Biomass and Green Chemistry (eBook)

Prof. Dr. Sílvio Vaz Junior holds a BSc degree in Chemistry, a MSc degree in Physical Chemistry and a PhD degree in Analytical Chemistry from University of São Paulo, Brazil. He was director and partner of two private analytical laboratories related to environmental analysis technologies. Since 2010, he is a research scientist at the state-owned Brazilian Agricultural Research Corporation (Embrapa) working on the development of renewable chemicals from biomass and analytical chemistry applied to bioenergy and biomass chemistry. He is a member of IUPAC and has published articles and books related to renewable chemistry and analytical chemistry.

Preface 5
Contents 6
Contributors 8
Chapter 1: Biomass and the Green Chemistry Principles 10
1.1 Introduction 10
1.2 Exploring the Green Chemistry Principles in Biomass Conversion 15
1.3 Aspects of Industrial Ecology Related to Biomass Processing 15
1.4 Conclusions 17
References 18
Chapter 2: Saccharide Biomass for Biofuels, Biomaterials, and Chemicals 19
2.1 Introduction 19
2.2 Chemical Constitution and Physicochemical Properties of Saccharides 21
2.3 Economic Aspects: Global Production, Availability, and Distribution of Sucrose 22
2.4 Main Products: Considering Energy, Biofuels, Biomaterials, and Chemicals 24
2.4.1 Energetics Products 26
2.4.2 Nonenergetic Products 30
2.4.2.1 Bioplastics/Biopolymers 31
2.4.2.2 Biochemicals 35
2.5 Conclusions 36
References 37
Chapter 3: Oleaginous Biomass for Biofuels, Biomaterials, and Chemicals 39
3.1 Introduction 39
3.1.1 Oils and Fats 41
3.1.2 Fatty Acids Composition 43
3.2 Vegetable Oils as Biofuels 47
3.2.1 Vegetable Oil Micro-Emulsions 47
3.2.2 Vegetable Oil Cracking 48
3.2.3 Transesterification/Esterification 48
3.2.4 Biodiesel Production 50
3.2.4.1 Biodiesel Quality 50
3.2.4.2 Biodiesel Glycerin 52
3.2.5 Hydrotreating 52
3.3 Bio-Based Polymers 53
3.3.1 Functionalization of Vegetable Oils to Produce Bio-­Based Polymers 53
3.3.2 Vegetable Oil-Based Polymers 63
3.3.3 Analytical Techniques 64
References 70
Chapter 4: Starch Biomass for Biofuels, Biomaterials, and Chemicals 77
4.1 Introduction 78
4.2 Conventional and Novel Feedstocks for a Starch-Based Biorefinery 79
4.3 Thermoplastic Starch: Challenges and Properties 81
4.4 Enzymatic Hydrolysis of Starch-Based Feedstocks 83
4.5 Value-Added Biofuels, Biochemicals, and Biomaterials from a Sugar Platform Perspective 84
4.5.1 The Biological Route 87
4.5.1.1 Ethanol 87
4.5.1.2 Lactic Acid and Polylactic Acid (PLA) 89
4.5.1.3 Polyhydroxyalkanoates (PHAs) 91
4.5.1.4 Succinic Acid 92
4.5.1.5 1,4-Butanediol (BDO) 93
4.5.1.6 Farnesene 94
4.5.1.7 Isobutene 95
4.5.1.8 Acrylic Acid 95
4.5.1.9 Adipic Acid 96
4.5.1.10 Ethylene and Polyethylene (PE) 97
4.5.2 The Chemical Catalytic Route 98
4.5.2.1 Furan-2,5-Dicarboxylic Acid (FDCA) 98
4.6 Concluding Remarks 98
References 99
Chapter 5: Lignocellulosic Biomass for Energy, Biofuels, Biomaterials, and Chemicals 103
5.1 Introduction 104
5.1.1 Status Quo of Biorefinery Systems for Biomass Conversion 104
5.1.2 Consideration of Green Chemistry Principles 106
5.1.2.1 Lignocellulosic Feedstock for Energy Production 107
5.1.2.2 Lignocellulosic Feedstock for Biofuels Production 107
5.1.2.3 Lignocellulosic Feedstock for Biomaterials and Chemicals 109
5.2 Lignin as Agro-industrial Feedstock 110
