Davide Ravelli is Assistant Professor at the PhotoGreen Laboratory of the University of Pavia. His research focus is on photochemical reactions and their applications in various fields, especially sustainable organic synthesis.Chiara Samorì is Assistant Professor at the Green Chemistry Lab of the University of Bologna. She is primarily interested in the extraction of biomass using sustainable solvents for producing third generation biofuels, bioactive compounds, and bioplastics.

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• Foreword xiPreface xiii1 Role of Biomass in the Production of Chemicals 1Layla Filiciotto, Evan Pfab and Rafael Luque1.1 Introduction 11.2 Biomass Valorization 31.3 Lignocellulosic Biomass 51.4 Key Biomolecules 61.5 Solvents 101.6 Pretreatment of Lignocelluloses 121.7 Conclusions and Perspectives 15References 15Section I Catalytic Strategies 232 Biomass Processing via Acid Catalysis 25Iurii Bodachivskyi, Unnikrishnan Kuzhiumparambil and D. Bradley G. Williams2.1 Introduction 252.1.1 Is an Acid the Best Catalyst? 262.2 Acid-Catalyzed Processing of Cellulosic Polysaccharides 292.3 Acid-Catalyzed Processing of Lignin 442.4 Conclusions and Perspectives 47References 473 Biomass Processing via Base Catalysis 57Lichen Liu, Maria J. Climent and Sara Iborra3.1 Introduction 573.2 Aldol Condensation 603.2.1 Aldol Condensation of Furanic Aldehydes 603.2.2 Self-Aldol Condensation of Acetone 633.2.3 Aldol Condensation Between Alcohols: Guerbet Coupling Reaction 643.3 Ketonization Reaction of Carboxylic Acids 653.4 Transesterification Reaction 683.4.1 Biodiesel Production 683.4.2 High Value-Added Chemicals from Transesterification Reactions 703.5 Conclusions and Perspectives 73References 744 Biomass Processing via Metal Catalysis 81Sofia Capelli and Alberto Villa4.1 Introduction 814.2 Synthetic Strategies for Supported Metal Nanoparticles 834.2.1 Impregnation 834.2.2 Precipitation 844.2.3 Sol Immobilization 854.3 Furfural 864.3.1 Furfural Hydrogenation 874.3.1.1 Furfural to Furfuryl Alcohol 874.3.1.2 Furfural to Tetrahydrofurfuryl Alcohol 884.3.1.3 Furfural to Pentanediols 894.3.1.4 Furfural to 2-Methylfuran 904.3.2 Furfural Oxidation 924.3.2.1 Furfural to Furoates 924.4 5-Hydroxymethylfurfural (HMF) 924.4.1 HMF Hydrogenation 934.4.1.1 HMF to 2,5-Dimethylfuran (DMF) 944.4.1.2 HMF to 2,5-Dihydroxymethyltetrahydrofuran (DHMTHF) 954.4.2 HMF Oxidation 964.4.2.1 HMF to 2,5-Furandicarboxylic Acid (FDCA) Using Monometallic Systems 964.4.2.2 HMF Oxidation over Bimetallic Catalysts 1004.5 Conclusions and Perspectives 103References 1035 Biomass Processing with Biocatalysis 113Roger A. Sheldon5.1 Introduction 1135.2 Generations of Renewable Biomass: Advantages and Limitations 1135.3 Advantages and Limitations of Biocatalysis 1165.4 Enzyme Discovery and Optimization of Enzyme Performance 1175.5 Enzyme Immobilization 1185.5.1 Enzyme Immobilization by Cross-linking Enzyme Molecules 1195.5.2 Advantages and Limitations of Cross-Linked Enzyme Aggregates (CLEAs) 1205.5.3 Magnetically Separable Immobilized Enzymes 1205.6 Enzymatic Hydrolysis of Starch to Glucose 1215.7 Enzymatic Depolymerization of Lignocellulose 1225.8 Enzymatic Hydrolysis of Cellulose and Hemicellulose 1235.8.1 Magnetizable Immobilized Enzymes in Lignocellulose Conversion 1245.9 Enzymatic Hydrolysis of 3rd Generation (3G) Polysaccharides 1245.10 Commodity Chemicals from Carbohydrates (Monosaccharides) 1265.10.1 Fermentative Production of Commodity Chemicals 1265.10.2 Deoxygenation via Dehydration of Carbohydrates to Furan Derivatives 1295.10.3 Polyethylene Furandicarboxylate (PEF) as a Renewable Alternative to PET 1295.10.4 Enzymatic Synthesis of Bio-based Polyesters 1315.11 Enzymatic Conversions of Triglycerides: