requirement, less catalyst activity, and requirement of
higher reaction temperature, the acid catalyst has some important advan-
tages for the transesterification reaction [49]. Low sensitivity for the high
FFAs present in the non-edible oils (>5%) and the chances for esterification
O O
Acid catalyst
R” -C-OH + R’-OH R” -C-OR’ + H2O
Carboxylic acid Alcohol Biodiesel Water
Figure 8.5 Mechanism of the esterification reaction.
and transesterification reaction to occur simultaneously are some notable

advantages of the acidic catalyst [50]. Esterification is carried out of FFA
and alcohol (e.g., methanol) with the help of a strong acidic catalyst to form
at least one ester and water as a reaction product (Figure 8.5). The common
acid catalyst used for esterification includes sulfuric, hydrochloric, phos-
phoric, ferric sulfate, and organic sulfonic acid. The yield of biodiesel was
reported up to 90% in many studies of transesterification with an acid cata-
lyst, but a much longer reaction time (3–48 h) was required, in comparison
to the alkali-catalyst transesterification reaction, except for those carried
out with higher reaction temperatures [51–53]. The main variables that
influence the transesterification yield are the amount of catalyst, alcohol
type, and the reaction time [52]. Hence, the main benefit of using an acidic
catalyst is the low-cost production of biodiesel by using high FFA non-
edible oil in a single step [54]. However, these acidic catalysts are corrosive
and create a handling issue during the operation.
8.3.4.1.3 Two-Step Process

Two-step acid/base catalytic process has been developed to address the
drawbacks of single-step homogeneous acid and base catalytic processes
for biodiesel production using high FFA non-edible oils. In this two-
step method, the first step comprises of acid catalyst esterification of FFA
(pre-treatment) for minimizing the FFA below 1% followed by alkali-
catalyzed transesterification [55]. The acid pretreatment process eliminates
the problem of slow reaction rate and soap formation. The higher cost of
production is the only problem associated with the two-step transesterifi-
cation process [49, 56]. Apart from the great advantages of homogeneous
catalysts for transesterification, numerous disadvantages like huge energy
requirement, the produced soap as a by-product, difficult and costly sep-
aration of catalyst, and a large amount of wastewater generation are also
associated with them [57, 58].
8.3.4.2 Heterogeneously Catalyzed Transesterification Processes

The catalyst which is not miscible with the reaction mixture is known as
heterogeneous. It may be a basic or acidic type and is more conveniently
separated from reaction products. Acidic heterogeneous catalysts could be
used for transesterification of high FFA oil as they avoid undesirable sapon-
ification reaction. Solid heterogeneous catalysts could lead to cheaper pro-
duction of biodiesel as it can be reused and enable both esterification and
transesterification to be carried out simultaneously [59]. However, a slow
reaction rate due to difficult diffusion in immiscible phases of oil, alcohol,
and catalyst mixture, complex catalyst production method, followed by
a considerable effect on the environment are the major disadvantages of
heterogeneous catalysts [60]. The basic heterogeneous catalyst commonly
used is alkaline earth metal oxides (SrO, BaO, CaO, MgO), alkaline earth
metal carbonates (CaCO3), alkaline metal carbonates (K2CO3, Na2CO3),
and transition metal oxides (ZnO) [44, 61–63]. However, acidic heteroge-
neous catalysts for transesterification such as Nafion-NR50 (perfluorinated
alkane sulfonic acid resin), Zirconium oxide (ZrO2), sulfated zirconia-
alumina (SZA), sulfated oxides, cation-exchange resins, and tungstated
zirconia–alumina (WZA) are being utilized for the synthesis of biodiesel
[64, 65]. Besides, a solid acidic catalyst like sulfated zirconia and tungstated
zirconia can be used to support the transesterification as well as the esteri-
fication reactions [66, 67].
8.3.4.3 Enzymatic Catalyzed Transesterification Processes

Normally, enzymes are a bio-oriented catalyst, primarily natural lipases
that are separated from some bacterial species like Pseudomonas fluo-
rescens, Rhizopus oryzae, Thermomyces lanuginosus, Candida antarctica,
Pseudomonas cepacia, Candida rugosa, and Rhizomucor miehei [68].
Biodiesel production using enzymes has no problems of washing, purifica-
tion, neutralization, and saponification, so it is usually recommended from
these aspects. It can be used for those non-edible feedstocks having a high
amount of FFA and gives appreciable yield. Enzymatic catalysts are typi-
cally used in the immobilized form to ensure their stability and reusability.
The different ways by which immobilization can be provided are entrap-
ment, adsorption, encapsulation, covalent bonding, cross-linking, and by
the process of enzyme embedding on a solid support. These methods are
useful to give the stability and recycling of the enzyme and decrease the
total expenses on the catalyst that was the main challenge in commercial-
ization [69].
8.4 Intensification Techniques for Biodiesel

Production
Numerous novel techniques are being used in the past few years for the
enhance the biodiesel yield especially from low-cost non-edible oils such
as supercritical alcohol method, microwave heating, ultrasonic irradiation,
co-solvent method, in situ transesterification processes, motionless mixer
technique, and membrane reactors.
8.4.1 Supercritical Alcohol Method

Biodiesel production by transesterification method with alcohol (metha-
nol, ethanol, propanol, and butanol) in its supercritical stage with or with-
out catalyst has been considered as the most promising technique. The
supercritical method takes very little time to complete the reaction, whereas
conventional catalytic transesterification method needs many hours to fin-
ish [70]. At conventional processing temperatures, oils (non-polar) and
alcohol (polar) form heterogeneous mixture because of the limited misci-
bility of the polar and non-polar reactants. In a supercritical environment,
the alcohol and triglyceride mixture turns into a single homogeneous
phase, which will enhance the reaction rate due to the non-existence of
any interphase mass transfer. The typical range of operating conditions
applied for the supercritical zone has been temperatures of 280°C–400°C
and pressures of 10–30 MPa [71]. The supercritical approach is found to be
more water and FFA resistant and more easily separated and purifies the
biodiesel more than the conventional catalytic transesterification method
[72, 73]. Alternatively, in the supercritical condition along with transes-
terification, esterification of FFA and hydrolysis of triglycerides due to the
presence of moisture takes place simultaneously and enhances the yield of
methyl ester [72, 74, 75]. The cost of high temperature and pressure reactor
is the main drawback that limits its use on a large scale in the industry [76].
Co-solvents, like carbon dioxide [77, 78], hexane [76, 79], propane [80],
and calcium oxide [81, 82] with a little quantity of catalyst added during
the reaction can reduce the temperature, pressure and the alcohol quantity.
8.4.2 Microwave Heating

The transesterification by microwave heating is an effective way for the
rapid production of biodiesel. During this process, heat is produced by
the friction of molecules due to the alignment of polar alcohol molecules
by the constantly varying magnetic field of microwaves. Due to very

effective heat transfer, reactions under microwave heating can take place
in a greatly reduced reaction time than those with conventional heating
[83, 84]. Microwaves which are of 0.3- to 300-GHz frequency range have
both thermal and non-thermal types of effects and generate heat due to
its molecular interaction in the sample without changing their structures
[85, 86]. Apart from the high yield of biodiesel, microwave heating also
reduces the separation and purification time [87, 88]. The microwave heat-
ing method has many advantages over the conventional heating method,
such as reduction of a thermal gradient, low overheating of surfaces due to
contactless heating, energy transfer rather than heat transfer, and heat gen-
eration from inside of the mass. In sum, microwave-induced transesteri-
fication offers a much-purified product with a high yield and reduces the
separation and purification time [87, 88]. Therefore, microwave heating
is a more environmentally compatible, more energy-efficient, and favor-
able technique as compared to conventional heating, where heat trans-
fer mainly takes place by conduction and convection by the walls of the
sample container to reach inner materials resulted in inefficient and slow
heating due to high thermal gradient because of non-uniform heating [89,
90]. Apart from the enormous advantages of this method, there are also a
few drawbacks. The scale-up of microwave technique from laboratory to
industrial multi-kilogram production is not very easy. Penetration depth
which is only a few centimeters is the major constraint for the scale-up of
Figure 8.6 Microwave reactor.

this technology. The safety is another cause of rejecting microwave heating

in the industry [89]. Figure 8.6 shows an open view of a microwave reactor
used for laboratory purposes.
8.4.3 Ultrasonic Irradiation

The ultrasonic method is a newer mixing technique which is more efficient
for the production of biodiesel, compared to the conventional way of agi-
tation. Ultrasound is sound waves with frequencies higher than the upper
audible limit of human hearing. The typical range of hearing is between
16 Hz and about 18 kHz and ultrasound is normally known to be between
20 kHz and more than 100 MHz [91]. The ultrasonic mixing improves the
mass transfer among the immiscible oil and alcohol phase, accelerates the
chemical reaction and conversion of triglyceride, and reduces the reaction
time and energy consumption. One of the types of ultra-sonicator (probe
sonicator) that is normally used in laboratories is shown in Figure 8.7.
The molecular spacing of the medium gets compressed and stretched on
the application of high-frequency ultrasonic sound wave that continuously
vibrates the molecules and creates the cavities. The created micro-fine bub-
bles by sudden collapse and expansion and generate energy for chemical
and mechanical effects [92]. Additionally, the phase boundary is disrupted
by the collapsed bubbles, and micro-jets are created by the impinging of
the liquids, leading to extensive emulsification of the system [93].
Figure 8.7 Probe type ultra sonicator.

8.4.4 Co-Solvent Method

During the transesterification reaction, the oil and methanol phases are
immiscible with each other which affects the rate of mass transfer among
these phases. This mass transfer constraint could be overcome by the addi-
tion of a small amount of co-solvent which is soluble both in methanol as
well as in the triglycerides. The addition of the co-solvent increases the
transesterification rate because of the elimination of mass transfer resis-
tance between the phases. Many studies have revealed that the presence
of co-solvent significantly reduces the reaction temperature, pressure,
and quantity of alcohol and enhances the reaction rate [94–96]. Various
co-solvents like tetrahydrofuran (THF), hexane, and a mixture of THF
and hexane, acetone, propane, heptane, carbon dioxide (CO2), dimethyl
ether (DME), and diethyl ether (DEE) have been used in biodiesel produc-
tion [97, 98]. However, the use of co-solvent increases the cost of biodiesel
production due to the extra cost of separation of the co-solvent from the
methanol and product phase [99].
8.5 Other Techniques of Biodiesel Production

Some other techniques like in situ transesterification, membrane reactor,
reactive distillation, static mixers, micro-channel, oscillatory flow have
also been used to make the process economical by either improving sepa-
ration and purification method, reducing equipment cost, or making the
process simpler.
During the in situ transesterification method, extraction and transes-
terification of oil take place simultaneously. The used alcohol behaves as
a solvent for extraction as well as a reagent for transesterification reaction
[100]. After the oil is extracted from the seeds by the alcohol, it is simul-
taneously converted into ester due to already present alcohol. Hence, this
process not only reduces the processing time but also reduces the cost. The
only drawback associated is the requirement of a large volume of alcohol
as compared to other traditional processes [18].
Membrane reactors combine reaction and separation in a single step
which reduces recycling and separation costs and increases conversion due
to the enhancement of product inhibited reactions. Inorganic membranes
are much better than the organic (polymeric) ones as these are generally
more thermally stable [101, 102]. A higher amount of methanol and ultra-
low catalyst concentration is needed as compared to the conventional pro-
duction methods [103, 104].
The distillation in which the reaction and the separation of the associated
products take place in the same column is known as reactive distillation.
Both packed and tray-type columns are suitable for reactive distillation,
even though tray columns are recommended for the homogenous type of
reactions due to the better liquid hold-up and prolonged retention time
[105, 106]. Higher conversion, reduced energy consumption, lower capital
cost, better selectivity, none or reduced amount of solvents throughout the
reaction, and avoidance of azeotrope formation are some benefits of reac-
tive distillation [107, 108]. The continuous removal of products from the
reaction system not only increases the conversion but also helps to reduce
capital and investment costs [109, 110].
Static mixers are made up of specially designed static helical mixing part
in a hollow cylinder that creates intense mixing and needs less energy in
comparison to conventionally used mechanical mixers [111, 112]. They are
usually used in continuous processes for biodiesel production. This has
no moving elements and therefore carry the benefit of low maintenance
and operating costs, along with low space requirements [113, 114]. By
static mixer, more fine and uniform droplets of methanol are generated,
which enhances the interfacial surface area between raw oil and metha-
nol. Thus, a higher reaction rate and a greater yield of FAME are obtained
than that with the mechanical mixer [115, 116]. Apart from the aforemen-
tioned technologies, micro-channel [117–120] and oscillatory flow [121,
122] techniques can also improve reaction rate and reduce the alcohol-
to-oil molar ratio and energy input by the intensification of mass transfer
and heat transfer, thus helping in attaining continuous production in the
reactor.
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9
Methods for Biodiesel Production
M.Gul1,2*, M.A. Mujtaba1,3, H.H. Masjuki1,4, M.A. Kalam1 and N.W.M. Zulkifli1
1
Center for Energy Science, Department of Mechanical Engineering,
University of Malaya, Kuala Lumpur, Malaysia
2
Department of Mechanical Engineering, Faculty of Engineering and
Technology, Bahauddin Zakariya University, Multan, Pakistan
3
Department of Mechanical Engineering, University of Engineering and
Technology, City Campus Lahore, Pakistan
4
Department of Mechanical Engineering, Faculty of Engineering, IIUM,
Kuala Lumpur, Malaysia
Abstract
This chapter discusses all types of feedstocks used for synthesizing biodiesel
and feedstock’s selection criteria. Moreover, all biodiesel production meth-
ods (i.e Dilution with hydrocarbons blending, Micro-emulsion, Pyrolysis, and
Transesterification) are also described in detail with their advantages and dis-
advantages. The major focus is given to the various Transesterification methods
because of their simplicity, easy handling, less time consumption, and maximum
biodiesel yield. Production methods also include experimental setup layouts, all
process parameters, reaction conditions, the latest advancement in reaction pro-
cesses, and their effects on biodiesel yield.
Keywords: Biodiesel, pyrolysis, transesterification, supercritical methanol
9.1 Selection of Feedstock for Biodiesel

There are different types of biodiesel feedstock that mainly comprised of
fatty acids (triglycerides) or lipids depending on local soil conditions in dif-
ferent regions and climate. Genetic engineering is also playing important
role in growing biodiesel feedstock crops to achieve desired composition
*Corresponding author: mustabshirha@bzu.edu.pk
267
according to application and to overcome their drawbacks. So, selection of

feedstock includes fatty acids (lipid) content/oil percentage, free fatty acid
(FFA) contents, moisture content, and its availability and productivity per
hectare [1].
The major biodiesel producers all over the world are the European Union
(EU) (rapeseed, soybeans), the United States (Soybean), Brazil (Soybean),
Indonesia and Malaysia (palm oil), and China (rapeseed) that use edible
vegetable oil (VO) for synthesizing biodiesel. The following are the kinds
of biodiesel feedstock.
9.1.1 First-Generation Feedstock

Edible vegetable oils like palm oil, soybeans, rapeseed, coconut, sunflower,
safflower, sesame, corn, peanut, groundnut, almond, barley, poppy seed,
okra seed, oat oil, camelina (camelina sativa), fish oil, and cottonseed oils
are considered as first-generation feedstock for producing biodiesel. Most
of the biodiesel are synthesized from edible oils. But, in future, world will
face severe malnutrition and serious basic food shortage issues. Growing
of crops for getting biodiesel feedstock will utilize land, water, and other
energy resources that are also required significantly to fulfil basic food pro-
duction for human beings.
9.1.2 Second-Generation Feedstock

Non-edible oils are defined as second-generation feedstock of biodiesel
production that obtained from jatropha tree/ratanjyote (jatropha curcas),
jojoba (simmondsia chinensis), neem (azadirachta indica), karanja/honge
(pongamia pinnata), desert date (balanites aegyptiaca), koroch seed oil, silk
cotton tree (ceiba pentandra), mahua (madhuca indica or madhuca longi-
folia), pachira glabra nagchampa (calophyllum inophyllum), tobacco seed
(nicotiana tabacum L.), sea mango seed (cerbera odollam), rubber seed tree
(hevea brasiliensis), aleurites moluccana, croton megalocarpus, terminalia
belerica, babassu tree, euphorbia tirucalli, and rice bran.
Significant non-edible oils are getting attention in developing countries
as these have no competition and dispute with food. Non-edible oil crops
are also environment friendly, efficient, and very economical, can easily
grow on wastelands, and reduce deforestation rate. Moreover, animal fats
like tallow from beef, sheep and poultry, pork lard, Chinese tallow, waste
cooking oils, and grease are also categorized as second-generation feed-
stocks for biodiesel synthesis. Utilization of these feedstock for biodiesel
production also eliminates their disposal problems but collection of waste
Methods for Biodiesel Production 269
oils from scattered sources required logistics and proper infrastructure.

Transesterification of some animal fats is not so easy because those have
high concentration of saturated fatty acids and exist in solidified form.
9.1.3 Third-Generation Feedstock

Recently, microalgae emerged as third-generation promising feedstock
for biodiesel production. Microalgae are photosynthetic microorganisms
having different varieties that convert CO2 and water into algal biomass
by photosynthesis process. Algal biomass has high productivity, faster
growth rates, and high yield of oil as compared to VO sources. Microalgae
can be grown in farm or in bioreactors that needs high production costs.
Moreover, its commercialization requires large-scale bioreactors so more
researches are required to explore its production methods in future [2].
9.2 Methods for Biodiesel Production

VOs in pure form are not good quality fuels for IC engines because of their
polyunsaturated fatty acids characteristics, high viscosity, and low vola-
tility in comparison to diesel fuels. These drawbacks can be resolved by
conventional methods like dilution by blending hydrocarbons and micro-
emulsion. Both of these are physical methods so do not involve any chem-
ical reaction.
9.2.1 Dilution With Hydrocarbons Blending

VOs cannot replace diesel fuels completely, so high viscosities of VO can be
decreased by blending it with diesel. In addition, 20% VO and 80% diesel
blend was successfully implemented in IC engines as described in earlier
literatures [3–5]. High percentage blends are not recommended because
these do not fulfill ASTM standard limits.
9.2.2 Micro-Emulsion
In this method, oils are mixed and blended with immiscible solvents
including ionic/non-ionic amphiphiles and methanol, ethanol, butanol,
and hexanol to reduce their viscosities. This method ensures the thermo-
dynamically stable colloidal dispersions of micro-phase particles having as
small diameter as ¼ part of visible light’s wavelength. As micro-emulsions
contain alcohol so give low volumetric heating values in comparison to
diesel fuels, but useful cooling effect developed in combustion chamber

because of high latent heat of vaporization of alcohol.
These above two methods have improved the viscosity issues and rec-
ommended as fuel for short term applications. However, these fuels gave
incomplete combustion in diesel engines, premature injection‐nozzle dete-
rioration occurred, and high carbon deposits are observed on the piston
lands, intake ports and exhaust valves, and piston ring grooves. These car-
bon deposits also caused degradation of lubricating oil. So, at present, fuels
prepared from pure VOs by dilution and micro-emulsion are not suggested
suitable anymore for long term utilization in diesel engines [6].
Some new techniques/methods are adopted to solve all these problems
associated with dilution and micro-emulsion. These methods involves
pyrolysis, transesterification, and supercritical methanol [7].
9.2.3 Pyrolysis (Thermal Cracking)

In pyrolysis heat is used to decompose VOs, fatty acids, and animal fats
by using different types of catalysts without oxygen to synthesized suitable
potential fuel for DI-diesel engines. Pyrolysis is a chemical reaction tak-
ing place by thermal energy that convert triglycerides of VOs into alkanes,
alkenes, alkadines, linear and cyclic paraffins and olefins, aromatics, alde-
hydes, ketones, and carboxylic acids [8], as described in Figure 9.1.
O
CH3 (CH2)5 CH2 –CH2 CH=CHCH2 –CH2 (CH2)5C–O–CH2R
CH9 (CH2)5 CH2 –CH2 CH=CHCH2 –CH2 (CH2)5C–OH
CH3 (CH2)5CH2• CH2 =CHCH=CH2 • CH2 (CH2)5C–OH
H
O
Diels-
CH9 (CH2)3CH2 • + CH2=CH2 Alder CH3(CH2)5C–H
–CO2
–H2
CH3(CH2)3CH3 CH3(CH2)4CH3
Figure 9.1 Pyrolysis of vegetable oils into alkanes, alkenes, and aromatics [4].
Saponification and pyrolysis of VOs directly produce the hydrocarbon-

rich products [9] that are very good alternative of gasoline (a competitive
biodiesel fuel) as presented by Equations (9.1) and (9.2)
Saponification:
Vegetable oil/fats + NaOH RCOONa (sodium soap) + Glycerin
(9.1)
Pyrolysis of sodium soap:

4 RCOONa + (1/2) O2 R—R (biodiesel) + Na2CO3 + CO2
(9.2)
The products obtained after pyrolysis have good cetane no and low vis-
cosity with acceptable range of copper corrosion value, sulfur, and water
content. But, their poor pour point, low higher heating values (HHVs),
more carbon residues, and ash content have limited their utilization in spe-
cific applications [10].
9.2.4 Transesterification (Alcoholysis)

Transesterification is most preferable chemical reaction and consid-
ered best method among all other processes because of its simplicity
and less cost [4, 11]. Synthesis of biodiesel by transesterification pro-
cess can be performed by conventional transesterification method or by
microwave/ultrasound-assisted method. Microwave/ultrasound-assisted
method takes very less reaction time and synthesizes biodiesel more
quickly at laboratory scale.
9.2.4.1 In Situ Transesterification (Reactive Extraction)

In in situ transesterification process, crop seeds containing oil are crushed
and directly reacted with methanol/ethanol (alcohol) and catalyst (acid
or alkali based) to produce biodiesel, thereby excluding the need for oil
extraction and reducing the intensive running and capital cost of biodiesel
synthesis methods [12]. Some co-solvents are also used to speed up the
reaction rate [13].
Some significant parameters of in situ transesterification process are
moisture content of seeds, oil-to-alcohol molar ratios, type of alcohol, type
and concentration of catalyst, reaction temperature, agitation speed, and

size of crushed seeds [12].
9.2.4.2 Conventional Transesterification

In conventional transesterification, oils are extracted from seed by crush-
ing, pressing, and solvent extraction (mostly by n-hexane) and then used
as raw material.
Figure 9.2 shows the difference between in situ and conventional trans-
esterification processes. Conventional process requires crushing and sol-
vent extraction steps so having more cost than in situ.
VO is pre-heated at 100°C to evaporate water; then, this VO is trans-
ferred into double jacket glass reactor and heated up to desired tempera-
ture. Optimized amount of catalyst is dissolved in alcohol and poured into
reactor and temperature of mixture is maintained below the boiling point
of alcohol (65°C) by using hot water bath. Chemical reaction between oil
and alcohols proceeds for 2 hours under continuous stirring. Then, this
mixture transferred into separating funnel for 12–20 hours at room tem-
perature; after that, two layers are formed by sedimentation. Conventional
transesterification experimental setup for biodiesel production is described
in Figure 9.3. Bottom layer of glycerol is removed and top layer containing
biodiesel is heated at 80°C to remove excess methanol. At the end, this
biodiesel is washed with 40°C warm water to eliminate remaining alcohol,
glycerol, and catalyst. Water is absorbed anhydrous Na2SO4 from biodiesel
and after filtration purified biodiesel is obtained.
There are various types of transesterification process [2] based on differ-
ent types of catalysts and without catalyst as classified in Figure 9.4.
Steps Conventional method In-situ method
1. Raw Material Crop seeds Crop seeds
2. Maceration Crushed into small size Crushed into small size
3. Crushing & solvent Oil extraction

extraction
4. Transesterification Biodiesel + Glycerol Biodiesel + Glycerol
(oil+alcohol+catalyst)
5. Purification Pure Biodiesel Pure Biodiesel
Figure 9.2 Comparison between conventional and in situ transesterification.

Stirrer
Separating
funnel
Condenser
Thermometer
Biodiesel
Glycerol
Double jacket Circulated Refrigerated

glass reactor hot-water bath cooling solvent
Figure 9.3 Conventional transesterification process experimental setup.
Acidic: H2SO4, HCL, H3PO4

ferric sulfate, and organic
sulfonic acid
Homogeneous
Alkaline: KOH, NaOH,
Catalysts NaOCH3, KOCH3, and
K2CO3 etc
Catalytic-based Enzymes e.g immobilized
process lipase, Ryzopus oryzae
Heterogeneous lipase, CH2N2,
Catalysts
Titanium silicates, Sulfated
Titanium, Alkaline earth
metal (MgO, CaO, SrO),
Amorphous zirconia,
Transesterification Potassium zirconia
Supercritical
Methanol (SCM)
Ethanol/Propanol
Butanol
Non-catalytic
based process
BIOX co-solvent
Process
Figure 9.4 Classification of transesterification process.
9.2.4.2.1 Catalytic-Based Process

9.2.4.2.1.1 Homogeneous-Acid-Catalyzed-Esterification
(Pre-Transesterification Treatment)
If oils have FFA > 3 wt%, then esterification process (pre-transesterification
treatment) is carried out to reduced FFAs less than 3 wt%. FFA can be
determined from the acidic values of oils by using Equation (9.3).
FFA = 0.5% * AV (9.3)
In pre-transesterification treatment, VO having high FFA is reacted

chemically with alcohol (methanol) in the presence of homogeneous acidic
catalyst like sulfuric acid/H2SO4 or ferric sulfate which convert the FFA
into biodiesel [14] as shown by Equation (9.4)
Free Fatty Acids (FFA) + ROH(Alcohol) Catalyst

 → FAME (Biodiesel) + H 2O
Acid
(9.4)
Then, this mixture is transferred into separating funnel along with cold
water and allowed to settle for appropriate time until two phases appeared.
Upper layer contains excess of water-methanol fraction that is removed,
and bottom layer containing fatty acid methyl ester, VO, and methanol
was transferred into evaporator to remove existing methanol, and then,
its acid value is determined prior to transesterification process. Then, this
obtained biodiesel + VO is purified and neutralized by different kind of
methods [15]; most preferable is transesterification.
9.2.4.2.1.2 Homogeneous Alkaline-Catalyzed

Transesterification
Most efficient alkaline-catalyzed transesterification is carried out on those
oils that have less than or equal to 1–3 wt% range of FFA ≤ 1–3 wt% [16,
17] because presence of more FFAs produce soaps by reacting with alkaline
catalyst that makes difficulty in separating the biodiesel and glycerol [18].
It is necessary that FFA content should be less than 3% to achieve greater
biodiesel conversion efficiency/yield [19].
Transesterification is the most popular method for producing biodiesel
[11, 20]; in this process, short-chain alcohols (methanol, ethanol, propa-
nol, butanol) are reacted chemically with VO (crop seed oils) or fats in the
presence of alkali catalysts (like KOH, NaOH, and sodium methoxide) as
shown by Equation (9.5). Mostly, methanol is preferred among all other
alcohols due to its low cost. VOs have long-chain triglyceride structure of
fatty acids. Mostly, methanol is preferable alcohol because of its low cost
among other alcohols.
CH2 COOR1 CH2 OH CH3 COOR1
Alkaline
CH COOR2 + 3 CH3OH
Catalyst
CH OH + CH3 COOR2 (9.5)
CH2 COOR3 CH2 OH CH3 COOR3
Triglyceride of oil Alcohol (Methanol) Glycerol Biodiesel (FAME)
The conversion of triglyceride (VO) into diglyceride, monoglycer-

ide, and glycerol along with biodiesel is a reversible three-step process as
described by Equation (9.6) [4].
End products of alkaline-catalyzed transesterification process are glyc-
erol and biodiesel (FAME). When this mixture is transferred to separating
funnel, then glycerol sinks to the bottom of funnel and biodiesel remains
at the top of glycerol. After removing glycerol from bottom, biodiesel is
heated and filtered to remove alcohol and catalyst than biodiesel is washed
and purified with warm water.
Catalyst
1. Triglyceride (Vegetable oil) + ROH (Alcohol) → Diglyceride +FAME (Biodiesel)
Catalyst
2. Diglyceride + ROH → Monoglyceride +FAME
Catalyst
(9.6)
3. Monoglyceride + ROH → Glycerol +FAME
∴ R is alkyl group of hydrocarbons

9.2.4.2.1.3 Heterogeneous-Catalyzed Transesterification

Transesterification process also used heterogeneous catalysts like metal
oxides, oxides, mixed metal oxides, hydrotalcites (like aluminum and
magnesium hydroxycarbonates, and zeolites), and supported hydroxides.
Heterogeneous catalysts increase the biodiesel production, reduce sapon-
ification, and easy to recover from biodiesel than homogeneous catalyst.
But, these required high temperature and pressure [21].
Alkaline earth metal (CaO, MgO, SrO), titanium silicates, sulfates, tita-
nium, amorphous zirconia, potassium zirconia, and unsupported mixed
metal oxides including CaO-La2O3 CaMnOx, BaMnOx, CaFeOx, BaFeOx,
CaZrOx, and CaCeOx are the examples of heterogeneous catalyst. Table 9.1
showed the Comparison b/w heterogeneous and homogeneous catalytic
transesterification process.
9.2.4.2.1.4 Enzymatic-Catalyzed Transesterification

There are various types of eco-friendly immobilized or soluble enzymatic
catalysts that are also suitable for feedstock having more FFA and water
under mild reaction conditions [22]. Enzymes include immobilized lipase,
ryzopus oryzae lipase, liquid lipase eversa transform, callera trans L lipase,
liquid lipolase, lipozyme, novozyme, ZIF-67, novozym 435, lipase immobi-
lized, and CH2N2. Lipases enzymes are synthesized from plant, animal, and
microorganism sources. These are relatively costly but require low energy
consumption. Some companies are using enzymatic catalysts at industrial
Table 9.1 Comparison between heterogeneous and homogeneous catalytic

transesterification process.
Heterogeneous Homogeneous
Factors catalytic process catalytic process
Existence of water/free Not sensitive Sensitive
fatty acids
Cost Potentially cheaper Comparatively costly
Reaction rate Moderate conversion Fast and high
conversion
Catalyst reuse Possible Not possible
Post-treatment Catalyst can be Acidic catalyst are used
recovered in neutralization so
cannot be recovered,
and produce
chemical waste
levels including Piedmont Biofuel (USA), Sunho Biodiesel Corporation

(Taiwan), Lvming Co. Ltd, and Hainabaichuan Co. Ltd (China). Cost-
effective catalysts can also be synthesized by combining multiple types of
enzymes and lipases but alkali or acidic catalyzed transesterification pro-
cesses are more economical and practical than enzymatic catalyzed.
9.2.4.2.2 Non-Catalytic-Based Process

Non-catalytic transesterification process does not use catalyst, so there is
no need of catalyst removal and no saponification occurs, so glycerol is
removed easily. It takes very less reaction time because of high solubility
between alcohol and triglycerides of oils. Mostly, non-catalytic transesteri-
fication is performed by following two routes: (a) supercritical alcohol pro-
cess and (b) BIOX co-solvent process [4, 23].
9.2.4.2.2.1 Supercritical Alcohol Process

The non-catalytic transesterification of VO can be performed with super-
critical alcohols (like methanol/ethanol/propanol/butanol) which requires
high temperatures (170°C–350°C), high pressure (10–60 MPa), and high
alcohol consumption (molar ratio as 40–42), thereby increasing opera-
tional costs. In this process, fats or oils are treated with subcritical water
then glycerol is removed from fatty acids (oil) phase by decantation. Fatty
Vegetable oil (Triglyceride + free fatty acids)
Hydrolysis by subcritical water
Phase separation
Oil phase (fatty acids) Water phase
Transesterification with Phase separation

supercritical alcohol
Phase separation
Waste water Glycerol
Alcohol recovery by Biodiesel

rotary evaporator
Biodiesel ready
Purification
for marketing
Figure 9.5 Supercritical transesterification process.
acid phase reacts with methanol under supercritical conditions to synthe-

size biodiesel (methyl ester). At the end, unreacted methanol and water
is removed to get purified biodiesel as described in Figure 9.5. Schematic
experimental setup is also described in Figure 9.6.
Supercritical method can also be performed with appropriate co-solvent
(CO2, etc.) to lower critical point of alcohol and decrease severity of super-
critical reaction condition [24].
9.2.4.2.2.2 BIOX Co-Solvent Process

BIOX co-solvent transesterification is a commercialized approach that
decreases the reaction time by enhancing the solubility of alcohol in co-
solvent that quickly reacts with triglyceride phase of VO. This process
4 1. Electric furnace
3 2. Autoclave
3. Temperature control monitor
4. Pressure control monitor
5. Biodiesel exit valve
6. Condenser
5 7. Biodiesel collector vessel
6
2
7
1
Figure 9.6 Supercritical transesterification experimental setup.
requires low temperature. Methyl tert-butyl ether (MTBE) and tetrahydro-

furan (THF) are utilized as recycled inert co-solvent to make a one-phase
system by solubilizing alcohol in it, and biodiesel is synthesized in very
short time of 5–10 min. Mostly, THF are preferred because its boiling point
is closer to methanol boiling point. As no catalyst was used, so there is no
need of catalyst removal from biodiesel or glycerol.
9.2.4.3 Microwave/Ultrasound-Assisted Transesterification

Transesterification can also be performed by 300-MHz to 300-GHz micro-
waves containing high-frequency radio and infrared waves. These waves
accelerate the chemical reaction between alcohol and VO to produce bio-
diesel [25], thus decreasing the reaction time from hours to few minutes.
Similarly, ultrasound waves generate expansion (−ive pressure) and com-
pression (+ive pressure) waves giving eddies/currents that increase the heat
and mass transfer in the VO and alcohol mixture. Ultrasound waves vary
between low frequency range of 20–100 kHz to high-frequency range of 2–10
MHz [26]. Both of these processes are efficient, economical, and time saving
because these require less amount of catalyst. Figures 9.7a and b represent
the experimental setup of microwave and ultrasound transesterification.
Table 9.2 shows the comparison between different biodiesel production
methods.
9.2.4.4 Variables Affecting Transesterification Reaction

There are various variables that influence the biodiesel yield and quality
but critical variables are moisture and FFA contents, oil-to-alcohol molar
ratios, type of alcohol and catalysts, reaction time, and reaction tempera-
ture [27]. All these variables have great influence on reaction rate, biodiesel
yield, and its conversion efficiency.
Transducer
Water out
Microwave Water in
Oven
Ultrasonic generator
Ultrasonic
Power setting prob
Reactor Al-foil
Time setting
Magnetic Glass
stir bar beaker
Magnetic stirrer
(a) (b)
Figure 9.7 (a) Microwave assisted transesterification. (b) Ultrasonic assisted

transesterification process experimental setup.
Table 9.2 Comparison between biodiesel production methods [7].