5.2.1 Lignin Isolation Processes 111
5.2.1.1 Kraft Process 111
5.2.1.2 Organosolv Process 114
5.2.2 Structure Analysis of Lignin 115
5.2.2.1 Spectroscopy 115
5.2.2.2 Chromatography 119
5.2.2.3 Thermal Analysis 122
5.2.2.4 Microscopy and X-ray Techniques 123
5.2.3 Antioxidant Activity and Total Phenol Content of Lignin 125
5.2.4 Storage and Temperature Effects on Lignin Structure 126
5.3 Lignin Valorization and Potential Applications 128
5.3.1 Lignin-Based Polymer Blends, Composites, and Hydrogels 128
5.3.2 Composites Based on Lignin and Cellulose 129
5.3.3 Antimicrobial Activity of Lignin to Be Used in Biomedicine 131
5.3.4 Structure–Property Relationship: Effects of Resource, Purification, and Storage on Antioxidant and Antimicrobial Activity 132
5.3.5 Applications of Lignin-Based Polymers in Packaging 134
5.4 Conclusions 135
References 135
Chapter 6: Microalgae for Industrial Purposes 141
6.1 Introduction 141
6.2 What Are Algae? 142
6.3 Algae Produce Biomass Through Photolithotrophy, Heterotrophy, or Mixotrophy 144
6.3.1 Photolitothrophy 145
6.3.2 Mixotrophy 146
6.4 Cell Composition Results from a Combination of Genotypic and Environmental Constraints 147
6.4.1 Elemental Stoichiometry and Organic Cell Composition 147
6.5 Genetic Modification of Algae: Tools and Aims 148
6.6 How Are Algae Cultured? 151
6.6.1 Harvesting and Dehydration of Algal Biomass 153
6.7 Products and Applications 154
6.7.1 Biofuels from Algae 154
6.7.1.1 Biodiesel 155
6.7.1.2 Other Microalgal Biofuels 156
6.7.1.3 Challenges and Solutions for Algal Biofuel Production 157
6.8 Microalgae for Bioremediation 158
6.8.1 CO2 Fixation and Flue Gas Treatment 158
6.8.2 Wastewater Treatment by Microalgae Cultivation 160
6.9 Microalgal Cultivation for Food or Feed Production 162
6.10 Conclusions 164
References 164
Chapter 7: Enzymatic Conversion of First- and Second-­Generation Sugars 176
7.1 Introduction 177
7.2 Enzymatic Hydrolysis of Starch to Glucose 178
7.3 Enzyme Immobilization 179
7.3.1 Immobilization Via Cross-Linking: CLEAs 180
7.3.2 Advantages and Limitations of CLEAs 182
7.4 Magnetically Separable Immobilized Enzymes 182
7.5 Enzymatic Depolymerization of Lignocellulose 184
7.5.1 Pretreatment of Lignocellulose 184
7.5.2 Enzymatic Hydrolysis of Cellulose and Hemicellulose 186
7.5.3 Magnetic Immobilized Enzymes in Lignocellulose Conversion 188
7.6 Conclusions and Future Outlook 189
References 190
Chapter 8: Sustainability of Biomass 197
8.1 Introduction 197
8.2 The Scientific Arguments 199
8.3 Sustainability Initiatives 200
8.3.1 Technical Regulations 201
8.3.2 Technical Standards 202
8.3.3 Conformity Assessment Procedures 203
8.4 Requirements of Sustainability Initiatives 203
8.5 Sustainability Aspects Addressed by Certification Schemes 206
8.5.1 Aspects Addressed by Certification Schemes 206
8.5.2 Environmental Aspects 206
8.5.2.1 GHG Emissions 206
8.5.2.2 Water 209
8.5.2.3 Soil 211
8.5.2.4 Air 211
8.5.2.5 Biodiversity 212
8.5.2.6 Wastes 213
8.5.3 Social Aspects 213
8.5.3.1 Human Rights, Labor Rights, and Labor Conditions 213
8.5.3.2 Land Use and Water Use Rights 213
8.5.3.3 Food Security 214
8.5.3.4 Rural Development 215
8.5.4 Economic Aspects 216
8.6 Land Use Change 216
8.7 Final Remarks 218
References 221
Erratum to: Lignocellulosic Biomassfor Energy, Biofuels, Biomaterials,and Chemicals 226
A Glossary of Green Terms 227
References 256