Biodiesel science and technology from soil to oil

Biodiesel science and technology

i

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ii

CRC Press

Boca Raton Boston New York Washington, DC

Wo o d h e a d p u b l i s h i n g l i m i t e d

Oxford   Cambridge   New Delhi

Woodhead Publishing Series in Energy: Number 7

Biodiesel science

and technology

From soil to oil

Jan C. J. Bart, Natale Palmeri and

Stefano Cavallaro

iii

Published by Woodhead Publishing Limited, Abington Hall, Granta Park, Great Abington,

Cambridge CB21 6AH, UK

www.woodheadpublishing.com

Woodhead Publishing India Private Limited, G-2, Vardaan House, 7/28 Ansari Road,

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Published in North America by CRC Press LLC, 6000 Broken Sound Parkway, NW,

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First published 2010, Woodhead Publishing Limited and CRC Press LLC

© 2010, Woodhead Publishing Limited

The authors have asserted their moral rights.

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cannot assume responsibility for the validity of all materials. Neither the authors nor the

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iv

About the authors xi

Woodhead Publishing Series in Energy xiii

Preface xv

1 Biodiesel as a renewable energy source 1

1.1 Introduction 1

1.2 Energy policy 2

1.3 Transformation of biomass 20

1.4 Global biodiesel development 26

1.5 Value chain of biodiesel 38

1.6 Bibliography 40

1.7 References 44

2 Development of non-food agricultural industries

for biofuel applications 50

2.1 Introduction 50

2.2 Biofuels 51

2.3 Biomass potentials and limitations 52

2.4 Advanced agroenergy crops 56

2.5 Bibliography 59

2.6 References 60

3 Oleochemical sources: basic science, processing

and applications of oils 62

3.1 Introduction 62

3.2 Biochemistry of lipid metabolism 64

3.3 Modification of vegetable oil quality 76

3.4 Industrial use of vegetable oils 80

3.5 Unusual fatty acids 85

Contents

v

3.6 Oil processing techniques 90

3.7 Bibliography 100

3.8 References 103

4 Vegetable oil formulations for utilisation as biofuels 114

4.1 Introduction 114

4.2 Fuel properties of oils and fats 116

4.3 Low-viscosity formulations 121

4.4 Bibliography 125

4.5 References 125

5 Feedstocks for biodiesel production 130

5.1 Introduction 130

5.2 Global oilseed and oil production 135

5.3 Resources for biodiesel production 137

5.4 Main biodiesel crops 143

5.5 Minor edible oil crops 159

5.6 Fish oils 163

5.7 Algae mass culture systems 168

5.8 Oleaginous microorganisms 187

5.9 Non-edible oilseeds 188

5.10 Low-quality feedstocks 197

5.11 Bibliography 206

5.12 References 208

6 Emerging new energy crops for biodiesel production 226

6.1 Introduction 226

6.2 Crop selection criteria for biodiesel application 227

6.3 Structure and quality parameters for evaluating alternative

feedstocks 231

6.4 Agronomic potential of underexploited oil crops by region 244

6.5 Bibliography 273

6.6 References 274

7 Transesterification processes for biodiesel production

from oils and fats 285

7.1 Introduction 285

7.2 Process variables 287

7.3 Transesterification kinetics 295

7.4 In-situ transesterification 308

7.5 Non-catalytic fatty acid alkyl ester production 310

7.6 References 314

vi Contents

8 Biodiesel catalysis 322

8.1 Introduction 322

8.2 Homogeneous alkaline catalysis in biodiesel synthesis 327

8.3 Liquid-phase acid catalysis 340

8.4 Heterogeneous catalysis in biodiesel synthesis 348

8.5 Bibliography 371

8.6 References 371

9 Processes for biodiesel production from unrefined

oils and fats 386

9.1 Introduction 386

9.2 Fatty acid esterification 389

9.3 Transesterification of acidic feedstocks 394

9.4 Jatrodiesel 412

9.5 Algal biodiesel 414

9.6 Vegetable oil soapstocks for biodiesel application 420

9.7 Tall biodiesel 423

9.8 Bibliography 425

9.9 References 425

10 Biocatalytic production of biodiesel 434

10.1 Introduction 434

10.2 Enzymatic (trans)esterification 435

10.3 Bioplastic-to-biodiesel 454

10.4 Bibliography 454

10.5 References 455

11 Industrial process technology for biodiesel production 462

11.1 Introduction 462

11.2 Biodiesel plant design and engineering 467