Biodiesel
production
methods Advantage Disadvantage
Dilution Simple process, high Unsaturated hydrocarbon
viscosity, low chains reactivity, gum
production, and formation, high free fatty
capital costs acid (FFA), not good to use
in diesel engines directly,
poor atomization, high
viscosity, bad volatility, bad
stability, incomplete fuel
combustion, solidification
of blend occurs at cold
temperatures, injector
nozzles plugging, engine
durability of engine
reduced, higher engine
wear, higher engine
running and maintenance
costs, higher air pollution
emission, lubricating
oil thickening and
deterioration
(Continued)
Table 9.2 Comparison between biodiesel production methods [7]. (Continued)

Biodiesel
production
Micro-emulsion Low viscosity biodiesel Heavy carbon deposition,
formation with incomplete combustion,
no by-product, lubricating oil degradation
single phase, lower and thickening, sticking of
nitrogen oxide injector needle
emissions, good
atomization of
biodiesel
Pyrolysis Simple process, good Require complex and
for hydro-processing expensive equipment,
industry, useful high temperature, high
by-products like production cost, short-
syngas is produced, chain molecules are
No-pollution, produced in biodiesel
biodiesel has that are much similar to
satisfactory gasoline than diesel fuel,
physiochemical low purity of biodiesel
properties
Transesterification The most preferable Vegetable oils with low
method for biodiesel free fatty acid and very
production, low less water content are
cost, Simple required (with base
equipment, suitable catalyst), reversible side
for industrialized reactions also occurred,
production, high reaction time,
high conversion obtained biodiesel must
yield, glycerol as be neutralized and
by-product can washed. Non-catalytic
be transformed transesterification required
into value- complex equipment due
added products, to high temperatures and
satisfactory pressure.
viscosities, biodiesel
properties are
similar to diesel fuel
(Continued)
Table 9.2 Comparison between biodiesel production methods [7]. (Continued)

Biodiesel
production
Supercritical Good adaptability, Equipment cost is high; high
methanol no catalyst, high energy consumption, high
conversion yield, temperature, and pressure
very less reaction are required
time
For transesterification process, moisture and FFA content should be

very low; otherwise, alkali-type catalyst will be consumed in neutralizing
FFAs and moisture will produce soap and frothing that will make the bio-
diesel and glycerol separation difficult. Transesterification is a reversible
process so higher alcohol-to-oil ratio is recommended than stoichiometric
ratio so that high yield of biodiesel can be achieved in less time. Mostly,
in catalytic transesterification, 1:6 oil-to-alcohol ratio is preferred, and in
non-catalytic transesterification process, 1:40 oil-to-alcohol is preferred,
but it can vary according to type of VO.
Among different type of alcohols, methanol is preferred due to its low
cost and low boiling point.
Many different types of catalysts (acidic, alkali, enzyme, homogeneous,
heterogeneous) are available but these are selected according to cost, avail-
ability, reaction condition, and type of oil. Concentrations of catalysts are
also important but their optimum range should be determined because
sometime higher concentrations have no or negative impact on biodiesel
synthesis.
Conventional transesterification takes more time (120 min), but time
can be minimized by using advanced equipment as used in microwave,
ultrasound or supercritical methods, etc. As it is reversible process, so it is
necessary to suitable biodiesel production time.
Similarly, transesterification occurred on different temperatures that
influenced the biodiesel yield. In case of conventional transesterification
temperature should be sustained below boiling point of alcohol. But, increas-
ing of temperatures in supercritical process also increases the biodiesel yield.
Optimum values and quantity of different variables should be determined
to get maximum yield of biodiesel form various feedstock having different
composition so behave differently. Production optimization for biodiesel
synthesis form different VOs should be carried out by varying types/values
and quantities of all variables involve in transesterification process.
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10
Non-Edible Feedstock for
Chikati Roick1, Kabir Opeyemi Otun2, Nkazi Diankanua1
and Gorimbo Joshua2*
School of Chemical and Metallurgical Engineering, Faculty of Engineering and the

1
Built Environment, University of the Witwatersrand, Johannesburg, South Africa

2
Institute for the Development of Energy for African Sustainability (IDEAS),
University of South Africa’s College of Science, Engineering and Technology,
Florida, South Africa
Abstract
Continuous increase in the world’s population and high energy demand together
with environmental concerns have called for a sustainable and renewable substi-
tute for fossil fuels. Of all the existing solutions, biodiesel which can be gener-
ated from either edible and non-edible sources and these resources have proven
to be an appropriate alternative due to its renewable, low toxic, and environmen-
tally friendly nature. However, the use of non-edible feedstocks can be certain
to be a sustainable source of biodiesel production because they can be grown on
abandoned/wasteland, where they do not have competition with food crops, they
are relatively cost-effective and produce a similar and sometimes higher yield and
fuel properties as the edible feedstocks. This chapter is, therefore, on the poten-
tials of non-edible feedstocks such as non-edible vegetable oils, waste cooking oil,
waste animal fats, and microalgae for biodiesel synthesis. Among the highlights of
this chapter are the reports relevant to global warming and climate change, mod-
ern technology for biodiesel synthesis from non-edible sources including transes-
terification, fuel properties of the biodiesel produced from non-edible feedstocks,
the economic benefits, as well as the environmental concerns. It can be concluded
from this chapter that non-edible feedstocks are promising for biodiesel industri-
alization as they meet the worldwide internationally recognized standards.
*Corresponding author: joshuagorimbo@gmail.com
285
Keywords: Biodiesel, renewable energy, non-edible feedstocks, global warming,

transesterification, climate change
List of Abbreviations
IMF International Monetary Fund
MDG Millennium Development Goals
AREI Africa Renewable Energy Initiative
SADCC Southern African Development Community
GHG Greenhouse gases
FAME Fatty acid methyl esters
WCO Waste cooking oil
ASTM American Standards for Testing Materials
10.1 Introduction
The 21st century is plagued with series of challenges that cause degradation
of our soils, freshwater, oceans, forests, and biodiversity. The scourge of cli-
mate change is also not helping the matter as it is even adding more pres-
sure on the resources we rely upon by aggravating the risks connected with
disasters, such as droughts and floods. Although, intensive efforts at all lev-
els of governance have contributed greatly in the campaign against climate
change. Yet, global warming continues to threaten the ecosystem and the
standard of living around the world, and the solutions to mitigate climate
change to barest minimum seem not adequate. The major contributor to
this is the greenhouse gas emission which contain majorly carbon dioxide.
While mitigation policies can help in no small way to mitigate the risks
associated global warming caused by human (anthropogenic), increasing
the capacity of carbon sinks via reforestation is another great measure. For
instance, several approaches have already been adopted to mitigate climate
change these include energy use reduction by increasing energy efficiency,
using alternative energy source to substitute petroleum-based fuels and
removal of carbon dioxide (CO2) from the atmosphere.
Biofuel, such as biodiesel and bioethanol, has no significant CO2 con-
tribution to the accumulation of greenhouse gas emission and, hence, can
serve as a viable solution to climate change. They are defined as liquid or
gaseous fuels which can be sourced from biomass and used chiefly in the
transportation sector. As a key replacement to petroleum, biodiesel is con-
sidered sustainable and environmentally benign which has elicited a surge
Non-Edible Feedstock for Biodiesel Production 287
of interest from researchers across the globe in the last few years. Biodiesels
are esters of long chain fatty acids that range in size from C12 to C24 [1, 2]. By
using biofuel produced from biomass for transportation, we can help pro-
mote the solution to meeting ever-increasing global energy demands and
restoring natural balance of CO2 in the atmosphere. Apart from replacing
fossil fuels, the feedstocks employed in producing biofuels require CO2 to
germinate and they absorb their food from the atmosphere. So, most, if not
all the CO2 released to the atmosphere when biomass is burnt in engines is
captured again when new biomass is cultivated to produce more biofuels.
Therefore, biofuel is a very effective way of reducing these emissions. The
last few years has witnessed a rapid growth in biodiesel production to curb
the adverse effects of CO2 emissions. This chapter, therefore, focuses on the
reports relevant to global warming and climate change and modern tech-
nology for biodiesel synthesis from non-edible sources including trans-
esterification with a view of mitigating the effects of climate change. We
also discuss the fuel properties of the biodiesel produced from non-edible
sources, their economic benefits, as well as the environmental concerns.
10.2 Reports Relevant to Global Warming

and Renewable Energy
Renewables may hold the key to a clean energy future. The main goal of
climate change mitigation as contained in the Paris Agreement is to limit
the world-wide average temperature increase to below 1.5°C above pre-
industrial levels. To meet this goal, the final energy consumption must
have a share of renewable energy that will increase from 19% in 2017 to
65% by 2050. The last few years has witnessed a surge of interests from
different nations implementing national or regional plans to mitigate the
adverse impact of carbon dioxide (CO2) emissions. Fossil fuels are now
considered as an unsustainable source of energy due to contamination of
the environment and causing climate changes. Some repercussions of cli-
mate change include new weather patterns that continue to exist for con-
siderable amount of time. Renewable energy as a source got attention due
to strict environmental regulations. Technologies for renewable-energy
production are comparatively cheap and sustainable than the existing coal
generation [3]. According to International Monetary Fund (IMF), some
governments, local and regional policymakers must bring to a resolution
whether to close down or reduce energy production from existing coal
plants en route toward decarbonization [4].
Global warming is now a pursuit central to many research laborato-

ries all over the world. Its effects are now visible and a present threat. Our
actions and commitments thus far are not good enough. International and
regional organizations have been pivotal in awareness and developing pol-
icies to curb climate change. For instance, UN is suggesting tax structures
and fiscal blueprint to put a stop emission of carbon from fossil fuels.
Climate related monitoring reports and agreements such as the IMF
[4], Paris Agreement [5], Copenhagen accord [6], United Nations, General
Assembly [7], Africa Renewable Energy Initiative (AREI) [8], Renewable
Energy and Energy Efficiency Strategy and Action Plan for the Southern
African Development Community [9], Millennium Development Goals
(MDG) [10], Kyoto Protocol [11] all aim at stabilizing GHG concentra-
tions in the atmosphere. Some of the objectives of the selected agreement
and reports, and in response to these, some countries have put through
comprehensive governmental climate action schemes to control climate
change. Up to the present time, these commitments are still not sufficient
to achieve the agreed temperature objectives as per the Paris Agreement;
nevertheless, the mentioned agreement draws up the way to further action.
Climate researcher and technologist proclaim that carbon emissions must
be rapidly reduced with the objective of achieving a net zero by 2050, or
earlier [12].
10.3 Biofuels as an Alternative Energy Source

Biomass is defined as the plant or animal matter that can be utilized for
energy production such as electricity or heat. Biofuels are categorized as
natural, primary and secondary biofuels. Generally, natural biofuels are
extracted from organic materials, in particular vegetables, waste from ani-
mals, and landfill gas. Primary biofuels are fuels from wood usually used
for cooking and heating in most rural areas and, in some case, electricity
production. Secondary biofuels refers to bioethanol and biodiesel that are
sourced from processing biomass. The secondary biofuels are additionally
grouped into first-, second-, and third-generation biofuels based on their
source, development levels, and the processing technology as shown in
Figure 10.1.
10.3.1 First-Generation Biofuels

This generation of biofuels is those fuels originating from what human
beings use as food for example sugar, starch, vegetable oil, animal fat, etc.
1st Generation 2nd Generation 3rd Generation 4th Generation

• Edible biomass • Non-edible • Algal biomass Breakthrough
• E.g. sugar beet, biomass • Microalgae
corn, wheat, etc. • E.g. Wood, straw, Genetically
• Macroalgae
grass, waste, etc. engineered
crops and
algae
Figure 10.1 Biofuels production sources adapted from [13].
Some examples of the most common types of first-generation biofuels are

as follows:
• vegetable oil,
• biodiesel,
• syngas,
• biogas, and
• bio-alcohols.
Despite of these first-generation fuels possessing potential to be used

in generating carbon neutral biofuels, this approach could have notables
economic and political concerns as grain and food prices will go up [13].
Martin (2010) looked at the conflicts of first-generation biofuels and the
implications it has on developed and developing economies [14].
The major downside of using the first-generation fuels is the use of ara-
ble agricultural lands and as a consequence shortage of land for animal
and human food production rendering the food-vs-fuel quandary a moot
point.
10.3.2 Second-Generation Biofuels

Biofuels under this category are also referred to as advanced biofu-
els, and these fuels originate from various types of non-food biomass.
Lignocellulosic biomasses (such as agricultural waste, and woody crops)
are the major feedstocks in the production of second-generation bio-
fuels. Second-generation biofuel feedstock can also be the nonedible
by-product of food crops such as the corn husks or Panicum virgatum

(wheat straw) and other variety of plants that are not edible, for instance,
switch grass. The technology used allows the plant cellulose and lignin
to be separated in order for cellulose to be fermented into alcohol. These
biofuels can be sourced from a variety of biomass. A considerable number
of companies and research groups are venturing into cost effective pro-
cessing for producing second-generation biofuels such as ExxonMobil
which is pursuing research to determine how these biofuels may best fit
into future energy.
10.3.3 Third-Generation Biofuels

Beyond second-generation biofuels, engineers and scientists have also
looked at the so-called third-generation biofuels, largely derived from
algae (microalgae and cyanobacteria) [15, 16]. Different from the first-
and second-generation derived biofuels, algae poses no threat to food
security. Algae can be grown in brackish water and in some cases sea-
waters making it human friendly source of biofuel, as it does not put an
enormous strain on the freshwater. More so, no agricultural land is used
to grow the algae; therefore, little or no competition exist land for food
production. Algae are defined as photosynthetic organisms that convert
atmospheric CO2 and H2O to oil using light from the sun, and it is the oils
that gets converted to biodiesel portion via a series of processes [17]. Also,
of interest is the water hyacinth (scientific name Eichhornia crassipes)
which has been reported to have a high biomass yield and can grow expo-
nentially. These too can be a potential feedstock for biofuel production
and related bioactive ingredients [18]. The advantages of both algae and
the water hyacinth is the fact that they are aquaculture, that they repro-
duce exponentially, and can be cultivated in salty water giving biomass
of higher energy content. The amount of oil produced in both systems,
however, is a function of parameters such as sunlight exposure times and
atmospheric CO2 levels.
10.4 Benefits of Using Biodiesel

The advantages of utilizing biodiesel in internal combustion engines are
overwhelming and relate to its broader applications based on the following
highlights:
a. Biodiesel is less toxic and safer to handle than petroleum-

based diesel due to its relative high flash point.
b. Biodiesel is a sustainable and renewable source of energy
with zero harmful emission.
c. The simplicity and low capital cost of biodiesel production
enhances its wider distribution and use commercially.
d. The starting materials for biodiesel synthesis are organic and
can be sourced locally. In fact, more biodiesel can be reaped
from non-edible and waste oils nowadays.
e. In terms of energy conversion and power outputs, generally,
diesels engines are more efficient than petrol engines.
f. Most countries have adopted biodiesel as a means of foreign
exchange. The availability of raw materials for biodiesel pro-
duction has encouraged local farmers to embark on mass
plantation which in turn has created more job opportuni-
ties and serves and increasing the production of foreign
exchange.
g. Biodiesels are clean burning fuels with low emission of
greenhouse gases [14, 19].
10.5 Technologies of Biodiesel Production

From Non-Edible Feedstock
Generally, four main methods have been developed to produce biodiesel to
fit in into our conventional engines without any amendments [20]. These
are as follows.
1. Direct use or blending (Dilution): This method is the oldest and
easiest method of biodiesel production. Vegetable/animal oils are not
advisable to use as is in engines because of its high viscosity which
may trigger other challenges. To circumvent these challenges, vege-
table oils can be blended with diesel oils in some limited ratio. Blend
ratios which results in optimum performances in diesel driven engines
are generally of less viscosity which is achieved by mixing considerable
proportion of petrodiesel (preferably 80%) with lower percentages of
renewable vegetable/animal oils (preferably 20%). Carbon deposition in
engine cylinder and improper combustion are some of the demerits of
this process.
H2C OH H3C OCOR1

H2C OCOR1
base OCOR2
+ HC OH + H3C
3 CH3OH
HC OCOR2
H3C OCOR3
H2C OCOR3 H2C OH
Triglyceride Methanol Glycerol Fatty acid methyl esters (Biodiesel)
Figure 10.2 Transesterification reaction for biodiesel production [24].
2. Micro emulsification: This is basically prepared by mixing alcohol,

surfactants, vegetable/animal oil, diesel fuel, and cetane improver in dif-
ferent fractions. This process is easy but produces a less volatile, less stable,
and highly viscous mixture, which is the main drawback of the process.
The challenges associated with the viscosity of vegetable oils can be cur-
tailed by making of microemulsion. It is the solubilization of oils with the
aid alcoholic solvents and surfactants [21].
3. Thermal cracking or pyrolysis: This process involves heating of veg-
etable or animal oils at high temperature (usually 300 to 1,300°C) in the
presence or absence of a catalyst and absence of oxygen. It is simple and
produces less waste and less emission. It is very effective when compared
with other cracking processes. High installation cost and oxygen removal
during pyrolysis are some of the challenges encountered by this process
[22].
4. Transesterification: This is considered as the reaction in which
triglycerides (oils/organic fats) are reacted with suitable alcohol in the
presence of acidic/alkaline catalyst to yield fatty acid esters (biodiesel)
and glycerol. This process produces biodiesels that have comparable
features with diesel fuels and is the most promising route for commer-
cial production of biodiesel from the economic point of view [23]. The
transesterification process is the most convenient method because it is
cheap and simple while the choice of feedstock is key since it contrib-
utes a significant seventy percent of the total production cost from edible
and non-edible sources [20]. The transesterification reaction is shown in
Figure 10.2.
10.6 Biodiesel Production by Transesterification

Among the methods previously discussed, transesterification is the com-
monest and the most preferred method to produce biodiesel because of
its simplicity and it has been widely employed in industry to convert oils
into biodiesel. It also affords the use of a wide range of feedstocks to
produce a biodiesel that greatly resembles conventional diesel in terms
of quality.
First-generation biodiesel is produced via transesterification of tri-
glycerides from vegetable oils, while second-generation biodiesels are
obtained from feedstocks like lignocellulose and non-edible triglycerides.
Transesterification involves chemically converting various types of oils
into fatty acid methyl esters (FAME) and glycerol in the presence of cata-
lysts [25]. FAME, commonly known as biodiesel, is the monoalkyl esters of
long chain fatty acids. Table 10.2 shows the major free fatty acids present
in biodiesel production. Type of catalyst, nature of raw material, reaction
conditions, type of solvent, reactor type, and solvent to oil ratio are some
of the key variables required to obtain optimum yield for biodiesel produc-
tion via transesterification process [26]. Of all these factors, catalyst type
and type of feedstocks are the key parameters for effective biodiesel pro-
duction because they both determine the price of biodiesel production to
a greater extent. These catalysts are divided into two major types, homog-
enous or heterogeneous:
a) Homogeneous catalyst: In homogenous catalysis for trans-

esterification, alkaline or basic catalysts are more preferred
to the acid catalysts choice because of their high conver-
sion rate in relatively short time. In addition, basic catalysts
do not corrode easily with industrial equipment. The most
common examples of homogeneous catalysts for this reac-
tion are KOH, and NaOH (alkaline) and H2SO4 and H3PO4
(acidic). The major demerit of the basic catalysts is their
high sensitivity to fatty acids contained in the feedstock.
Acid catalysts are also well suited for the transesterification
reaction of highly fatty materials present in fats and oil.
However, they are slower than base catalyzed reaction and
require high temperature and pressure and high amount of
alcohols for the esterification reaction. In general, homoge-
nous catalysts is majorly at disadvantage because of the sep-
aration of the catalysts from the products and inability to
reuse. Removal of catalysts involves several washing steps
and activation which increases the total cost of production
[27].
b) Heterogeneous catalysts: Heterogeneous catalysts which

offers to replace homogeneous catalysts are usually solid
materials that can be obtained from renewable materials
following pyrolysis at high temperature between 500°C and
900°C [28]. They are better than homogeneous catalysts in
the sense that they are easy to separate from the products can
be reused, and no side reaction. Moreover, the biodiesel pro-
duced from these catalysts yielded about 96% FAME content
[28]. The most frequently used heterogeneous basic catalysts
are oxides and carbonates of alkali and alkaline-earth metals.
c) Enzymatic transesterification: Diesel production via this
enzyme-catalyzed transesterification pathway experimented
by Dhawane et al. (2018) [29] and Andrade et al. (2017) [30]
with the use of lipase enzyme and methanol [31]. It involves
hydrolysis and esterification of triglycerides (substrate) to
produce FAMEs (diesel). This process is highly promising
because of their high conversion rate, ease of separation
from the product, good glycerol recovery and high yield
when compared with the homogenous and heterogeneous
catalysts. Nonetheless, biodiesel synthesis via enzymatic
transesterification is expensive because of lipase manufac-
turing and other intricate stages involved in cellular enzyme
synthesis and separation. Table 10.1 gives some of the com-
mon free fatty acids in biodiesel production with Figure
10.3 showing a flow chart of biodiesel production process
through transesterification process.
Table 10.1 The common free fatty acids in biodiesel production [32].
Entry Name of fatty acid Chemical name Structure
1 Palmitic Hexadecanoic acid C16:0
2 Stearic Octadecanoic acid C18:0
3 Oleic Octadecenoic acid C18:1
4 Linoleic Octadecadienoic acid C18:2
5 Linolenic Cis-9, cis-12, cis-15- C18:3
octadecatrienoic acid
Alcohol
Biodiesel
+
catalyst
Drying
Washing 350-400ºC,
Transesterification
(oil/alcohol ratio) To remove 20 h
unreacting raw To remove
t
en materials contaminants
atm
e
etr l,
Pr ysica ical,
Feedstock Ph olog Glycerol
bi
Figure 10.3 Flow chart of biodiesel production process through transesterification

process.
10.7 Non-Edible Feedstocks for Biodiesel Production

Mostly, biodiesels can be prepared from two major sources (feedstocks),
namely, edible and non-edible feedstocks as shown in Figure 10.4. In 2017,
the worldwide biodiesel production was credited to palm oil (31%), soy-
bean oil (27%), rapeseed oil (20%), waste cooking oil (WCO) (10%), ani-
mal fats (7%), and others (5%) [33]. Although, the use edible feedstocks
may be the cheapest feedstock for biodiesel production for the future, but it
is not sustainable to meet the increasing demand for biodiesel [34]. Hence,
the use of non-edible feedstocks is a sustainable alternative in the sense
• Corn, soybean,
Edible sunflower, etc
Biodiesel
Feedstocks
• Vegetable oil
Non • Waste animal oil
• Waste cooking oil
edible
• Algae, lignocellulose,
etc
Figure 10.4 Biodiesel production from edible and non-edible feedstocks.

that it does not compete with the food crops for limited plantation region
and has the potentials of reclaiming the wastelands [35]. Based on the data
available from the literature, WCO, animal oil, non-edible vegetable oil,
waste animal oil, and alga oil are the most promising alternatives for edible
oils and are elucidated as follows.
10.7.1 Non-Edible Vegetable Oils

The toxic chemicals present in non-edible vegetable oils make them unus-
able for human consumption. In addition, the threat posed by both the
food security and economic issues also make non-edible vegetable oils
more preferred than edible vegetable oils in the sense that it does not
encourage serious competition over land for food production and for the
food supply chain.
i) Jatropha is a tropical and drought-resistant plant that can thrive in an
abandoned and fallowed farmland [20]. It has been recognized as one of
the suitable non-edible sources for biodiesel production due to its phys-
iochemical properties. It is a rich source of hydrocarbons and has picked
the interest of researchers all over the world because of the use of its seed
oils as alternative feedstock for biodiesel production. There are about
20%–60% oil in the seeds of jatropha plant and contain mainly unsaturated
fatty acids likes oleic (42%) as the major component, followed by linoleic
(35%) and smaller percentage of palmitic (14%) and stearic acid (6%) [36].
Recently, Salar-Garcia et al. (2016) obtained 99.5% biodiesel production
yield from Jatropha oil and 100% conversion rate of triglycerides at 325°C
in 90 min [37].
ii) Karanja (botanical name Pongamia pinnata) is another potential
non-edible vegetable oil feedstock that can be used to produce biodiesel.
Countries like Southeast Asia, US, Australia, New Zealand, India, and
China are the main producers of this plant [38]. Interestingly, these trees
can grow in many places including roadsides, canals, and boundaries of
farmlands. The oil content of its seed ranges between 30% and 40%, and
can yield 97% FAME (biodiesel) via transesterification process at a tem-
perature of 65°C using 1 wt% of KOH and alcohol to molar ratio of 6:1
in 2 h. Karanja oil contains stearic acid (up to 8.9%), linoleic acid (up to
18.3%), and oleic acid (up to 71.3%) [39].
iii) Linseed which is also referred to as Linum usitassimum is another
potential non-edible feedstock for biodiesel production. Linseed can
produce oil up to 47% under optimum conditions [40]. The main fatty
acids which are mainly found in linseed oils are linolenic (up to 51%),
oleic acid (up to 21%), linoleic acid (up to 15%), and small amounts of
Table 10.2 Current research on non-edible vegetable oils as low-cost feedstocks

for biodiesel production via transesterification.
Non-edible
vegetable Methanol/ Temperature Time Yield
source Catalyst oil (°C) (h) (%) Ref.
Jatropha KOH, 1 wt% 6:1 60 1 96.1 [42]

curca
Linseed KOH, 1 wt% 9:1 60 2 95.5 [43]
Karanja γ-Alumina 1:9 50 0.83 69.3 [44]
Neem Cu/ZnO 10:1 55 1 74% [45]

nanocatalyst,
10 wt%
Rapeseed 6 wt% Na/FAP 10:1 120 8 98.5 [46]
Cotton seed KOH, 1 wt% 6:1 25 5 min - [39]
Castor KOH, 1.25 wt% 12:1 60 1 95 [47]
Jojoba KOH, 1 wt% 6:1 50 1 78.5 [48]
palmitic acid (6%) and stearic acid (5%) [41]. Other non-edible vegeta-
ble feedstocks include but not limited to neem, jojoba, desert date, sea
mango, rubber, tobacco, and castor, among others. Recent studies on
non-edible vegetable oils as sources for the production of biodiesel are
shown in Table 10.2.
10.7.2 Waste Cooking Oil

WCOs are the left over oils after a deep-frying procedure and the used oil
can be a suitable feedstock for biodiesel production. According to Loizides
et al. (2019), about 16.5 million tons of WCO is produced annually [49].
The lower solubility of these oils makes their disposal very challenging.
Therefore, the conversion of WCO into biodiesel will greatly help to mit-
igate the disposal problem while helping to solve the energy crisis. WCO
can be categorized according to the source such as household, food indus-
try, and non-food industry. Acid, base, and enzymes can be used to pro-
mote the conversion of WCO into biodiesel. Recently, it was reported that
demonstrated that sulfonated catalysts can effectively convert WCO into
biodiesel [50]. The FAME content obtained from pyrolyzed rice straw was
around 97.7%, conversion efficiency was 90.4%, and 91.1% free fatty acid
conversion rate with 10 wt% catalyst, methanol-to-oil ratio of 20:1 at 70°C
Table 10.3 Recent studies on waste cooking oils as feedstocks for the production
of biodiesel via transesterification reaction.
Loading Temperature
Catalyst (wt%) Alcohol Oil/alcohol (°C) Time Yield (%) Ref.
KOH/Clinoptilolite 9.1 MeOH 2.25:1 61 13.4 min 97.5 [52]
ZnAl2O4 5 MeOH 1:18 100 3h 94.9 [53]
RS-SO3H 10 MeOH 1:20 70 6h 97.7 [50]
CaO 4 MeOH 1:8 65 75 min 98.2 [27]
Kaolinite/K+
15 MeOH 1:14 70 3h 94.8 [54]
for 6 h [50]. Similarly, Maneerung and co-workers produced biodiesel with

90% FAME yield using calcined chicken manure as a precursor of CaO cat-
alyst [51]. The result was obtained under optimum conditions at 7.5 wt%
catalyst, the obtained methanol-to-oil ratio was 1:15 at 65°C [51]. Recent
studies on WCOs as feedstocks for the production of biodiesel via transes-
terification reaction are tabulated below (see Table 10.3).
10.7.3 Algal Oil

Algal species, which are regarded as the third-generation feedstock, are
a promising non-edible source of biodiesel. Algae can grow in both nat-
ural and artificial environment, and they are more economically viable
than edible oils. There are about 44,000 species of microalgae and a careful
selection of an appropriate algal strain is crucial to the overall performance
of biodiesel production [55]. Different microalgae including Chlorella sp.,
Chlorella vulgaris and Dunaliella salina algae, among others, have been
reported to be valuable in biodiesel production (see also Table 10.4). Algal
biodiesel has no sulfur and performs just like petroleum diesel, while min-
imizing the emission of harmful gases like CO, SOx, and NOx. Algal oils
have been one of the best choices for researchers as algae provides more
oil yield per area of arable land. To make microalgae more economically
viable, attention should be shifted to minimizing the cost of feedstocks,
inducing the lipid content, improving extraction efficiency, increasing the
area productivity, and helps to convert of algal lipids to biodiesel. Of all
these, the feedstock alone equals about 80% of the total production cost,
which can be drastically lowered by the use of waste and less costly raw
materials [56].
Transesterification is the most preferred process to produce biodiesel
from algal oil. This process can be economical and time-saving if key factors
Table 10.4 Recent studies on algal oils as feedstocks for biodiesel production
via transesterification method.
Loading Temperature
Feedstock Catalyst (wt%) Oil/MeOH (°C) Time (min) Yield (%) Ref.
Chlorella NaOH 38 1:600 60 10 96 [57]

Vulgaris
Algal lipids Ca(OCH3)2 3 1:30 80 150 99 [58]
Algal oil CaO 1.25 1:9 55 - 96.3 [55]
Algal oil Waste clay/ 3.5 1:9 60 240 97.4 [59]

ZnO
Algal lipid Immobilized 1.39 1:19 70 180 92.03 [60]

C. rugiza
lipase
like time of reaction, catalyst amount, and oil/alcohol ratio are optimized.
Narula et al. (2017) produced 88.9% yield of biodiesel from algal oil via
transesterification reaction by using CaO and CaO.Al2O3 as catalysts [55].
10.7.4 Waste Animal Fat/Oil

Animal fat is classified under the third-generation feedstock for biodiesel
production. The co-product of meat and fishery is animal fat. Examples
include beef tallow or mutton and yellow grease. These feedstocks, unlike
edible oils, are important for their food security, economic, and environ-
mental benefits. Presently, the co-products obtained from animal fats have a
very low market price and hence can be instrumental as an important source
of biodiesel production (see Table 10.5). In addition, most animal fats are
no longer allowed to be used as food any longer due to the many infections
that ravaged animals. For instance, tallow from diseased livestock is a key
feedstock for biodiesel production for the same reasons above. However,
inconsistent supply poses a great challenge for all these feedstocks because
animal fat is not only produced for biodiesel production [61].
10.8 Fuel Properties of Biodiesel Obtained

From Non-Edible Feedstock
Different factors affect the fuel properties of biodiesel obtained from
non-edible feedstock. This includes, but not limited to, quality of raw
Table 10.5 Recent studies on waste animal fat/oil as feedstocks for production of
production via transesterification process.
Waste animal Loading Temperature Time
fats/oils Catalyst (wt%) Oil/MeOH (°C) (min) Yield (%) Ref.
Animal tallow NaOH - 1:6 60 180 - [62]

oil
Mutton fat KOH/MgO 4 1:22 65 20 98 [63]
Fish oil CaO-Ca3Al2O6 10 1:12 54 90 96.4 [64]
Waste shark NaOH 5.9 1:6 65 60 96 [65]

liver
Waste chicken CaO/CuFe2O4 3 1:15 70 240 94.52 [66]

fat
materials and fatty acid compositions, method of production, pro-

cesses involved in refining, and final production conditions [60]. There
are different measures to classify fuel properties of biodiesel, the most
important of which are: influence of activities taking place in the engine
(such as ignition quality, calorific value, combustion of air-fuel mixture,
and formation of exhaust gas among others), low temperature prop-
erties (like cloud point, pour point, etc.), transportation and storage
properties (flash point, oxidation and hydrolytic stability, etc.), wear of
engine parts (viscosity, lubrication, etc.) [50]. In addition, these prop-
erties must meet the internationally established worldwide standards
in order to make the biodiesel useful for commercial purposes, which
are American Standards for Testing Materials (ASTM D6751) and
European (EN 14214) Standards for biodiesel fuel. In order to obtain
high quality biodiesel, as per ASTM and EN standards, optimization
of the pretreatment processes, separation of the product, and the final
purification steps should be done optimally. Additionally, the free fatty
acid contained within the oil blend to a large extent influences quality
and the properties of the fuel.
The literature reports that factors like cetane number, flash point, viscos-
ity, cloud point, and iodine value are the most important physicochemical
qualities of biodiesel and are strongly affected by the composition of FAME
[67]. A summary of the physicochemical properties of biodiesel obtained
from selected non-edible feedstock vis-à-vis the ASTM and EN standards
are given in Table 10.6.
Table 10.6 Summary of the physicochemical features of biodiesel produced from non-edible feedstocks.
Non-edible Cetane Viscosity Flash Density Cloud
feedstock number (mm2/s) point °C Kg/m3 point Standard Ref.
Waste 59 4.63 161 887 - ASTM D [25]
cooking 6751
oil
Cotton seed 54 4.06 200 850 −10 EN 14214, [39]
ASTM
D6751
Castor 80 13.75 149 927 - ASTM [47]
D6751
Jatropha 59.64 5.65 184 862 - ASTM [37]

curcas D6751
Chicken fat - 5.3 171 858 18 ASTM [66]
D6751
Chlorella sp 56.1 4.6 113 886 −2.2 ASTM [24]
D6751,
EN
Non-Edible Feedstock for Biodiesel Production
301
10.9 Advantages of Non-Edible Feedstocks

The various results obtained from different researchers across the globe
have shown that non-edible feedstock have the following advantages with
respect to biodiesel production [68].
1. Non-edible feedstocks can be cultivated in marginal land

and non-agricultural lands.
2. Non-edible sources do not contend with available agricul-
tural resources.
3. They do not threaten food security because they are inap-
propriate for human consumption due to the non-toxic
components they contain.
4. Most of the non-edible feedstocks are free from pests and
diseases.
5. Oils obtained from non-edible feedstocks are readily avail-
able, renewable, and biodegradable, with low sulfur and aro-
matic contents.
6. Non-edible feedstocks produce useful by products. For
example, the seed cakes obtained after oil expelling can
enhance soil enrichment.
7. Most non-edible feedstocks have a considerable amount
of short-chain fatty acids, which gives special features to
biodiesel.
8. They are more eco-friendly than non-edible feedstocks.
9. Non-edible feedstocks can be cultivated in wastelands that
are not ideal for human food crops.
10. They have the potentials to restore degraded lands and cre-
ate job opportunities.
10.10 Economic Importance of Biodiesel Production

Capital cost, raw materials cost, process technology, plant capacity, and
chemical costs are key economic factors in biodiesel production. Of all,
the cost of feedstocks alone is equivalent to 80% of the total production
cost, while the cost of catalyst, methanol, and utilities are equally import-
ant [69]. For instance, it costs 0.82 USD/litre to make biodiesel from palm
oil including the feedstock price of 0.73, while it takes 0.6 USD/litre to pro-
duce the same biodiesel from tallow fat including the feedstock cost of 0.4
USD [70]. Most importantly, biodiesel production helps to boost economy
in both developing and developed countries by creating job opportunities

for the rural community, minimizing greenhouse gas emissions, boosting
income tax revenue, and reducing country’s over dependence on crude
oils. Recently, the use of non-edible feedstocks that do not contend with
the food crops is a reasonable way of improving biofuel production.
In terms of socio-economic effects, biodiesel, a sustainable and renew-
able energy source, is good substitutes for petroleum fuels. Hence, they can
help to reduce greenhouse gases that bring about global warming, promotes
regional development, and boosts food security and supply. Biodiesel also
have health, environmental, safety, and other benefits in addition to eco-
nomic advantages [3].
10.11 Conclusions
In this chapter, we discussed the production pathways of biodiesel from
non-edible feedstocks, with respect to their benefits, up-to-date technol-
ogy, properties of the fuel produced, the economic benefits, and the envi-
ronmental concerns which provides some key conclusions.
Different methods can be used to produce biodiesel from oils. These
include pyrolysis, dilution, micro-emulsion, and transesterification.
Among these, the most economically viable is transesterification and the
produced biodiesel compares favorably with the petroleum-based biodiesel
Choice of feedstocks is a crucial factor in the synthesis of biodiesel.
Based on the various feedstocks, non-edible oils, algal oils, waste animal
fats, and WCOs are promising sources for biodiesel production.
Production of biodiesel from non-edible sources has become attractive
because they are renewable and sustainable source that guarantees food
security, improves local economy, and reduces pollution.
Of the various costs of biodiesel production, the feedstock price is almost
80% of the total production cost. A better way of lowering the cost of bio-
diesel production is to develop technology that will make use of bye products
and makes judicious and favorable choice of the feedstocks. The biodiesel
made from non-edible sources meet internationally recognized standards.
Acknowledgments
The authors are grateful for the financial support provided by the
University of South Africa (UNISA), University of the Witwatersrand,
National Research Foundation (NRF) of South Africa, and the Institute for
the Development of Energy for African Sustainability (IDEAS) research

unit at UNISA.
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11
Oleochemical Resources for
Gayathri R., Ranjitha J. and Vijayalakshmi Shankar*
CO2 Research and Green Technologies Centre, VIT University,

Vellore, Tamil Nadu, India
Abstract
Oleochemicals are materials composed of high energy molecules made up of tri-
glycerides (lipids) with more than 96% present inform of MG, DG, and FFA. The
energy produced when the oleochemicals heated is nearly 91% close to diesel fuel.
The major difference between the oil of fossil fuel and plant oils is due to variation
in the percentage of oxygen present in it. The direct usage of triglyceride in diesel
engines is possible but it causes lot of problems as result of reduced volatile, thick-
ness, and its properties in cold flow, which will be rectified by improving the prop-
erties of plant oil. Non-edible feedstocks including AFW have recently gained high
interest due to the quality of biodiesel produced from them and they are low cost,
eco-friendly, with reduced emission of NOx and properties such as high cetane
number and oxidative stability. Oleochemicals can be used to produce three major
biofuels which includes biodiesel, bio-oil, and renewable diesel. The advantages
of renewable biofuels are that they are similar to fossil fuels but eco-friendly with
reduced emission of greenhouse gases.
Keywords: Oleochemicals, plant oils, animal oils, biodiesel production,

optimization, purification, biodiesel properties
11.1 Introduction
Biodiesel (FAME/FAEE) is an alternative, inexhaustible, and green energy
resource than fossil fuels in order to meet the energy crisis. Utilization of
*Corresponding author: vijimicro21@gmail.com
311
fossil fuel results in the elevated emission of environmental pollutants/

contaminants including nitric oxides, sulfur oxides, and carbon monoxide
and other toxic volatile organic compounds which are the major causes for
deforestation, depletion of ozone, global warming, photochemical smog,
and Eutrophication of aquatic ecosystem. The amount of the emitted envi-
ronmental pollutants/contaminants can be highly reduced by replacing the
fossil fuel with biodiesel [1].
There are variety of raw materials/feedstocks available for the produc-
tion of biodiesel which include first-generation feedstock mainly focusing
on food crops, second-generation feedstocks are materials that are pro-
cessed form of first-generation feedstock such as derived products of plants
and animals in form of vegetable oil and lignocellulosic materials, animal
products including fat, oil, waxes obtained from tallow, and dairy products.
These second-generation residues are categorized into four groups. Primary
residues are materials obtained while cultivating the desired plants and in
the forest. Secondary residue comprises of intermediate and by-products
formed during the processing of food crops into their final products (e.g.,
food processing waste). Tertiary residue includes the final products result
from the derivative products of biomass available only after its consumption
by humans or animals in form municipal solid waste (MSW) that are fur-
ther subjected waste water/sewage treatment for proper disposal. The last
group involves the utilization of algal biomass. Third-generation feedstocks
are materials with high carbon content utilized for biodiesel production and
also include chemical and enzymatic conversion of algae [2].
Utilization of used waste frying oil (WFO) for FAME synthesis through
process of recycling is a potential and eco-friendly technique. This tech-
nique gives promising results in the yield of biodiesel ranging from 60% to
90%. The yield can be increased up to 95% by adjusting some physiochem-
ical and biological parameters during the process of production and sim-
ple pre-treatment before subjecting it for biochemical reactions [3]. This
method is economically feasible by cutting down the production cost up to
60%–70% [1]. This method is an eco-friendly technique which involves the
proper disposal of waste cooking oil (WCO) that is unpalatable because of
elevated level of FFA [4]. Recycling of the WCO is subjected for oleochem-
ical production [2].
11.2 Definition of Oleochemicals

Chemicals produced from natural oils and fats are called oleochemicals.
From the overall production of oils and fats (around 105 million), 80% is
Oleochemical Resources for Biodiesel Production 313
used for human consumption, 5% for animal feed, and 15% for chemical
production. For industrial production of chemicals every year 16 million
tons of fats and oils were utilized. There are two categories of oils-lauric
oils (e.g., coconut and palm kernel) with rich carbon chains involving of 12
and 14 linked carbon atoms, and (tallow and palm) with 16 and18 carbon
atoms. Rapeseed, soybean, and sunflower oil are also used for oleochemi-
cal production [5].
Oleochemicals are typically derived products of fatty acids (FAs) and
glycerol obtained through variety of chemical/biological reactions in
which separation of the triglyceride (TG) structure of oil and fats occurs.
Oleochemicals can also be synthesized from FA through modification of
their carboxylic group. The basic oleochemicals include FA, FAME, fatty
alcohols, fatty amines, glycerol/glycerine, and products obtained by hydro-
genation of FAME and fatty alcohols. Fatty chemical derivative such as
methyl ester (ME) and FAs plays a major role in the field of oleochemistry
and oleochemical-based industries [6].
11.3 Oleochemical Types

There are five different types of oleochemicals which includes ME, FAs,
fatty alcohol, fatty amines, and glycerol. FA is a lipid molecule made up of a
long fatty chain combined with a carboxyl group at the end. FAs are present
in two forms, the saturated (absence of double bond) and unsaturated FAs
(presence of double bond) based on the types of bond present in that FA
chain. Lipids such as fats and oil are made up of TGs (single glycerol mole-
cule bounded with three FA chains) and these TGs can be split into FA and
glycerol by hydrolyzing the oil/fat and then subjecting it for further reac-
tion under high temperature, pressure, or lipase catalyst under 37°C with
controlled pressure and stirring speed. The TGs present in oils and fats
are converted into ME by a process called methanolysis. The process was
illustrated in Figure 11.1. When oil/fat is subjected to react with methanol
and catalyst, the FAs get detached from the glycerol and bond with meth-
anol thus resulting in a compound called MEs and glycerol is recovered as
by-product. MEs are reported to be superior than FAs for production of
various FA derivatives. Fatty alcohols are long-chain high molecular weight
primary alcohols derived from oil and fats (lipids). They are produced by
methanolysis process in which the esters react with alcohol after the for-
mation of ME. Fatty amines are derivative products of fatty alcohol and
FAs. The production of primary amines is gradually declining, but there
is an increased utilization and demand for secondary and tertiary amines.
Animal
products
Edible
products
Fish industry Poultry

Cattle and sheep products
waste products
Crushing process
Wet
crushing Dry crushing
Pressing
Separation of solid and

liquid materials
Rendering process
Evaporation of
liquid
solid waste of solid waste solid waste of

Chicken fat of chicken cattle/sheep
fish
Fish oil and Protein meal Pet feed and

Protein meal tallow
Fish oil, tallow, chicken

fat usedas feedstock for
biodiesel production
Figure 11.1 Process flow of methyl ester production from animal fat.
They are used as biocides, mineral oils, corrosion inhibitors, in the oil field
as additives (demulsifiers), used in textiles, fibers, industrial dyes and pig-
ments, soft detergents, softening agents, and also used in the following
fields, as anti-cracking agents for road construction, etc. Fatty amines con-
taining ca. 25% are used as anti-cracking agents and ca. 75% derived product
are used as conditioning agents in cosmetics, amine oxides, and amine-
EO-adducts [7]. Glycerine occurs as a by-product when oil/fats are sub-
jected for any reactions in which water (hydrolysis), methanol (meth-
anolysis), and acid/base catalyst (saponification) takes place, this due to
breaking of glycerol from FAs. Glycerine is primarily used for its viscosity
and moisture retaining capacity [1, 4–8].
11.4 Production of Biodiesel