Production of Biodiesel and Bulk Chemicals 1325.12 Conclusions and Perspectives 133References 133Section II Thermal Strategies 1476 Biomass Processing via Pyrolysis 149Daniele Fabbri, Yunchao Li and Shurong Wang6.1 Brief Introduction 1496.2 Chemicals from Cellulose Pyrolysis 1516.2.1 General Aspects 1516.2.2 Levoglucosan 1546.2.3 Levoglucosenone 1566.2.4 LAC,(1R,5S)-1-Hydroxy-3,6-Dioxabicydioxabicyclo-[3.2.1]octan-2-one 1576.3 Chemicals from Lignin Pyrolysis 1606.4 Pyrolysis of Biomass 1616.4.1 Levoglucosan 1616.4.1.1 Effects of Metal Oxides 1626.4.1.2 Effects of Alkali and Alkaline Earth Metals 1626.4.1.3 Effects of Acid Impregnation 1626.4.1.4 Effects of Other Components 1636.4.2 Levoglucosenone 1636.4.2.1 Effects of Metal Chlorides 1636.4.2.2 Effects of Acid Catalysts 1636.4.2.3 Others 1646.4.3 Furfural 1646.4.4 Aromatic Hydrocarbons 1676.4.5 Phenolic Compounds 1696.5 Conclusions and Perspectives 170References 1717 Biomass Processing via Thermochemical–Biological Hybrid Processes 181Cristian Torri, Alessandro Girolamo Rombolà, Alisar Kiwan and Daniele Fabbri7.1 Introduction 1817.1.1 Hybrid Thermochemical/Biological Processing with Single-Strain Microorganisms 1837.1.2 Hybrid Thermochemical/Biological Processing with Microbial Mixed Consortia (MMC) 1837.2 Pyrolysis Products (PyP) from the Microorganism’s Standpoint 1857.2.1 What Pyrolysis Can Do for Microorganisms: Yields and Bioavailability of PyP 1867.2.2 Viable Pathways According to Thermodynamics Laws 1887.2.3 Rate of MMC Biological Conversions in Relationship with PyP Treatment 1917.2.4 Toxicity of PyP Toward MMC 1937.3 Conversion of PyP with MMC: Survey of Experimental Evidence 1987.3.1 Syngas Conversion to Methane 2037.3.2 Syngas Conversion to H2, Volatile Fatty Acids (VFA), and Alcohols 2037.3.3 Conversion of Condensable PyP to Methane 2057.3.4 Conversion of Condensable PyP to VFA and Other Intermediates 2067.4 Feasible Pathways for Producing Chemicals from PyP with MMC 2077.4.1 Hybrid Pyrolysis Fermentation and Extraction of Mixed VFA/Alcohols 2077.4.2 Alkaline Fermentation of Pyrolysis Products to VFA Salts, Ketonization, and Hydrogenation to C3–C6 Mixed Alcohols 2097.4.3 Alkaline Fermentation of Pyrolysis Products to VFA Salts and Polyhydroxyalkanoates (PHA) Production via Aerobic MMC 2117.4.4 Direct Alcohol Production by Means of Fermentation of PyP under High Hydrogen Pressure 2137.5 Conclusions and Perspectives 215References 216Section III Advanced/Unconventional Strategies 2258 Biomass Processing via Electrochemical Means 227Roman Latsuzbaia, Roel Johannes Martinus Bisselink, Marc Crockatt, Jan Cornelis van der Waal and Earl Lawrence Vincent Goetheer8.1 Introduction 2278.2 Electrochemical Conversion of Bio-Based Molecules 2288.3 Conversion of Sugars 2308.4 Conversion of Furanics 2348.4.1 5-(Hydroxymethyl)furfural (5-HMF) 2348.4.1.1 5-HMF Oxidation 2358.4.1.2 5-HMF Reduction 2388.4.2 Furfural 2408.5 Conversion of Levulinic Acid 2448.6 Conversion of Glycerol 2468.7 Lignin Depolymerization 2488.8 Scale-up of Electrosynthesis of Biomass-Derived Chemicals 2488.9 Conclusions and Perspectives 254References 2549 Biomass Processing via Photochemical Means 265Andrey Shatskiy and Markus D. Kärkäs9.1 Introduction 2659.2 Fundamental Aspects of Photoredox Catalysis 2669.3 Photochemical Valorization of Lignin 2679.3.1 Strategies for Cα—Cβ Bond Cleavage 2689.3.2 Strategies for Lignin Oxidation and Cβ—O Bond Cleavage 2729.3.3 Strategies for Ar—O Bond Cleavage 2789.4 Conclusions and Perspectives 281References 28210 Biomass Processing via Microwave Treatment 289Roberto Rosa, Giancarlo Cravotto and Cristina Leonelli10.1 Introduction 28910.2 Microwave–Matter Interaction: Advantages and Limitations in the Processing of Biomass 