11.3 Selected proprietary transesterification processing

technologies 487

11.4 Selected biodiesel producers 497

11.5 Biodiesel blending techniques 505

11.6 Bibliography 508

11.7 References 509

12 Analytical methods and standards for quality

assurance in biodiesel production 514

12.1 Introduction 514

Contents vii

12.2 Quality control of biodiesel feedstocks 515

12.3 Biodiesel standardisation 516

12.4 Biodiesel quality management 526

12.5 Biodiesel analytical methodology 540

12.6 Bibliography 562

12.7 References 563

13 Valorisation of the glycerol by-product from biodiesel

production 571

13.1 Introduction 571

13.2 Industrial glycerol production 572

13.3 Glycerol purification 575

13.4 Industrial uses and markets 579

13.5 Innovative use of glycerol 584

13.6 Renewable diesel synthesis without glycerol co-production 611

13.7 Bibliography 615

13.8 References 615

14 Sustainability and use of biodiesel 625

14.1 Introduction 625

14.2 Energy balance 627

14.3 Life cycle assessment of biodiesel 630

14.4 Performance characteristics for biodiesel 637

14.5 Biodiesel cost structure 658

14.6 Biodiesel use and markets 677

14.7 Bibliography 701

14.8 References 703

15 Evolution of biodiesel and alternative diesel fuels 713

15.1 Introduction 713

15.2 Second-generation biofuels 719

15.3 Biodiesel: the next generations 724

15.4 Hydroprocessing technology 742

15.5 Perspectives of biomass-to-liquid fuels 756

15.6 Renewable energy and biomass 772

15.7 Bibliography 775

15.8 References 776

16 Epilogue: outlook for biodiesel science and technology 783

16.1 Introduction 783

16.2 State of the biodiesel industry 784

viii Contents

16.3 Challenges for the global biodiesel industry 789

Appendix I Acronyms/abbreviations of techniques 799

Appendix II (Bio)chemical nomenclature 801

Appendix III Physical and mathematical symbols 810

Appendix IV General abbreviations 814

Appendix V Main websites 820

Index 822

Contents ix

x

About the authors

Jan C. J. Bart (PhD Structural Chemistry, University of Amsterdam) is a

senior scientist with a wide interest in materials characterisation, heterogeneous

catalysis and product development who spent an industrial carrier in chemical

R&D with Monsanto, Montedison and DSM Research in various countries. Dr

Bart has held several teaching assignments in universities in the Netherlands

and Italy, researched extensively in both industrial and academic areas, and

authored over 250 scientific papers and chapters in books; he is also author

of three recent monographs on polymer additive analytics. Dr Bart has

acted as a Ramsay Memorial Fellow at the Universities of Leeds (Colour

Chemistry) and Oxford (Material Science), a visiting scientist at the Institut

de Recherches sur la Catalyse (CNRS, Villeurbanne), and a Meyerhoff

Visiting Professor at the Weizmann Institute of Science (Rehovoth), and

held an Invited Professorship at the University of Science and Technology

of China (Hefei). He is currently a Full Professor of Industrial Chemistry

at the University of Messina (Italy).

Natale Palmeri (PhD Industrial Chemistry, University of Messina) has

interest in heterogeneous catalysis and energy carriers. He acted as a guest

junior researcher at the Nicola Giordano CNR-TAE Institute of Advanced

Technologies for Energy (Messina) and at the Boreskov Institute of Catalysis

(BIC) of Novosibirsk (with Prof. Vladimir Sobyanin). Dr Palmeri has authored

several research papers and presently serves as a technologist at ISAB Srl’s

Priolo refinery (Sicily).

Stefano Cavallaro graduated with an honours degree in Chemistry from

the University of Messina, where he now acts as an Associate Professor

of Industrial Chemistry in the Department of Industrial Chemistry and

Materials Engineering. His interests are applied industrial chemistry, in

particular heterogeneous catalysis and transformation and storage of energy.

Dr Cavallaro has a standing cooperation with the National Research Council

Institute of Advanced Technologies for Energy (CNR-TAE) in Messina and

is author of over 110 research papers.

xi

xii

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xiv Woodhead Publishing Series in Energy