The synthesis and utilization of FAME have created a great interest in the
financial investment and implementation of biodiesel production plants
among various countries. Based on the report of the European Biodiesel
Board, the production of Biodiesel by the European Union in 2011 was
24.7 × 109 L yr−1 and 4.16 × 109 L yr−1 by the USA in 2011 [4]. The amount
of biodiesel produced by Canada has increased twice when comparing its
annual production in 0.210 × 109 L yr−1 (2012) and 0.471 × 109 L yr−1 (2013)
[20]. In USA, Europe, and Canada, the biodiesel was produced from rape-
seed oil, soybean oil, and canola oil with low content of erucic acid [9].
There is an increased demand for production of biodiesel in Malaysia,
Canada, Europe, USA, and China. So, in order to meet the demand, there
is a need for use of rendered oils, palm oil (Elaeis guineensis jacq.) and
rendered animal fats. The animal fat was classified as feeds by the interna-
tional market, and their price become low. Hence, the cost of biodiesel will
be extremely lowered by the AFWs to increase the production of biodiesel
to compete with Petro-diesel.
The various feedstocks to produce ME include animal fats and vegeta-
ble oils both edible and non-edible oils [10–14]. The two major limiting
factors involved in the use of various substrates for the production of bio-
diesel are their obtainability and price. The industries store their feedstock
which serves as a limiting factor for sustainability of biodiesel regardless of
their current growth. There are limitations in the sustainability of biodiesel
production regardless of its current growth is due to inefficiency of the
industries to safely store their cheapest feedstocks. The chief source for the
production of FAME in Canada is Canola oil. The feedstocks used by USA
and Europe is edible vegetable oil but this leads to an increased demand for
vegetable oil supply that will result in food security, ethical issues, and pro-
voke worldwide arguments regarding the level of effect on the diversity of
food crops at global level. This could be sought by replacing the feedstocks
that produce good quality biodiesel with low capital cost and not a threat
to food safety [15].
The feedstocks that can be used to avoid such issues include chicken fat,
tallow, lard, and solid waste materials produced in leather industry, etc.
In some regions, the animal fat waste (AFWs) are abundant that result in
lowering the cost of feedstocks. The advantage of using waste animal fat for
producing biodiesel is that it emits NOX which will be below or equal to
vegetable oil biodiesel with a reduced amount of environmental pollutant
and thus preventing environmental damage. Quality of the produced diesel
fuel is determined by the cetane number. The ratio of saturated FAs is high
in AFWs which is the major reason for high cetane number (460) when
compared with most of the vegetable oils. The advantage of high cetane
number is that it reduces the temperature during the early combustion
process resulting in low NOx emission. The presence of saturated FA in
the AFWs is responsible for better oxidative stability of biodiesel [16–19].
There is a huge challenge in producing biodiesel by alkali-catalyzed trans-
esterification because of the presence of more free FAs in AFWs. Efficiency
of the biodiesel is based on the techniques involved during the construction/
development of the biodiesel plant. Chemical and biological techniques are
the two important techniques currently used for the synthesis of FAME
from plant oil and animal fats. Synthesis of biodiesel using chemical tech-
niques includes acidic or basic catalytic conversion reactions. Enzymatic
conversion of biodiesel takes place in biological technique. Lipase enzyme
is mainly used in biological techniques. Other than these two techniques,
the use of other techniques such as non-catalytic and superficial tempera-
ture conversion methods is still under the process of investigation. Even
though chemical-based biodiesel production is widely used in industrial
scale, they have certain limiting factors such as high energy, equipment, and
alcohol requirements, and the downstream and purification process was
complex. Through enzyme catalyzed transesterification process, there is an
advantage of overcoming a specific limitation in producing diesel with the
feedstock having low FFA content and moisture that are required for chem-
ical techniques. Development of high molar ratio of animal fat and soap
required for production of biodiesel during which chemical-based catalysis
will be comparatively low in the biological method. Enzyme immobilized
techniques made the lipase enzyme reusable and developed high alcohol
tolerant lipases; thus, this technique become cost efficient by overcoming
the inactivation of enzyme lipase and its higher cost [15, 20].
There are many new techniques emerging for biodiesel production

which involves many treatments for maximum yield with the reduced
reactor operating time. The microwave-assisted (MA) transesterification
and ultrasound-assisted (UA) transesterification are the two major emerg-
ing techniques for biodiesel production. The use of cheap reagents, short
reaction time, and simple process reactors created a great interest in the
UA techniques for biodiesel production. There is also a positive approach
toward MA technique due to its great energy efficiency, improved yield,
short reaction period, and highly purified products [15].
11.5 Types of Feedstocks

11.5.1 Non-Edible Feedstocks
There is a global demand for edible oil and animal fat due to increased pop-
ulation and resulted in elevating their price on the world market that many
developing countries had limited the utilization of plant oil and animal
fat as fuel. Several studies stated that grease and fat obtained from animal
source waste are feasible, good, and eco-friendly feedstocks for FAME pro-
duction. These materials are easily accessible in many developing countries
through placing order in units of teragrams. There is a worldwide availabil-
ity of non-edible oil plants. But there will be a problem leading to strong
debate due to the inaccessibility of land for food crops vs. non-edible oil
crops [15].
11.5.2 Non-Edible Vegetable Oil

Oil from non-edible sources for synthesizing biodiesel from Oleagnious,
Leguminosae, Brassicaceae, and Euphorbiaceae have been under several
investigations in recent years. These plants produce oil-rich seeds but their
high FFA level made them toxic and inedible for both animals and human
consumption. The use of non-edible oil can directly gain opposition with
respect to safe and availability of food. Pongamia, Jatropha, Brassica,
Madhuca, Gossypium, Cerbera, Nicotiana, Thevettia, Ricinus, and Hevea
sps are the common non-edible crops used for the production of biodiesel.
The non-edible plants used for the research of biodiesel production and
their cultivation varies according to its place of growth. For example, sev-
eral types of researches mainly concentrating on oleaginous microorgan-
ism for lipid-based biodiesel feedstocks are currently going in the USA,
Canada, and EU [15].
11.5.3 Tall Oil

Tall oil is the secondary product produced by wood pulp industry. It con-
tains 42% resins and 45% of FAs. Distillation method is used to separate
the resin and FAs which are present together and only in the form of free
acids [21].
11.5.4 Waste Cooking Oils

There is no direct opposition for the usage of WFO as a source for biodiesel
concerned with land usage and availability of food. Yellow grease and brown
grease are the two groups of waste cooking or frying oil (WFO). WFO is
highly concentrated with grease after cooking bacon, meat appetizers, and
hamburgers, and this is due to the method used for the extraction of cook-
ing oils. Since the cooking oil is extracted by the melting of fat obtained
from AFW and heating of vegetable oil that is used for cooking various
foods including meat, fish, and vegetable oils. This is the major reason for
the formation of grease after cooking. WFO collected from the restaurant or
industrial operations with the presence of less than 15% of FFA in the grease
produced from WFO, fats, and oil act as feasible potent and inexpensive raw
material for biodiesel production. Restaurants and industries involve the use
of grease trap to collect brown grease in order to separate oil and grease from
the wastewater for municipal sewage facilities. Grease traps allow floating
of light grease and oil at the top of the trap when flushed in the drain and
thus facilitating the free flow of wastewater into the water treatment unit.
Difficulties in the potential conversion of biodiesel from brown grease with
greater than 15% FFA are due to the presence of H2O content in it. The tech-
niques used for conversion of biodiesel from WFO include various types
of transesterification process such as acid-catalyzed transesterification, alka-
line-catalyzed transesterification, two-step transesterification, enzymatic
catalysis, and supercritical temperature processing methods. Heating virgin
oils for long duration leads to higher FFA concentration of FFA in WFO.
Biodiesel yield from WCO is lowered and involves a complex downstream
process during the separation of ME, C3H8O3, and washing H2O, and this is
due to the saponification reaction taking place when the alkaline catalyst acts
on FFA during the alkaline transesterification process [15].
11.5.5 Animal Fats

The by-products of processed and rendered animal meats from facilities are
the primary source used for deriving fats from animals. From cattle processing
facilities and rendering process, tallow can be obtained; grease and lard can
be obtained from processing the pork, and poultry fat can be obtained from
chicken and other birds processing; oil fish industry and waste from leather
industry are the major animal fats used for synthesis of FAME. Chicken, tal-
low, and lard fats are some of the animal fat-based feedstocks used for large
industrial scaled biodiesel production. Compared with edible plant oils, AFW
used as feedstock for FAME production have economical environmental and
food security advantages. Production of FAME from AFWs involves complex
techniques when saturated FAs (FFA) is present at a high level, and the result-
ing biodiesel will have low chemical and physical quality. There are certain
advantages in low unsaturated FAs of AFWs such as increased cetane num-
ber, increased oxidation stability, and increased calorific value [15].
11.5.6 Chicken Fat

During the feather meal preparation, the chicken fat can be produced.
Head, intestine, undeveloped eggs, and feet other than feathers are clean
carcass available in poultry by-products found in different portions of wet
rendered or dry grounded forms. Based on the type of feather used, the fat
thus obtained varies from 2% to 12%. Biodiesel has been produced by Guru
et al. (2010) [66], with fat from chicken using catalytic process which con-
tains two steps involving catalyst such as CH3OH, H2SO4, and NaOH. The
effects on performance in engine and exhaust emission when injected in a
diesel engine with produced biodiesel from synthetic Mg additive chicken
fat have been reported by the author. The decrease in the viscosity (5.184
to 4.812) and flash point (129°C to 122°C) due to rise in concentration of
Mg have been reported by the author. There was a decrease of 7°C pour
point in the chicken fat ME with the addition of Mg. Yield of ME was about
87.4% when the conditions for animal fat was optimized by pre-treatment.
When converting chicken fat into biodiesel the point at which best TG
conversion and glycerol decomposition were obtained at 400°C, 300 bar
pressure, 9:1 molar ratio, with 6-min time [15].
11.5.7 Lard
Rendered fat of pig is termed as lard. Dry or wet process is used for render-
ing the pig fat. Wet rendering involves high temperature boiling of pig fat in
water/steam and the insoluble lard is formed as an upper layer in the mix-
ture which is skimmed off or centrifuged. Pig fat is subjected to higher heat
treatment in the absence of water in oven or pan. These two processes result
in the yield of two different products. Lard with a neutral flavor, light color,
and high smoke point can be obtained from the process of wet rendering
process and dry rendering results in lard production with brown color and
low smoke point. According to Dias et al. [67] on the generation biodiesel
by acid transesterification, the lard was pretreated with KOH to enable it
to be a potential feedstock for FAME production with suitable quality but
the yield is low with only 65% by weight. The yield of biodiesel from waste
lard and WFO ranges from 81.7 to 88.0 (wt.%) has been reported from the
investigation done on the synthesis of FAME from mixtures of WFO; thus,
the yield is low when only WFO and lard have been used as raw materi-
als. Investigations have been done on the conversion of biodiesel from lard
using the Candida sp. (fungus) as a biocatalyst in transesterification process
shows the optimal condition for the reaction in order to process a gram
of lard involves immobilized lipase (0.2 g), 8-ml n-hexane, a ratio of 20%
of water to the weight of fat, 40°C and adding CH3OH produced 87.4% of
FAME. This investigation gives a detailed report about the effect of biocata-
lyst used in transesterification of lard involving the parameters such as tem-
perature, water content, the quantity of enzyme used, solvent, in three-step
methanolysis process for biodiesel production. The ME production was
directly affected by the concentration of catalyst used and agitation speed,
and the optimal agitation speed is found to be 600 rpm found in a regression
model used to the predict concentration of ME with sufficient experimental
parameters. According to the experiment of Shin et al. [68], on production
of biodiesel with lard without pre-treatment and using the technique with
supercritical without adding the catalyst under optimal reaction conditions
produced biodiesel which is similar to biodiesel synthesized from refined
lard, although it has free FA and water in it [15].
11.5.8 Tallow
Animal by-products from slaughter house can be rendered to produce fat and
protein meal. More than 50% of FAs in the tallow are in saturated form. The
high melting point and viscosity is because of the presence of palmitic and
stearic acid in the tallow leads to makes it solid at room temperature. Edible
or non-edible tallow are derivatives of beef or mutton which are mostly used
to produce FAME. For alkaline transesterification reaction process, edible
tallow acts as a potential substrate having low FFA content. Biodiesel pro-
duction from beef tallow that was studied and reported conclusively stated
that tallow from beef obtained from cattle house remarkably acts as an inex-
pensive feedstock for FAME production with an immense energy, along with
economic and environmental advantages and this report also included the
economic feasibility, energy efficiency, and resource availability of beef tallow
and its conversion into biodiesel. The yield of FAME from edible tallow and
the effect of catalyst, FFA, water content, and mixing intensities have been
investigated by Ma and Hanna and reported that reaction takes place only
when NaOH and CH3OH were added and mixed with melted beef tallow
with limited stirring speed and also stated that higher stirring speed for a lon-
ger period is required to mix the two phases when a blend of sodium hydrox-
ide and methanol solution is added before stirring the melted beef tallow.
Biodiesel production from non-edible tallow requires highly expensive pro-
cessing methods, which leads to higher FFA. Viability of FAME conversion
from inedible tallow has also been reported. Based on the report of Bhatti
et al. (2008) [69] and their studies on biodiesel production, its reaction param-
eters for the conversion of 5 grams of tallow waste are 60°C, 1:3 molar ratio,
and addition of sulfuric acid (2.5g) [22]. Oner and Altun (2009) have done an
experiment in which they directly injected the biodiesel produced from non-
edible tallow in a diesel engine and studied its emission and performance.
This experimental report clearly shows that there was a significant decrease
in the emission of carbon monoxide (15%), NOX (38.5%), sulfur dioxide
SO2 (72.7%), and smoke opacity 56.8% for ME (B100) from tallow [23].
Teixeira et al. (2009) did a comparative study on FAME production from
beef tallow by using ultrasonic and conventional method and reported that
only the time for reaction is reduced but the reaction rate and quality of
biodiesel remained the same for both. Kumar et al. (2013) [24] reported the
effect of enzyme ns88001with CH3OH and n-hexane used as solvent. This
report shows that n-hexane reduced the toxicity of alcohol by stabilizing the
enzyme and the NS88001-enzyme is reduced a little bit after 10 cycles [25].
Immobilized PS-30 lipase enzyme used for transesterification of Primary
alcohol (methanol) resulted in the effective conversion of biodiesel ranging
from 82% to 94% when compared with free lipase enzyme with low conver-
sion efficiency ranging from 47% to 89%, and ME showed poorest yield [15].
11.5.9 Leather Industry Solid Waste Fat

Leather industry generates huge amount solid waste fat during various
processes. This fat remains solid at room temperature with high H2O con-
tent in it. The water content is eliminated by treating the fat at 110°C for
1 hour and insoluble materials are removed by filtering it. A study [26]
experimentally proved the utilization of these fuels in engine (without any
modifications) and synthesized from the fat produced in tannery flesh-
ing waste. The reaction parameters were studied by Isler et al. (2010) [70]
which includes molar ratio (1:6), weight percentage (0.75%), and cata-
lyst and temperature for production of ME from raw fleshing oil through
base-catalyzed transesterification reaction and found that the efficient bio-

diesel yield can be achieved 1:6 molar ratio, temperature (50°C), 0.75 per-
centage weight of catalyst, and time of reaction is about 15 min. Evaluation
of FAME production from leather industry waste as feedstock in alka-
line catalyzed transesterification reaction was reported by Alptekin et al.
(2012) [27]. Property of produced ME met the biodiesel standard, and to
enhance the cold flow property or cold flow, enhancers can be added to
it. Supercritical CH3OH approach in transesterification of leather tanning
waste for production of FAME was first applied by Ong et al. (2013) [65].
A model was developed by the author for the kinetic reactions of FAME
production from leather industry waste [15].
11.5.10 Fish Oil

FAME can be produced from oil-rich waste obtained in a significant
amount during the processing of fish from the fish processing industry.
Large fraction of the effluent contains oil (6%–11%) will be utilized as a
feasible feedstock for FAME production with good yield can be obtained
with proper separation techniques. Recovery of fish oil from the effluent
involves the following methods such as grinding/homogenizing of solid
fish waste followed by heat treatment for 15–20 min at 95°C–100°C, screw
pressing of the solid waste to remove liquids, centrifugation of the liquid
to separate oil and remove wastewater, and final polishing of oil by water
washing. Colak et al. (2005) [26] investigated production of FAME with
fish oil and reported that catalyst concentration gives greater yield and
quality of biodiesel. This report shows that optimum condition for bio-
diesel production is 1 wt.% catalyst and 60 vol% of CH3OH solution. Waste
characterization and quality assessment of fish processing plant effluent for
FAME production have been investigated by Tanwar et al. (2013) [28] and
Jayasinghe and Hawboldt (2013) [29]. The major factors which determine
the suitability of the transesterification technique for FAME production
are the type and quality of the feedstock used.
11.6 Uses of Oleochemicals

11.6.1 Polymer Applications
Linoleum is produced from the linseed oil. The demand for linoleum has
been increased from 10,000 tons to 50,000 tons from the year 1975–1998.
Epoxidized soybean oil is used for plastic and coating additives, and the
production is around 100,000 tons/year. Industrial production of dicar-

boxylic acid involves ozonolysis of oleic acid to produce diacids [4].
Hydrocarbons and chlorinated compounds are used in large volume as
solvents for coating and other various polymer applications. Ester solvents
are the largest groups representing the Green solvents naturally obtained
from the FAs and alcohols [5].
11.6.2 Application of Plant Oil as a Substitute for Petro-Diesel

Ground nut was used as a fuel for demonstration in 1900 [30]. In 1930s and
1940s, experimental work has been done with plant oil in diesel engine.
Due to depleting non-renewable energy and fuel energy crisis during the
year 1970–1980 lead to the development of alternatives to petroleum-based
fuels. This gives rise to many investigations in finding various alternatives
for Petro-diesel and resulted in the production of biodiesel. Currently, bio-
diesel have become commercial and have a global level demand. Several
plant oils were investigated for the production of FAME. FAME produc-
tion will be determined upon availability of substrates such as palm oil,
coconut oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, and some
vegetable oil used for cooking. Plant oil directly in diesel engine is still
problematic because of its high viscosity; further development is needed to
overcome this problem. Following techniques can be applied to maximize
the quality of the fuel from plant oil which includes dilution of oil from
plant (25 parts) with Petro-diesel (75 parts). The physiochemical prop-
erties of biodiesel (FA esters) are similar to Petro-diesel. The production
process is simple and the burning efficiency of methyl or ethyl ester of FA
in diesel engine does not require any modifications. When compared to
microemulsion and dilution techniques, transesterification is a best choice
for biodiesel production [5].
11.6.3 Used as Surfactants

Oleochemicals are used as surfactants used to bring two different types of
compounds together. Oleochemicals with FA chains or long-chain alcohol
are used for this purpose. Oleochemical used as surfactant involve com-
pounds such as bio-based hydrophiles including amino acid [31], poly-
saccharide, and FA chains with carboxylate groups. Bio-based surfactant
should have its hydrophobic or hydrophilic group to be derived. Group
of bio-based surfactants includes oleochemical-based fatty esters that are
used as hydrophobe group to combined with ethylene oxide as hydrophile
group. Carbohydrates were used as hydrophilic group of surfactants for
more than half of a century. Carbohydrates such as sorbitol (lignin, lecithin

to sugars) are used surfactants. Some surfactant has both the hydrophilic
and hydrophobic groups to be bio-based such as sugar and FA, which
is beneficial in case of SpanTM 60. Glycerol produced in excess during
biodiesel production can be used as a cheap material for the bio-based
surfactant production as a precursor. Polymers of glycerol such as such
as polyglycerides act as good hydrophobes. Surfactant with polyglycerol
properties will be produced either from compound contains epoxide such
as glycidol or by polymerization of glycerol. The utilization of surfactants
involves various fields. The most important field where more than 50% of
surfactants used includes washing and cleansing sector, textile treatment,
and cosmetics. Other fields such as mining, protection of crop, paints,
coatings, inks, and adhesives also involve the application of surfactants [5].
11.6.4 Oleochemicals Used in Pesticide

Plant-based oils and fats act as an important raw material for chemicals
industry [32]. Plant-based oleochemicals are more advantageous than min-
eral oil that they are renewable, biodegradable, and widely available (by-
products from industries). Pesticide formulation is mainly composed of
two major components such as inert and active ingredients [33].
11.6.5 Oleochemicals Used in Spray Adjuvants and Solvents

Oleochemicals have been used as spray adjuvants due to their high adher-
ence capacity to the leaves of plants or insects. The polyunsaturated nature
of this plant oil made them persistent on leaves and insects even after rain-
fall. Palm olein in liquid fraction from palm oil also used as spray adjuvants.
MEs and hydrocarbons act as potential vehicles for transporting pesticides
on the surface of plant and insects. This is due to high viscosity and surface
tension of methyl eater and hydrocarbons. They are biodegradable with
less toxicity and less viscous with better solvency. The solvency property to
pesticide is better in ME produced from plant oils [5].
11.7 Methyl Ester or Biodiesel Production

Biodiesel (ME) from plant oil and fat resulting with the glycerol release
[15].
Conversion of plant oil into biodiesel includes TGs’ reaction such
as methanol with catalyst resulting in FAME and C3H8O3. Initially, in
transesterification process, the TGs are converted into DG followed by

a series of reactions involving larger glycerides converted into smaller
glycerides and finally into glycerol (Figure 11.2), with one ME molecule
at the end of each steps of the subsequent reactions [10]. In this revers-
ible reaction, the equilibrium is shifted toward the product side by using
excess alcohol [15]. Solubility of alcohol will be improved by the catalyst,
thus result in increasing the reaction rate and yield. Utilization of catalyst
depends upon the substrate and content of free FA. The FFA and H2O con-
tent should be below 0.5 and 0.05 wt.%, to prevent saponification during
the reaction [34]. FFA can be converted into FAEE through esterification
reaction as a pre-treatment process for effective conversion of oil into
biodiesel [35]. The TG and DG can be hydrolyzed into FFA using water.
Temperature is an important parameter influencing the rate of reaction,
which is fast when the temperature is high [36]. Many techniques were
used in the transesterification reaction which includes the usage of cata-
lysts of heterogeneous type (e.g., magnesium oxide, calcium oxide, and sul-
fated zirconia) [35]. BIOX process is also a noncatalytic transesterification
method used for ME production from WCO, animal fat, and vegetable oil
[7, 37–39]. For transesterification process, the WCO has to be pre-treated
Step 1
Esterification
feed stock oil extraction
(pre-treatment)
Step 2
Transesterif ication • addition of methanol/ethanol
Ester recovery • release of by-product (glycerol)
Biodiesel
FAME/FAEE
Figure 11.2 Production of biodiesel by transesterification reaction. Step1. Pre-treatment

of oil to treat FFA and water through esterification reaction. Step 2. Transesterification of
pre-treated oil to produce fatty acid methyl ester/ fatty acid ethyl ester (biodiesel).
due to presence of high FFA (0.5%–15%) content for proper conversion

and yield [36].
11.7.1 Palm Oil

Acidic crude palm oil (ACPO) can be utilized as potential substrate for
the production of ME production. Cost for production can be lowered
by using the by-products of APCO [40]. The catalyst commonly used for
the pre-treatment of acidic oils in esterification reaction includes sulfu-
ric acid—conventional catalyst [41] (lipase-biocatalyst, Ferric sulfate-
heterogeneous catalyst (widely used). Ethane sulfonic acid is a catalyst used
for treating high FFA content in industrial ACPO by [41] for esterification
process. Methane sulfonic acid (MSA) is a catalyst used for pre-treatment
of FFA in APCO by (Adeeb Hayyan et al., 2012) [40].
Materials used in this reaction are APCO, CH3OH 99.8 %, potassium
hydroxide pellets 85%, and MSA. Before starting the esterification reac-
tion, the ACPO has to be melted at a 65°C. Then, the FFA content was
measured and reported. For FAME production, 200g of ACPO was taken
for each experiment in which both transesterification and esterification
reactions were involved. Conversion of FFA into FAME through ester-
ification reaction is a preliminary stage. There is a high yield of FAME,
and enhanced esterification reaction due to addition of MSA catalyst was
observed by Adeeb Hayyan et al. (2012) [40]. The liquid phase of APCO
and MSA were found to be responsible for enhanced esterification reac-
tion. It also converted triacylglycerols (TAGs) into FAMEs. In the second
reaction, the TAG is converted into FAME by using KOH as a catalyst [40].
11.7.2 Sunflower Oil

Production of ME from sunflower oil by alkali-catalyzed transesterifica-
tion reaction was done by Umer Rashida et al. (2008) [42]. About 500 g
of sunflower oil was preheated for setting the temperature that ranges from
(30°C, 45°C, or 60°C) [43] with known catalysts and mixed well. Each
experiment was subjected for 120 min at 600 rpm. Different molar ratio
was used including 3:1, 6:1, 9:1, 12:1, 15:1, and 18:1 [44]. The sunflower
oil methyl oil (SOME) was purified by distillation around 80°C in which
the left out methanol is removed by subsequent washing with distilled
water and Na2SO4 along with filtration. The unreacted catalyst is treated by
neutralization with concentrated sulfuric acid and decomposition of soap
formed during the reaction. Methanol is recovered by vacuum treatment
under 80°C to purify the C3H8O3.
Results reported from this experiment were mentioned in the following:

In this experiment, temperature variation has no significant effect on bio-
diesel yield. After the reaction was completed, it is more than 80% without
the influence of temperature change. The yield was reported to be 97.1% at
60°C, 92.8% at 45°C, and 90.9% at 30°C, and this indicates the efficiency of
base catalyst to be high nearly to the boiling point of alcohol. Different con-
centrations of NaOH (0%, 0.25%, 0.50%, 0.75%, 1.00%, 1.25%, and 1.50%
w/w) [45] were used among four different catalysts in same experimental
conditions mentioned above, and the yield was found to be 97.1% at a con-
centration of 1.00% NaOH. Six different molar ratios were used in each of
the experiments ranging from 3:1, 6:1, 9:1, 12:1, 15:1, and 18:1, and 97.1%
was found at 6:1. This experiment shows that the optimal reaction condition
for the production of ME from sunflower oil through transesterification was
found to be at 60°C,6:1, concentration of catalyst 1.00% with 97.1% yield.
11.7.3 ME From AFW

Production of ME from various animal fat sources was explained in Figure
11.3. Guru et al. (2010) [66] reported the production of FAME from
chicken fat. They reported that yield of biodiesel to 87.4% with an opti-
mal reaction condition of 20% H2SO4 at 40:1 methanol molar ratio with
13.45% FFA in chicken fat was subjected to reaction for 8 min at 60°C. The
yield of FAME was 88% when the lard was subjected under the following
reaction conditions: 1-g lard, with 20% H2SO4 based on weight of the fat,
0.2g of immobilized lipase catalyst, and 8 ml of n-hexane. The ME yield
was reported to be 93.21% when 5 g of mutton tallow was treated with 2.5g
of H2SO4 at CH3OH molar ratio of 1:3 for 24 h under 60°C [15].
11.8 Parameters Affecting the Yield of Biodiesel

11.8.1 Reaction Conditions
The production of FAME can be affected by the reaction conditions such as oil
to alcohol ratio, temperature, catalyst concentration, and type of reactor used.
11.8.2 Catalyst
11.8.2.1 Alkali Catalyst
Saponification reaction reduces the FA yield and forms emulsions which
cause difficulties in glycerol and biodiesel separation. Singh et al. reported
Seed storage
Removal of cortex
(Decortication)
Size reduction by flaking
Breaking of seeds
Pre-expelling of
crude oil
Solvent extraction
Oil cake or oil meal Crude oil
Oil storage
Refining of oil
Figure 11.3 Process of extraction of vegetable oil (e.g., sunflower seed oil extraction
process).
that better yield was obtained when hydroxide catalysts is replaced with
methoxide catalysts and sodium-based catalysts replaced by potassium-
based catalysts [46].
11.8.2.2 Acid Catalyst

There is a slow reaction rate when acid catalyst is used and it requires more
TGs and high ratio of alcohol; hence, they are usually a best choice for
feedstock pretreatment with maximum FFA where conversion of soap into
ester is required [15].
11.8.2.3 Biocatalyst
Lipase immobilized transesterification is a very slow process and requires
more reaction time and temperature ranging from 4 to 40 h and 35°C
to 45°C, respectively. But, this process gives promising results only for
feedstocks containing high FFA contents. The FA ME produced by using
various strains of fungus Aspergillus sp. has been reported to have high
biodiesel properties (lubrication and fuel properties) [47].
11.8.2.4 Heterogeneous Catalyst

CaO and Ca(OCH3)2 are usually used heterogeneous catalyst for biodiesel
production. Slow reaction is seen due to low mass transfer ability and
requires a co-solvent with a boiling point similar to methanol for enhanced
mass transfer among the reactants and thus resulting in the fast reaction
without leaving the catalyst as residue with a reaction period of 5 to 10 min
at 30°C. Alkali doped metal oxides were used as an alternative for homog-
enous catalyst [48].
11.8.2.5 ME Conversion by Supercritical Method

Supercritical methanol transesterification is a modified method used to
avoid initiation time lag during biodiesel production. The solvents are
kept in a temperature and pressure beyond its critical point there will
be only liquid phase which facilitates simple, fast, and eco-friendly pro-
duction of biodiesel. The recovery of glycerol and separation of biodiesel
becomes much easier due to the absence of catalyst. This method involves
alcohol to oil ratio of 42:1 under 80 atm pressure at 350°C to 500°C in 2
to 4 min [15].
11.8.3 Properties of Feedstock

Quality of produced biodiesel is based on feedstocks used for its produc-
tion. The factors that affect the biodiesel production are FA contents and its
composition present in the selected feedstocks. Other factors such as elim-
ination of unsaponifiables and water and titer property oil also influence
the properties of biodiesel produced [15].
11.8.3.1 Composition of FA
The FAs present in the feedstock in different compositions highly influence
the physical and chemical properties. FAs and its composition of various
feedstocks were presented in Table 11.1 [15].
11.8.3.2 FFA
These are FAs produced as a consequence of breakage in the long car-
bon chain in a FA that result in the detachment of TG molecule due to
heating/overheating of the oil/fat. Over-heating of oils and fats results
in the production of high FFA contents and they present in the ratio
of FA wt.% in oil. This FFA leads to saponification reaction during the
transesterification process and slow down the biodiesel production
[15, 49].
11.8.3.3 Heat
The calorific value of feedstock greatly influences the energy content of the
biodiesel. Fuels with high saturation give high energy (on weight basis),
and high unsaturation provides lower energy content. The fuel has high
energy when it is denser. Heat is an important factor that affects biodiesel
quality [50].
11.8.3.4 Presence of Unwanted Materials

The feedstock contains undesirable materials that hinder the biodiesel pro-
duction, which has to be eliminated before or in the purification process.
Water content and impurities are filterable solids (including solid wastes,
bone fragments, and food particles) and unsaponifiable are non-TGs
which are incapable of producing mono alkyl fatty esters when subjected
for esterification or transesterification process [15].
Table 11.1 Fatty acid contents of vegetable oils and animal fats.
Soybean oil Palm oil Sunflower oil WCO Tallow Lard Poultry oil Fish oil
Fatty acids (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
Palmitic acid 10.2 42.8 5.8 8.5 23.3 23.6 23.9 14.3
Stearic acid 3.7 4.5 2.9 3.1 19.4 14.2 6.0 3.0
Oleic acid 22.8 40.5 35.0 21.2 42.4 44.2 44.0 15.0
Linoleic acid 53.72 10.1 74.5 55.2 2.9 10.7 19.9 1.4
Lauric acid 0.1 0.1 – – 0.1 0.1 – 0.2
Myristic acid 0.1 1.0 0.9 – 2.8 1.4 – 6.1
Linolenic acid 8.6 0.2 1.5 5.9 0.9 0.4 1.9 0.7
Oleochemical Resources for Biodiesel Production
331
11.8.3.5 Titer
Titer is the temperature required for melting of oil from solid into liquid
phase. Titer is an important factor which influences the biodiesel produc-
tion. Oil with high titer leads to high production cost [15].
11.8.4 Characteristic of Feedstock

The characteristics of feedstock are directly reflected in the biodiesel
obtained from it. Since the transesterification process does not have any
effect on the composition of FAs that already exist in the feedstock, this
greatly influences the quality and physiochemical properties of the bio-
diesel. Factors which affect the quality of biodiesel are oil or fat with high
FFA content which leads to high production cost, presence of MIU involv-
ing additional processing methods including filtration, heat treatment and
centrifuge, and some critical parameters like cetane number, cold flow
properties, saturation level of FAs, cloud point, flash point, and oxidative
stability [15].
11.9 Optimization of Reactions Conditions for High

Yield and Quality of Biodiesel
11.9.1 Pre-Treatment of Feedstock
11.9.1.1 Elimination of Water
During the transesterification reaction, the water present in the feedstock
at high temperature forms FFA by hydrolyzing the TG into DG, and as
a result, saponification reaction takes place even a very low amount FFA
(less than 1%) is present. To avoid the saponification reaction, the water
has to be removed from the feedstock in order to obtain good biodiesel
yield from transesterification reaction. Heat treatment and centrifuge are
some of the methods used to remove water content from the feedstock
[51].
11.9.1.2 Elimination of Insoluble Impurities

The feedstock must be filtered before subjecting it to the conversion reac-
tion in order to remove the presence of solid impurities in the form of
sand, dirt, fragments, etc., in vegetable oil and small fragments of gums,
bones, etc., and in animal fats and WCO [51].
11.9.1.3 Elimination of Unsaponifiables

Unsaponifiables are organic compounds such as hydrocarbons, alcohol
with high molecular weight, sterols, waxes, and pigments from which soaps
cannot be formed during transesterification process. These compounds are
removed during refining process of crude oil or with water washing tech-
nique during glycerol phase if the crude oil is directly used for biodiesel
production [15, 51].
11.9.2 Characterization and Selection of Feedstocks

The followings conditions should be taken into account for selection of the
feedstock to obtain better yield and quality in biodiesel.
FFA content of the feedstock should be low, the FA composition should
be considered since it directly influences the properties of the biodiesel,
either the feedstock should be free from MIU or pre-treated before subject-
ing it transesterification reaction, and the saturation level of FAs should be
considered for better quality of biodiesel [15, 51].
11.9.3 Selection of Reaction Conditions

Biocatalyst is better, and as a pre-treatment step for producing FAAE from
FFA, acid catalyst transesterification method is suitable. Heterogeneous cata-
lyst such as calcium methoxide can be used when solvent with boiling point
equal to methanol is used. To avoid initiation time lag, supercritical methanol
transesterification can be adopted. In order to get a better yield and higher
quality biodiesel, reaction parameters have to be optimized by proper selec-
tion of feedstock, and reaction conditions play an important role [15, 51].
11.10 Oil Recovery

11.10.1 Alkaline Flooding Method
Alkaline flooding is a method used to improve oil recovery from crude
oil. NaOH, Na2CO3, and sodium orthosilicate are some of the alkali com-
pounds used for oil recovery [52]. Based on the results reported from the
experiment done by Abhijit Samanta et al. (2011) [53], there is conclusive
proof that alkali flooding enhances the oil recovery by formation of in situ
surfactant. When the alkali slug concentration was increased, the recovery
of oil was found to be increased about 15% more than the conventional
water flooding in which the recovery of oil is ~50%.
11.10.2 Additives
Hydrocarbon solvents are commonly used for extraction of TG oil
directly derived from seeds of feedstocks, e.g., sunflower seeds. Hexane
is widely as solvent in plant oil industry [54]. Fishwick and Wright
(1997) [55] have experimentally proven that chloroform-methyl alco-
hol can be used as potential solvent for extraction of plant lipids such as
sterol lipids, phospholipids (both bounded and free), and glycolipids.
Supercritical carbon dioxide is also used as a solvent for oil recovery
[56].
11.11 Quality Improvement of Biodiesel

The properties of FAME/FAEE can be enhanced by addition of different
types of additives based on the requirements.
11.11.1 Additives for Improving Combustion Ability

Barium, platinum, iron, cerium, manganese, and calcium can be used as
additives with metal based to enhance the ability to combust and less emis-
sion [57, 58].
11.11.2 Additives for Enhancing the Octane Number

Oxygenated additives are fuel containing oxygen. It is used for enhance-
ment of octane rating and improving the combustion quality. Commonly
used oxygenate additives include alcohols, ether, and ester. Alcohol
includes C2H5OH, CH3OH, C4H10O, and C₃H₈O. Ethers used are C5H12O,
C6H14O, (C2H5)2O, C2H6O, and C6H14O, etc. [59].
11.11.3 Additives for Improving the Stability

Antioxidant additives are used improve the stability and deterioration of
biodiesel during storage. Alkyl phenols, hindered phenols, and aromatic
diamines are commonly used as antioxidant additives [60–62].
11.11.4 Additives to Enhance Cold Flow Property

Ethylene vinyl acetates are used as cold flow improver additives [63].
11.11.5 Additives to Enhance Lubricity

These surface-active compounds allow the protective film formation for
assisting the solubility of fuel and to improve the lubrication property of
biodiesel [64]. Ester, FAs, and amides are used as lubricity improver addi-
tives to reverse the lubricity lost during refining of oil [65].
11.11.6 Additives to Enhance Cetane Number

Alkyl nitrates especially 2-ethyl hexyl nitrate (2-EHN) is an important cetane
number improver additive used to enhance the cetane number. Tertiary
butyl peroxide can be used for improving the quality of biodiesel [64].
11.12 Conclusion
Oleochemicals are a capable substrate for renewable and production of
biofuel and it has advantages over fossil fuels due to its carbon renewabil-
ity, but there is an issue due to the threating of food safety and security
and loss of agrobiodiversity when edible feedstocks are used. Techniques
such as transesterification, pyrolysis, and hydrotreatment are the success-
ful process adopted for large-scale biofuel production including biodiesel,
bio-oil, and renewable diesel. This would act as an alternative method for
glycerol production that, in turn, produces a good impact on biodiesel pro-
duction. Biodiesel blend that is available commercially has the potential-
ity to perform as same as Petro-diesel in diesel engines in an eco-friendly
manner with reduced emission of greenhouse gases. This production may
be increased when there is an increased demand for renewable fuel occurs.
Abbreviations
AFW Animal Fat waste
ACPO Acid crude palm oil
DG Diglyceride
FA Fatty acid
FAEE Fatty Acid Ethyl Ester
FAME Fatty Acid Methyl Ester
FFA Free Fatty Acid
ME Methyl ester
MG Monoglyceride
MSA Methane Sulfonic Acid

MSW Municipal Solid Waste
PTSA p-toluene sulfhonic monohydrate acid
TAG Triacylglycerol
TG Triglyceride
WCO Waste Cooking Oil
WFO Waste Frying Oil
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12
Overview on Different Reactors
for Biodiesel Production
V. C. Akubude1*, K.F. Jaiyeoba2, T.F Oyewusi2, E.C. Abbah1,
J.A. Oyedokun3 and V.C. Okafor1
1
Department of Agricultural and Bioresource Engineering, Federal University of
Technology, Owerri, Nigeria
2
Department of Agricultural Engineering, Adeleke University, Ede, Nigeria
3
National Centre for Agricultural Mechanization, Ilori, Nigeria
Abstract
Biodiesel is alternative source of energy which has gained wide research input.
Notwithstanding, its wide utilization in energy systems like fossil fuel is still facing
challenges due to high production cost. This bottleneck can only be eradicated by
developing a better cost-effective and productive approach that can lead to afford-
able end product at the long run. Biodiesel reactor plays a key function in the over-
all production cost of biodiesel; therefore, a careful selection of a reactor that can
help eliminate the challenges faced by convectional reactors is paramount. Batch
reactors are widely used for biodiesel production but its disadvantages has led to
development of continuous flow reactors and even novel reactors like microreac-
tors. This chapter features the general concept of various configuration of reactors
currently been utilized in biodiesel production. Their merit and limitations as well
as their properties are captured.
Keywords: Biodiesel, reactor, batch reactors, continuous flow reactors,

microreactors
12.1 Introduction
Alternative source of energy has been the current center of research in
developing countries to provide the global energy need with its rising pop-
ulation and limited source of petroleum. Also, a cleaner, sustainable, and
*Corresponding author: akubudevivianc@gmail.com
341
eco-friendly source of energy [1, 2] is another aim of the research commu-

nity to reduce the pollution caused by the fossil fuel. Biodiesel is energy
product that is gotten from biological sources like animal fat, vegetable, or
waste oil. It is derived from chemical reaction between bio-oil and alco-
hol in the presence of a catalyst [2]. It is a type of biofuel comprising of
mono-alkyl esters of long-chain fatty acids produced by transforming veg-
etable oil via transesterification reaction [3]. It offers lots of advantage to
the environment, society, and economy including lower sulfur and aro-
matic content, non-toxic, renewable, biodegradable, clean burning, reduce
greenhouse gas emission, reduce the carbon monoxide, and good lubricity
[4–8]. Despite the numerous benefits of biodiesel, it has not gain public
acceptance because of the price when compared with fossil fuel. Hence,
to make biodiesel more appealing to the society, well-developed strategy
that is void of the various problems relating to the production processis
essential [9].
Reactor is known as a compartment where chemical conversion takes
place during any processing activity. It is a chamber used in transform-
ing raw materials to desired products via chemical reaction. A reactor
must provide enough time for chemical reaction to occur [10]. Reactor
design should consider the following key factors: construction mate-
rial, stirring system, size of reactor, hydrodynamics, physical properties
of the reactants, and methods for in-take or discharge of heat as this
will ensure high effectiveness and productivity [11]. Several configura-
tions of continuous reactors have been developed. This work reviews
many technological developments within literature with respect to these
reactors.
12.2 Biodiesel Production Reactors

Generally, reactors are classified as batch or continuous [12, 13]. The design
of the reactor depends on how the biodiesel is produced, either in batches
or as a continuous process. Many investigations have been carried out in
order to realize the right type of reactor to surmount some technical chal-
lenges during production of biodiesel by transesterification. In the recent
time, the technical methods or processes in production of biodiesel have
improved tremendously with the advent of various types of reactor in dif-
ferent sizes. This study therefore examines several types of reactor such as
batch reactors (BRs), continuous stirred tank reactors (CSTRs), fixed bed
reactors (FBRs), bubble column reactors (BCRs), microchannel reactors
Different Reactors for Biodiesel Production 343
(MCRs), membrane reactors (MRs), reactive distillation, and hybrid cata-

lytic plasma reactors.
12.2.1 Batch Reactor

Batch production of biodiesel via the use of BR is the basic method that has
been used for biodiesel synthesis [14] before the emerging of continuous
processes [15]. BRs are as simple as tanks with different forms of agitat-
ing equipment as shown in Figure 12.1 [16]. The chamber/tank remains
occupied with the processing reactants (catalyst, oil, and alcohol) with
operation of the agitators for a certain period. In the reactor, the reactants
are charged at a predetermined period of time. The chemical structure in
the reactor transforms with time along with the product concentration
by closing the reactor and then taking it to the required reaction states
(pressures, temperatures, and agitation rates). Subsequently, the result of
reaction inhibition by reaction products can be reduced. After completion
of the reaction time, the chemical substances from the reactor are isolated
and sent for consequent processes. One of the major features of BRs is that
it begins with unreacted substance, cause it to react, and then finish with
reacted substance after a while. Other helpful characteristics of BRs include
suitable mixing features and comparative ease of controlling homogeneous
catalysts as used in the biodiesel transesterification reaction.
Cooling water Condenser

Speed controller
Thermometer and
sampling outlet Cooling water
Agitator/stirrer
Three-neck flask
Hot plate
Figure 12.1 Schematic diagram of batch reactor apparatus [16].

In some literature, reports have mostly focused on maximizing the

experimental factors of BRs to obtain high biodiesel yield. Price et al. [17]
performed a modeling study on optimal yield of biodiesel in a BR by means
of a liquid lipase formulation. A simulated biodiesel yield of 90.8% (wt.)
was reported at optimum parameters for the model. Leadbeater et al. [18]
reported a typical reaction procedure of a BR which involved two-neck
round bottomed flask of 31 containing a stirrer with soybean oil (1 kg),
sulfuric acid solution (5% by weight, 27 ml) with 630 ml of butanol. This
blend was laid inside hollow of a microwave through an immersion in one
side of the flask necks with a glass connector into one another. In addi-
tion, an optic’s fiber probe was dipped inside the immersion. This blend
was allowed to heat from room temperature to 120°C by means of a pre-
liminary microwave powered at 1,600 W and allowed to stay for 2 min
at 120°C. Then, reaction compartment was detached from the hollow of
the microwave, and upon cooling to normal temperature, the substance
was transferred into another chamber to settle. Thereafter, the substance
was rinsed with water followed by brine. By solution of nuclear magnetic
resonance spectroscopy with respect to hydrogen (HNMR), the degree of
transesterification of oil was measured. The groups of −OCH2in the butyl-
ester-chain with α-methylene proton presents inside the triglyceride (TG)
by-products of the oil were related signs selected for incorporation. After
estimating the conversion completely from the incorporated area of the
signal, 93% conversion of biodiesel was the highest reported.
However, BRs have drawbacks, for instance, bulky reactor size, wide sep-
aration processes, and high cost of labor [19]. More so, the main restriction
of BRs is commonly connected near mass transfer control relating the oil
and solvent [20]. To rise above these challenges, several forms of reactors
were developed with improving usage of solvent, catalyst, and energy; fur-
thermore, to streamline improvement phases by incorporated separation
techniques. The extent of mixing in BRs increases as the totality of energy
presented from the stirrer increases and vice-versa [11, 12].
12.2.2 Continuous Stirred Tank Reactor

Most CSTRs are well configured in order to give room to continuous
pumping of the reactants [21] for efficient working of the reactors as shown
in Figure 12.2 as given by [22]. At first glance, a CSTR seems to be similar
to a BR. Actually, the reactors can be so alike except that CSTR requires
some controls to be set up inside the reactor. At the beginning, after load-
ing the continuous reactor with reaction substances, the process is agitated
adequately until the reaction is accomplished. The major components in
electronic
reactant 1 valve
control level gauge
reactant 2
to vent
system
floor level
products
overflow
from
coolant reactor
stirrer
Figure 12.2 Schematic diagram of continuous stiired tank reactor.
CSTRs include the agitation speed and in-out flow rate which influences
the residence time, rate of mass transfer, and efficiency of mixing [23].
Thorough mixing is required for assurance of adequate homogeneity of
the products; this always caused more energy to be consumed. Thus, many
efforts have been made with the use of different kinds of CSTR to exchange
the mechanical agitators in order to minimize the energy consumed. So
far, CSTR has been extensively employed for production of biodiesel in
large scale due to its adequate technologies and wide understanding of
operations.
While the continuous steady tank reactor worked continuously at a
steady condition, the ideal thing is that the concentrations of some chem-
icals used should be nearly constant all time at everywhere in the reactor.
However, this ideal condition is rare to achieve; hence, adjustment needs
to be done to working parameters to make sure reaction is completed. It
must be noted that, two reactors may be used sometimes. For the two-stage
process, almost 80% of catalyst with alcohol can be combined with oil in
the first stage of CSTR. After which, the reacted flow passes within glycerol
removal phase prior to its entrance to second stage of CSTR. The other 20%
of catalyst with alcohol can be placed inside the reactor at the second stage.
This process offers an extremely completed reaction with the possibility of
utilizing a smaller amount of alcohol than single phase process. So, due to
consistency of quality products required and inadequate capital with oper-
ational cost for each product, transesterification by CSTR process is prefer-
able to BR process [24]. When comparing CSTR with BR, CSTR provides
quality operation to improve thermal and mass transfer, less production
cost, provides a uniformity of product, and supports scale up [25, 26].
12.2.3 Fixed Bed Reactor

FBR as shown in Figure 12.3 [16], sometimes, called packed bed reactor,
is a cylindrical-tube full of catalytic agents (pellets) packed in a fixed bed
with the flowing of the reactants within the bed which are transformed
to fatty acid methyl esters (FAMEs). It uses heterogeneous catalysts to
simplify actions in improving process since no separation technique
common to the catalyst and product is needed. Also, FBR improves the
heterogeneous reaction of the catalyst because of the delay in deactivation
outlet
stainless steel
column
(Φ25х450mm)
water jacket
pump
inlet
pump
accumulation
tank
feedstock thermostat
tank water bath
Heater
Figure 12.3 Schematic diagram of fixed bed reactor [16].

and longevity in duration of the catalytic agent; hence, there is reduction

in cost of production. However, the main parameters in this reactor are
amount and size of the catalytic agent, feed flowrate, bed height, molar
ratio, and residence time. When comparing with another heterogeneous
catalytic reactor, FBR lowers the reaction time and raises the link combin-
ing bio-oil and alcohol with catalyst; yet, a greater molar ratio is required.
Likewise, the by-product (resultant glycerol) dwells in the bottom most
part of the reactor and accumulates on the surface of the catalytic agent.
Hence, it lowers the effectiveness of the catalyst which causes a further
process removal [27].
Previous works on FBR have been reported by some researchers [28]
who extensively examined the production of FAME from esterification of
acidified oil alongside methanol in FBR with cation exchange resin, and a
better result was attained. Also, esterification of crude triolein with ethanol
in FBR was examined at 60-min residence time, and thereafter, about 80%
of FAME was achieved [29]. In a recent study, esterification of processed
coconut oil using methanol in FBR was carried out with mass transfer as
recovery step and 78% conversion rate was obtained [30]. An optimum
FBR for biodiesel production using soybean oil in a solvent process of
tert-butanol achieved a molar conversion of 83.31%. The FBR can work
over 30 days with no meaningful loss noticed in the substrate conversion.
Also, the FBR shows the ability for industrial-scale production of FAME
utilizing a tert-butanol solvent system. Some common advantages of using
FBR are constant discharge of glycerol with excessive alcohol, effectual
reuse of enzymes, and preservation of particulate enzymes from mechan-
ical shear stress [31–33]. Conversely, short-term operation of FBR is a big
problem; however, using a solvent-free system can operate for 3 to 7 days
without reduction in ester yield [34, 35].
12.2.4 Bubble Column Reactor

This is broadly used in industrial production of biodiesel. It has been gen-
erally utilized for performing gas-to-liquid reaction for many industrial
applications. It is a better reactor for production of biodiesel that requires
a substantial interaction area for gas-to-liquid mass transfer and effective
blending for reacting species. Figure 12.4 [36] gives a schematic diagram of
BCR. The heterogeneous somatic scheme in the BCR is classified into two
fragments: vapor and liquid phase. Vapor phase contains water vapor and
methanol, whereas the liquid phase contains oil, biodiesel, methanol, water
and catalyst (H2SO4). For simplicity, both phases are assumed to be well
Gaseous Phase
(Unreacted Methanol)
Condenser
Reactor Vessel
(520-620 K, 0.1 MPa)
Liquid Phase
Vegetable Oil
FAME
(Biodiesel Fuel)
Dehydration
Column
Glycerol
Methanol (By-Product)
Heater
Figure 12.4 Schematic view of bubble column reactor for biodiesel production [36].
blended without spatial concentration gradient inside the reactor. Often,

BCR makes use of acid catalysts without soap but produces high tempera-
ture that boils the methanol. The bubbling methanol produces agitation
and removes the by-product water. Production of biodiesel with super-
heated methanol-vapor occurs under atmospheric pressure and higher
temperature between 250°C to 300°C, this necessitates for stainless-steel
reactor with insulation [37].
Kocsisova et al. [38] reported that supplying methanol into BCR with
operation at temperature greater than 100oC under atmospheric pressure
supports water ejection from oil during transesterification that enhances
conversion of the final biodiesel. Suwannakaran et al. [39] discovered the
viability of utilizing blended feedstocks [TGs and free fatty acid (FFA)] for
production of biodiesel using solid catalyst (Calcined Tungstated Zirconia)
through BCR at high temperature of 130°C. Conversion of 85% (FFA)
and 22% (TG) was achieved under 2 h of reaction. The fairly low conver-
sion rate achieved is on account of the competition between FFA and TG
during early protonation of their carboxylic functionality following nucle-
ophilic attack by methanol producing biodiesel. Also, BCR has been oper-
ated previously at upper temperatures (250°C to 290°C) by means of palm
oil in deficit of catalytic agent to envisage its functionality with increased
methanol flow rate but low conversion of 60% was recorded [40]. In a sub-
sequent report, an increased conversion rate of 95% was observed at 290°C
but esterification rate increases as temperature increased [41].
In another related development, utilization of BCR in preparing bio-

diesel was reported by Joelianingsih et al. [40, 41]. The studies established
that catalyst free biodiesel can be successfully produced using BCR at
ambient pressure. BCR provides the opportunity of achieving vigorous
agitation as gas is circulated in a sparger that brings out bubbles through a
vertical-ylindrical column [42, 43]. Reduction in enzymes’ wears and tears,
and provision of longer duration using a highly viscous and s olvent-free
system agitated by gas bubbling has been reported by Manman et al. [43].
Benefit of this process is that catalytic agent is not needed; thus, esterifica-
tion of oil with high FFA substance can be achieved with no initial treat-
ment. Also, methanol bubbles coming up in the reactor provides adequate
agitation to permit dispersal of methanol steam to enter the oil phase for
reaction; hence, there is reduction in the cost of mechanical agitation [44].
However, the main drawbacks of using BCR in production of biodiesel
are the condition for even bubble size dispersal and gas/vapor delay pro-
file. These drawbacks are as a result of somekey factors including column
height and diameter, geometry of sparger, liquid phase viscosity, and gas
velocity [42]. The problem of improving these factors is the major con-
straint to the use of BCR for industrial-scale production. Also, it exhibits
ill-effect when biocatalyst (enzyme) is used since the enzyme carrier can
be broken-down through mechanical agitation thereby deactivate the cat-
alytic activity.
12.2.5 Reactive Distillation Column

This is a reactor type in which chemical reactions and product separations
occur concurrently in a single unit. Reactive distillation column (RDC)
consists of a reactive section, non-reactive rectifying and stripping sections
as shown in Figure 12.5 [45]. The product removal and formation hap-
pens simultaneously giving rise to its capacity to overbear the equilibrium
thermodynamics of the reaction, reaching high conversion and selectivity.
Therefore, it can serve as a good option to the conventional combination
of reactor and separation units [46–49]. Usually, vegetable oil is fed to the
top of the column and alcohol is fed to the bottom as vapor. The product
formed (biodiesel) is pumped from the bottom while the water by-product
is distilled from the top [21]. The merits of using this process include
maintaining a high alcohol-to-oil molar ratio, reduction in excess alcohol
usage, and combination of reactor and separation chamber in a single unit
thereby saving cost [50–52]. This technique has been utilized in biodiesel
production by researchers [53].
Rectifying section
Feed
Reactive section
Stripping section
Figure 12.5 The general configuration of reactive distillation [45].
12.2.6 Hybrid Catalytic Plasma Reactor

The potential of the plasma technology is the utilization of high energetic
electrons because of a collision between the high energetic electrons and
the reaction mixtures. The high energetic electron is generated from a
high-voltage power supply through high-voltage electrode. The advantages
of this plasma electro-catalysis system only require very short time reac-
tion, do not need a catalyst, do not form soap, and do not produce glycerol
as a by-product. However, there was difficulty in regulating the main reac-
tion process during the plasma process due to the action of high energetic
electrons [54]. Figure 12.6 shows a schematic diagram of hybrid catalytic
plasma reactor [16].
12.2.7 Microreactors Technology

They are of different configuration, namely, MCR, MR, microtube micro-
reactor (MM), and oscillatory flow reactors (OFRs). The sizes of these reac-
tors are quite small compared to the conventional types. This will result to
reduction in capital cost.
MCR as shown in Figure 12.7 [55] is made up of channels whose diam-
eters are very small like less than few millimeters [55]. The merits of
MCR are reduced reaction time, fast phase separation, excellent blending,
Oil Tank Methanol Tank

flowmeter
AC/DC High Voltage

Voltage Generator Settler
Regulator (AC/DC)
BIODIESEL
PRODUCT
High Mixing Tank
Voltage
Electrode
Ground
Electrode
Hybrid Catalytic Plasma Reactor
Figure 12.6 A schematic diagram of hybrid catalytic plasma reactor system in the future
works [16].
Outlet
Middle Sheet
Inlet
Zig-zag Mirochannel
(with 90º turn)
Figure 12.7 Schematic diagram of a microchannel microreactor [55].
less cost of scale-up, large surface area–to-volume ratio, effective mass and
thermal, and safe and stable operations. Its demerit is limited capacity [21].
MR as shown in Figure 12.8 [9] is a reactor type was reaction, and mem-
brane-based separation occurs concurrently in the same chamber [21, 56].
It has high selectivity and ability to regulate the blending of components
between two phases and provide high surface areas per unit volume. The
membrane acts as a selective barrier thereby controlling the movement of
Pressure
guage
Membrane reactor
Heat exchanger
Oil tank Back
pressure
Circulating pump valve
chiller
Methanol tank Mixing tank

Methanol recovery
Biodiesel tank unit
Figure 12.8 Schematic diagram of a membrane reactor for biodiesel production [9].
substances using different mass transfer rates. During production process,

the membrane isolates the glycerol from the product stream [57, 58] or
keeps the unreacted TGs within the membrane [59–61]. Various forms
of membrane that have been utilized in biodiesel production include as
ceramic carbon membranes, polymeric membranes, and polyethersulfone
[59–63]. Study by [56] shows that using ceramic membrane gave a yield of
96.42% under optimal conditions.
MM as shown in Figure 12.9 [55] is a type of reactor where heat and
mass transfer are expected to remain notably reinforced due to its small
High Pressure Pump

(HPLC)
Hot Water Tube Containing

Microreactor Cooling Tube
Mixing
Substrate Unit
Product
(I-Mixer)
Hot Water Hot Water Cold Water Cold Water

Inlet Outlet Inlet Inlet
Ice-Water Bath
Methanol+Catalyst
Figure 12.9 Schematic diagram of microtubemicroreactor [55].

space with a large surface area–to-volume ratio. Resulting in molecular

diffusions via the edge and in the two-phase reaction, it should come to be
much less considerable [64].
12.2.8 Oscillatory Flow Reactors

This is a continuous process reactor type that is made up of tubes enclosing
equally spaced orifice plate baffles on a piston that create an oscillatory
motion generating recirculation flow pattern that ensures effective blend-
ing of fluid inside it, resulting in increased heat and mass transfer. This
piston is electrically or pneumatically operated. It helps to enhance the
residence time for the reaction [65, 66]. Production of biodiesel using an
oscillatory flow biodiesel reactor (OFBR) has been reported to be another
effective continuous process [14].
12.2.9 Other Novel Reactors

Novel reactors such as sonochemical reactor, cavitation reactor, and micro-
wave reactor have been used as intensification technology for biodiesel
production.
Cavitation is the formation of small bubbles that grows and collapses
resulting in discharge of high level of energy [2, 67, 68], generating very
high pressure and temperature gradient which improves the mass transfer
rate of the reaction by creating a state of intense violent movement and
liquid microcirculation currents in the reactor [67–69].
Sonochemical reactor is a novel reactor that works based on the genera-
tion of cavitation using energy from ultrasonic irradiation [68]. The merits
include savings on energy and cost, high yield and selectivity, and safer
operating conditions [70]. Also, studies report that in ultrasound-assisted
process, the operating parameters are meaningfully decreased [71, 72].
However, its demerit is that of erosion and particle shedding at the delivery
tip surface because of the high surface energy intensity [2, 68].
Microwave reactor utilizes microwave radiation in conveying energy
directly into the reactants and thus speeds up the transesterification pro-
cess. It plays a vital function in heating of reactants to the desired tem-
perature [73]. It is more advantageous in terms of energy and time saving,
steady internal heating, and safe operating conditions. It is easy to regulate
and gives higher yield under mild reaction conditions and less environ-
mental pollution [67].
12.3 Future Prospects

BRs are basic mode of biodiesel production. However, several continuous
process reactors are emerging with specific benefits to tackle the draw-
backs of BRs. Most of the reactors have been utilized at laboratory level
and needs a scale up for large-scale production. Therefore, there is need for
more research on how to improve on the existing technologies for large-
scale production. Also, the cost that will be incurred to build the reactors
for scale up should be considered carefully as this will have effect on the
cost of production of biodiesel.
12.4 Conclusion
Biodiesel are produced using reactor which vary in type, configuration,
and design. Reactor has a direct effect on the biodiesel produced. The var-
ious types of bioreactors include batch, CSTR, FBR, BCR, RDC, hybrid
catalytic plasma reactor, microreactors technology, and OFRs. Each con-
figuration of reactor has varying degrees of merits and demerits; most of
the reactors have been utilized at laboratory level and needs a scale up for
large-scale production thus calling for more research on improvement
of existing technologies for large-scale production considering cost of
production.
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13
Patents on Biodiesel
Azira Abdul Razak, Mohamad Azuwa Mohamed* and Darfizzi Derawi
Department of Chemical Sciences, Faculty of Science and Technology, Universiti

Kebangsaan Malaysia, UKM Bangi, Malaysia
Abstract
Biodiesel is a renewable fuel that is made from edible or non-edible feedstock
and it has high potential to compete with the diesel fuel. In this paper, the pub-
lished patents from 2003 to 2018 related to biodiesel were reviewed, and they were
retrieved from Justia Patent Database. This paper is divided into five sections:
started with the introduction to biodiesel, the generation of biodiesel that depends
on the feedstock used, the development of catalysts, the latest method for biodiesel
production, and the technology of reactor used to produce biodiesel. The second
generation of biodiesel has gained interest as it can be produced from waste which
lowering the production cost. The use of a catalyst can facilitate the reaction, but
it is crucial to choose the best type of catalyst. There are various methods used to
produce biodiesel, and the most common method used is transesterification due
to its simplest and efficient method for biodiesel production. To produce biodiesel
in large amounts, the reactor’s technology is used and it was found that continuous
stirred tank reactor is a more practical and simpler reactor that can be used.
Keywords: Biodiesel, feedstock, catalyst, production method, reactor technology
13.1 Introduction
The change in the global climate is one of the most serious problems faced
by the world nowadays. The major contribution to this problem is the high
utilization of fossil fuel, where the burning of them leads to the release of
carbon dioxide (CO2) to the atmosphere and cause global warming [5].
Based on the data obtained by International Energy Agency, the utilization
*Corresponding author: mazuwa@ukm.edu.my
361
of energy continues to increase within the years, and it is reported that the
energy demand for oil showed the highest amount, where it has increased
from 3,232,737 kiloton (1990) to 4,449,499 kiloton (2017). High demand
for fossil fuel not only becomes the environmental issue, but it is also a
non-renewable source of energy. If the consumption continues to increase,
then fossil fuel is expected to be completely used up by 2050 [1–3].
To overcome the problems discussed earlier, biofuels show a high poten-
tial to be an alternative solution to replace the usage of fossil fuels as energy
and expected to satisfy the global energy demand. Biofuels are known as
liquid or gaseous fuels produced through a biological and chemical process
or derived from biomass of living organisms such as microalgae, plants,
and bacteria and used for transport sectors [2]. Biodiesel is one of the types
of biofuel that most commonly used in European Countries. Biodiesel can
be produced by converting fats or oils from animal fat and vegetable oil
chemically to esters because they have similar properties to mineral diesel.
U.S. Energy Information Administration indicated that the United States
(U.S.) showed the highest amount of biodiesel production, which is 6.9
billion liters [4]. Indonesia has become the leading for Asian Countries,
which produced 4.0 billion liters of biodiesel and fall as the third-highest
production of biodiesel in 2018.
13.2 Generation of Biodiesel

Biodiesel can be classified into different generations depending on the
feedstock used either edible, non-edible, or waste oil which determines the
qualities of biodiesel produced. It also depends on the major sources of
feedstock from the countries to produce biodiesel. For example, the com-
mon feedstock used in the U.S. is refined vegetable oil such as soybean and
canola oil. However, they also produced biodiesel from used cooking oil
and animal fats to cut the production cost [4]. The patent for biodiesel pro-
duction from first to the fourth generation, which is still in an early stage.
The first generation of biodiesel is quite popular at the beginning of
the biodiesel era, where edible oil used as feedstock to produce biodiesel.
For E.U. and U.S., rapeseed oil and soybean oil are widely used, while for
Asian countries such as Malaysia and Indonesia, palm and coconut oil is
the most common feedstock used. The difference in feedstock used will
affect the production process, quality, and cost because the produced bio-
diesel depends on the types of fatty acid that attached to the triglycerides
molecules [6]. Saka and Kusdiana (2001) have proposed the transesterifi-
cation of rapeseed oil in supercritical methanol without catalyst consumed.
Patents on Biodiesel 363
They found that by using the new supercritical methanol, the process
became shorter in time and has a simpler purification procedure [7].
However, there is a limitation for this generation because of the competi-
tion between food supplies that increase the production cost is the main
drawback for edible oil-based biodiesel. The disadvantages showed by the
first generation of biodiesel caused the development of the second gener-
ation of biodiesel. The feedstock for second-generation biodiesel is non-
edible oil such as Neem oil, Jatropha oil, Karanja oil, Rubber seed oil, and
waste oil. This type of biodiesel has advantages compared to the first gen-
eration because there is no competition between the food supply and also
less production cost [8].
However, there is still a need for land for growth which causes competi-
tion between food and fiber production. The high competition will lead to
limited nutrient supply for the land and it will be hard to maintain the qual-
ity of oil produced [9]. Algae-based biodiesel, known as third-generation
biodiesel, has gained much attention to overcome the disadvantages of the
first and second generation of biodiesel. They could produce less green-
house effect, elevated growth rate and productivity, lesser struggle toward
farming land, and a higher amount of oil. However, the limitations for
third-generation biodiesel are higher production cost, high need for sun-
light, need to produce on large scale, and difficult for oil extraction.
13.3 Development of Catalyst

Catalyst is a substance that facilitates a chemical reaction, which makes
the reaction go faster without itself being consumed in the reaction.
Catalysis can be divided into three categories, which are homogeneous,
heterogeneous, and bio-catalysis. A homogeneous catalyst involves the
reaction between a catalyst and the substrate in different phases. Recently,
the heterogeneous catalyst is preferable over the homogeneous catalyst in
the production of biofuels. This is because it is easier to separate from the
mixture after the reaction process by filtering [10], their reusability, and
low production cost due to a single-step reaction [11]. The catalyst used
for industrial production of biodiesel is the alkali-based catalyst method,
where Sodium Hydroxide and Potassium Hydroxide are commonly used
as a homogeneous catalyst. By using alkali catalyst, the reaction can be car-
ried out in mild temperature and pressure condition. However, this process
requires additional steps of separating and removing the catalyst used. The
free fatty acid (FFA) produced also will react with the alkali catalyst to
form soap which will be lowering the function of the catalyst [12].
13.3.1 Homogeneous Catalyst

Homogeneous catalyst refers to a catalytic reaction involving catalyst and
reactant within the same phase that can be divided into two types which
are alkali and acid catalyst. Alkali catalyst (NaOH, KOH) for biodiesel
production is widely used because they are cheap and readily available.
Transesterification of low-grade safflower oil with methanol in the pres-
ence of alkaline-catalyst (NaOH) has produced a high yield of methyl
ester [13]. However, the utilization of sodium or potassium hydroxide as
an alkaline catalyst caused the decrease of biodiesel yield. This is due to
the presence of the hydroxide group originally attached from triglyceride,
which will dissolve with glycerol [14].
An acid catalyst such as sulfuric, sulfonic, and hydrochloric acid is
the most common acid catalyst used in transesterification and preferable
because it can produce a high yield of the product. However, the reaction
rate when using an acid catalyst is too slow and the heat is required to
accelerate the reaction which makes it unsuitable for larger-scale produc-
tion [15]. Other than that, the homogeneous catalyst also difficult to be
separated from the reactant which makes it unsuitable to reuse and pres-
ence acid could lead to corrosion.
The present invention for the homogeneous catalyst is to provide a
neutral, non-corrosive homogeneous catalyst for transesterification of
triglycerides. The design for the catalyst is based on organometallic com-
pounds that contain at least one −OCH3 functional group that will catalyze
the transesterification and esterification efficiently to produce biodiesel.
This invention made to solve the disadvantages of using a homogeneous
catalyst by offering a non-basic and non-acidic homogeneous catalyst [16].
13.3.2 Heterogeneous Catalyst

A heterogeneous catalyst is the type of catalysis that involves different
phases of catalyst and reactant which contrast with homogeneous cata-
lyst. A heterogeneous catalyst is widely used in many industries such as
chemical, petrochemical, agrochemical, and pharmaceutical industries.
The most important factors in choosing good catalysts are the choice of
catalyst support, type of supported catalyst, and interaction between
catalyst and support [17]. In the previous study, several types of hetero-
geneous catalysts have been developed for biodiesel production such as
Amberlyst 36, Purolite CT482, Purolite CT275DR, Amberlyst-15, and
Sulfuric Silica-Acid. In a study by Kuzminnska et al. (2014), they found
that Amberlyst 36, Purolite CT482, and Purolite CT275DR were able to
produce biodiesel from Trimethylolpropane (TMP) and Oleic Acid [18].

In another study, Akerman et al. (2011) produced heterogeneous catalysts
such as Amberlyst-15 and Silica-Sulfuric Acid for biodiesel production
from TMP and Oleic Acid. They found that the Silica-Acid catalyst shows
better properties and efficient catalysts compared to Amberlist-15 [19].
The present invention provides a heterogeneous catalyst that has high
tolerance toward the presence of water and FFAs in the production of bio-
diesel. The catalyst is designed by a class of zinc and lanthanum oxide het-
erogeneous catalysts, with different ratios of the metal. The metal catalyst
will give effect to both esterifications of fatty acid and transesterification of
oil simultaneously [20].
13.4 Method Producing Biodiesel

The present invention to produce biodiesel and/or glycerine from feed-
stock includes pre-treatment process, esterification of FFA, and transester-
ification of triglycerides. The pre-treatment process involves the separation
of biodiesel feedstock from impurities such as sulfur, phosphorous, phos-
phatides, gums, sterols, metals, and other color bodies. As for esterifica-
tion, the FFA content in biodiesel feedstock will react with methanol in the
presence of a catalyst to form biodiesel and water. Meanwhile, transester-
ification involves the reaction between triglycerides of biodiesel feedstock
with methanol in the presence of a catalyst to produce biodiesel and glyc-
erine [21]. Other methods used for biodiesel production, such as direct use
and blending of oils and pyrolysis methods, also will be discussed further
under this topic.
13.4.1 Pre-Treatment Process

According to U.S. Patent No. 20090071063 (2009), by applying the
pre-treatment process, low quality of feedstock could be used as a source
of FFA to produce good quality of biodiesel. The pre-treatment process
involves the filtration and distillation process, which first started by heat-
ing to 43°C, followed by filtering the feedstock from solid particles to pro-
vide filtrate, which then further distilling repeatedly until the final distillate
is obtained [22]. This process is important to ensure all the impurities are
removed completely from the feedstock before they are used to produce
biodiesel. The production of low-cost biodiesel is a necessity to compete
with petroleum-based diesel. Utilizing waste such as waste cooking oil,
brown greases, and crude corn oil as feedstock could be a better alternative
for more practical and economical biodiesel. However, high FFA con-
tent in these wastes will become the obstacle which is the reason why the
pre-treatment process becomes necessary to produce biodiesel [23].
13.4.2 Direct Use and Blending of Oils

Direct use of vegetable oils as biodiesel is not preferable because of their
properties due to the effect of cold temperature, which not suitable to be
used as fuel. Therefore, vegetable oil usually will be blended with biodiesel
with a certain concentration. The amount of biodiesel blending with diesel
varies depending on the country which used biodiesel. The most common
are B5 (5% of biodiesel) and B20 (6%–20% of biodiesel). An invention
by U.S. Patent No. 20180223202 proposed four stages of principle which
apply for biodiesel blending. The first principle is an automated method
of blending that provides a distillation stream, separation of distillate, pro-
vides target pf biodiesel content, and measure of actual biodiesel content.
The second principle is an automated system for blending, which applies
the same principle with the addition of an analyzer for measuring actual
biodiesel content. The third and fourth principles are automated methods
and systems for blending, which provide a blending of biodiesel not to
exceed the maximum biodiesel content [24].
Another invention by U.S. Patent No. 7458998 proposed a method of
blended biodiesel by heating the biodiesel and diesel at a temperature
above the cloud point of the first blended. Then, the heated biodiesel will
be added to the unheated diesel to provide the second biodiesel blend.
The blended biodiesel produced by this method is maintained in a heated
environment which compatible with fuel purposes [25]. It is important to
ensure that the blended fuel meets the standard requirement of diesel in
terms of its kinematic viscosity, density, and the flashpoint of the blend.
Arabi et al. (2017) studied the characteristics of palm oil-biodiesel-diesel
fuel blend, where they found that the fuel properties for the blended oil
showed no significant difference compared to diesel fuel up to 30% of the
volume of biodiesel of palm oil [26].
13.4.3 Esterification of FFA

Biodiesel can be produced via an esterification reaction between fatty acid
and methanol with the presence of a catalyst. The most common catalyst used
in esterification is liquid acid such as sulfuric acid, hydrochloric acid, and
p-toluenesulfonic acid (p-TsOH). Esterification is considered as an attractive
method for producing biodiesel because it allows the use of FFA which can
H2C O R Hydrolysis
O O Esterification O
3 + 3 R OH 3 R + H2O
HC O R R OH R O
O
H2C O R
Triglycerides Fatty acid Alkyl Ester
of Oil (Biodiesel)
Figure 13.1 General reaction for esterification.
be obtained from refinement of vegetable oils and waste oil such as animal
fats and waste frying oil. The use of low-value fatty acid gives the advantage
for biodiesel produced, where it could compete with diesel in terms of their
low cost. Figure 13.1 illustrates the general reaction for esterification.
The invention for the production of biodiesel by esterification of FFA
using niobic acid as a heterogeneous catalyst has been proposed. Long
chain of carboxylic acid-containing 6–24 carbon atoms is used to react with
short-chain alcohol (methanol and ethanol), which act as esterifying agents.
Before the niobic acid catalyst is used in the reaction, it must be calcined to
maximize the acid strength of the catalyst [27]. An invention by U.S. Patent
No. 20080289248 proposed a process of producing biodiesel by involving
the contact of lipid material with alcohol in the presence of Zirconium (IV)
metal salt conjugated to the solid support. The temperature for the process
is between 25°C and 75°C, in which the esterification process runs within
the lipid material. The purpose of this invention is to enhance the conver-
sion of fatty acid and efficiently producing biodiesel [28].
13.4.4 Transesterification of TAG

Transesterification of TAG in biodiesel feedstock is the most common
and widely used method to produce biodiesel, as shown in Figure 13.2.
Transesterification is a reversible reaction, where triglyceride of oil reacted
with short-chain alcohol with the presence of catalyst either a strong base
or strong acid to produce Fatty Acid Alkyl Ester, which is the biodiesel.
In transesterification, the most preferable alcohol used is methanol and
ethanol, especially methanol because of its low cost, polar solvent, and the
shortest chain of alcohol [29]. If methanol is chosen, then the product gen-
erated is Fatty Acid Methyl Ester (FAME), which is the biodiesel that has
been well established in the oleo-chemical industry.
The present invention for the transesterification of biodiesel is by con-
trolling the removal of glycerin, which is the major by-product in biodiesel
H2C O R H2C OH
O
O
+ 3 R OH 3 R + HC OH
HC O R R O
O
H2C O R H 2C OH
Triglycerides Alkyl Ester Glycerol

of Oil (Biodiesel)
Figure 13.2 General reaction for transesterification.
production. The removal of glycerin can be done in a reaction vessel, either

continuous, semi-continuous, or batch reaction. By removing glycerin from
the biodiesel product, the reaction can be carried out with lower ratios of
alcohol to oil and will increase the rate of production for biodiesel [30].
13.4.5 Pyrolysis
Pyrolysis is defined as a thermochemical reaction which involved reaction
at high temperature (280°C–850°C), with the absence of an oxidizing agent
to produce different products such as solid (biochar), gaseous (biogas), and
liquid (bio-oil) [31]. High oxygen content in biodiesel from the transester-
ification reaction has become a disadvantage as it could lead to corrosion.
In contrast, biodiesel from pyrolysis appears as the solution as no oxygen
involved in the reaction and also it produced hydrocarbon diesel [32]. An
invention by U.S. Patent Application 20070144060 proposed a method
of producing biodiesel from triglycerides feedstock by pre-treating with
thermal cracking or rapid pyrolysis. By applying this method, the con-
taminants from the biodiesel can be removed and will produce distillate
fraction that rich in FFA content [33]. The general reaction of pyrolysis is
shown in Figure 13.3.
H2C O R R + CO2
O
HC O R
O
R + CO + H2O
H2C O R
Triglycerides
of Oil Hydrocarbon
Figure 13.3 General reaction for pyrolysis.

Table 13.1 Comparison between the pyrolysis method by operating parameters

and product yield [34].
Product yield (%)
Pyrolysis Temperature Residence Heating rate
method (°C) time (s) (°C/s) Oil Char Gas
Slow Medium-High Long Low (10) 30 35 35
(400–500) (450–550)
Fast Medium-High Short (0.5–10) High (100) 50 20 30

(400–650)
Flash High (700–1,000) Very short Very high 75 12 13

(<0.5 s) (>500)
The pyrolysis method is considered a complex process because of

two reactions condition, which is temperature and non-reactive atmo-
sphere that must be kept simultaneously within the reaction. The reaction
involved the breakdown of long chains of carbon, hydrogen, and oxygen
compounds in biomass into smaller molecules. Pyrolysis can be classified
into three main categories: slow, fast, and flash pyrolysis.
Among the methods, fast and flash pyrolysis is considered a better
method for producing biodiesel because these methods are able to produce
high yield of biodiesel with 50 and 75% respectively, in a high reaction
temperature but within a very short residence time as stated in the Table
13.1 [34]. By referring to Takuya (2012), triglycerides of oils decomposed
to fatty acid chains and further decomposed to the hydrocarbon chain at
390°C. By increasing the reaction temperature and heating rate, the prod-
uct yield of oil can be increased [35].
13.5 Reactor’s Technology for Biodiesel Production

General reactors used for biodiesel production are batch reactors, semi-
continuous-flow reactor, and continuous-flow reactor. Reactor becomes an
important technology for producing biodiesel on a large scale with more
economic value. By referring to U.S. Patent No. 20080282606, a biodiesel
reactor is a material that consists of a housing enclosing chamber that con-
tains four parts. The part in a biodiesel reactor is an inlet (for the inflow of
raw material), stir bar (inner part for stirring), baffle (partially segmenting
chamber for mixing), and outflow (for the outflow of the reaction mixture).
It is also stated that the process for producing biodiesel started by selecting
the feedstock oil and followed by measuring alcohol and catalyst need to
be used. Then, the feedstock, alcohol, and catalyst are mixing in the reactor
to form a mixture. The product and by-product will be separated from the
mixture and further distillate to purify the biodiesel product [36]. For cur-
rent status, there are various types of reactors used nowadays to increase
biodiesel production, which will be discussed further within this topic.
13.5.1 Continuous Stirred Tank Reactor

A continuous stirred tank reactor (CTSR) is an advanced technology for
a reactor that applies the same fundamental processing mechanism as a
batch reactor. CTSR allowed the continuous production of biodiesel in a
simple step, which makes the production cost become lowered. There is
two important part in CTSR: the reactor and phase separator. The first past
of the reactor involved the conversion of alcohol and triglycerides into bio-
diesel. The process followed by the removal of glycerol from the reaction
mixture in the second stage of CTSR. The second stage: phase separator
used to promote the reaction of transesterification through chemical equi-
librium shifting. CTSR has proved to produce a high yield of biodiesel,
which is about 97.3% yield [37]. CTSR has been used widely in industrial
scale due to the simpler and deep understanding operation of CTSR.
An invention from U.S. Patent No. 2005052103 provides an improved
process for the preparation of biodiesel using modified CTSR. The feed-
stock oil is taken into the modified reactor equipped with the alcohol
recycle/recovery system, condenser, thermometer, and feeding funnel. By
using the CTSR, two layers are formed, and the mixture is allowed to settle
for four hours and the top layer is taken for further processing [38].
13.5.2 Fixed Bed Reactor

Fixed bed reactor (FBR) involved the flowing of oil and solvent through a
cylindrical tube filled with catalyst pellets, which packed in static bed for
the conversion of biodiesel shown in Figure 13.4. A heterogeneous cata-
lyst is used in FBR because of their simple recovery steps which do not
involve any separation process between product and catalyst. Other than
that, the heterogeneous catalyst used in FBR would enhance the reaction
due to slow deactivation and longer durability of the catalyst. By offering
these advantages, the production cost can be reduced. However, the higher
molar ratio is needed during the process due to the remaining glycerol (by-
product), which will remain at the bottom of the reactor and will adsorb on
the surface of the catalyst. This condition will affect the catalyst efficiency
and an additional removal process will be needed [39].
Condenser
Thermometer
Sampling
Biodiesel
Separator
Feedstock Alcohol and Reactor

oil catalyst
Glycerol
Heating and Stirring
Figure 13.4 Schematic diagram of a single reactor CTRS. Reproduced with permission
from [37]. Copyright 2019 Elsevier.
The invention proposed by U.S. Patent No. 2011/0245551A1 introduced

the process for hydroprocessing an acidic biomass feedstock in a guard
bed, which aims to prevent undesired polymerization from occurring. The
guard bed reactor is used to saturate the olefins with hydrogen and prevent
the olefins and other compounds from polymerizing. The reactor, which
can be either a noble metal or non-metal catalyst, is run at low tempera-
tures and able to recycle back the product into the reactor [40].
13.5.3 Micro-Mixer Reactor

Micro-mixer reactor also known as micro-reactors and micro-
structured reactors has been used widely in biodiesel production. The
micro-mixer reactor uses numerous channels with millimeter range
in diameter, which allowed better separation of oil. This is because of
high surface-to-volume ratios and low distance between heat and mass
transfer for diffusion. An invention from U.S. Patent No 8.404,005 stated
the method and system to produce biodiesel using an improved cat-
alytic transesterification process. In this process, the first and second
reactant is dispersed to form a laminar slug flow pattern within the
micro-channel of microreactor and both of them become immiscible.
The mixing between the reactant will trigger the reaction between them
to produce biodiesel and glycerol [41].
13.6 Conclusion
This paper has discussed and analyzed patents related to biodiesel, and the
following conclusion can be made. The demand for fuel energy continues
to increase each year and biodiesel has become a solution to replace diesel
fuel for a more sustainable and greener environment. The use of feedstock
for biodiesel production must come from non-edible feedstock to avoid
the competition between food and fuel. For the current status of biodiesel
production, the second generation of biodiesel, which is from waste, is
more preferable because it does not only produce low-cost biodiesel but
also helps in properly managing waste. In biodiesel production, the use of
catalyst is crucial to fasten the reaction and to produce a better quality of
biodiesel. A heterogeneous catalyst is more suitable to use as it is easier to
separate after the reaction and it can be reused for five to six cycles of reac-
tion. There are few methods for biodiesel production that have been dis-
cussed, and most of the patents have been made for the transesterification
process. This shows that the trend nowadays is more to using transesteri-
fication as a method to produce biodiesel due to the easier reaction which
will lower the production cost. Lastly, the utilization of the reactor in pro-
ducing biodiesel is very helpful for the industrial scale. Among the reactor
used, the CTSR has been used by many biodiesel industries because of the
operation method is more practical.
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14
Reactions of Carboxylic Acids With
an Alcohol Over Acid Materials
J.E. Castanheiro *
MED, DQ, ECT, Universidade de Évora, Évora, Portugal
Abstract
Biodiesel is an alternative to fossil diesel. It is biodegradable and non-toxic. The
production of biodiesel is carried out by transesterification and/or esterification
reactions.
Usually, reactions between a carboxylic acid with an alcohol are carried out
using sulfuric and phosphoric acids. Mineral acids (e.g., sulfuric acid) have some
problems, such as the separation of reaction mixture. Heterogeneous catalysts can
used to replace the homogenous ones.
These catalysts have been used for biodiesel production. Recently, acid solids,
such as heteropolyacids, activated carbons with sulfonic acid groups, and cation-
exchange resins, have been used as catalysts on esterification of free fatty acids (FFAs).
This present work is a review about the esterification reactions of carboxylic
acid (fatty acid) with an alcohol over solid materials.
Keywords: Fatty acids, esterification, heterogenous catalysts, biodiesel
14.1 Introduction
Traditionally, the biodisel is obtained by reaction between one molecule
of triglyceride in conjunction with three molecules of an alcohol, using
NaOH as catalyst. However, if the quantity of carboxylic acid presents in
fat is high, processes will become inefficient, due to the soap formation. It
is necessery an esterification reaction step before the transesterification.
Email: jefc@uevora.pt
*
377
Esterification of a molecule of free fatty acid (FFA) with a molecule of alco-

hol (methanol or ethanol) yields an ester molecule and water molecule.
Figure 14.1 shows a scheme of a fatty acid esterification with an alcohol
(methanol, ethanol, 1-propanol, and 1-butanol) [1, 2].
R1– COOH + R2 – OH ↔ R1 – COOR2 + H2O
Figure 14.1 Scheme of reaction between a carboxylic acid and an alcohol.
where R1 represents a carbon atoms and R2 represents an alkyl group of

the alcohol.
The reactions of carboxylic acids with a alcohol are performed using
homogeneous substances (one phase formed with reactants and catalyst)
and heterogeneous catalysts (two phases: the catalysts are solid and the
reactants are liquid) [1, 2].
To become the biodiesel production as a “eco-friendly processes”, the tradi-
tional sulfuric acid has been substituted for solid catalysts. The homogeneous
catalysts are corrosive, and it is neutralized after reaction. The heterogeneous
catalysts are more environmentally friend and can be reused [3–5].
This chapter focuses on solid acid materials on esterification of FFA.
14.2 Zeolites
Zeolites are aluminosilicates crystalline with micropore system. These
catalysts have an important propriety: shape selective. Due to the surface
acidity, the zeolites can be used as heterogenous catalyst in the synthesis
of different areas such, fine chemistry, and petrochemical industry [6–8].
However, only zeolites with large porous are applied on reactions between
carboxylic acids with alcohols. The zeolite’s activity improves with the
increases of the ratio silicon to aluminum, which can be an indication that
the zeolite reactivity is influenced by the hydrophobic/hydrophilic balance
of its surface The activity of zeolites for esterification reactions is affected
by the aluminum amount present in its framework [6–9].
The reaction between hexadecanoic acid and methanol was done over
four zeolites (H-Y, ZSM-5) as catalysts [10]. When the reaction was carried
out without zeolite (Blank), the conversion was lower than with zeolite.
With H-Y-60 zeolite, a conversion of 100% was obtained. This behavior
was explained due to difference on zeolite’s porous system. H-ZSM-5
contains medium-sized micropores, with avarege pore size (5.6 Å × 5.3
Å channels) lower than H-Y zeolite (7.4 Å). The reaction over H-ZSM-5
Reactions of Carboxylic Acids 379
zeolites, probably, occurs at the external surface area, due to the molec-
ular size of ester. In contrast, H-Y zeolites offer high surface and porous
volume. The H-Y-60 catalyst showed the highest catalytic activity for this
reaction. Under optimazed reaction conditions, a 100% conversion was
obtained. The H-Y-60 zeolite can be recycled [10].
14.3 SO3H as Catalyst

The reaction between oleic acid and ethanol was performed using sulfon-
ated polystyrene [11]. This reaction without polystyrene yielded only about
10% of the ethyl oleate. When it was used sulfonated polystyrene, the yield
increased from 30% to 90%. The optime reaction conditions were found to
be amount of ethanol (219.0 mmol), amount of oleic acid (7.45 mmol), and
amount catalyst (25 mg). Under this reaction conditions, the ethyl oleate
yield was about 90%. These catalysts can be reused several times [11].
When octadec-9-enoic acid reacted together with methanol over
Amberlyst-15, using a continuous reactor, over of Amberlyst-15, the con-
version increased with reaction temperature [12]. The reaction conditions
were as follows: methanol flow 6.4 ml/h, oleic acid flow 9.0 ml/h, and bed
height of 10 cm, and the temprature was 80°C, 100°C, and 120°C. Under
this conditions, the yields were 69.9%, 72.7%, and 84.0%. It was observed
that the catalyst does not loss activity during the reaction [12].
The esterification of palmitic acid with methylic alcohol was done over
PVA cross-linked with sulphosuccinic acid (SSA) and PS cross-linked
with divinylbenzene containing −SO3H [13]. It was observed that the PVA
catalysts showed high activity than the PS. PVA_SSA40 material showed
a good stability [13]. This reaction was also studied over chitosan with
sulfonic acid [14]. Catalyic actvity of these materials increased when the
amount of sulfonic groups increases, until a maximum (sample CT4). The
catalyst sample CT4 showed a good catalytic stability [14].
The reaction of octadec-9-enoic acid and n-butanol was done over poly-
styrene-modified organosilicas with sulfonic acid groups [15]. These mate-
rials demonstrated high activity. The optimal conditions were T = 130°C,
catalyst amount = 2 wt%, and molar ratio oleic acid to n-butanol 1:1.4,
which led a oleic acid conversion about 92% [15].
Activated carbons with −SO3H have been utilized as material for reac-
tions between carboxylic acids with alcohols. These materials can be
obtained from sugar, starch, or cellulose [16, 17].
The reaction between octadec-9-enoic acid and octadecanoic acid and
ethanol were performed using activated carbons prepared from d-glucose
with −SO3H. The materials exhibited high activity, probably by the high
quantity of −SO3H groups [17].
The reaction between octadec-9-enoic acid and ethyl alcohol was done
over carbons (CMK) with −SO3H [18]. A yield of ethyl oleate about 60%
was obtained, after 6 h of reaction, at 353 K, when it used 0.005 mol of
octadec-9-enoic acid and 0.05 mol of ethyl alcohol. After four uses, high
catalytic activity was observed [18]. These reaction was studied over acti-
vated carbon prepared from bamboo with sulfanilic acid [19]. The opti-
mized conditions were as follows: m activated carbon = 12%; octadec-9-enoic
acid: ethyl alcohol = 7, T = 85°C; t = 3 h. In these conditions, a catalytic
efficiency of 91% was obtained [19].
The reaction between octadec-9-enoic acid and methyl alcohol was done
on activated carbons [20]. These catalysts are mesoporous materials, and
sulfonic acid groups were introduced in its surface. The performance of
these materials was greater than Amberlyst-15 [20]. The same reaction was
studied using ordered mesoporous carbons (OMCs). The catalysts showed
a methyl oleate yield of 96.25%. After nine reuses, the catalyst is active [21].
The esterification of fatty acid was performed using sulfonated meso-
porous carbon catalysts [22]. After eight cycles, the FFA conversion was
>91% [22].
14.4 Metal Oxides

The reaction between n-octanoic acid and methyl alcohol was carried over
metal oxides (tin and zirconia) sulfated. The sulfated tin material revealed
high performance for the esterification, which can be explained due to its
strong acidity [23].
The reaction between of octadecanoic acid and methyl alcohol was per-
formed over aerogel sulfated zirconia (A-SZr) and xerogel sulfated zirco-
nia (X-SZr) [24]. A-SZr catalyst has greater textural properties, like total
porous volume than X-SZr material. After 7 h of reaction, the A-SZr cat-
alyst showed 88% yield to product. The activity of aerogel material was
better than xerogel. A-SZr catalyst was reused [24].
The reaction of octanoic acid and ethyl alcohol was performed using
zirconia catalysts. The SZ500 material exhibited high performace for this
reaction [25].
The reaction between octadec-9-enoic acid and methy alcohol was done
using titanium oxide [26]. It was observed that the catalyst [TiO0 /SO42− ]
showed the greatest performed of all material used in the esterification
(after 3 h, about 82.2% oleic acid conversion) [26]. This reaction was also
studied over WOx immobilized on MCM-41 [27]. It was prepared materi-
als with several WO3 amount. It was observed a conversion near 100% with
catalysts loading of WO3 higher than 10 wt%. The catalyst with 15 wt%
WO3 can be reused [27]. This reaction was studied over sulphated Zr-KIT-6
(x) material [28]. Under optimized conditions (T = 393 K, methy alcohol:
octadec-9-enoic acid = 20:1, mcatalyst = 4 wt%, t = 6 h), it was obtained
an ester yields of 95%. The catalyst was reused. After three cycles, it was
observed that the material has a good activity and stability [28].
The reaction between octadec-9-enoic acid and n-butyl alcohol has
been studied using zirconium sulphate immoblized on silica (ZS) [29]. It
was observed that the performance of ZS was greater than ZS not immo-
bilized. The catalytic activity increased with amount of ZS. However,
when the ZS amount is high, the catalytic activity decreased. The octadec-
9-enoic acid conversion increased with the amount of solid. Molar ratio of
octadec-9-enoic acid:n-butyl alcohol was also optimized. The conversion
of octadec-9-enoic acid enhanced with the molar ratio. Silica-supported
ZS was reused [29].
The reaction between octadec-9-enoic acid and ethyl alcohol was done
over oxides of tin sulfated [30]. At T = 353 K with molar ratio 1:10, the
octadec-9-enoic acid conversion improved with the acidity. The mate-
rial can be recycled [30]. This reaction was also studied over mesoporous
SnO2/WO3 [31]. The reaction was permormed using three temperatures:
313, 333, and 353 K. The octadec-9-enoic acid conversion increases with
the reaction temperature. Also, the catalyst loading was studied. It was
observed that increases with the amount of catalyst. The catalyst can be
reused, after regeneration [31]. The reaction between octadec-9-enoic acid
and ethyl alcohol was done over WO3 supported on a USY zeolite [32].
Catalysts with different amounts of WO3 (from 2.5% to 20.5% WO3) were
prepared. It was observed that the WO3/USY catalysts were more active
than USY. The material perormance enhanced with quantity of WO3 sup-
ported on USY, until the top (11.4% of WO3). After this activity maximum,
when the amount of WO3 increases the catalytic activity decreases. The
material could be recycled [32].
The reactions between octadec-9-enoic acid, octadecanoic acid and
dodecanoic acid and methyl alcohol, and ethyl alcohol and butyl alcohol
was carried out over niobium materials [33]. The reaction between dodeca-
noic acid and butyl alcohol was studied over niobic acid and niobium
phosphate, being phosphate material that showed the best performance.
The dodecanoic acid conversion improved with the temperature. The
effect of carbon chain legth was also studied. The conversion reduce from
dodecanoic acid (97%) to octadecanoic acid (94%). The octadec-9-enoic
acid conversion was smallest of all carboxylic acids. The niobium phos-
phate catalyst was reused without loss its activity [33].
The reaction between octanoic acid and ethyl alcohol was carried out
over SO24− /Fe x Al1− x PO4 acid catalysts [34]. The presence of Fe on this mate-
rials improved the conversion of octanoic acid. This materials can be recy-
cled [34].
14.5 Heteropolyacids
These materials (HPAs) are polyoxometalates, which are catalysts of differ-
ent reactions. The HPAs have got a low surface area. The heteropolyacids
have been supported on different materials like silica, zeolites, zirconia,
and polymers [35, 36].
The reaction between octadec-9-enoic acid and ethyl alcohol was carried
out in the presence of H3PW12O40 immobilized in ZrO2 [37]. Catalysts with
different amount of heteropolyacids were prepared. The octadec-9-enoic
acid conversion enhanced with the amount of H3PW12O40 immobilized on
zirconia. Optimum reaction conditions were obtained with mcatalyst = 20
wt%, T = 100°C, t = 240 min, and an octadec-9-enoic acid:ethyl alcohol=
1:6. In these conditions, it is obtained a 88% of octadec-9-enoic acid con-
version. This material can be recycled [37].
The reaction between acid hexadecanoic (0.01 mol) and methanol (2.5
mmol) was performed using insoluble HPA salts with Cs [38]. The opti-
mum activity was obtained over a material with Cs equal to 2.3. Material
Cs2.3H0.7PW12O40 was reused [38]. This reaction was studied using het-
eropolyacids in SiO2 [39]. The materials activity reduced in the following
order: HPMo-SiO2 < HSiW-SiO2 < HPW-SiO2. Different catalysts with
HPW immobilized in SiO2 were made. The catalyst PW-silica2 reveals
the greatest reation rate. The material was reused [39]. This reaction was
studied over differents amount of HPW (5% to 30% wt) immobilized on
niobia [40]. The conversion of acid hexadecanoic increases with HPW
quantity supported on Nb2O5. High conversion was obtained with mate-
rial (HPW)25%/Nb2O5. When amount of HPW increases, the conversion
do not change to much. The conversion of acid hexadecanoic increased
when the temperature increased as well. Material (HPW) 25%/Nb2O5 was
recycled [40, 44]. This reaction was studied over different heteropolyacids
(HPW, HPMo, and HSiW) immobilized on SBA-15 [41]. Material HPW1
showed highest conversion of all prepared materials. It was also made

materials with various HPW quantity. The acid hexadecanoic conversion
improved when the quantity of heteropolyacid supported on silica until
a maximum, which was obtaind using HPW3-SBA-15 catalyst (6.7% wt).
The effect of catalyst loading (HPW3-SBA-15) on esterification was also
studied. The acid hexadecanoic conversion improved when the catalyst
quantity improved. The HPW3-SBA-15 catalyst could be reused [41]. The
reaction between hexadecanoic acid, octadecanoic acid, octadec-9-enoic
acid, and ethyl acohol was done in the presence of HPW immobilized in
SBA-15 (12.5% wt) [42]. The highest conversion was obtained with hexa-
decanoic acid. This material could be recycled [42].
The reaction between hexadecanoic acid and methyl alcohol was done
over HPW on MCM-41 [43]. Materials with various quantities of HPW
were made. The hexadecanoic acid conversion enhanced with quantity of
HPW anchored to MCM-41. However, for catalysts with high amount of
HPW (for 30% and 40% loading), the palmitic acid conversion did not
increase significatively. The material with 30% loading of HPW (HPW3/
MCM-41) was used for optimize the reaction conditions. Under opti-
mized conditions (T = 333 K; mcatalyst = 0.1 g; t = 360 min; hexadecanoic
acid:methyl alcohol = 1:40), a 90% of hexadecanoic acid conversion
was achieved. Catalyst can be reused [43]. This reaction was also done
over 12-tungstophosphoric acid on SnO2 [44]. Material with 15 wt% of
12-tungstophosphoric acid supported on SnO2 revealed the greatest con-
version. Material was reused. After five reaction cycles, the hexadecanoic
acid conversion stayed high level [44].
The reaction between octadec-9-enoic acid and methyl alcohol was
done over HPW anchored to SBA-15, as catalyst [45]. Under optimized
condition (octadec-9-enoic acid: methyl alcohol = 1:40; mcatalyst = 0.1 g;
T = 313 K; t = 240 min), the conversion of octadec-9-enoic acid was 90%.
Materials could be recycled [45].
The reaction between hexanoic acid and methyl alcohol was done on
HPA supported in Nb2O5, ZrO2, and TiO2 [46]. These materials demon-
strated higher performance than Amberlyst-15, H-Beta, and HY zeolite.
Under optimized condition (hexanoic acid:methyl alcohol = 1:20, mcatalyst =
0.1 g, T = 333 K), a 53.2% conversion was obtained [46].
The reaction between dodecanoic acid and ethyl alcohol was done over
H3PW12O40 (HPW) immobilized on Ta2O5 support [47]. The TOF of HPW
(1.62 min−1) is lower than the TOF of HPW/Ta2O5 (5.58 min−1), which is an
indication that the HPW immobilized on Ta2O5 shows more activity than
the HPW. The catalysts showed high stability [47].
14.6 Other Materials

The reaction between dodecanoic acid and ethyl alcohol was done over clay
mineral (montmorillonite STx1-b) as catalyst [48]. Under optimized con-
dition (dodecanoic acid: ethyl alcohol = 1:6; mcatalyst = 10 wt%; T = 453 K;
t = 1.5 h), the conversion of octadec-9-enoic acid was 90%. Catalyst STx1-b
can reused. After four cycles, a good catalytic activity was observed [48].
This reaction was also done over Zr-MOF [49]. These materials showed
performance similar to other solids [49].
The reaction between dodecanoic acid, octadecanoic acid, octadec-
9-enoic acid, and ethyl alcohol was preformed using montmorillonite K10
as catalyst [50]. Under optimized conditions (carboxylic acid:ethyl alcool =
1:12, mcatalyst = 12%, T = 453 K, t = 240 min), high conversions (about 90%)
were achieved [50].
The reaction between octanoic acid, dodecanoic acid, octadecanoic
acid, octadec-9-enoic acid, and methyl alcohol was carried out over
Brazilian smectite natural clay [51]. The acid treatment of material gave a
catalyst with high catalytic activity. Under optimized condition (carbox-
ylic acid: methyl alcohol = 1:3; mcatalyst = 10 wt%; T = 373 K; t = 240 min),
the conversion of octanoic acid, dodecanoic acid, octadecanoic acid, and
octadec-9-enoic acid was 99%, 98%, 93%, and 80%, respectively. The mate-
rial could be recycled [51].
14.7 Conclusions
The reaction between a carboxylic acid (like octanoic acid, dodecanoic
acid, octadecanoic acid, and octadec-9-enoic acid) and an alcohol is an
important step in biodiesel production. The existence of high amount of
free carboxylic acids in raw material (like waste cooking oil and animal fat)
can complicate the process of transesterification of triglycerides, which is
done with KOH or NaOH. An alternative to produce biodiesel from oils
or fats with high level of carboxylic acids, it is a esterification of carboxylic
acids before transesterification reaction.
Reactions between carboxylic acids and alcohols are carried out over
homogenous catalysts, which have some environment problems. In order
to become the process as a “environmentally friendly process”, sulfuric acid
can be substituted by solid materials. Some materials like zeolites, hetero-
polyacids, materials with sulfonic groups (MCM-41, SBA-15, activated
carbons, organic polymers), and modified inorganic mixed oxides have
been applied on this type of reaction.
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15
Biodiesel Production From Non-Edible
and Waste Lipid Sources
Opeoluwa O. Fasanya1, Aishat A. Osigbesan1 and Onoriode P. Avbenake2,3*
1
Petrochemical and Allieds Department, National Research Institute for Chemical
Technology, Zaria, Nigeria
2
Chemical and Petroleum Engineering Department, Bayero University,
Kano, Nigeria
3
School of Science & Technology, Pan-Atlantic University, Ibeju-Lekki, Nigeria
Abstract
Biodiesel has become a very popular renewable/alternative fuel. The popularity of
biodiesel is driven by the relative ease of synthesis and the wide array of feedstock
from which it can be produced. These include vegetable oils, animal fats, and other
sources of biomass. Vegetable oils are the main feed stock that have been used for
biodiesel synthesis. To the extent that oils meant as food for humans and animals
are being diverted for biodiesel production. To stop this unsustainable practice,
nonedible vegetable feedstocks are constantly identified, researched, and culti-
vated. Much progress has been made over the last few years in this especially in
terms of oils from seeds of plants such as Jatropha curcas, Calophyllum inophyllum,
Azadirachta indica, Hevea brasiliensis, and Ricinus communis, among others. In
addition, waste vegetable oils are also being harnessed for the purpose of biodiesel
production, rather than being discarded once they degrade. Furthermore, the
use of microalgae, a third-generation source of biodiesel, was equally discussed,
owing to their popularity among researchers. The increased interest is a conse-
quence of the speed and ease of cultivation and to a larger extent the quantity of
oil that could be harvested. As a matter of fact, fourth-generation biodiesel is now
being derived from genetically modified algae strains which contain even more
oils. Accordingly, this chapter aims to critically review a portion of the numerous
developments concerning biodiesel from non-edible sources.
*Corresponding author: paulavbenake@gmail.com
389
Keywords: Biodiesel, lipids, renewable energy, waste utilization, methyl esters,

fuel, non-edible oils, deacidification
15.1 Introduction
The ever increasing energy requirements in the world today have placed a
large demand on limited quantity of fossil based fuels in the world at large.
The increase in energy demand is due to technological advancement, indus-
trialization, and population growth all over the world. The International
Energy Agency (IEA) estimates that 50% more energy will be required
in 2030 when compared with present energy consumption [1]. There is
no gain saying that copious levels of environmental pollution particularly
crude oil spills and CO2 emissions are associated with extraction and use
of fossil fuels. Coupled with fluctuating crude oil prices, there is pertinent
need of generating alternative sustainable fuels for energy consumption.
Some alternate sources of fuel that have generated a lot of interest include
solar cells [2], fuel cells powered by hydrogen [3], ethanol [4], methanol [5],
and diesel derived from biological materials or biomass. Biomass as a source
of fuel is quite advantageous because it is renewable and also has relatively
low carbon foot print during synthesis of fuels. This guarantees some mea-
sure of environmental stability while energy requirements are being met.
Globally, the United States of America, Brazil, and European Union are
the main consumers of bio-based fuels. As at 2000, annual biodiesel pro-
duction was recorded to be about 0.8 million tons [6]. In 2007, Germany
alone marketed 3.2 million tons of biodiesel [7]. Despite this production
rate, the IEA claims that global biofuel production rate is not able to keep
up with the present demand for the product. As at 2018, renewable energy
met only 3.7% of transportation fuel demand [1]. The IEA have, however,
predicated that between 2019 and 2024, a 25% production increase corre-
sponding to approximately 190 billion litres would be achieved.
Diesel produced from biomass is popularly referred to as biodiesel. It
is a fuel which is made up of monoalkyl esters of long-chain fatty acids
derived from biomass which are sourced from plants or animal fats. Better
combustion efficiency has been observed in biodiesel synthesized by this
route [8]. The International Association for Testing and Materials (ASTM)
has set out criteria in the ASTM D6751 (Table 15.1) which lists out prop-
erties that a fuel must possess to be called biodiesel. Inherent advantages
of biodiesel use include its blending capacity with other energy sources,
lubricity which could invariably help extend engine lifespan, higher flash
point, and lack of toxicity [9, 10].
Biodiesel Production From Non-Edible Sources 391
Table 15.1 Biodiesel specifications and their limits.

Properties EN 14214 ASTM D6751
Composition of biodiesel C12-C22 C12-C22
Esters content Greater than 96.5% (m/m) –
Density at 15°C 860–900 kg m−3 –
Viscosity at 40°C 3.5–5.0 mm2 s−1 1.9–6.0 mm2 s−1
Flash point ≥101°C ≥ 130°C
Sulphur content ≤10 mg kg−1 50 mg kg−1
Carbon residue ≤0.3% (m/m) ≤ 0.05 (m/m)
Cetane number ≥51 ≥ 47
Sulfated ash ≤0.02% (m/m) ≤ 0.02% (m/m)
Water content ≤500 mg kg−1 ≤ 0.05% (v/v)
Corrosion – 3h
Oxidative stability 110°C 4h 3h
Acid value ≤0.50 mg KOH g−1 ≤ 0.50 mg KOH g−1
Iodine value 130 g I2/100 g –
Methanol content ≤0.02% (m/m) –
Monoacylglycerols ≤0.8% (m/m) –
content
Diacylglycerols content ≤0.2 (m/m) –
Triacylglycerols content ≤0.2 (m/m) –
Free glycerine ≤0.02% (m/m) ≤ 0.20% (m/m)
Total glycerrin ≤0.25% (m/m) ≤ 0.25% (m/m)
Pour point – −15 to −16°C
Phosphorous amount ≤4 mg kg−1 ≤ 0.001% (m/m)
Cloud point – −3 to 12°C
Adapted from Fonseca et al. (2019) [11].
Generally, biodiesel is produced by transesterification of triglycerides

with a short chain alcohol in the presence of a catalyst to form fatty acid
alkyl esters and glycerol as products. The reaction scheme is shown in
Figure 15.1 and in Equations 15.1 to 15.3. Transesterification is a relatively
simple and cost-effective process [12]. Though some challenges with sepa-
ration of the final products from catalyst may occur depending on whether
homogenous or heterogeneous catalysts are employed. Transesterification
catalysts could either be acidic [13], basic [14, 15], or enzymatic [16].
While homogeneous catalysts such as NaOH and KOH are generally more
effective, separation after reaction requires thorough washing with large
amounts of water to ensure complete removal of the catalyst. This chal-
lenge was resolved with use of solid catalysts such as CaO. Though these
are not quite as reactive and are often prone to deactivation or single digit
limited cycles of use. Strides have made to develop stable heterogeneous
catalysts which are resistant to rapid deactivation.
Triglycerides + Methanol = diglycerides + FAME (15.1)
Diglycerides + Methanol = Monoglycerides + FAME (15.2)
Monoglycerides + Methanol = Glycerol + FAME (15.3)
For oils with high free fatty acid (FFA), an initial pre-treatment step is
required where esterification of the oil with methanol in the presence of an
acid catalyst (usually sulphuric acid) is carried out as seen in Equation 15.4
FFA + Methanol = FAME + Water (15.4)
One major point of concern in biodiesel synthesis is the biomass feed-

stock. Globally, oil-bearing plants have been widely explored for biodiesel
production. Typically, plants with seeds that yield high amounts of oil are
usually preferred as starting triglyceride sources, since these would result in
large volumes of biodiesel being produced. Economically, this is the route
H2C COO R1 CH3 H2C OH

Catalyst COO R1
HC COO R2 + 3CH3OH CH3 COO R2 + HC OH
CH3 COO R3 H2C OH
H 2C COO R3
Triglyceride Methanol Fatty acid methyl ester Glycerol
Figure 15.1 Transesterification reaction showing reaction of methanol and triglyceride to

form Fatty acid methyl ester (FAME) and glycerol.
to follow. The challenge, however, is that edible oils which are in large
demand as food sources such as palm oil [17, 18] and soybean oil [19, 20]
are being used to produce the fuel. This has led to unhealthy competition
between use of oil as food or fuel. Inadvertently, resulting in global deple-
tion of edible oils for food and consequently affecting the price of food
and fuel dependent on these oils. It is expected, therefore, that this would
birth major economic crisis in future [12]. Available arable land for agri-
cultural cultivation would reduce and lose nutrients due to large volumes
of plants constantly being cultivated to meet the ever increasing energy
and food requirements. Edible biodiesel feedstocks are generally termed
first-generation feedstock. They were initially explored for large-scale pro-
duction. Currently, it is estimated that over 90% of current biodiesel pro-
duction is from edible vegetable oils [21]. Palm oil, sunflower oil, coconut,
groundnut, and soybean [19] oils all fall in this category [12].
To forestall the impending crisis associated with the use of edible
crops, attention has been focused on utilization of non-edible oils. These
are generally classified as second-generation biodiesel feedstock. Some
of which include but not limited to Jatropha curcas, Hevca brasillenis,
and Azadirachta indica. Biodiesel from waste oil is also considered to be
second-generation feedstock. Using these types of feedstock offers the
advantage of reducing pollution concerns and costs associated with safe
disposal. It is estimated that production costs can be reduced by as much
as 70% when non-edible oils are utilized [22].
There are numerous reviews on the use of non-edible oils for biodiesel
production [6, 23–27]. Atadashi discussed the effect of using high FFA
oils, many of which are not fit for human consumption [28]. The review
by Balat discussed about trends in non-edible feedstock that were gain-
ing traction as of 2011 [29]. Discussions were oils derived from Jatropha
curcas, Pongamia pinnata, Madhucca indica, and microalgae among others
were reviewed. Although there are now more recent reviews highlighting
developments using micro-algae [30], some of which we will discuss here.
The review by Sajjadi and co-workers contained prediction models for
parameters such as viscosity, density, flash point, cetane number, and heat-
ing value of both edible and non-edible based biodiesels [31]. Pereira and
co-workers also reviewed models but their focus was on thermos-physical
models to estimate melting points of fats and cold flow properties of bio-
diesel [32]. While Kirubakaran and Selvan focused their review on using
waste chicken fat [33]. Some other reviews are location specific, highlight-
ing potential feedstock and production strategies [34, 35].
In the end, the choice of non-edible feedstock for biodiesel produc-
tion will be highly location dependent. Such as in the case of Jatropha,
Callophyllum innophyllum, and neem which are native to India. Another

important property that would determine choice of feed for biodiesel pro-
duction is its ability be grown rapidly and under a wide variety of con-
ditions. This will definitely reduce competition on the use of arable land
for cultivating crops for energy for plant based sources. For animal-based
sources feeds with low FFA or with FFA that can be reduced with ease are
feedstock of choice. This chapter highlights both plant and animal-based
sources feedstock that are non-edible and shows progresses made in utiliz-
ing them for biodiesel production.
15.2 Non-Edible Plant-Based Oils

15.2.1 Jatropha curcas
Jatropha curcas is a drought resistant crop that is capable of growing in fal-
lowed land. It has the ability to withstand a variety climatic zones and soil
conditions. In addition to these, its short gestation period and fast growth
have led to its widespread cultivation. It is a highly suitable crop for bio-
diesel production in developing countries especially in the tropical and
subtropical parts of the world [36]. Commercial growth of the crop has,
however, experienced setbacks all over the world due to poor understand-
ing of the crop [37]. Recently, detailed studies have, however, shown that
optimum growing conditions such as an excess of 700-mm rainfall annu-
ally, soil pH ranging between 6 and 9, and annual temperature between
16°C and 28°C are required for commercial Jatropha plantation [38]. A
lot of attention is given to its cultivation as it is responsible for 36%–44%
of the biodiesel selling price depending on where it is planted [37, 38].
Deliberate J. curcas plantations are currently being grown in Rwanda [39],
China, Ethiopia, India, Nepal, and Tanzania [38].
Its combustion and emission properties closely resemble that of petro-
leum diesel. Properties such as flash point and ignition point are higher
for J. curcas derived fuels [36]. As far back as World War II, J. curcas oil
was used was blended with diesel and used as a fuel alternative [28]. A
number of authors have maintained that it is the best non-edible oil for
biodiesel production [36, 39, 40]. The oil content of the seed appears to be
dependent on location and probably variety as values seen in literature fall
between the range of 25% to 59% [28, 36]. Oil from J. curcas can also be
used for producing soaps and candles.
The use of Jatropha for biodiesel has been widely investigated. Its high
FFA usually entails that a two-step production process is often required.
Table 15.2 Different catalysts, reaction conditions, and yield during synthesis of biodiesel from Jatropha seed oil between 2015
and 2019.
Catalyst Methanol
Yield Time Pressure Temperature loading oil Catalyst
Catalyst (%) (hours) (MPa) (°C) (wt %) ratio Pre-treatment type Ref.
CaSO4/ 94 4 Atm 120 12 9 None Amphoteric [42]
Fe2O2-SiO2
Sr+2 - CaO/ 99.6 2 Atm 65 5 9 Not stated Basic [60]
MgO
Zn8FeC 100 4 4.5 MPa 160 7 40 None Amphoteric [41]
Na2SiO3@Ni/ 97.7 2 Atm 65 7 9 Esterification Basic- [61]
JRC magnetic
KF supported 92.2 1 Atm 75 7 21 Not stated Alkaline [62]
on red
mud
nano CaO 98.54 2.1 Atm 60 2 5.15 Esterification Basic [63]
SO2−4/TiO2 85.3 24 0.2 140 4 9 Acidic [64]
(Continued)
Biodiesel Production From Non-Edible Sources
395
396
Table 15.2 Different catalysts, reaction conditions, and yield during synthesis of biodiesel from Jatropha seed oil between 2015
and 2019. (Continued)
Catalyst Methanol
Yield Time Pressure Temperature loading oil Catalyst
Catalyst (%) (hours) (MPa) (°C) (wt %) ratio Pre-treatment type Ref.
Al-SBA-15 99 24 4 180 6.5 12 None Acidic [43]
Fe-Zn-1 – 4 Atm 160 4 10 Acidic [65]
Na2ZrO3 99 1 Atm 65 30 3 [20]
Cs-Na2ZrO3 90 1 Atm 65 15 3 Basic [20]
Ca-La-Al 96.91 3 Atm 150 15 7 [44]
Si-MMT-Ph- 98 2.5 Atm 110 6 5 [66]

SO3H
Calcined 96.1 3 Atm 70 6 9 Basic [67]
animal
bones
The discovery and use of amphoteric catalysts has been suggested as a way
of combining the esterification and transesterification step into one. The
use of Zn-FeC catalysts resulted in as much as 100% biodiesel yield with
extremely high stability [41]. Other studies using amphoteric catalysts
have given yield of 94% after 4 hours of reaction [42]. Table 15.2 contains
data on recent catalyst developments for biodiesel synthesis from Jatropha.
Interestingly, one report has shown that under the right conditions some
transformation can occur without the use of catalysts [43]. Jatropha still
remains one of most widely researched oils for biodiesel production. As
can be seen from Table 15.2, there is still a lot of room for research espe-
cially in terms of catalyst development. Reusability of catalysts for multiple
runs remains a challenge. Though some work has shown reusability of up
to five times with just a 5%–10% drop in FAME yield [44].
15.2.2 Calophyllum inophyllum

Calophyllum inophyllum is a perennial plant that grows predominantly in
Australia, Sri Lanka, India, and Southeast Asia. It is a mangrove plant with
oil containing seeds [45]. The relatively high oil content in its kernels has
also made the plant attractive for biodiesel production in parts of the world
where its growth is prevalent. About 46%–60% of toxic non-edible oil can
be extracted from its kernels [45, 46]. Apart from biodiesel synthesis, the
oils have been found to have properties which can be used to treat skin
diseases, arthritis, and burns, to salve wounds, and many others [47].
Biodiesel from C. Inophyllum generally has high oxidation stability but
it is improved further with the use of additives such as Butylated hydroxy-
tolune, 4-methyl-6-tert-butyphenol and antioxidant extracted from pon-
gamia leaf [48]. As with other oils previously discussed, the biodiesel yield
is dependent on reaction conditions and catalyst type with yields of over
85% reported by different groups [49, 50]. Various reports have also been
written describing its performance in diesel compression engines [51–54].
15.2.3 Mesua ferrea

Mesua ferrea L. also known as Nahar or Ceylon ironwood [55] is a non-
edible evergreen timber plant native to Sri Lanka and rather abundant in
Northeast India [56, 57]. It also grows freely in Nepal, Indonesia, Vietnam,
Cambodia, and Singapore [58]. Its seeds containing between 55% and 57%
of oil [56]. The timber plant is its unsaturated fatty acid content is between
65.85% and 68.31% [56]. With regard to biodiesel production, this plant
is relatively underutilized but this trend is changing. The reason for this is
attributed to some shortfalls experienced in Jatropha yield over the last few
years [58]. When tested on compression injection engines, results obtained
were comparable with conventional diesel [58, 59]. Suggesting that the bio-
diesel from this oil is suitable for blending or as a complement to Jatropha
derived biodiesel.
15.2.4 Jojoba Oil

Simmondsia chinensis (linn) Schneider (commonly identified as jojoba but
is also called deer nut, oat nut, wild hazel, and coffee berry) is a prom-
ising oil seed crop for the economic development of the arid and semi-
arid land all over the globe. The jojoba plant is a monogenetic dioecious
gray-green shrub belonging to Simmondsiaceae family. It is native to the
North American deserts, especially those of south western states in the
United States (California, Arizona, and Utah) and Northwestern Mexico
(Baja California and Sonora). Jojoba oil became widely known through
the Spanish missionaries of the 18th and 19th centuries. Native Americans
used the crushed seed oil for skin care and medicinal purposes. The
Spanish missionaries became aware of its uses and introduced it to other
parts of the world. The plant has been cultivated for more than 30 years
in many countries worldwide, such as India, Mexico, Chile, Argentina,
Australia, Tunisia, the Palestinian territories, Saudi Arabia, and Egypt, due
to its promising economic value [3], with the United States considered the
largest jojoba oil-producing country, followed by Mexico. The jojoba oil
has been reported previously as having potential capabilities for the cos-
metics and skincare industry [68].
The oil extracted from Jojoba seeds is golden colored and odorless with
relatively high viscosity which is much higher than petroleum fuels [69,
70]. It has wax-like unsaturated esters, consisting of a straight chain of fatty
acids and higher alcohols. It has been stated severally that wax and not
oils are extracted from Jojoba due to their peculiar nature [71, 72]. The
main constituent of these FFA is gondoic acid (C20:1) with a concentration
of 59.5%. Other components as reported by Shah and co-workers include
oleic acid, erucic acid, and arachidonic acid with concentrations of 10.7%,
12.3%, and 9.1%, respectively [68].
15.2.5 Azadirachta indica

Oil can be extracted from seed kernels of the Azadirachta indica (Neem
tree). Depending on the source, neem seeds could have as low as 30% oil
[73] or between 40% and 45% oil [74]. It has been found to have diverse
applications. One of the main uses of neem seed oil (NSO) has been
widely used as a pesticide due to the presence of Azadirachtin [75, 76].
Due to the presence of this compound and other similar ones, neem oil
is toxic to humans. Children are especially more vulnerable to neem oil
poisoning [77].
NSO has been reported to have high levels of FFA. Like Jatropha and
other high FFA oils, this invariably requires a two-step pre-treatment
during biodiesel synthesis [78]. This involves the use of an acid catalyst
for esterification with methanol to reduce the FFA. This is then followed
by transesterification with a base or acid catalyst to produce the required
methyl ester. H2SO4 has been predominantly used to reduce FFA but solid
catalysts are also being explored. Solid acid catalysts have the advantage
of easy separation after reaction though activity at times may not be
comparable to homogenous catalysts [13]. Recently, solid catalysts with
improved activity are being reported. The use phosphoric mordenite was
reported to result in a 92% reduction on neem oil FFA after just 60 min-
utes of reaction [73].
The performance of biodiesel from neem oil has been evaluated either
as a blend or as a standalone fuel. It was reported that methyl esters from
NSO blended with diesel gave better performance provided the concentra-
tion was below 20% [79]. Higher blends resulted in increased NOx emis-
sions though engine performance was marginally better. Besides, catalytic
converters are currently being employed to reduce emissions from neem
oil derived diesel [80].
15.2.6 Rubber Seed Oil

Rubber tree (Hevea brasiliensis) is one of the abundant natural resources
found in humid tropical countries. Seed yield from rubber plantations
varies from 100 to 150 kg/ha, depending on soil fertility and crop den-
sity. Extensive plantations can be found in Nigeria [81], Malaysia, India
[82], Indonesia, Liberia [83], Thailand [84], and China [85]. As at 2009,
plantations in Malaysia produced more than 1.2 million hectares pro-
ducing roughly 1.2 million tons of seeds per year [86]. It is primarily
grown for latex production as a source of foreign exchange, though its
usefulness is not maximally explored. The tree produces oil-bearing
seeds with oil content far more than that obtainable from the likes of
Jatropha and Karanja seeds. Yields of kernel from rubber seeds range
from 57% to 63% [87]. This leads to yield about 5,500 tons of rubber seed
oil and about 6,000 tons of defatted protein meal for animal and human
consumption [81].
400
Table 15.3 Comparison of FFA composition of selected non-edible oils.
Palmitic Stearic Oleic Linoleic Linolenic Myristic
acid acid acid acid acid Malvalic Palmitoleic Lauric acid
(C16:0) (C18:0) (18:1) (C18:2) (C18:3) acid Ricinoleic Arachidic (C16:1) (C12:0) (C14:0) Ref.
Rubber seed 9.1 5.6 24 46.2 14.2 – 0.9 [84]

oil
Castor oil 1.3 1.2 3.6 4.6 0.4 – 88.9 [21,

91]
Jatropha Oil 13.37 6.1 41.71 36.42 – – – 0.82 [92,

93]
mango seed 15.6 30.2 48.2 6.9 – – – [94]

oil
Neem seed oil 18.1 18.1 44.5 18.3 0.2 – – 0.8 [95]
Yellow 26.4 3.86 39.4 27.03 – – 1.1 [96]

oleander
Spent coffee 32.4 7.5 10.1 43.1 0.9 – 3.1 [97]

seed
grounds
Euonymus 14.5 3.1 49.8 29.3 – – 0.07 2 [98]

maackii
Ceiba 22.37 3.8 23.24 33.63 9.14 [99]

pentandra
(Continued)
Table 15.3 Comparison of FFA composition of selected non-edible oils. (Continued)
Palmitic Stearic Oleic Linoleic Linolenic Myristic
acid acid acid acid acid Malvalic Palmitoleic Lauric acid
(C16:0) (C18:0) (18:1) (C18:2) (C18:3) acid Ricinoleic Arachidic (C16:1) (C12:0) (C14:0) Ref.
Attalea 8.5 16.1 1.4 44.0 15.4 [100]

speciose
oil
Mesua Ferrea 13.63 13.65 50.71 19.47 0.316 1.3 0.087 [101]
Prunus [30]
armeniaca 3.31 1.625 71.76 20.19 1.03
Cerbera [102]
odollam 24.86 5.79 52.82 13.65 0.75
Karanja
Tobacco
401
The extracted oil from rubber seed is non-edible and rich in unsatu-
rated FFA(roughly 80%) [88], and this is a property essential to making it
a prominent raw material for biodiesel production [89]. This, in turn, gives
more economic value to growth of rubber plantations. It becomes impera-
tive to obtain specific data for sample of rubber seed oil from a particular
area because there is a range of variation in the physicochemical parame-
ters of the oil due to environmental factors such as rain-fall, soil fertility,
agronomic practices, maturation period, and genetic substitution [89, 90].
For biodiesel production, the foremost characterization to consider is
the FFA composition and value of the oil. A freshly extracted rubber seed
oil (RSO) has a total acid value of about 47% [90]; this implies FFA of
23.5% comprising of the saturated and unsaturated acids. The fatty acid
composition of RSO along with other oils is captured in Table 15.3.
Saturated fatty acids are responsible for higher cloud point, cetane num-
ber, and general stability of the oil and diesel synthesized from it [103]. As
with other non-edible oils the high FFA of RSO requires that it under goes
acid esterification before transesterification to FAME. This is a problem
that is encountered even when utilizing continuous flow setup invariably
making a system as proposed by Sai and coworkers a semi batch process
[104]. Some authors have proposed the use of co-solvents during transes-
terification as a way of getting higher ester yield at with relatively milder
transesterification conditions. One such report indicates that using aceto-
nitrile as co-solvent, 99% ester yield was obtained at 40°C after 30 minutes
of reaction [105].
15.2.7 Ricinus communis as Feedstock (Castor Oil)

The castor plant, which has numerous varieties, bears seeds that contain
between 40% and 55% oil. Castor oil has a relatively low cost but it is of
immense value as it can be utilized in a number of different applications.
It is utilized in production of pharmaceuticals [106], paints [107], poly-
mers [91], and for fuel production [108]. As of 2015, the estimated average
castor oil seed worldwide was put down as 1.1 tons ha−1 [21]. This value
is expected to grow exponentially. It is said that the plant is able to thrive
under harsh conditions. It is believed to originate from either Africa or
Asia.
Castor oil is inedible and is composed of mostly ricinoleic acid, between
80% and 90% [108] depending on location and variety of the seeds from
which the oil is extracted. It has a yellow-green hue and the biodiesel
from castor oil is viscous and is usually blended with fossil fuel derived
diesel. Castor oil is rather peculiar in the sense that it possesses high
OH O
18 16 14 10 9 7 5 3
12 1 O
17 15 13 11 8 6 4 2
OH O
OH O
Figure 15.2 Chemical structure of riconelic acid, major component of castor oil [106].
concentration of riconelic acid which has an OH group as seen in the

structure in Figure 15.2.
As a result of riconoleic acid, castor oil is highly viscous and the bio-
diesel produced from it also has high viscosity. Nevertheless, blending with
fossil derived diesels and others with very low viscosity usually results in
overall improved characteristics [109]. Biodiesel from castor oil has been
heavily researched over last two decades [108–114].
Recent focus has however been geared towards process optimization,
intensification and the development of more efficient catalysts. One such
development is the one-step transesterification process which has been
proposed with varying degrees of success. The use of sulphonated phenyl
silane montmorillonite catalyst was reported to have 89% conversion of
castor oil to FAME after 300-minute reaction time [66].
Moradi and Ghanadi [113] evaluated the feasibility of producing bio-
diesel directly from castor seed in a one-step route. Their model developed
using centre composite design predicted a 91% FAME yield.
15.2.8 Other Non-Edible Oils

Oils from plants such as Thevetia peruviana have also been explored as a
potential biodiesel feedstock. The plant is highly toxic in nature [115] and is
commonly known as yellow oleander or milk bush. However, the seeds can
also be used to treat cardiac problems, skin issues, and asthma [96]. The oil
content of the seeds ranges from 60% to 65% and can grow in a variety of
arid areas [116] where it is usually used for decorations. Interestingly, a yield
of 96 wt% biodiesel has been reported by Deka and Basumatary [116] after
reaction for 3 hours at room temperature. The duo carbonized the trunk
of Musa balbisana plant and used it as catalyst for transesterification with
methanol. Other groups who have used the same plant report 90 wt% yield
after 75 minutes at 70°C using 2.8 (w/v)% of CaO as catalyst [96].
The efficacy of spent coffee grounds (SCG) as potential biodiesel feed-
stock has also been investigated. The drawback with this feedstock is the
high moisture content which the spent grounds possess as a result of brew-
ing. In addition to this, they also are characterized by high FFA content
ranging between 21 and 38 w/w % [97]. Some other authors have proposed
in situ transesterification of the seeds as a way of improving process eco-
nomics of production from SCG [117].
Also, Silybum marianum L., a wild plant native to Iraq, Iran, Syria, and
some parts of China on the Asian continent, produces seeds which have oil
content of between 23% and 45% depending on the variety. Esterification
of high FFA oil from S. Marianum using a sulfonated acid carbon catalyst
resulted in low FFA oil [118]. They utilized 6% w/w of the carbon acid
catalyst, 68°C reaction temperature, and 15:1 methanol-to-oil ratio with a
reaction time of 180 minutes resulted in FFA reduction of over 90% from
an initial value of 20.0 mg KOH/g. Transesterification with KOH at 60°C
gave ester yield of 96.69% after 75 minutes of reaction. Table 15.4 contains
physico-chemical properties of different oils.
There are so many other plants which have not been discussed in this
list. In different regions of the world, scientists are investigating different
oils to see which contain the appropriate esters and which have high oil
concentration [119]. These factors greatly affect the economics of the bio-
diesel synthesis process and are key to ensuring reduced dependence on
fossil derived diesels.
15.3 Waste Animal Fats

Animal fats (tallow) have also been considered as potential biodiesel
sources. There are challenges when dealing with this feedstock which
result in necessary pre-treatment steps before conversion to biodiesel. The
major challenges include (1) high moisture content, (2) high FFA, and (3)
fats that are solid at room temperature. Nevertheless, research is exploring
ways to harness the tallow as an economically viable feedstock. Different
animal fats have been investigated on. Some of which include duck [123],
beef [124, 125], sheep [126], and chicken fats [127].
Similar to other high FFA feedstock, esterification with methanol in the
presence of an acid such as H2SO4 is a method that has been explored but
not as extensively as with vegetable oils. However, water content should be

less than 0.1 wt% before the reaction is carried out as water hampers the
reaction. Laboratory scale studies have been successfully carried out using
microwaves to shorten the esterification time [128]. The cost of utilizing
microwaves at an industrial scale may lead to increased price of biodiesel
due to larger energy requirements.
15.4 Expired and Waste Cooking Oils

Vegetable oils after being used for extensive frying are classified as inedi-
ble. The oils have been said to degrade, due to harmful compounds which
are produced during frying. Initially, the oils were sold as feed to the ani-
mal industry which has now been banned by the European commission
in 2002 [129]. This is to forestall consumption of these chemicals which
could contaminate the meat of animals which consumed. Generally, waste
cooking oils (WCO) are generated in bulk by households, hotels, and
the food industry. To illustrate this, in 2015, 69% of the 77,000 tons of
WCO generated in Portugal came from hotels and food catering services,
while domestic use accounted for 25% [130]. The use of expired and waste
vegetable oils as feedstock for biodiesel is timely as these oils are usually
discarded into sewage systems which invariably become a problem for
wastewater treatment plants [131]. To this end, many developed countries
have established laws prohibiting and penalizing disposal of WCO during
sewage systems [132]. Consequently, utilizing WCOs in biodiesel produc-
tion reduces pollution and gives them added value. The potential for waste
cooking oil (WCO) biodiesel is much higher in European and American
countries where copious amounts of WCOs are generated [133].
The source of WCO may not particularly have an effect on the final
biodiesel produced. Studies have shown that properties such as acid value
and density may have appreciable effect on the biodiesel synthesis process
[134]. Therefore, to obtain higher acid value oils a two-stage reaction pro-
cess is required: first is esterification and then followed by transesterifica-
tion. Some authors have also suggested that FAME yields with WCOs are
marginally lower due to some of these compounds formed as oils degrade
while cooking/frying [11].
Purification of WCO before use in biodiesel synthesis presents a chal-
lenge in some situations. Food debris and water often pose problems as
contaminants, which could have adverse effects in the synthesis process.
Filtration or gravity settling may be employed to remove debris that may
accompany the WCO.
Also, the level of saturation of the WCO used is apposite. Although deg-
radation is certain, it is not possible to predict the exact level of degrada-
tion that will take place. Generally, degradation of the oil while cooking
results in the oils becoming more saturated due to FFA. As a result, FFA
content of most WCO typically ranges between 2% and 10% [135] which
has a negative effect on the viscosity of the final biodiesel [135]. For bench
scale synthesis, this can be overlooked. It, however, is a major challenge in
plant design, as a flexible system which can cater for oils with a wide range
of FFA would be required.
15.5 Algae/Microalgae
Harnessing algae for biofuels production is gaining widespread attention.
Initially, algae were used for just lipid and protein production. But, it was
since discovered that a good portion of the lipids were suitable for pro-
duction of biodiesel. Fuel applications exploiting algal components include
transesterification of lipids to biodiesel, saccharification of carbohydrates
to ethanol, gasification of biomass to syngas, cracking of hydrocarbons to
gasoline, and biosynthesis of hydrogen gas [136]. This is due to the expand-
ing use of fossil fuels, increasing CO2 emission into the atmosphere, and
consequently contributing to climate change. With depleting fossil fuel
reservoirs coupled with global clampdown on greenhouse gases spur the
motivation for the development of renewable energy sources such as algae/
microalgae [136].
Algae require carbon dioxide, sun light, and water for growth in non-ar-
able land, arid land, and in waste water. They grow very fast in a short
period, producing as much as double their mass in few hours. The lipid
content of algae is higher than that of seed plants, producing not less than
30 times more oil per acre than seed plants [137]. Algae can be subdivided
into microalgae and macroalgae; either of them has different metabolic
behaviors during their growth. These include (1) autotrophic behavior
where algae make use of light solely as a source of energy where the light
energy is converted to chemical energy using CO2 via photosynthesis;
(2) mixotrophic behavior allows algae to perform photosynthesis using
both organic compound and CO2 in the presence of light energy for growth;
(3) heterotrophic behavior where algae utilize only organic compounds as
energy and carbon source; and (4) photoheterotrophic behavior makes
algae use light as well as organic compounds as carbon source [136, 138].
They can change the metabolic pathway according to the changes in
the environmental conditions. The ability of algae to fix CO2 is a method
of removing CO2 from flue gases of power plants, thereby reducing emis-
sions of greenhouse gases [9]. Photoautotrophic means of algae cultivation
is recommended for when growing algae for biodiesel production. This
ensures cost reduction and CO2 sequestration [139]. Figure 15.3 shows
the pathways of biodiesel production from microalgae and by products of
the production process. Large scale growth of algae is conducted either in
open ponds or photobioreactors [140]. The photobioreactors reportedly
have higher algae yield as cultivation conditions can be controlled to max-
imize production.
It has been established that oil yields from microalgae can be as much
as 31 to 72 times that obtainable from Jatropha [30]. The bottleneck in
biodiesel production from algae is to identify the strains with high oil pro-
ductivity and to develop cost-effective growing and harvesting systems
[141]. There is a disagreement on exact quantity of algae strains that have
been identified in the world today. There are possibly between 44,000 and
100,000 different algae strains depending on the source of the information
[140, 142].
Harvest & Drying
Lipid extraction
CO2 + Nutrients
Biodiesel
Animal feeding
Glycerol
Cosmetics
Figure 15.3 Microalgal biodiesel refinery producing multiple products from algal
biomass [136].
Table 15.4 Some selected algae strains and their production data.
408
Total Lipid
Biomass Biomass Lipid extracted
production yield production (wt% of
Strain Habitat Nutrients (g/L/day) (g/L) (g/L/day) biomass) Ref.
Chlorella vulgaris Fresh Water Thin Stillage 2.5 9.8 1.1 43 [145]
Chlorella vulgaris Fresh Water Soy Whey 1.6 6.3 0.2 11 [145]
Chlorella vulgaris Fresh Water Modified 2 8 0.6 27 [145]
basal
Medium
Chlorella pyrenoidosa Fresh Water Bold’s basal 0.106 na 0.019 29.68 [146]
medium
Chlorella vulgaris Fresh Water Bold’s basal 1.65 na 0.44 26 [147]
medium
S. obliquus (YSL02) Fresh Water Bold’s basal 1.84 na 0.53 29 [147]

medium
Spirulina sp Fresh Water Zarrouk’s 1.37 na 0.66 20 [148]
medium
Aurantiochytrium sp. Marine Defined 6.69 31.8 Na 38.1 [149]
(KRS101) water medium
Chlamydomonasreinhardtii Fresh water na 2 na 0.505 25.25 [150]
Table 15.5 Some properties of biodiesel synthesizes from microalgae.
Density Iodine Kinematic Oxidation
Acid value Cold filter 15°C value viscosity stability
(mg plugging (kg/ (g I2/100 40°C 110°C Cloud Pour Cetane
KOH/g) (°C) m3) g) (mm2/s) (h) Saponification point point number Ref.
From microalgae 0.29 –13 0.88 4.43 4.52 NA [151]

(Chlorella
protothecoides)
From microalgae NA –4.8 0.88 4.2 95.7 55 [152]

(Nannochloropsis
oculata)
From microalgae na 7.8 0.89 3.74 NA 47.3 [152]

(Phaeodactylum
tricornutum)
From microalgae na –4.6 0.91 4.63 5.6 32.9 [152]

(Scenedesmus
dimorphus)
From microalgae NA –0.99 NA 54.57 [153]

(Chlorella
protothecoides)
(Continued)
409
410
Table 15.5 Some properties of biodiesel synthesizes from microalgae. (Continued)

Density Iodine Kinematic Oxidation
Acid value Cold filter 15°C value viscosity stability
(mg plugging (kg/ (g I2/100 40°C 110°C Cloud Pour Cetane
KOH/g) (°C) m3) g) (mm2/s) (h) Saponification point point number Ref.
From microalgae 3.55 54.24 [153]

(Chlorella
emersonii)
From microalgae 2.58 49.93 [153]

(Chlorella salina)
From microalgae 4.6 44 [153]

(Chlorella
vulgaris)
From microalgae NA 0.9 88.5 4.5 7.4 233.71 9.2 3.1 50 [154]
(Chlorella
vulgaris)
spirulina 0.83 2.9 44.55 [155]
Chlorella sorokiniana –9.66 0.875 48.411 4.9 13.58 59.68 [156]
Micractinium sp. 1.69 0.873 28.33 5.07 17.19 61.48 [156]

The oil content of each algae strain varies with Colonial, Capsoid,
Coccoid, Palmelloid, Filamentous, and Parenchymatou as some of the
various forms of algae. Chlorella zofingiensis, Chlorella protothecoids, and
Schizochytrium limacinum have been identified as strains with large oil
production capacity [143]. Table 15.4 lists some strains with their growth
per day and lipid content, and extensive lists can be found in literature
[144]. Table 15.5 shows the properties of biodiesel synthesized from differ-
ent algal strains.
15.6 Insects as Biodiesel Feedstock

The use of insects as biodiesel feedstock is still a relatively virgin area of
focus. They had hitherto been mainly considered as a source of protein
for animal feed [157]. They have been identified as viable sources of fats
for biodiesel production but there is a lot that is yet to be researched upon
using this feedstock. Insects offer the advantage low cost of rearing, large
insect yield, and relatively small space is required for cultivation [158].
Of which, methods of improving insect yields are constantly being devel-
oped [159]. As with other feedstock, there are criteria to be considered
when selecting an insect as feed for biodiesel production. These include
fat content usually of larva, speed of completion of insect life cycle, space
requirements, and feeding costs. Detailed discussions on this can be stud-
ied in the review by Manzano-Agugliaro et al. [160]. At their larva stage,
metabolic reserves for non-feeding periods are developed. These reserves
are majorly composed of high quantities of fat, in addition to glycogen and
proteins [160]. Insects which have shown high lipid content include Musca
domestica, Hermetia illucens, and Rhynchophorus sp. with lipid contents
of approximately 21%, 29%, and 43%, respectively [161]. Table 15.6 shows
acid content of biodiesel produced from some larva, while Table 15.7 pres-
ents properties of some biodiesel synthesized from insects.
The use of insect larva is also seen as a means of tackling environmental
pollution. The larva can feed on residual food grease, animal waste, sew-
age sludge, and other such contaminants [162], effectively reducing cost of
purchasing feed. This was demonstrated in the work of Zheng et al. [163]
who were able to increase biodiesel yield and reduce food grease consid-
erably by using it as feed for the larva. With regard to process economics,
important factors to consider asides from oil content and cultivation of the
larva include extraction temperature, solvent types, and quantity of solvent
required. The use of microwaves has been studied and recommended as a
means of increasing the rate of lipid extraction [158].
412
Table 15.6 Fatty oil composition of diesel derived from insect larva.
Palmitic acid Stearic acid Oleic Linoleic acid Linolenic acid Myristic Palmitoleic Lauric Capric
(C16:0) (C18:0) acid (C18:2) (C18:3) (C14:1) (C16:1) (C12:0) (C10:0)
Hermetia illucens 18.2 5.1 27.1 7.5 3.7 9.4 23.4 1.8 [163]
Boettcherisca 18.9 0.2 44.5 4.1 7.6 1.4 18.3 1.6 [164]
peregrine
Zophobas morio 32.74 9.36 29.43 22.53 0.85 2.16 [165]
Musca domestica 28.4 2.2 24.1 18.1 1.1 3.3 20.1 [166]
L. (grown
on poultry
manure)
Musca domestica 28.2 3 22.9 18.8 1.4 2.91 20.6 [166]

L. (grown on
kitchen waste)
Musca domestic 27.14 5.01 24.54 13.45 0.36 5.96 17.4 1.21 [167]
(food waste
and wheat
bran)
Table 15.7 Fuel properties of biodiesels synthesized from insect larva.
MeOH- Water
to- Density content
oil Acid @ Flash (mg/ Cloud Cetane Kinematic Calorific Oxidative
Catalyst Temperature ratio % Cata value 15°C point kg) point number visco value stability Ref.
Hermetia NaOH 62 10 1.1 0.875 143 387 5.6 49 4.6 [168]
illucens
Boettcherisca 0.62 0.884 130 <.03% 5.6 [164]
peregrine
Musca 0.875 166 <0.03% 56 4.19 39.56 3.2 [166]
domestica
L. (poultry
manure)
Zophobas KOH 50 5 1.25 0.15 0.871 159 <0.03% 57.3 4.22 [165]
morio
413
15.7 Deacidification
Majority of the oils discussed above are characterized by high FFA. High
FFA leads to saponification which results in difficulty in obtaining pure
methyl esters. To combat this, copious amounts of water usually required
to wash followed by drying to in order to make it suitable for use. In some
instances, soap emulsions form making washing even more difficult [169].
This is especially the case when alkali catalysts are used. To this end, a
number of methods have been explored to reduce the FFA.
Esterification as mentioned earlier entails the reaction of high FFA
oil with methanol in the presence of a concentrated acid, usually H2SO4.
Neutralization of high FFA oils by an alkali is presently the commercial
means of reducing FFA [170]. The soap formed is washed and subsequently
the oil is dried before transesterification.
Steam deacidification is well utilized in is refining oils for consump-
tion following degumming and bleaching. Operating conditions for
deacidification are largely dependent on the type of oil used. Major
variables that dictate the extent of FFA removal are the temperature
and quantity steam employed in the process. For Jatropha, 3.0 wt % of
steam in relation to oil used at 225°C was reported to achieve 97.33%
reduction in FFA content [169]. Other methods include transesterification
using glycerol [171], microorganisms or enzymes, solvent extraction [172],
or extraction using supercritical fluids. The final choice is inadvertently
decided by the process economics.
15.8 Other Technologies

Asides transesterification, other technologies have been developed for the
production of diesel and other fuel fractions from waste. Most popular
technologies include pyrolysis [173] and thermal cracking [174–176].
Pyrolysis is advantageous in that a wide variety of materials can be used
as feedstock. Vegetable oils [177], animal fat [173], or even plant husks can
be used.
The pyrolytic process, however, requires temperatures as high as 400°C.
Despite the higher energy requirements, pyrolysis offers the advantage of
handling feedstock with high FFA. The complexity of product washing due
to saponification is removed via this process. It, however, would require the
use of catalysts which are selective to diesel fractions. Apart from hydro-
carbons, typical pyrolysis products include solid char and gases such CO
and CO2.
15.9 Conclusion
In conclusion, the use of non-edible oils as biodiesel feedstock is undoubt-
edly the preferred pathway for future energy generation. It will reduce
pressure on edible feedstock such as palm oil, soybean oil, and rapeseed oil
which have been widely used for large-scale biodiesel production.
On the one hand, transesterification is still the more preferred route,
although optimization of other methods is still being developed. Processes
will employ either heterogeneous catalysts with high methyl ester yield or
one-step processes with better economics of production. Algae has been
found to be rather promising non-edible alternative, and it appears that
it just may be the preferred feedstock of choice for a very long while to
come. Though technological and scientific research are already heralding
fourth-generation sources.
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16
Microalgae for Biodiesel Production
Charles Oluwaseun Adetunji1*, Victoria Olaide Adenigba2,
Devarajan Thangadurai3 and Mohd Imran Ahamed4
Applied Microbiology, Biotechnology and Nanotechnology Laboratory,

1
Department of Microbiology, Edo State University Uzairue, PMB 04,

Auchi, Edo State, Nigeria
2
Department of Science Laboratory Technology, Ladoke Akintola University of
Technology, Ogbomosho, Nigeria
3
Department of Botany, Karnatak University, Dharwad, India
4
Department of Chemistry, AMU, Aligarh, India
Abstract
It has been observed that the application of petroleum fuel is not sustainable and
environment-friendly due to the release of high level of contaminants as well as
the high amount of money involved in their production. Hence, there is a need to
search for carbon neutralization, transport fuels, and renewable, cost-effective, and
eco-friendly energy with little amount of NOx and less CO2 emissions. The utiliza-
tion of algae has been identified as a great source of biodiesel generation without
any adverse effect. Therefore, this chapter intends to provide detailed information
on the fabrication of biodiesel from microalgae. Specific information on the phys-
ical properties, amount of biodiesel production, and level of transesterification of
biodiesel were discussed. The application of photobioreactors for the production
of biodiesel with the special consideration of several factors, such as flow rate,
temperature, light intensity, CO2 concentration, and time, was highlighted. Several
techniques for the extraction of biodiesel such as supercritical CO2, physicochem-
ical, direct transesterification, chemical solvents, and biochemical, respectively,
were highlighted. The structural elucidation of the biodiesel produced by micro
algae using high pressure liquid chromatography, thin-layer chromatography, gas
chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic
resonance was highlighted.
*Corresponding author: charliguitar@yahoo.com; adetunjicharles@gmail.com;

adetunji.charles@edouniversity.edu.ng
429
Keywords: Transesterification, biodiesel, microalgae, petroleum fuel, cost

effective, eco-friendly
16.1 Introduction
The total dependence on fossil fuel as a source of energy has become a
major problem in the world’s economy with potential challenge in energy
depletion and environmental pollution [13]. The increase in the world’s
population has a direct impact on the energy reserve, thereby resulting
in depletion in the energy reserve as a result of overdependence on a
non-renewable energy source. In addition to the explosion in popula-
tion, another challenge from dependence on fossil fuel is the production
of toxic gases during refinery process. The presence of these gases in the
environment results in global warming which is another environmental
concern [13].
The need for energy sources which are renewable and at the same time
environmental compliant cannot be overemphasized [32]. Microalgae
possess the potential as a feedstock for production of renewable energy
in place of fossil fuel [2]. Microalgae are considered as third-generation
biofuel and they have several advantages over both first-generation biofuel
(feedstock such as cash crops) and second-generation biofuel (lignocel-
lulosic feedstock) [36]. The merit of microalgae as feedstock for biofuels
includes rapid growth in a variety of aquatic environment, ease of cultiva-
tion without dependence on large farm land and food industry, ability to
absorb atmospheric CO2 for carbon fixation, and maximum biomass pro-
duction within a short time and high lipid invention [24, 29]. Microalgae
are able to biodegrade inorganic matter present in wastewater, and this
alleviates the change of supplying nutrients to the culture and these nutri-
ents attract high cost.
Algae could produce renewable energy due extraordinary lipid and bio-
mass production, photosynthetic nature, and rapid growth rate [4]. Algal
cultivation can play an extensive role in carbon emission reduction as it
captures large amount of CO2 (up to 2 kg of CO2 per 1 kg of dry biomass)
due to photosynthesis [34]. Algae can be produced through autotrophic
or chemoheterotrophic conditions by using solar energy and an artificial
light source. Furthermost of their indispensable nutrient can be provided
by wastewater and CO2 from the atmosphere principal to high efficiency
and an connected extraordinary lipid content creation them a very attrac-
tive alternative [1].
Microalgae for Biodiesel Production 431
Microalgae could be used in the generation of methanol [9], bio-oil [18],

hydrogen [14], and methane [19]. There are several ways in which micro
algae can be used in the production of energy in different forms which
are sustainable and can be used to alleviate the impending challenges of
depletion of fossil fuel.
Therefore, this chapter has provided detailed information on the sus-
tainable production of biodiesel from microalgae. Specific information
on the physical properties, amount of biodiesel production, and level of
transesterification of biodiesel were discussed. The application of photo-
bioreactors for the production of biodiesel with the special consideration
of several factors such as flow rate, temperature, light intensity, CO2 con-
centration, and time was highlighted. Several techniques for the extraction
of biodiesel such as supercritical CO2, physicochemical, direct transesteri-
fication, chemical solvents, and biochemical respectively were highlighted.
The structural elucidation of the biodiesel produced by microalgae using
high pressure liquid chromatography, gas chromatography, Fourier trans-
form infrared spectroscopy, thin-layer chromatography, and many more
was highlighted.
16.2 Physicochemical Properties of Biodiesel

From Microalgae
The properties of biodiesel depend on the strain of microalgae from which
the oil was extracted. There are several techniques which can be adopted
in the determination of both quantitative and qualitative characteristics
of biodiesel; some of these techniques are with flame ionization detector
which is specifically used in the analysis of feedstock for the fabrication of
biodiesel [20]. It is expedient to first determine the composition of lipid in
an alga of choice for biodiesel invention. The presence of poly unsaturated
fatty acids which has at least four double bonds is a characteristic of oils
obtained from algae [29].
The properties that any fuel must possess in order to fit in as a replace-
ment for fossil fuel include stability to oxidation, the extent of lubricat-
ing, viscosity, ignition, and combustion potential [37]. The length of chain,
quantity of fatty esters, and quantity of double bonds also regulate the
chemical and physical characteristics of the triglycerides and fatty acids
and obtained in microalgae-based biodiesel [27]. There are more physical
and chemical properties that define the suitability of biodiesel produced
by microalgae and other petroleum diesel. The standards that determine
the quality of biodiesel are controlled by the European Committee for

Standardization in the European Union and many other relevant organi-
zations [6].
The chemical and physical features of biodiesel from microalgae differ
from one strain to another. The following are some of the parameters that
measure the suitability of microalgae biodiesel as a dependable and sus-
tainable biofuel: kinetic viscosity and the chain length of fatty acid along
with the degree of unsaturation that determines how viscous a microalgae
biodiesel will be. A high degree of unsaturation can result in modifica-
tion of fatty acid composition at the different phases which are transpor-
tation and fluctuation in temperature and storage [17]. Soares et al. [35]
described that the development condition and extraction of lipid have a
tendency of affecting the fatty acid profile and the final features of the bio-
diesel manufactured.
Another important property is acid value known as the quantity of free
fatty acids available in the biodiesel and this is determined by the quantity
of potassium hydroxide which will be needed for neutralization. Also a
biodiesel can be defined by its cetane number which shows the effect of
biodiesel on engine ignition [5]. The lowest temperature at which a known
quantity of diesel will flow through a standard filter in 1 minute is referred
to as cold filter plugging point [16] while the cloud point is the lowest tem-
perature when formation of crystal in diesel can be visualized as a suspen-
sion which appears cloudy [31]. These two properties are also crucial in
determining the status of biodiesel produced by microalgae. Knothe [16]
further explain that the content of saturated fatty acids has an impact on
both cold filter plugging point and cloud point.
Flash point is another temperature-related property of biodiesel and it is
the lowest temperature required for the oil to give the vapor which activates
ignition and subsequent production of flame. Biodiesel from microalgae
has a lower flash point compared to that from some other sources [31]. The
purity of the biodiesel produced depends on the content of ester and lino-
lenic acid. Microalgae possess unique abilities to regulate their metabolic
activities based on the growth conditions [6].
16.3 Genetic Engineering/Techniques Enhancing

Microalgae multiply rapidly through cell division and this accounts for
their fast growth rate which has presented them as a more preferable
feedstock for biodiesel production. Their ability to divide rapidly has
given access for genetic manipulation to be able to produce strains with

improved potential for biofuel production [7]. Apart from rapid repro-
ducibility, a large number of algae (micro and macro) are known for their
ability to accumulate fatty acids which have up to 16–20 carbon in terms
of length [10]. In order to obtain maximum biodiesel production from any
strain of algae, the knowledge of the liquid content in relation to length of
carbon chain is required. This knowledge will be used for manipulation
which is expected to yield trait improvement through bioengineering of
algae strain with biofuel production that can contribute greatly to yield an
improved output [38].
A large number of algae (micro and macro) are known for their ability
to accumulate fatty acids with the carbon length as much as 20. In order
to obtain maximum biodiesel production from any strain of algae, the
knowledge of the lipid content in relation to the length of carbon chain is
required. This will be a template for manipulation with the expectation of
a better yield [7]. The production of biodiesel by microalgae can only be
a replacement for fossil fuel if the adequate techniques are put in place to
enhance the production process in terms of time, quality, and quantity of
fuel produced.
The economic viability of biodiesel from algae is still a concern since the
cost of operation and corresponding output is lower than what is required
to meet the energy demand (Gouveia et al., 2017).
In algae, the chloroplast is the center of activity where lipids are syn-
thesized with fixed atmospheric CO2 as a source of acetyl-CoA, and it is
responsible for the production of the different carbon atoms available in
the chain of the fatty acid [60]. Genetic engineering targeting the chloro-
plast of the algae could result help in improving the biodiesel produced.
Zienkiewicz et al. [63] also discussed the importance of genetic tools
in characterizing the exact gene responsible for biosynthesis of lipids in
microalgae. They further highlighted some microalgae which have the
potential as research tool in the synthesis of both triacylglycerol and lipid
synthesis; these are Phaeodactylum tricornutum, Chlamydomonas rein-
hardtii, Ostreococus tauri, and Chlorella spp.
The production of biomass and high lipid are two important parame-
ters that will favor biodiesel production by any microalgae strain. There
are some enzymes which are directly involved in the biosynthesis of bio-
diesel from microalgae. Overexpression of the target enzyme responsible
for the synthesis of fatty acids is very crucial. Davidson et al. [3] pointed
out the fact that one of the ways by which biofuel can replace fossil fuel is
by genetically engineering key enzymes to promote large-scale production
of biofuel.
16.4 Nanotechnology in Microalgae Biodiesel

Production
Apart from genetic engineering, another technology which can enhance
the quality and quantity of biodiesel production from microalgae is nan-
otechnology through the addition of nanomaterial in the form of nano-
droplets, nanocrystals, nanomagnet, and nanofiber [21, 23]. Application of
nanotechnology in biofuel production can be employed at different point
in the production process. Reports have been documented on the contri-
bution of nanomaterial as catalyst in the production of biofuel with a con-
sequential improvement in the fuel produced [8, 11]. Biomass production
and cell harvesting are crucial to algae cell culture for biodiesel produc-
tion, and there are various factors that contribute to biomass production
and one of these important factors is light intensity. If the light available to
the algae culture is not adequately and uniformly distributed in the pho-
toreactor, then it can have a negative impact on biomass production and
cell harvesting. Addition of nanoparticles to the cell culture of microalgae
has been employed in order to improve light distribution in the reactor
and this resulted in improvement in yield and ease in cell harvesting [30].
Biofuel doping is another area where nanoparticles have been found use-
ful, and the addition of nanoparticles to fuel enhances fuel efficiency of
engines [12, 26].
16.5 Specific Examples of Biodiesel Production

From Microalgae
Microalgae over the last few decades till date have been considered as
a major source of biofuel, their rapid growth, friendliness in handling,
and ultimately the absence of threat to the food industry in terms of
cultivation accounts for global choice as feedstock for biofuel produc-
tion especially biodiesel [13, 25, 28]. Some microalgae with high lipid
production have been investigated for their biodiesel producing poten-
tial. Neochloris oleoabundans, Spirulina maxima, Chlorella vulgaris,
Scenedesmus obliquus, Dunaniella tertiolecta, and Nannochloropsis
sp. were screened as feedstock for biofuel production. Scenedesmus
obliquus had the most suitable fatty acid profile (polyunsaturated fatty
acids and linolenic) required to be used in the production of biodiesel
while both Nannochloropsis sp. and Neochloris oleoabundans had high
oil content when the culture was put under nitrogen stress [6]. The
potential of Nannochloropsis sp. as feedstock for bioduesel production
was also documented by Nobre et al. [22]. Both fatty acids and carot-
enoids were targeted and an appreciable quantity of lipids (45 g/100
g biomass) and pigments (70%) was obtained. Euglena sanguinea was
equally screened for biodiesel production and both saturated and unsat-
urated fatty acids produced were confirmed with the possible poten-
tial of being used as fuel in the present-day automobiles [15]. Sharif
et al. [33] also reported the potential of Oedogonium spp. and Spirogyra
spp. for biodiesel production. Biomass production was greater in
Spirogyra while Oedogonium sp. had a biodiesel production. Both algal
strains were confirmed as biodiesel producers.
The application of biodegradable fuel, with little amount of NOx and
less CO2 emissions. It has been stated that the utilization of petroleum fuel
has been recognized not to be sustainable which might be linked to a high
reduction in the amount of supplies and the buildup of the carbon dioxide
in the environment is not eco-friendly. Therefore, the utilization of carbon
neutralization, transport fuels, and renewable energy has been recognized
as an alternative option because it is eco-friendly and cost effective. The
utilization of algae has been identified as a great source of biodiesel genera-
tion. It has been discovered that brown algae cultivated in CO2-enriched air
could be transformed into oily substances. It has been identified that such
a techniques could play a crucial role in the resolution of all the significant
problems regarding the release of pollutant generated from CO2 evolution
as well as the forthcoming predicament due to decrease of energy source.
Hossain and Salleh [46] performed a research study on the physical prop-
erties, amount of biodiesel production, and level of transesterification of
biodiesel. The authors utilized common species Spirogyra and Oedogonium
so as to evaluate the level of biodiesel fabrication. It was discovered that the
biodiesel and algal oil generation was in higher quantity in Oedogonium
spp. when compared to Spirogyra spp. Moreover, it was discovered that the
biomass obtained immediately after the extraction was in a higher qual-
ity in Spirogyra than Oedogonium spp. Also, the sediment obtained from
Spirogyra spp. than Oedogonium spp. in terms of water, pigments, and glyc-
erine was in a higher quantity, while there was no observable variation
in their pH. The result obtained indicated that the biodiesel derived from
the Oedogonium spp. is showed more quality when compared to that of
Spirogyra spp.
Fossil fuel has been recognized as a non-renewable, and the volume of
the required quantities has diminished over period of time due the high
rate of pumping. The high rate in the global population has led to increase
in traffic which always necessitate more fuel to meet their demand as well
as increase in the prices of crude oil and gas. Diesel could be derived from
numerous feedstock such as algae, sunflower, palm, oil rape, waste animal
fats, and soybean respectively. Bošnjaković [45] evaluates the possibilities
of utilizing biodiesel derived from algae and the potential of utilizing such
techniques for generation of biodiesel. The biodiesel derived from algae
was evaluated and the system that could support their mass production
was also highlighted. The authors stated that algae are very grow anywhere
in the desert most especially in fresh and salt water even in the presence
of waste water and with resistance in nature. It has been realized that they
multiply quickly and they possess the capability to utilize CO2 for photo-
synthesis and require minimal amount of water when compared to other
crops. Also, the biofuel derived from algae is biodegradable without the
presence of sulfur without the presence of any contaminants.
Biodiesel has been recognized as a natural biofuel with several attri-
butes which includes lower net carbon cycle, eco-friendly nature, bio-
degradability, and non-toxic characteristics, respectively. In view of the
aforementioned, Ihsanullah et al. [44] utilize the effectiveness of algal spe-
cies of spirogyra derived from numerous region of Khyber Pakhtunkhwa,
Pakistan, and the algae were engaged as a feedstock for biodiesel fabrication.
Initially, the oil derived from algae species was obtained utilizing di-ethyl
ether and n-hexane, while the second stage which involves the process of
oil extraction was obtained using the dig out oil converted into biodiesel
through the process of transestrification rejoinder. Furthermore, the level
of biodiesel generated was quantified based on the following parameters:
temperature, reaction time, amount of catalyst (sodium hydroxide), and
influence of molar ratio during the period of transestrification reaction.
Beetul et al. [43] performed an investigation that evaluates the amount
of lipid from endosymbiotic dinoflagellates and the cyanobacterial mats
were determined using genetically and morphology utilizing RFLP. The
level of samples was evaluated utilizing 1H and 13C NMR spectroscopy and
quantified gravimetrically, respectively.
Microalgae have been identified to possess that capability to generate
proteins, lipids, and carbohydrates as significant fractions. Typical example
of biofuel includes biogas, biohydrogen, biodiesel, bio-oil, and bioethanol
through numerous processes and conditions. Moreover, the application of
microalgae has been shown to possess the capability to serve as a replace-
ment for CO2 emissions fixation because it has been observed that the gas
could be utilized for their metabolism. Moreover, microalgae have been
considered as a feedstock that could be incorporated a bio-refinery, the
process by which numerous product can derived from biofuel to food.

Cuellar-Bermudez et al. [42] carried out an extensive review on the appli-
cation of biofuel derived from microalgae, and the disadvantage and lim-
itation that could prevent increase in the production of microalgae were
also elaborated.
It has been stated that the recent fossil fuel reserve might not be enough
to meet the daily increase in request for the biofuel. The high increase in
price of oils, pollution, and global warming has led to increase in request in
renewable energy sources. Therefore, the utilization of biofuel derived from
algae might represent a typical example of renewable energy sources. The
biofuel obtained from algae feedstock that could be utilized for production
of bioethanol and biodiesel generation due to the fact that they could be
easily be mass produced with interesting biomass yield, high level of car-
bohydrate, and lipids contents. This shows that the quantity and quality of
biodiesel derived from algae might surpass those derived from second- and
first-generation feedstock. It has been stated that only few algae species
have been examined as a probable biofuel sources. Therefore, Saad et al.
[41] wrote a comprehensive review on the application algae for sustainable
production of biofuel, which significantly needs to be produced, and some
of the problem encountered during their commercial production.
The increase in the level of the carbon dioxide (CO2) in the atmosphere
could be linked to the numerous dangerous activities generating numer-
ous changes in the world carbon cycle which draw the attention of sev-
eral people around the globe. The availability of the carbon dioxide in the
atmosphere could be linked to several processes such as volcanic eruption,
forest fires, power plants, decomposition of organic matters, and automo-
biles. All these CO2 could be utilized through the help of microalgae which
could be subsequently be converted into the lipids for the production of
biofuel as a substitute petroleum-product transport fuel starved of having
any adverse effect on the supply of food and crop. Therefore, in view of
these aforementioned, Mondal et al. [40] wrote a comprehensive review
on the recent advances on the application of microalgae for the utilization
of the carbon capture for the production of biodiesel. Numerous features
such as selection of efficient strains, production inside closed and open
system, metabolism of microalgae, and production of biomass together
with international and natural biodiesel specification. The application of
photobioreactors for the production of biodiesel with the consideration of
several factors such as flow rate, temperature, light intensity, CO2 concen-
tration, and time was highlighted. Moreover, the economic overview and
the future outlook as well as necessary strategies that could enhance the
production of biodiesel from microalgae were also highlighted.
The utilization of energy sources has been discovered to be reducing

gradually because of the increase in the demand for a safe biofuel. The
application of microalgae has been identified for the production of a sus-
tainable biofuel because the application of food and crop producing plants
will not be enough to meet the demand required for the production of bio-
diesel. It has been realized that numerous types of algae possess the capa-
bility to produce biodiesel. Almost 20%–80% oil contents are produce from
the algae which can be transformed into numerous varieties of oil such as
biodiesel and kerosene. This might be linked to the fact that the biodiesel
derived from algae is easier and cost effective. Numerous types of algae
have been realized to possess the capability to produce biodiesel. Typical
examples of these algae strain include euglena, ulothrix, and tribonema,
respectively. The application of gene technology could be utilized for the
generation of biodiesel and oil contents and for improving the stability of
algae. This can go a long way to increase the genetic expression required for
increasing the total amount of biofuel available in different strains. Khan
et al. [13] perform a comprehensive review on the application of algae as a
permanent replacement to fossil fuel.
Aljabarin and Al Jarrah [39] performed an experiment that involves
the production of biodiesel from algae. The algae were obtained from
Almansora stream at Tafila Governorate, Jordan, after which it was sub-
jected to drying for a period of 12 hours at 80°C in an oven. The dried
form of the algae was later grind into powder. The powdered algae were
later subjected into the process of distillation through the incorporation
of hydrate solution of FeSO4 to the algae utilizing a distillation column so
as to obtain the oil. Methanol was also incorporated into the oil which was
derived through the process of distillation utilizing KOH as a catalyst. The
product was removed using funnel for effective separation of the two layers
of the solution. The top layer which contains the organic layer denotes the
biodiesel. The biodiesel qualities are comparable to the diesel oil, excluding
that it decreases the production of CO2 without any generation of sulfur
dioxide.
16.6 Methodology Involved in the Extraction of Algae

It has been recognized that biodiesel could be produced from microalgae
through the aids of lipid extraction methodology using supercritical CO2,
physicochemical, direct transesterification, chemical solvents, and bio-
chemical, respectively.
16.6.1 Chemical Solvents Extraction

This is one of the most adopted methodology that is mostly utilized but
with little efficiency.
Most especially when the microalgae are in a wet stage [47]. The applica-
tion of freeze-drying techniques is utilized for the extraction of lipids most
especially in the laboratory [48], oven-drying [50], while the other tech-
niques used for drying of microalgae includes vacuum evaporation [49]. It
has been stated that the process involved in the drying of the microalgae
involved the preliminary drying which might necessitate 2.5 greater energy
than a process in the absence of drying [51]. It has been observed that sol-
vent such as hexane is preferable when compared to chloroform-methanol
[52], because they possess lesser affinity for non-lipid pollutants and their
minimal level of toxicity [53]. Moreover, at industrial level, the application
of Soxhlet extraction is not preferable because there is a need for a great
rate of energy [53]. Also, the application of other toxic solvents contain-
ing 8-diazabicyclo-[5.4.0]-undec-7-ene and alcohols (octanol, ethanol)
has been evaluated but five times of the amount of fatty acid methyl ester
was in a lower amount when compared to the extraction carried out sing
n-hexane [47].
16.6.2 Extraction by Supercritical Carbon Dioxide

The supercritical CO2 have several merits which include nontoxic and the
high rate of recovery most especially at a lower temperature which is lesser
than 40°C [54]. This technique has been established to require a very high
amount of equipment with high level of energy which is required during
the process extent great pressures [55]. It has been observed that super-
critical CO2 extraction could be utilized for the recovery of microalgae
lipids and their eventual transformation into biodiesel [53] while some
level of lipid containing n26% (g lipid/g dry weight) from Nannocloropsis
spp. [54].
16.6.3 Extraction Using Biochemical Techniques

It has been stated that little studies have been carried out that involves that
application of biochemical extraction for effective extraction of lipids from
microalgae. Fu et al. [57] utilized a 72-h cellulase break down pretreatment
using microalgae most especially from Chlorella sp. The author discovered
that break down yield of sugars of 70%. The following parameters were
tested: total sugar concentration and concentration reducing sugar. It was

later observed that there was significant upsurge in the lipid content which
varies from 52% to 54% (g lipid/g dry weight).
16.6.4 Extraction Involving Direct Transesterification

Direct transesterification involves that combination of microalgae together
with an alcohol in the presence of a catalyst. This methodology did not
involve the prior stage of extraction [61].
The quantity of acid catalysts which was examined mainly for the het-
erotopic microalgae biomass entails sulfuric acid (H2SO4) and hydrochloric
(HCl) but the application of acetyl chloride (CH3COCl) could lead to more
enhanced biodiesel [50]. Moreover, the addition of a less polar solvent such
as chloroform or hexane could be added to improve the yield and quality
of biodiesel obtained [62]. Furthermore, the application of heterogeneous
catalyst could be used during direct transesterification in the presence of
microwaves heating.
16.6.5 Extraction Using Transesterification Techniques

It has been observed that the application of basic vegetable oil in engines
utilizing diesels has been established but it might led to several practical
challenges which includes struggle to vaporize in cold circumstances, high
viscosity, and high density. All this could be linked to the deposit most
especially in the ignition chamber without the presence of polluting and an
upsurge in the emission level [59]. Therefore, the application of biodiesel
derived from algae might be an alternative to those derived from the veg-
etative oil [58]. Therefore, in order to overcome all these highlights, there
is a need to base more emphasis on the conversion of microalgae lipids in
equivalent in necessary.
16.7 Conclusion and Future Recommendation

to Knowledge
Microalgae are energy-rich organisms because they are reservoir of lipids
and fatty acids, and this is one of the many reasons they have been called
third-generation biofuel. Out of the various biofuels available, biodiesel
has drawn intense research attention in a bid to overcome the challenge of
energy depletion and environmental pollution from the overdependence

and refinery process of fossil fuel, respectively. Even though microalgae
have been appraised as a biofuel producer, there is still need to improve the
invention of biodiesel from microalgae in order to meet up with energy
demand. Different techniques majorly, genetic engineering and nanotech-
nology were discussed in this review as tools that could deliver the required
microalgae biodiesel into the system in terms of both quality and quantity.
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17
Biodiesel Production Methods
and Feedstocks
Setareh Heidari1* and David A. Wood2
1
Faculty of Chemical Engineering, Sahand University of Technology,
Tabriz, Iran
2
DWA Energy Limited, Bassingham, Lincoln, United Kingdom
Abstract
Biodiesel is an attractive alternative transportation fuel to crude oil–derived diesel
because it is sustainable and can be produced in almost carbon-neutral supply
chains that avoid the accumulation of greenhouse gases in the atmosphere. There
are three generations of biofuel production options: involving food crops on agri-
cultural-quality land, involving non-food crops and low-grade land, and involving
algae (naturally occurring). A fourth-generation option is to genetically engineer
algal to generate higher lipid yields. Also, waste oils, such as cooking oils, are also
a common feedstock for biodiesel production. There are several methods used to
produce biofuels including the transformation of lipids into microemulsions by
mixing with alcohols, pyrolysis of solid biomass, including woody materials and
transesterification. The latter is the most widely used for large-scale biodiesel pro-
duction. Catalyst selection, plant operating conditions, and the alcohol:plant lipid
ratio influence the conversion efficiency of transesterification. Overcoming metal
corrosion issues and achieving commercial price parity with crude oil–derived
diesel are two key challenges the biodiesel industry currently faces.
Keywords: Transportation fuel, pollution control, biodiesel, waste oils,

transesterification, enzymatic catalysis, nanocatalysts, alcohol:lipid ratio
*Corresponding author: setarehaidari@yahoo.com
447
17.1 Introduction
In recent decades, there have been some concerns about fuel supply and
fuel security of supply globally. A realistic expectation is to increase con-
sumer confidence in emerging biofuel technologies to meet growing
demands for sustainable fuel supplies in the next decades. Unfortunately,
around the world, the primary energy and fuel sources are mostly provided
for by fossil fuels, with their negative consequences for the environment
and violation of sustainability development obligations. Crude oil–refined
products such as gasoline, diesel, and aviation fuel dominate transporta-
tion fuels. However, there is a small contribution from biofuels, mainly
ethanol, with some biodiesel produced and/or consumed in many coun-
tries. Biofuels provide a substantial opportunity to deliver a supply of road
transportation fuels that is sustainable into the far future and limits the
greenhouse gases emitted to the atmosphere and reduces pollution more
generally during its consumption. Biodiesel shows many attractive charac-
teristics that are considered in detail in this chapter.
Today, there is a broad range of fluids, like water [1], solvents, fossil
energy [2–5], supercritical carbon dioxide [6–9], and biofuels that can be
utilized to promote the world’s economy effectively. The exploitation of
these substantial sources must be administered efficiently and their sup-
ply chains developed in ways that are efficient and sustainable in the long
term. Biodiesel is generated from waste oils, vegetable oils, and/or fatty
compounds extracted from animal tissue, more generally referred to as
lipids. It is valued as a biofuel because it can be produced from a broad
range of feedstocks. It produces diesel-fuel specifications including a blend
dominated by straight-chain alkanes with number carbon of 16 to 20 other
hydrocarbon molecules such as the functional alkyl group and organic
esters [10, 11]. These components of biodiesel are mostly generated as a
consequence of the transformation reactions imposed on the lipids to form
alcohols and esters.Throughout the 20th century, vegetable oils were used
in small quantities to form biodiesel for road vehicle utilization. In the
1920s, vehicle engines were adapted to consume cheaper, crude oil–based
diesel fuels provided from refineries [10]. Biodiesel received significant
attention on a mercantile scale in South Africa before World War II to sup-
ply a road vehicle fuel for heavy-duty vehicles; however, it was rarely used
at that time in other countries. Years later, in the 1970s, the oil tensions
caused a fuel deficiency and a commercial motive to produce at least some
biodiesel, and bioethanol, as alternatives to fossil-fuel-based diesel. There
are various factors, such as political policy, commercial viability, subsidies
and incentives for sustainable products, and environmental factors that
Biodiesel Production Methods and Feedstocks 449
affect governments’ and industries’ motivations and attraction to biodiesel.

Typically, it has had to be justified, either on commercial or sustainability
grounds, to compete as a substitute for traditional diesel in miscellaneous
countries for the past two to three decades [12]. Today, there is a wide
range of countries that are keen to generate biodiesel in Asia, Europe, and
North America and are striving to reduce its cost of supply and improve
the efficiencies and capacities of the processes used to generate it. As a
rule of thumb, a typical plant is able to produce some 6 million liters (~1.5
million gallons), or more, specification-grade biodiesel fuel annually [13].
17.2 Biofuel Classification in Terms of Origin

and Technological Conversion of Raw Materials
Biofuels refer to the fuel types derived from biological/organic feedstocks
[14–16]. When the feedstocks are processed, they are transformed into
renewable and, in most cases, sustainable, carbon-based energy fuels. These
fuels can be used commercially, including ethanol and biodiesel for numer-
ous applications, but most of them end up as blendstocks for transporta-
tion usage [17]. Although ethanol, specifically that blended into refinery
gasoline, dominates the global biofuel markets, biodiesel is a substantial
and growing contributor. Generally, biofuels can be subdivided into first to
third generations, depending on the type of feedstocks involved.
The first-generation biofuel production method is the most widely used
technique to directly produce fuel from food crops (e.g., soybean, palm oil,
sugarcane, sugarcane, and sunflower) in the form of ethanol and biodiesel.
First-generation biofuels have clear benefits including producing valuable
fuel supply, burning cleaner with less emissions, little or no toxicity, and
sustainability compared to fossil fuels. However, when comparing the
impact of such production on the prices of the raw materials, particularly
cereal crops, and the plant operating costs and costs of supply, it is hard to
justify some biofuel supply chains to divert invaluable and comparatively
high-cost food crops to the biofuel industry [17–21]. Moreover, using palm
oil as a feedstock for biodiesel is not justifiable on environmental grounds,
if pristine rain forest is destroyed to give way to oil farm plantations, even
though palm oil delivers greater biodiesel yield than most other first-
generation feedstocks.
Second-generation biofuels, also known as an advanced biofuel, are
made from non-food crops or crops grown on very low-grade non-
agricultural land by generally more complex and costly methods [22, 23].
There are three main sources of second-generation biofuels production
including non-edible vegetable oils (e.g., cotton seed, milkweed, linseed,

rubber seed, and mahua), waste oils, and animal fat feedstocks. The main
advantages of second-generation biofuels are their positive sustainability
and environmental credentials, and potential economic profitability and
competitiveness at lower crude oil prices. Feedstocks used in producing
second-generation biofuels tend to be considerably cheaper than food
crop–derived vegetable oils. Also, they are beneficial as they significantly
diminish the cost of waste disposal and treatment. However, yields and
conversion efficiency from fast-growing lower-grade plants, e.g., Jatropha
curcas (with a natural oil content of about 37%, need to be improved to
further justify their development on low-grade semi-arid land.
Nevertheless, second-generation biofuels offer substantial potential to
reduce the planet’s dependence on crude oil–derived transportation fuels.
However, it is unlikely to grow medium-term demand for transportation
fuels around the world as they are still produced in relatively small quan-
tities, particularly biodiesel [20, 24–27]. Besides, when it comes to using
animal fat feedstock, the major barrier is the existence of a high amount
of free fatty acids (FFA) in conjunction with higher water content, which
tends to diminish the biofuel production yield [28–34].
Some countries, such as the United Kingdom, process a lot of waste oil,
particularly used cooking oils, in some cases blended with waste engine
oils (of fossil fuel origin), to produce biodiesel in a cost effective way. The
acquisition costs for waste oils are very low as most producers of large-
scale waste oils avoid disposal costs by “gifting” them to biofuels producers.
Most of the supply chain costs for the biodiesel producers are in the gath-
ering, transportation, and storage costs (handling logistics) collecting indi-
vidual small quantities of oil from many suppliers located in distal parts
of a catchment area. Additionally, because waste oils tend to be of vari-
ous compositions with variable contaminants within them, biodiesel pro-
ducers from waste oils have additional operating costs related to ensuring
specification grade fuel products and disposal costs of some contaminants
removed from the feedstocks.
The third-generation biofuels use various forms of algal biomass to gen-
erate biofuels. Although algal species may need relatively large volumes
of water, nitrogen, and phosphorus to grow especially at industrial scale,
certain species possess outstanding oil yields. Also, they have the poten-
tial to improve biodiesel production capacity and efficiency and reduce
the environmental footprint of individual biodiesel plants. Such plants
could be located on low-quality land and close to carbon dioxide emitters
(e.g., power plants and sewage processing plants) that could, in the future,
provide algal plants a regular supply of captured carbon dioxide. High
rapeseed oil
1% 1% 1%
13%
sunflower seed oil
soybean oil
84%
palm oil
other oils
Figure 17.1 Primary feedstocks used to produce biodiesel [37]. Other oils include those
derived from waste cooking oils, jatropha and tallow.
hydrolysis and/or fermentation efficiency, no need for herbicides or pes-

ticides in algal cultivation, relatively high resistance even in harsh condi-
tions (e.g., saline and brackish water) are some of the exceptional features
make algal biomass an attractive candidate for a new generation of biofuel
production. Even more appealing, though, is the possibility of genetically
modifying algae, also known as fourth-generation biofuels (FGBs), to fur-
ther increase the productivity of customized algal species. It seems very
likely that FGB will help to open new more-commercially viable options
for biodiesel production in the future [17, 35].
Despite introducing a few commercial-scale second-generation bio-
diesel production techniques, today, the majority of the world’s total bio-
diesel (above 95%) is synthesized from edible oils mostly from rape seed,
accounting for approximately 85% [36] (see Figure 17.1).
17.3 Techniques Capable of Producing Biodiesel

on Commercial Scales
Biodiesel may be produced via various techniques [38–41]. These include
the following:
• direct use of plant-derived and waste oils;

• blending of plant-derived oils and oil wastes with other fuels
(e.g., refinery diesel);
• microemulsion with excess methanol and ethanol to
decrease viscosity;
• thermal cracking to break down longer chain molecules;

• pyrolysis of oxygen-rich organic feedstock of algal, plant, or
animal origin; and,
• transesterification.
The most commonly used method in commercial biodiesel plants is

transesterification [40].
17.3.1 Direct and Blending Methods With the Aim

of Biodiesel Generation
There are some harmful materials in crude oil–derived diesel fuel, par-
ticularly the aromatic molecules xylenes, toluene, and benzene, and some
particulates. Diesel from refineries also consists of contaminants like sul-
fur and particles of heavy oil residues which are harming people’s health
and the atmosphere [42, 43]. On the other hand, the chemical components
of biodiesel are much cleaner and purer than those found in crude oil–
derived diesel due to the lack of such contaminants in the biological feed-
stocks [37, 44]. The hydrocarbon molecules in biodiesel are mostly straight
chains with carbon numbers ranging from 16 to 20, not aromatics. The
lack of sulfur in biodiesel decreases the accumulation of sulfuric acid in an
engine’s crankcase oil and subsequently, makes it less corrosive to engines
compared to the crude oil–derived diesel [45]. On the negative side, the
emissions of nitrogen oxides (NOx) can be higher with biodiesel than
refinery diesel [46, 47]. By weight, there is about 10% oxygen in biodiesel.
However, during the consumption of biodiesel in an engine, fewer hydro-
carbons, particles, carbon monoxide, and sulfur oxides (SOx) are released
than with crude oil–derived diesel [37].
17.3.2 Microemulsion Methods

Oil derivatives of vegetable tend to result in products with higher vis-
cosities, unless treated, leading to some biodiesel processing issues. To
overcome this obstacle, microemulsions with solvents [1, 48] such as eth-
anol and methanol can be utilized to effectively reduce product viscosities.
Microemulsions are defined as isotropic colloidal fluid dispersions utiliz-
ing particles with diameter of 1 to 150 nm. They are commonly generated
from two liquids which in standard conditions are mostly immiscible, i.e.,
a) ionic and b) non-ionic amphiphiles. Microemulsions typically promote the
spray characteristics of the oils because they vaporize immediately because

they contain components with lower boiling points within their micelles.
17.3.3 Pyrolysis Methods

Pyrolysis is the reaction in which primarily solid biomass is degraded by
applying high temperatures at different heating rates. This is mostly attained
through enhancing the temperature of the vegetable oils in the absence of
oxygen. This generates bio-oils (liquids) along with co-generation products
of charcoal (solid) and fuel gas. Biomass pyrolysis methods mostly produce
and recover biofuels with medium or low calorific amounts/energy con-
tents [49]. Based on the process conditions, biofuel pyrolysis methods are
divided into the “ordinary”, “quick”, and “flash” methods as follows:
a) Ordinary pyrolysis involves reactions which are stimulated by rela-
tively slow warming rates ranging from 0.1°K/s to 1°K/s over a residence-
time interval of 45 to 550 seconds. Initially, a pre-pyrolysis step is required.
This is typically conducted in the temperature range of 550–950°K, stim-
ulating biomass decomposition to occur. In this step, molecular restruc-
turing arises, such as water elimination, cracking of some chemical bonds,
free-radical liberation, creation of carbonyl functional groups, and, in
some cases, hydroperoxide functional groups [50].
b) Quick pyrolysis is implemented in a temperature range of 850°K to
1250°K exerting heating rates from 10°K/s to 200°K/s over a residence-time
interval of 0.5–10 s. Feedstocks that are fragmented into the very small
particle, i.e., less than 1 mm, are commonly utilized. This involves pre-
treatment preparations of most solid biomass feedstocks.
c) Flash pyrolysis is commonly applied to ground fragments of relatively
large chunks of woody materials as its biomass feedstock. It is accomplished
in a temperature range from 1,050°K to 1,300°K at high rates of heating
attaining more than 1,000°K/s. Residence-time intervals of less than 0.5 s
and particle sizes of <0.2 mm are typically involved.
17.3.4 Transesterification Methods

The other name for the transesterification method is “alcoholysis”.
Vegetable oils which are formed principally of lipids are mixed with alco-
hols, in which they are soluble, and react to generate esters and glycerin.
This is commonly directed in the presence of a catalyst to amend the effi-
ciencies and reaction rates [51]. Methanol or ethanol are typically chosen
from among a broad range of potential alcohols that could be utilized,
because they possess highly suitable chemical and physical properties and
are of low cost to procure [52].
17.4 Influential Parameters on Biodiesel Production

Fundamentally, the most influential parameters affecting biodiesel produc-
tion are the nature of feedstocks or raw materials. Additionally, the catalyst
type and the concentration of that catalyst, the alcohol:lipid ratio, reaction
temperature, and time are also key influencing factors [53].
17.4.1 The Choice of Transesterification Catalysts

The process of biodiesel synthesis is widely performed using the transes-
terification reaction, catalyzed by homogeneous and/or heterogeneous
catalysts [54]. Generally, homogeneous catalysts can be divided into two
types, namely, alkaline catalysts (e.g., NaOH, KOH, and CH3OK) and acid
catalysts (e.g., H2SO4, HCl, and Fe2(SO4)3). The main advantage of homo-
geneous catalysis is that they are capable of dissolving in the reaction mix-
ture, facilitating high interactions between catalyst and reactants. Despite
the wide application of homogeneous catalysts, in transesterifing feedstocks,
they suffer from process difficulties and very high costs, associated with the
requirement to pretreat low-quality feedstocks [54–60]. Thus, the develop-
ment of novel and more efficient catalysts to overcome the aforesaid issues is
of great importance. In this regard, heterogeneous catalyst, including solid
acid (e.g., SiO2/Al2O3 and ion-exchange resins), solid alkaline (e.g., CaO,
LiOH/g-Al2O3, ZnO, BaO, and MgO), enzymatic catalysis (e.g., Candida
Antarctica, a key source of lipases, and Pseudomonas cepacia), and nano-
material-based catalysts (e.g., nanostructured mixed-metal oxides of CaO-
MgO) have drawn considerable attention owing to their excellent results
from a wide range of potential biomass conversion applications tested [54,
59, 61–77]. Of particular appeal is the possibility of tuning the structure of
nanocatalysts, by initiating modification to their functional groups, in order
to maximize activity, selectivity, and stability. Such approaches result in opti-
mizing the catalyst reactions and, consequently, boosting biofuel yield [61].
17.4.2 Effects of Catalyst Characteristics on Biodiesel

Production Efficiency
Variations of catalyst type, changes in catalyst concentrations, reac-
tion times, and the ratios of alcohol/plant oil (lipids) all influence the
(a) 100 120 (b)
95 100
80
Yield (%)
Yield (%)
90
60
85 40
80 20
0
75 0 200 400 600
NaOH KOH CH30Na CH3OK Time (min)
(c) (d)
100 100
98
80
96
Yield (%)
Yield (%)
60 94
40 92
20 90
88
0 4:01 5:01 6:01 7:01 8:01
0.2 0.4 0.6 0.8 1 1.2 115 Methanol/Oil (molar ratio)
Catalyst Concentration
Figure 17.2 (a) Impact of catalyst type on esters yield for four different alkaline catalysts
to produce biodiesel product from sunflower and rape seed lipids (T = 65°C; methanol:oil
molar ratio is 6:1; catalyst 1 wt.% of plant lipids). (b) The effect of SnCl2/Nb2O5 catalyst
extraction time on the ethyl oleate yield (T= 60°C; 50 mg of 50% wt. SnCl2/Nb2O5) [78].
(c) the effect of catalyst concentration on biodiesel yield from coconut oil (T = 60°C; 350
rpm; 60-min reaction time; NaOH catalyst in methanol) [79]. (d) The effect of methanol
in the range of 4:1–8:1 molar ratio (T = 65 ± 1°C; reaction time = 1 (h) in the analyses of
Jatropha oil [80].
performance of biodiesel production techniques. These impacts are illus-

trated in Figure 17.2. Accordingly, substantial testing efforts are required to
determine the optimum reaction time, catalyst concentration, and relative
concentration of alcohol to plant oil to maximize the biodiesel yield.
17.5 Biodiesel Markets and Economic Considerations

Currently, the expansion of novel biodiesel technologies is affected by eco-
logical and economic obstacles which are attracting a high level of interna-
tional concern and attention. Carbon dioxide can be exploited beneficially
by some recent technologies [81, 82]; however, when emitted to the atmo-
sphere, it has harmful consequences for the environment. The “green-
house effect” is causing the atmosphere to warm due to the anthropogenic
emissions of carbon dioxide and other gases, thereby degrading the Earth’s
atmosphere, ecosystems, and surface environment. Various multi-national
accords and organizations are analyzing the impacts and seeking ways to
mitigate their detrimental effects on the atmosphere and the surface envi-
ronment. The further substitution of crude oil–derived transportation
fuels with biodiesel is one possible beneficial solution to address the cur-
rent climate emergency. Several directives issued by the European Union
support the increased uptake of biodiesel and encourage the more wide-
spread production and consumption of biodiesel as an alternative road
vehicle fuel, although its original targets of 20% biofuel contribution by
2020 [83] have not been achieved. Nevertheless, most of Europe’s large
road vehicles are diesel-powered and, consequently, there is a substantial
opportunity for biodiesel generated from plant lipid, waste oil, and algae
to expand. Ultimately, it will be government policies, fuel tax strategies,
and the cost of producing biodiesel compared to the cost of importing and
refining crude oil–derived diesel in Europe that will determine the uptake
of this environmentally friendly transportation fuel [10, 84].
17.6 Challenges Confronting Biodiesel Uptake

About 15 years ago, the world was faced with an energy shortage due, at
that time, to the decline of developed crude oil production sources. That
situation has been reversed over the past 15 years by the rapid expansion of
the United States shale industry leading to a massive oversupply of crude oil
and products globally in 2019 and 2020. However, the past 25 years has also
seen a growing awareness of the pending global climate catastrophe. With
such awareness, regardless of crude oil prices and abundant short-term
supply, countries continue to look for renewable fuel substitutes for crude
oil, which would be environment-friendly and sustainable. Rapid oil price
falls in 2014 (oversupply due to shale oil production in the United States),
2019 (exports of oil from United States flooding global markets), and 2020
(COVID-19 pandemic dramatically reducing global energy demand) have
made fossil fuels in the short-term substantially more cost effective than
biofuels. This situation, most likely, will adversely slow down the uptake of
biofuels around the world for the next few years. However, the prevailing
situation should also stimulate more research to improve biodiesel pro-
duction processes and make them cost competitive with crude oil–derived
diesel at oil prices of less than $40/barrel.
There are several energy resources of biological origin such as alco-
hols (butanol, ethanol, and methanol), plant and algal oils/lipids, woody
biomass, agricultural organic wastes and biogases, other waste oils, and
various synthetic fuels, which could all be usefully exploited to achieve
the objectives of substituting for fossil fuels. Biodiesel produced from such
sources, in particular, offers the opportunity to be blended with refinery-
derived diesel. Blending means that it can be used in existing vehicles, at
specifications close to refinery grade diesels, with no engine modifications
required [85]. Today, there are several countries like the USA, the EU
nations, and Brazil where government mandates exist to ensure that road
fuels contain minimum quantities of biofuels, mainly ethanol in gasoline,
but also biodiesel into refinery diesel. Such mandates have underpinned
the economics of the biofuels industry for more than 15 years and continue
to do so.
17.7 Corrosion and Quality Monitoring Issues

for Biodiesel
Corrosion of metals is of concern for the long-term storage of refinery
diesel and, particularly biodiesel, mainly due to its acidity. This impacts
storage facilities, including vehicle fuel tanks, and the quality of the fuel
itself with traces of metal potentially damaging vehicle engines [86–89].
This means that diesel vehicle engines that use large quantities of bio-
diesel require continuous checks for corrosion impacts. Further studies
are required to investigate traces of metals in biofuel and their impacts on
the oxidation stability of biodiesel. Developing effective antioxidants and
corrosion inhibitors for biodiesel tanks and engines is also required to mit-
igate or avoid metal corrosion.
Precise, fast, and readily available on-site analysis to verify blended die-
sel fuel specification is being met. These are typically required at vehicle
refueling stations and fuel storage terminals which handle large volumes
of biofuels [90]. This is particularly so for biodiesel, because it is manufac-
tured from a diverse range of feedstocks of quite disparate compositions.
This means that it is prone to contain small traces of unwanted contami-
nants if quality control during its production, blending, and storage is not
rigorously conducted.
17.8 Conclusions
Biodiesel is a proven, effective, and sustainable transportation fuel that can,
and does, substitute for refinery diesel in many supply chains. Biofuels can
be subdivided into first to third generations depending on the type of feed-

stocks involved; biofuels produced from food crops are first generation;
biofuels produced from non-food crops and/or on low grade land are sec-
ond generation; biofuels produced from algal feedstocks are third genera-
tion; and some refer to biofuels derived from genetically engineered algae
as fourth generation. Biofuels generated from waste oils (e.g., cooking oil)
are generally considered as second-generation products. This means that
there is a diverse range of feedstocks available for biofuel production.
Some plant-derived oils and waste oils can be used directly or in blended
form as vehicle fuels. Others, with little processing and low-cost treatments
and blending, convert viscous oils into low viscosity microemulsions with
methanol or ethanol render other biolipids ready to consume more effi-
ciently in vehicle engines. For solid biomass, including woody materials,
various pyrolysis methods, sometimes combined with gasification are
required to produce biofuels without leaving substantial solid residues.
The most common and efficient techniques that operate in larger-scale
commercial biodiesel production plants involve transesterification. These
produce biodiesel by mixing plant lipids with alcohols and catalysts.
There are some potential metal corrosion issues in engines and storage
facilities and fuel specification limits that need to be carefully adhered to.
These require careful monitoring, and in the case of corrosion mitigation
by corrosion inhibitors. Expansion of global biodiesel demand, consump-
tion, and production capacities in the long-term still depends on some
technology breakthroughs to increase product yields and reduce operating
costs. In the short term, the COVID-19 pandemic and the global recession
it has induced in 2020 is expected to negatively impact transportation fuel
demand around the world for the next year or so. This is also likely to
hinder investment and growth in this promising sector over the next few
years.
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18
Application of Nanoparticles for the
Enhanced Production of Biodiesel
Muhammad Hilman Mustapha, Akhsan Kamil Azizi, Wan Nur Aini Wan
Mokhtar and Mohamad Azuwa Mohamed*
Department of Chemical Sciences, Faculty of Science and Technology, Universiti

Kebangsaan Malaysia, UKM Bangi, Selangor, Malaysia
Abstract
Nanocatalysis has spotted as a promptly growing field in nanotechnological
advancement. Involving the application of nanoscale materials (nanoparticles,
NPs) or nanomaterials (NMs) as catalysts, they can be found in a variety char-
acter of homogeneous and heterogeneous catalysis applications. Their exqui-
site physical, chemical, and biological properties are gaining interest in diverse
fields, including in the production of biodiesel by transesterification reaction. To
improve the biodiesel production rate, nanocatalysts and NMs are bound with a
metal oxide or microbial enzymes to enhance the modification of triglycerides
into fatty acid methyl ester (FAME) yield. Thus, this chapter provides an insight
of NPs in the synthesis of biodiesel, beginning with a general introduction, then
recent progress of NPs in transesterification application, and, finally, conclusion.
Keywords: Catalyst, nanoparticles, nanocatalyst, biodiesel
18.1 Introduction
The typical transesterification reaction was intensively relied on hetero-
geneous catalysts to increase the production of biodiesel. Heterogeneous
catalysts were usually emphasized metal oxide-based, carbon-based, boron
group-based, waste material-based, or enzyme-based as agents to be per-
formed in the transesterification reaction. However, these non-nanoscale
*Corresponding author: mazuwa@ukm.edu.my
465
Nanoparticles/Nanomaterial catalysts
Characteristics Types of Nanomaterial

• Nanoscale size
• High surface area
• High catalytic activity Carbon-based Inorganic-based Organic-based Composite-based
• Natural and synthetic Fullerenes • Metal Organic matter Combination of
• Prone to agglomeration Carbon nanotubes • Metal oxides Dendrimers, carbon-based, metal-
Carbon nanofibers • semiconductors micelles, based, organic-based
Carbon black liposomes, with any form of
Graphene polymers metal, ceramic or
Carbon onions polymer bulk
materials
Figure 18.1 Characteristics and type of nanoparticles catalysts.
catalysts showed some downside as they were ineffective, mass transfer-

resistant, and leaching effect. Thus, nanocatalysts have been introduced to
resolve the difficulties mentioned above. The nanoscale of particle diam-
eter in the range of 1 to 100 nm allows a large surface area–to-volume
ratio and thus allows plenty active sites on the catalyst surface to be partic-
ipated in the reaction. Furthermore, different morphologies of nanoparti-
cles (NPs) vary their applications to be matched with other precursors and
fasten the transesterification reaction rate compared to the larger size of
heterogeneous catalysts.
In general, nanocatalysts can be organized into four categories, which
are carbon-based nanomaterials (NMs), inorganic-based NMs, organ-
ic-based NMs, and composite-based NMs (Figure 18.1). Typically, NPs
can be derived in many forms, such as powder, crystal, and cluster. NP
in powder usually forms from mixtures of a fine powder, while nano-
crystals described as mixtures of ultrafine particles [1]. Then, the cluster
form of NP is categorized as they have a narrow size distribution with a
range of 1–10 nm and one dimension only. Recently, NP including solid
NP, nanobioparticles, and magnetic NP is usually become favor candidates
for numerous researches in catalysis applications due to superhigh surface
area compared to other materials. Commonly, nanocatalyst describes as
heterogeneous nanocatalyst in the transesterification process for biodiesel
production.
18.2 Solid Nanoparticles

Metal NP (MNP) is one of the solid NPs used as nanocatalyst by many
researchers in enhancing the yield of biodiesel. The processes of MNP are
NPs for the Enhanced Production of Biodiesel 467
energy-dependent, performed mostly in laboratories by using either phys-

ical or chemical method. Both methods give different condition where
physical methods usually require huge capital costs but less impact to
environment, while chemical approach are cost effective due to less energy
requirement. The synthesis method of MNP consists of five steps [2].
Firstly, the clustering and complexation steps, the formation of nuclei with
uniform or non-uniform size distribution from the nucleation process.
The rise of nuclei from the NP and then the diffusional growth process
will take place. Moreover, there are two properties that can be governed by
using the nanotechnology that is size of NP and also molecular structure.
In recent years, the unique physical and chemical properties of heter-
ogenous nanocatalyst has risen the interest for its application in catalyst
for biodiesel production. MNPs in single catalyst such as nano-K2O, nano-
CaO, nano-MgO, nano-TiO2, and nano-ZnO are conventional nanocat-
alyst used that shown potential in produce high fatty acid methyl ester
(FAME) yield. Among others, CaO is the most metal oxide used in the
transesterification process of triglyceride due to high availability, cheap,
highly active, non-corrosive, and environmentally friendly [3, 4]. The pro-
duction of Nano-CaO can be from various materials, either natural such
as eggshells and animal bone or through a synthetic process with calcium
nitrate, calcium sulfate, etc. The synthesis of nano-CaO can be obtained
using two main steps, which are preparation and also activation of NP
[5]. Various preparation steps include (dry or wet) impregnation, mixing,
thermal decomposition, and precipitation, whereas for another step, which
is the most critical step to activate the active site of the catalyst by calci-
nation of catalysts with suitable temperature. By performing this critical
step, the specific surface area of the nano-CaO catalyst can be enhanced
or increased.
Various types of nanocatalyst can be produced by neat, doped, and
loaded. By neat-catalyst, pure metal is used. Nano-CaO derived from
calcination an eggshell assist by sonochemical can convert the algae oil
efficiently to biodiesel for 96.3% yield with optimum conditions 9:1 ratio
methanol/oil, 1.25% amount of catalyst, and 55°C reaction temperature
[6]. Another report shows that nano-CaO nanopowder was efficiently con-
verted soybean oil to biodiesel for 96.6% with methanol/oil molar ratio of
7:1, 3.0 wt.% amount of catalyst used, reaction temperature of 338 K, and
reaction time of 60 minutes [7].
Based on the research by Reddy et al. (2006), a very high conversion
of 99% biodiesel are obtained via the usage of nanocrystalline CaO as the
catalyst in the transesterification of soybean oil and poultry fat [8]. This
high conversion are due to high activity and surface reactivity of nanocrys-
talline CaO caused by high surface or volume ratio of nano-sized catalyst
particles.
Other than nano-CaO, nano-TiO2, and nano-ZnO are the most exten-
sively employed in NMs application. There are plenty synthetic approaches
available to produce TiO2 and ZnO NP. The synthetic approaches are
such as sol-gel processing, reverse microemulsion, dialysis hydrolysis,
microwave-assisted emulsion polymerization, alcohol-thermal method,
hydrothermal, chemical vapor, combustion, and gas-phase methods.
Between current available approaches, hydrothermal process is recognized
as promising method to prepare TiO2 and ZnO, where at a lower tempera-
ture condition (100°C), the reaction can be executed other than another
available approaches that requires higher temperature condition.
Bimetallic NP has shown dominant technological applications in het-
erogeneous catalysis. They possessed special properties, which lead better
reactivity, this is due to the core metal particle could adjust the lattice
strain of the metal, which emerge in a shift of the electronic band struc-
ture of the metal. Nano–CaO-K2CO3 catalyst has produced to achieved
97.67% ± 1.7 yield by using methanol to oil ratio of 9/1 and performed
in reaction time of 8 hours in a liquid batch reactor at 64.85°C [9]. The
NP of CaO-K2CO3 with approximately high surface-to-volume ratios in
which particle sizes range between 20 and 160 nm acts as catalyst sup-
ports. Moreover, high-temperature decomposition products of K2CO3
are deployed to functionalize and enhance the basicity of nanocatalyst.
Calcium methoxide was recorded develop at the surface of CaO through
the K2O phase or Ca–O–K groups and attacks the carbonyl group of the
triglycerides. A power law kinetics equation was used to calculate the
transesterification reaction rate for this reaction. In addition, this catalyst
can be reusable for five runs.
The underlying strength of CaO-K2CO3 reduced slightly upon reuse
compare to the fresh catalyst. As for basicity of the catalyst, it did not
decline further with the increasing number of catalyst reusability. The
transesterification reaction activation energy was determined as 25.34 ±
2.48 kJ/mol [9]. Therefore, the calculated activation energy of the reaction
was low and shows that this reaction was mass transfer controlled, which
lead on how to enhance the reaction rate. More than that, Chinese tallow
oil was converting to biodiesel with a 96.8% yield by KF/CaO nanocatalyst.
The formation of KCaF3 was formed and enhanced catalytic ability [10].
The doped Li toward MgO had enhanced biodiesel yield from soybean
oil which used Li/Mg catalyst with molar ratio of 0.08 and undergo calci-
nation process at 549.85°C, methanol/oil of 1:12, 9 wt% amount of catalyst,
and yield of 93.9% [11]. The production of strong base sites due to Li doped
influences the biodiesel yield. Nano-λ-Al2O3 as supported with doped KF
by wetness-impregnation method for the transesterification of canola oil
achieved for the yield of 97.7% with calcination temperature of 773 K, 15
wt% loading catalyst, 8-hour reaction time, 338-K reaction temperature,
3 wt% catalyst, and 15:1 molar ratio of methanol/oil [12]. The TiO2-ZnO
nanocatalyst shows an excellent catalytic activity compared to the single
ZnO nanocatalyst with 92.2% conversion of FAME from palm oil with 6:1
methanol to oil molar ratio, 200-mg catalyst loading, 5-hour reaction time,
and 60°C reaction temperature [13].
The ferric manganese–doped sulfated zirconia NP solid catalysts were
developed by impregnation reaction, which are purposely for the trans-
esterification of waste cooking oil. The optimum conditions for the nano-
catalyst for transesterification reaction were 160°C of temperature, 1:10 M
ratio of oil:alcohol, and 3 wt% catalyst dosage for 97.2% yield of biodiesel
[14]. The high conversion of biodiesel was caused by high acidity, large sur-
face area, and pore diameter provided from zirconia as nanocatalyst, which
results rapid diffusion of reactant within the internal pore of catalyst and
contact to the active sites. The bimetallic gold-silver core-shell NP, Au @
Ag NPs, was used as nanocatalyst to convert sunflower oil to biodiesel with
reaction condition of 65°C for temperature and 2 hours for reaction time,
while 5% for catalyst concentration and 5:1 for methanol or oil molar ratio
[15]. The highest yield of biodiesel of 86.9% with three cycles of transester-
ification reaction maintained as a results of greater concentration of highly
reactive sites affected by increased surface-to-volume ratio.
The sulfonated acid on single-walled carbon nanohorn (SWCNH) as a
solid acid catalyst was dissolved with Fe/Fe2O3-mixed NP was performed
for esterification of palmitic acid and transesterification of tributyrin to
produce methyl butyrate [16]. Tributyrin and palmitic acid are an exam-
ple of triglycerides and free fatty acid (FFA) to generate transesterifica-
tion and esterification process. As a results of SWCNH properties such as
high surface area, chemical resistivity, thermal stability, and its nature of
hydrophobic, made it is used as catalyst support. Other than that, for ester-
ification of palmitic acid, it was stated that sulfonated acid on SWCNH
have greater performance of catalytic on the reaction than another types
of sulfonated carbon-based catalyst developed from other sources. More
than that, the use of Fe of Fe2O3 was compared to other metal because it
was found that a catalyst that consists of kind of iron oxide (magnetite)
can simulate immense activity toward transesterification and esterification
reaction. In addition, iron oxide also possesses a good trait for carboxylic
acids and FFA high adsorption.
The catalytic reaction mechanism for the transesterification and esteri-

fication by using the acid catalyst and the reaction pathway in this mech-
anism is shown in Figures 18.2 and 18.3 [16]. Other than that, by one of
Lewis acid or Brønsted acid, the carbocation formation was stimulates by
the reaction of FFA or triglycerides with the acidic site, and results tetra-
hedral intermediate produces from nucleophilic attack of methanol. After
H2O or glycerin is eliminated, FAME can be produced while the acidic side
can revert to the original structure. This mechanism is genuine to −SO3H
group and a few types of solid acid catalysts [17–19]. Moreover, it can be
expected from this reaction, on the surface of Fe/F2O3 NP, the concentra-
tion of FFA molecules would be higher due to its interaction with the car-
boxyl group of FFAs, thus leads to increasing reaction catalyzed at –SO3H
due to the diffusion of concentrated FFAs molecules to –SO3H.
Other than that, the reaction will also lead to the adsorption of palmitic
acid on Fe/Fe2O3 NP on the catalyst surface due to the existence of hydro-
philic Fe/Fe2O3 surfaces that would attract the carboxylic part of palmitic
acid. While, concurrent with reactions of palmitic acid and tributyrin,
the hydrophobic alkyl parts of the adsorbed palmitic acid will attract the
hydrophobic tributyrin. There is a lot of research regarding production of
biodiesel that uses ferric mixture which is ferric magnetite (Fe3O4), Fe-Ti
mixed oxide, and ferric alginate as a solid catalyst [19, 20, 21]. Fe/Fe2O3
could have the same possibility to acts the same catalytic effect even no
SO3H OR’
O SO3H
Fe Fe2O3
+ ö C+
SO3H
SO3H
SO3H R OR’ R
SO3H
O+
R’ = alkyl group for +O CH3OH
triglyceride or H of FFA
R OR’
R OR’ OR’ H
ö C O+
R CH3
SO3H +
OHR’
Fe Fe2O3 +
O C O ö C O
SO3H
SO3H R CH3 R CH3

+ R’ OH
O O di-, mono glyceride
C Methyl ester or water from FFA
CH3
R
Figure 18.2 General reaction for possible mechanism of esterification and

transesterification with methanol on SO3H-Fe/Fe2O3-SWCNH. Reproduced with
permission [16]. Copyright 2015 Elsevier.
Tributyrin Alkyl group

molecule
Hydrophilic part
Alkyl group
Palmtic acid
molecule Hydrophilic part Diffusion of reactants
From bulk-liquid into pores on catalyst
methanol
acidic site (-SO3H) SWCNH walls
Diffusion of palmitic acid

from adsorbing zones
on Fe/Fe2O3 particles Diffusion of tributyrin
to acidic site (-SO3H) from concentrating zones
on palmitic acid layer to
acidic site (-SO3H)
Fe/Fe2O3 particles
Figure 18.3 Schematic image of diffusion of reactants in pores in SO3H-Fe/Fe2O3-

SWCNH. Reproduced with permission [16]. Copyright 2015 Elsevier.
researcher report on the catalyst. A magnetic field can recover the mag-
netic properties on SO3H-Fe/Fe2O3- SWCNH. In addition, based on the
research conducted, the esterification process to produce methyl palmitate
can achieve 90% yield or higher in a period of 3 to 7 hour [16].
18.3 Nanobioparticles/Nanobiocatalyst
Over the conventional process, the enzymatic process has several advan-
tages on separating byproduct of glycerol without any complicated oper-
ation steps [22]. There are many research has been reported using the
enzymatic process to enhanced biodiesel production. The use of micro-
organisms such as bacteria, yeast, and fungi as known as a biocatalyst
to improve the biodiesel yield with low-cost material compared to other
materials in biocatalyst such as lipase [23–25]. Lipase catalyst with immo-
bilized material shows the excellent conversion rate of biodiesel, easy sepa-
ration, and reusable catalyst. However, there are limitations in using lipase
due to its high cost that inhibited for wide applications in industrial [22].
In nanotechnology, the nanobiocatalyst (NBC) had not been explored
widely by researchers. NBC is known as promising innovation that
deployed advance nanotechnology with biotechnology and provides

attracting benefits such as enhancing enzyme activity, capability and sta-
bility, and also engineering performances in bioprocessing applications
[26]. It is also constructed by using functional NMs as enzyme carriers or
storage for immobilizing enzymes. In addition, for biocatalytic reactions,
nanoscale components are identified as ideal substrate materials for the
immobilization of enzymes used for the reactions.
Many researchers have modified the enzyme with the nanosupport or
known as enzyme immobilization, to enhance the biodiesel yield. The
nanostructured scaffolds are used for enzyme immobilization and it can
necessarily increase biocatalyst life cycles, thus decreasing cost needed
for biocatalytic process. This comprises nanofibers, NPs, nanotubes, and
nanocomposites [27–30]. In enzyme immobilization, the NMs possess
several advantages, which are the consistently high surface area for assists
in enzyme-loading capacity, lower-resistance against mass transfer, high
mechanical resistance, easy separation, activity enhancement, and enzyme
stability.
Most of the biocatalyst use immobilization enzymes, such as magnetic
NP. Other than that, immobilization of protein, peptide, and enzyme also
extensively used nanosized magnetic particles for recent development.
The magnetic NP as supports for enzyme immobilization has several ben-
efits such as for the binding efficiency, its offers high specific surface area.
Other than that, less contaminate and low mass transfer resistance, easy
segregation of immobilized enzymes by an external magnetic force, then
reduce operational expense, and a continuous biocatalysts system applica-
tion also provided by magnetic NP as support for enzyme immobilization
[31]. Moreover, the covalent coupling technique was used for immobi-
lization of enzyme onto different supports. The activated magnetic car-
ries and lipase could efficiently bound by a covalent bond and produce
better recovery activity. More than that, nanoparticles, like Fe2O3, Fe3O4,
polymeric, and silica NP, have been introduced for the immobilization
of lipases.
Moreover, Dang and Chin et al. (2012) reported lipase yielded from
an isolated strain Burkholderia sp. C20 was immobilized on magnetic NP
(Fe3O4) for biodiesel production [32]. The immobilize lipase used in pro-
duction of biodiesel from olive oil with 90% yield within 30 hours of reac-
tion time in batch operation with 11 wt% of immobilized lipases. These
immobilized lipases can be reused up to ten cycles without significant loss
in the transesterification reaction. Another research reported the use of
immobilized lipase on Fe3O4 nanocatalyst for synthesis of biodiesel from
soybean oil [33]. For preparation of magnetic Fe3O4 NP, it was done by
coprecipitating Fe2+ (FeSO4·7H2O) and Fe3+ (FeCl3·6H2O) ions under hydro-

thermal conditions in ammonia solution. The biodiesel yield reached over
90% by three-step addition of methanol when 60% immobilized lipase.
The reusability of catalyst is up to four times without a major decline in its
catalytic activity.
18.4 Magnetic Nanoparticles

Nanomagnetic catalyst has increase attraction and identified as promising
for biodiesel application in recent years. This nanomagnetic catalyst is con-
sidered as promising due to its properties that can made it easily separated
from the reagents by an external magnetic field, which can lead to preven-
tion of catalyst loss and enhance its recovery rate during the separation
process.
As a matter of fact, magnetic materials have arisen as one of promising
alternatives to conventional heterogeneous supports over recent years. The
magnetic catalysts have the advantage over the non-magnetic catalysts in
the separation process. The excellent improvements had made on filtration
and purification process which magnetic separation had been introduced
to replace standard filtration and purification methods which it can avoid
the loss of catalysts and increase its reusability. The different types of fer-
rites such as Fe2O3 and Fe3O4 have been used as a magnetic catalyst or cat-
alyst support and between many types of different ferrites, and nanoscale
magnetite (Fe3O4) is a center of attention in this industry due to its stability,
large surface area, and super paramagnetic properties.
Liu et al. (2016) stated that the catalyst of MgFe2O4 coated by CaO using
a simple alkali precipitation method [34]. The MgFe2O4/CaO nanocatalyst
used for biodiesel synthesis by using soybean oil with 1.0 wt.% catalyst
dosage, 12:1 of methanol/oil ratio, 70°C reaction temperature, and 3 hours
of reaction time. The modify catalyst with magnetic properties shows a
better catalytic activity and better performance in resistance toward water
and acid in the reaction in comparison with single CaO catalyst. These
catalysts contain superparamagnetic behavior that could achieve a yield of
biodiesel 98.3% and reuse for five times with no remarks for any catalytic
activity decline. This shows that MgFe2O4 NP had excellent stability and
recyclability.
Another magnetic NP of CaO catalyst by chemical precipitation is CaO-
Fe3O4 [35]. This magnetic nanocatalyst contains CaO and Fe3O4 accom-
panied by CaFe2O4 for the transesterification of palm seed oil. About
69.7% yield of biodiesel was determined under the reaction conditions of
300-minute reaction time, 65°C temperature, 20 methanol/oil molar ratio,

and 10 wt.% of CaO-Fe3O4 catalyst loading.
Tang et al. (2012) reported that the catalyst of Ca/Al/Fe3O4 NP
obtained via chemical synthesis method provide high yield of conversion
of biodiesel which is 98.71%. The reaction was catalyzed by calcium alu-
minate and performed under reaction conditions as follows: 15:1 molar
ratio of methanol/oil, 6 wt.% catalyst dosage of rapeseed oil, 65°C reac-
tion temperature, the stirring rate of 270 rpm, and 3-hour reaction time
[21]. This catalyst can stand up to five cycles of catalysis due to improve-
ment toward the stability of catalyst by magnetic NP as supported by
the catalyst.
Moreover, a reactant can contact more effectively on the high surface
of supported magnetic NP and shows high dispersion of magnetic NP–
supported solid catalyst. Due to this, the outcome of the reaction shows
high catalytic activity and also the benefits of efficient separation and good
term in reusability.
The two-step process of esterification of oleic acid and transesterifica-
tion of glyceryl trioleate as model reactions for biodiesel production by
sulfamic acid and sulfonic acid functionalized silica-coated crystalline Fe/
Fe3O4 core/shell MNPs has been reported [36]. The magnetic nanocat-
alyst was prepared by thermal decomposition and the high reactivity of
95% conversion of biodiesel achieved throughout five cycles of reactions.
The MNPs are used as solid supports to produce nanocatalyst that pos-
sess magnetic properties for ease the separation process. Furthermore, due
to the high surface area–to-volume ratio of the MNPs, a large number of
active site can be hold on the catalyst surface. Moreover, the active catalyst
on the surface freely available to the reactant due to the nanocatalyst is
highly soluble in solvents. The mechanism of the related reaction is shown
in Figure 18.4.
Other than that, the cost of biodiesel production can be reduce by reus-
ability and efficient separation of the catalysts. From the nanocatalyst,
the acid-functionalized MNP shows high magnetic moments due to the
existence of the iron (0) core. This magnetic benefit can be seen during
the transesterification process. It occurs when the reaction is completed
and the stirring process has stopped, and the catalyst was gathered on the
magnetic stir and eases the separation between the product and catalyst.
After that, the used catalyst that had been collected from previous reaction
was used for new transesterification reaction. Both catalysts can be reused
for five times, but sulfamic acid-functionalized MNP shows exceptional
reusability and stability which results retaining over 95% yield of biodiesel
compared to sulfonic acid functionalized MNP.
SH
SO3H
HS
SO3H
HO3S O Si
O
O Si O O SH
Si Si
HO3S SO3H O O O O O Si O
O O O Si
Si O
Fe3O4 O Si O O Si Si O O Si
SO3H HS O O Si O O
O Si O O Si O O O Si O O
O Si O Si
HO3S Si O O Fe3O4 O O
O
Fe 1) H2O2 O O Si O Fe O Si O
Si
Si O O O O O
2) H2SO4 O O Si
Si Si O O O O Si
O O
O Si O O O Si O
Si SH
HO3S O
O O O Si Si Si O O Si O
SO3H
SiO2 Si
O Si O O OO O O O O
HS O Si O Si Si O Si
HO3S O O O
SO3H Si
SH
HO3S SO3H SO3H
MPTMS SH
O
O O O O
1) 1-octadecene O O Si
Si Si O
O
OHOH
oleylamine/HDA x HCI HOHO OH O Si O O O Si O
HO Fe O4 OH TEOS O
Si O
O O Si O
120ºC - 180 ºC 3
NH4OH O Fe O
3 4 O O
Fe(CO)5 HO Fe OH O Si O O Si O
Fe
2) controlled HO
OH O O O O
Si O
OH
oxidation HO
HO OH
Si
OO O
O
O Si
O
OH Si O O O
O O Si Si Si O
O OO O O
APTES
NH2
NHSO2H
HO2SHN NH2
NHSO2H
O Si
O
O Si O O NH2
APTES Si Si
Si O
HO2SHN NHSO2H O O O O OO O
O Si O O Si Si Si O O Si O
HO2SHN
Fe3O4 NHSO2H H2N O O Si O O
O Si
O Si O O Si O O O Si O Si O
O Si
Si O O O Fe3O4 O O O
CISO2H O
Fe O
Si
O Si O Fe O Si
O
Si
HO2SHN O O O O
O Si OO
Si Si O O Si
O O OO O Si
O Si
O
NH2
HO2SHN O Si O O
NHSO2H O O O Si Si Si O Si O
Si O O OO O O O O
SiO2 O Si Si Si
H2N O O Si O Si
O O O
HO2SHN NHSO2H Si
NH2
HO2SHN NHSO2H
NH2
Figure 18.4 Preparation of sulfonic acid functionalized MNPs and sulfamic acid
functionalized MNPs. Reproduced with permission [36]. Copyright 2015 American
Chemical Society.
18.5 How Nanoparticles Enhanced Biodiesel

Production?
NPs can enhance biodiesel production by acting as an enhancer to increase
biodiesel production during the transesterification process. For solid NPs,
there is much research regarding solid NPs as an enhancer in biodiesel
production. As stated by Badnore et al. [37], commercial calcium oxide has

a lower specific surface area which is 1.54 times lower than nanocrystalline
CaO which make its less favorable than nanocrystalline CaO to use as cat-
alyst. Due to its larger surface area, the nano-sized catalyst showed a higher
conversion rate that is 18.81% than commercial calcium oxide at the same
experiment condition. The high surface area of nanocrystalline CaO is due
to its small particle size and crystallite of the catalyst itself. Therefore, reac-
tion rate is increasing due to large surface area of nanocrystalline CaO.
Moreover, based on Banković–Ilić et al. [40], the research shows great
extensive information regarding the production of biodiesel by the appli-
cation of nano-sized CaO. Nano-sized CaO showed good reusability and
its ability to restrain to leaching makes it as one of good materials as cata-
lyst. The research also stated that the reusability of neat nano-CaO could
affect catalytic activity which it can be used up to three to eight times with-
out showing any decreasing effect. This is due to nano-CaO that consists
of a great number of crystallites with precise edges. When the catalyst was
reused, it can be seen that the aggregates of polycrystals that are less precise
edges was formed [41].
Other than that, Hebbar et al. [38] reported that by using CaO nano-
particle, a huge yield of biodiesel which is 96.2% is produced at moder-
ate reaction conditions. Hsiao et al. [39] also reported that when using
microwave irradiation for biodiesel production, nano-CaO was more effi-
cient than larger sized CaO. Based on the experiment conducted for the
research, high conversion of biodiesel that is 71.6% was obtained using
nano-CaO compared with large-sized CaO that only recorded a 2.3% con-
version rate in the same operating condition.
As for the nano-biocatalyst, the application of nanotechnology in the
biofuel industry and how its enhanced biodiesel production is enzyme
(biocatalysts) immobilization during lipase-catalyzed biodiesel and cellu-
losic ethanol production processes [42]. The advantages that nanostructure
offers for biodiesel production are the large surface area for high enzyme
loading, higher enzymatic stability, and also enzyme reusability, which will
lead to reducing the operational cost of biodiesel production plants [43].
Based on Ahmad and Sardar (2015), NPs can serve as good effective
support components for immobilization of enzyme, by cause of their
excellent properties for stabilizing the key factors that decide the efficiency
of biocatalysts, including specific surface area, mass transfer resistance,
and effective enzyme loading [44]. Other than that, diffusion is always a
problem when dealing with the macromolecular substrates, and NPs are
the ideal candidates for solving the problem [45]. Moreover, the enzyme
that binds with NPs shows the Brownian movement when immersed in
aqueous solutions, which providing better enzymatic performance than

the unbound enzyme [46].
Besides, for magnetic NPs, its additional hold advantage than other NPs
is that it had easy separation method by just using an external magnetic
field. Furthermore, the enzymes immobilization with the NPs can results in
reduce protein unfolding and performed enhancement in terms of stability
and catalytic performance [46]. Furthermore, Xie and Ma (2009) reported
that for enzyme immobilization, the use of magnetic NPs as supports is
highly recommended due to the following advantages: a higher specific
surface that lead to effective binding, lower mass transfer resistance and
less fouling, easy separation method by using the external magnetic field
thus lowering the operational cost, and also the application of a contin-
uous biocatalysis system [33]. As for the conclusion, NMs were success-
fully proven as one of the enhancers in biodiesel production by providing
high surface area for high catalyst activity and also high enzyme loading,
higher catalytic and enzymatic stability, and also in terms of reusability of
the catalyst.
18.6 Conclusion
The review of NP catalysts for biodiesel production was showed that the
usage of nanocatalysts contributed a better performance of the transes-
terification reaction. Overall, we can conclude that the application of NP
catalysts would be economical, recyclable, and functionable for high or low
FFA feedstock to produce high quality of biodiesel and contributed to the
environment clean.
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Index
1,2-Propanediol, 137, 139, 141, Biodiesel, 3–8, 10, 11, 14, 86, 217, 342,
148–149, 159 362, 447–448, 451–452, 454–480
manufacturing, 137, 139–140
Acid catalyzed transesterification, 92 technology, 138
Acidic catalyst, 250–252 Biodiesel feedstock, 87, 242–248, 252
Acrylic resin, 22, 23, 32 Biodiesel production, 60–62
Activated carbon (AC), 111, 114–115 Biodiesel production from non-edible
Acyl acceptor, 4, 6, 9–15, 28–34 and waste lipid sources,
Acylglycerol, 19 algae, 406
Africa renewable energy initiative, 288 animal fat, 404
Alcohol, 2 azadirachta indica, neem oil, 398
Algae, 197, 203 calophyllum inophyllum, 397
Algal biomass, 450–451 castor oil, 402
Algal oil, 298, 299, 303 deacidification, 414
Alkali catalyzed transesterification, 94 jatropha, 394
Alkaline catalyst, 250 larva, 411
Alkaline earth metal oxides, 106–107 transesterification reaction, 392
Alkyl ester, 5, 7, 9, 167, 174, 180, 192 waste cooking oil, 405
Alternative fluid, 215 Bioethanol, 2, 3
Aluminum oxide (Alumina), 98, 111 Biofuel classification, 449
Amberlyst-15, 105–106 Biofuels, 2, 3, 38, 195, 196, 362
Anaerobic digestion, 195, 198, 201 Biogas, 3
Animal fat, 241, 242, 244 Biohydrogen, 3
Asthma, 2 Biomass support particles (BSPs), 23,
30
Bacterial lipases, 21 Biomechanical conversion, 195, 198,
Basicity, 468 201, 207
Batch reactor, 342–343 Biomethanol, 3
Benzene, 13, 27 Bioreactor, 10, 35, 37
Bimetallic, 468–469 Biorefinery design, 219
Biobutanol, 3 Blending, 173, 184, 189, 223
Biocatalysts, 8, 23, 30, 33, 38, 115, 232 Blending of plant-derived oils, 451
Biodegradability, 197 Box Behnken technique, 179
481
482 Index
Bubble column reactor (BCR), 342, Diacylglycerol (DAG), 7

347–349 Diglycerides, 5, 18, 19, 27
By-products, 169, 173 Dilution, 249
Dimethyl carbonate (DMC), 12, 14, 15,
Calcination, 142, 146, 149 24, 26
Carbon emissions, 169 Direct combustion, 195, 198, 201, 207
Carbon neutral biofuels, 289 Direct use of plant-derived, 451
Carboxylation, 141, 146
Catalysis, 7, 8, 17–19, 26, 27 EBD resins, 106
Catalyst, 137, 139–159, 453–455, 462–463 Edible oil, 243, 244, 250, 251, 253
heterogeneous, 364 Effect of initial water concentration,
homogeneous, 364 155
Catalyst selection, 139, 151 Encapsulation of enzyme, 116
Catalyst support, 111 Energy, 217
Catalytic, Energy generation, 168
dehydration of glycerol, 143 Environmental protection, 169
transformation, 137, 152, 159 Environment-friendly, 167
Catalytic methods, 89 Enzymatic, 471, 476–477
Catalytic transesterification, 174, 175, Enzymatic catalyst, 250, 252
190, 191 Enzymatic transesterification, 8, 14,
Cation exchange resins, 105–106 16, 17, 35, 38
Cavitation, 353 Enzyme immobilization, 115–116
Celite, 22 Enzymes, 146
Central composite design, 179, 190, 192 Epoxy acrylic, 22
Chromatography, 20 Esterification, 6, 7, 11, 19, 27, 365
Clays, 384 Ethanol, 10, 11, 14, 22, 24, 27, 30
Climate change, 138 Ethyl ester, 12, 17
Cloud point, 180
Comparative analysis, 21 Fatty acid profile, 245–247
Continuous stirred tank reactor Fatty acids, 6, 17–19
(CSTR), 342, 344–345 Fatty acids alkylesters (FAAEs), 3, 6, 7
Conversion of glycerol, 137, 139–141, Fatty acids methylesters (FAMEs), 3,
146–147, 151–152, 154–156, 11–14, 19, 25–27, 29, 31, 34, 465,
158–159 467, 469
Copenhagen accord, 288 Feed stock, 8, 9, 38
Corrosion, 457, 464 Feedstock sources, 215
Cost, 241, 243, 244, 251, 253, 256, 257 Fermentation, 195, 198, 201
Covalent bond, 472 First-generation biofuels, 288–289, 499
Covalently immobilization of enzymes, Fischer Tropsch, 196, 200, 202
116 Fixed bed reactor (FBR), 342,
Cracking, 174 346–347
Cross-linked enzyme aggregates Flash point, 170, 180, 183
(CLEA), 117–118 Fossil fuels, 2, 4, 38, 60
Crude oil refining industry, 147 Free fatty acids, 5
Index 483
Fuel security, 448 Immiscibility, 65–66

Fuel supply, 448–449 Impregnation, 467, 469
In situ method, 256
Gas chromatography, 183, Industrialization, 137–138
193 Influential parameters affecting
Gasification, 195, 198–200, 202 biodiesel production, 454
Genetic engineering/techniques Infrared spectroscopy, 182, 185, 193,
enhancing biodiesel production, 194
433 Intensification techniques,
GLC selectivity, 146 co-solvent method, 256
Global warming, 285–288, 312 microwave heating, 253, 254
Glyceric acid, 141–142, 159 supercritical alcohol, 253
Glycerol, 7–19, 33, 35, 137, 139–159 ultrasonic irradiation, 254
Gold, 140, 142–143, 151 International monetary fund, 287
Growth, 2, 5, 6, 20, 21
Jatropha, 203, 205
Helium, 137, 152 Jathropa oil, 22, 29–30
Heterogeneous, 465–466, 468, 473
Heterogeneous catalysts, 64–65, Kinetic, 468
252 Kyoto protocol, 288
Heterogeneous ultrasonic reaction,
72–78 Lactic acid, 148
Heterogenous catalyst, Leaching, 466
acid catalyst, 97 Lignocellulosic biomasses, 202, 289
base catalyst, 106 Lipases, 8, 9, 11, 13–15, 17–28, 31–35,
Heteropolyacids,101, 382 471–473, 476
High yield per hectre, 218 Lipozyme, 35, 37
High-performance liquid
chromatography, 184, 193 Magnetic, 466, 471–474, 477
Homogeneous catalyst, 63, 64, 250, Magnetic nanoparticles (MNPs), 111,
251 114, 116
acid catalyst, 89 Markets and economic considerations,
base catalyst, 93 455
Homogeneous ultrasonic reaction, Mechanism, 137, 157–159
69–72 Membrane reactor (MR), 256, 343,
Humanity, 237 350–352
Hybrid catalytic plasma reactor, 343, Membrane technology, 198, 202, 207
350 Mesoporous silica, 99–100, 112
Hydrogenolysis, 137, 139, 141, Metal oxides, 380, 465, 467
147–149, 151–154, 156–159 Methanol, 10–16, 22–24, 26
Hydrophobic, 469–470 Methanolysis, 11, 13, 15
Hydrothermal, 468, 473 Methodology involved in the
Hydrothermal liquefaction, 198, extraction of algae,
200 chemical solvent extraction, 439
484 Index
extraction by supercritical carbon Methyl acetate, 12, 15

dioxide, 439 Methyl ester, 9, 12, 13, 16, 17
extraction involving direct Microalgae, 5, 11, 12, 38
transesterification, 440 Microbial oil, 241, 242
extraction using biochemical Microchannel reactor (MCR), 342,
techniques, 439 350–351
extraction using transesterification Microemulsification, 173, 249, 292
techniques, 440 Microemulsion with excess methanol
Methods for biodiesel production, and ethanol, 451
269 Microtube microreactor (MM), 350,
dilution with hydrocarbons 352
blending, 269 Microwave, 33–35
micro-emulsion, 269–270 Microwave reactor, 255, 352
pyrolysis (thermal cracking), Millennium development goals,
270–271 288
transesterification (alcoholysis), 271 Mixed metal oxides, 110
conventional transesterification, Mutagenesis, 27
272–273
catalytic-based process, 273 Nafion NR50, 105
enzymatic-catalyzed Nano,
transesterification, 276 biocatalyst, 471
heterogeneous-catalyzed catalysis, 465–469, 472–474, 478,
transesterification, 480
275–276 materials, 465–466
homogeneous particles, 465–466, 472–473,
alkaline-catalyzed 475
transesterification, structure, 476
274–275 Nanotechnology in microalgae
homogeneous-acid- biodiesel, 434
catalyzed-esterification, Nature of feedstocks, 454
273–274 Non-edible oil, 241, 243, 244, 250, 251,
non-catalytic-based process, 253
276 Non-edible vegetable oils,
BIOX co-solvent process, jatropha, 296, 297, 301
277–278 karanja, 296, 297
supercritical alcohol process, linum usitassimum, 296
276–227 Non-toxic renewable fuels, 169
in-situ transesterification (reactive Novozyme, 11–15, 31, 32, 36
extraction), 271–272 Nuclear magnetic resonance
microwave/ultrasound-assisted spectroscopy, 184–185
transesterification, 278 Nucleophilic, 18, 19
variables affecting
transesterification reaction, Optimization, 137, 139, 151
278–281 Optimization techniques, 167
Index 485
Oscillatory flow reactor (OFR), 353 first-generation feedstock, 268

Oxalic acid, 141 second-generation feedstock,
268–269
Palladium, 140, 142–143, 151–152 third-generation feedstock, 269
Paramagnetic, 473 Serine, 18, 19
Parameters, 139–140, 153, 155 Silica gel, 11, 13
Paris agreement, 287, 288 Silver, 140
Penicillium, 28, 31 Sludge palm oil (SPO), 220
Pentapeptide, 18 SO3H as catalyst, 379
Petroleum, 137–138, 147, 149 Solvent, 149–151
Photobiological, 198, 201 Sonochemical reactor, 353
Physicochemical properties of Soybean oil, 22, 24, 27, 34
biodiesel from microalgae, Specific examples of biodiesel
431 production from microalgae,
Platinum, 140, 142, 145, 151–152 434
Polyurathane, 23, 27, 30 Spectrum, 148
Pour point, 180 Static mixers, 257
Production technologies, 248 Sulfated zirconia, 97
Psychrophilic Lipases, 26 Surface area, 466–467, 469, 472–474,
Pyrolysis, 224, 248, 368, 447, 452–453, 476–477
458, 462 Synthesis gas, 202
Pyrolysis of glycerol, 144
Tartronic acid, 141–142
Rancimat method, 185 Temperature, 137, 140, 144–148,
Reaction mechanism, 137, 157–159 150–151, 153–155, 157–159
Reaction parameters, 78–79 Thermal cracking, 292, 452
Reaction temperature, 454 Thermochemical conversion, 195, 198,
Reactive distillation, 257 199, 202, 207
Reactive distillation column (RDC), Third-generation biofuels, 288, 290,
343, 349 450, 460
Reactive distillation technology, 198, Transesterification, 6–17, 19, 21,
202, 207 25–28, 33, 38, 139, 145–146,
Reactor, 342, 369 195, 198, 199, 201, 202,
Renewable and sustainable energy, 249–251, 287, 292–300, 303,
138 365, 367, 447, 452–454, 458,
Renewable energy technologies, 138 462–463, 469–470, 472–475,
Reusability, 468, 473–474, 476–477 477
Triglyceride, 5, 6, 17–19, 31
Scientific, 138 Triolein, 22, 29, 32, 33
Second-generation biodiesel, 221 Tungstated zirconia, 99
Second-generation biofuels, 289, 290, Two step process, 251
449
Selection of feedstock for biodiesel, Ultrafiltration, 20, 21
267 Ultrasonicator, 255
486 Index
Ultrasonic, 33, 34 Waste biomass, 101

Ultrasonic energy, 66–68 Waste cooking oil, 295, 297, 298,
Ultrasonication, 33–35 301
Ultrasound, 35 Waste oil, 241, 242
Ultrasound technology, 198, 201, 202, 207 Water hyacinth, 290
Valorization, 137, 139–140 Zeolite, 378

Vegetable oil, 242, 248, 249 Zeolites, 102, 105
Also of Interest
Check out these other forthcoming and published titles

from Scrivener Publishing
Books by the same editor from Wiley-Scrivener

Applied Water Science Volume 1: Fundamentals and Applications, Edited by
Inamuddin, Mohd Imran Ahamed, Rajender Boddula and Tauseef Ahmad
Rangreez, ISBN 9781119724766. Edited by one of the most well-respected
and prolific engineers in the world and his team, this is the first volume in a
two-volume set that is the most thorough, up-to-date, and comprehensive
volume on applied water science available today. COMING IN SUMMER
2021
Applied Water Science Volume 2: Remediation Technologies, Edited by

Inamuddin, Mohd Imran Ahamed, Rajender Boddula and Tauseef Ahmad
Rangreez, ISBN 9781119724735. The second volume in a new two-volume
set on applied water science, this book provides understanding, occur-
rence, identification, toxic effects and control of water pollutants in aquatic
environment using green chemistry protocols. COMING IN SUMMER
2021
Potassium-Ion Batteries: Materials and Applications, Edited by Inamuddin,

Rajender Boddula, and Abdullah M. Asiri, ISBN 9781119661399. Edited
by one of the most well-respected and prolific engineers in the world and
his team, this is the most thorough, up-to-date, and comprehensive vol-
ume on potassium-ion batteries available today. NOW AVAILABLE!
Rechargeable Batteries: History, Progress, and Applications, edited by

Rajender Boddula, Inamuddin, Ramyakrishna Pothu, and Abdullah M.
Asiri, ISBN 9781119661191. Edited by one of the most well-respected and
prolific engineers in the world and his team, this is the most thorough,
up-to-date, and comprehensive volume on rechargeable batteries available
today. NOW AVAILABLE!
Other books on this subject from Wiley-Scrivener
Reverse Osmosis: Design, Applications, and Applications for Engineers 2nd
Edition, by Jane Kucera, ISBN 9781118639740. This is the most compre-
hensive and up-to-date coverage of the “green” process of reverse osmosis
in industrial applications, completely updated in this new edition to cover
all of the processes and equipment necessary to design, operate, and trou-
bleshoot reverse osmosis systems. NOW AVAILABLE!
Desalination: Water from Water 2nd Edition, by Jane Kucera, ISBN

9781119407744. This all-new revised edition of a modern classic is the
most comprehensive and up-to-date coverage of the “green” process of
desalination in industrial and municipal applications, covering all of the
processes and equipment necessary to design, operate, and troubleshoot
desalination systems. This is becoming increasingly more important for
not only our world’s industries, but our world’s populations, as pure water
becomes more and more scarce. NOW AVAILABLE!
Sustainable Water Purification, by Safiur Rahman and M. R. Islam, ISBN

9781119650997. This is the only book that takes a zero-waste approach
to propose 100% sustainable water purification techniques. NOW
AVAILABLE!
Electrochemical Water Processing, by Ralph Zito, ISBN 9781118098714.

Two of the most important issues facing society today and in the future
will be the global water supply and energy production. This book addresses
both of these important issues with the idea that non-usable water can
be purified through the use of electrical energy, instead of chemical or
mechanical methods. NOW AVAILABLE!

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Biodiesel Technology

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Library of Congress Cataloging-in-Publication Data

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Printed in the USA

1.11 Recent Strategies to Improve Biodiesel Production 31

3.4 Biocatalysts 115

5.3.1 Feedstocks Popular in India 169

6.1 Introduction 196

8 Biodiesel Production Technologies 241

9.2.4.4 Variables Affecting Transesterification

11.5.3 Tall Oil 318

11.9.1.3 Elimination of Unsaponiﬁables 333

13.3.1 Homogeneous Catalyst 364

15.3 Waste Animal Fats 404

17.4.1 The Choice of Transesterification Catalysts 454

substrates for biodiesel production including their percentage yields are

intensification techniques to manage mass transfer restrictions of oil and

Chapter 16 provides detailed information on the fabrication of biodiesel

Inamuddin, Mohd Imran Ahamed, Rajender Boddula

College of Chemistry, Chemical Engineering and Biotechnology,

Donghua University, China

*Corresponding author: habibullah@gcuf.edu.pk

1.1 Introduction and Background

1.2 Importance of Biodiesel Over Conventional

1.3 Substrates for Biodiesel Production

Moreover, it increases oxidative stability and cold filter plugging point of

1.4 Methods in Biodiesel Production

molecule of FAAE and diacylglycerol (DAG). In second step, DAG further

1.5 Types of Catalysts Involved in Biodiesel

1.5.1 Chemical Homogenous Catalysts

compared to alkaline process. Reactors, pipelines, and other equipment are

1.5.2 Solid Heterogeneous Catalysts

1.6 Factors Affecting Enzymatic Transesterification

1.6.1 Effect of Water in Enzyme Catalyzed Transesterification

1.6.2 Effect of Bioreactor

1.6.3 Effect of Acyl Acceptor on Enzymatic Production

transesterification reaction if short chain alcohols are being used as an

1.6.4 Effect of Temperature on Enzymatic Biodiesel Production

1.6.5 Effect of Glycerol on Enzymatic Biodiesel Production

(immobilized on polymeric resin) and Lipozyme TL IM (immobilized on

1.6.6 Effect of Solvent on Biodiesel Production

1.7 Lipases as Biocatalysts for Biodiesel Production

Lipases work on specific substrates and carry out catalysis of hetero-

of lid completely exposed, thus creating a non-polar surface around the

1.7.1 Mechanisms of Lipase Action

1.7.2 Efficient Lipase Sources for Biodiesel Producing

like lipase cost and methanol inhibition. We need to optimize reaction

their growth culture to get extracellular lipases after fermentation. Then,

1.8 Comparative Analysis of Intracellular and

Burkholderia Hydrophobic Jatropha oil Methanol 95% [125]

Hybrid matrix of Jatropha Ethanol 100% [126]

κ-carrageenan Palm oil Methanol 100% [127]

Modified Jatropha oil Methanol 94% [128]

SiO2-PVA Babassu oil Ethanol 100 % [129, 130]

SiO2-PVA Babassu oil Ethanol 100% [131]

Nb2O5 Babassu oil Ethanol 74.1% [132]

Pseudomonas Epoxy-acrylic Waste Ethanol 46–47% [133]

Phyllosilicate sol- restaurant Methanol 98% [134]

Fe3O4 nanoparticle Soybean oil Methanol >88% [135]

Accurel Madhuca Ethanol 96% [136]

Protein-coated Soybean oil Ethanol 98.93% [137]

Celite Jatropha oil Ethanol 98% [89]

Inamuddin - Biodiesel Technology and Applications-John Wiley & Sons (2021)

Inamuddin - Biodiesel Technology and Applications-John Wiley & Sons (2021)