29110.3 Microwave Pyrolysis 29610.4 Microwave-assisted Hydrolysis 29910.5 Microwave-assisted Extraction of Phytochemical Compounds 30310.6 Conclusions and Perspectives 306References 30711 Biomass Processing Assisted by Ultrasound 315Cezar A. Bizzi, Daniel Santos, Gabrielle D. Iop and Erico M. M. Flores11.1 Introduction 31511.2 Ultrasound Background 31611.3 Ultrasound-Assisted Biomass Pretreatments 31911.4 Ultrasound-Assisted Biomass Conversion 32211.4.1 Thermochemical Conversion Assisted by Ultrasound 32311.4.2 Biochemical Conversion Assisted by Ultrasound 32411.4.3 Chemical Conversion (Synthesis) Assisted by Ultrasound 32511.5 Ultrasound-Assisted Extraction of Value-Added Compounds 32611.5.1 Ultrasound Contribution to Biomass Extraction Processes 32611.5.2 Uses of Alternative Approaches for Biomass Extractions Assisted by Ultrasound 32811.6 Alternative Solvents 33111.7 Conclusions and Perspectives 332References 33312 Biomass Processing via Mechanochemical Means 343George Margoutidis and Francesca M. Kerton12.1 Overview and Introduction 34312.1.1 Background to the Method 34312.1.2 Properties of a Typical Laboratory Mixer/Mill 34612.2 Crystallinity Reduction in Biopolymers via Mechanochemistry 34812.3 Mechanochemical Transformations of Polysaccharides 35212.3.1 Cellulose Depolymerization 35212.3.2 Cellulose Modification Toward Composite Materials 35512.3.3 Transformations of Chitin 35512.4 Mechanochemical Transformations of Amino Acids, Nucleotides, and Related Materials 35712.5 Mechanochemical Treatment of Lignin 35912.6 Biominerals from Mechanochemical Processing of Biomass 36012.7 Conclusions and Perspectives 361References 361Section IV Closing Remarks 36713 Industrial Perspectives of Biomass Processing 369Tommaso Tabanelli and Fabrizio Cavani13.1 Replacing Existing Petrochemicals with Alternatives from Biomass: An Introduction 36913.2 Oleochemical Biorefinery: A Consolidated and Multifaceted Example of Biomass Processing 37113.2.1 Biofuels and Coproduced Chemicals from Oils and Fats 37113.2.2 Skeletal Isomerization of Unsaturated Fatty Acids for Isostearic Acid Production 37913.2.3 Bio-based Synthesis of Azelaic and Pelargonic Acids: A Renewable Route Toward Bio-based Polyesters and Cosmetics 38213.3 From Sugar to Bio-monomers: The Case of 2,5-Furandicarboxylic Acid (FDCA) 38513.4 From Bioethanol to Rubber: The Synthesis of Bio-butadiene 38813.5 Conclusions and Perspectives 391References 391Index 411

Davide Ravelli is Assistant Professor at the PhotoGreen Laboratory of the University of Pavia. His research focus is on photochemical reactions and their applications in various fields, especially sustainable organic synthesis.Chiara Samorì is Assistant Professor at the Green Chemistry Lab of the University of Bologna. She is primarily interested in the extraction of biomass using sustainable solvents for producing third generation biofuels, bioactive compounds, and bioplastics.

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• Foreword xiPreface xiii1 Role of Biomass in the Production of Chemicals 1Layla Filiciotto, Evan Pfab and Rafael Luque1.1 Introduction 11.2 Biomass Valorization 31.3 Lignocellulosic Biomass 51.4 Key Biomolecules 61.5 Solvents 101.6 Pretreatment of Lignocelluloses 121.7 Conclusions and Perspectives 15References 15Section I Catalytic Strategies 232 Biomass Processing via Acid Catalysis 25Iurii Bodachivskyi, Unnikrishnan Kuzhiumparambil and D. Bradley G. Williams2.1 Introduction 252.1.1 Is an Acid the Best Catalyst? 262.2 Acid-Catalyzed Processing of Cellulosic Polysaccharides 292.3 Acid-Catalyzed Processing of Lignin 442.4 Conclusions and Perspectives 47References 473 Biomass Processing via Base Catalysis 57Lichen Liu, Maria J. Climent and Sara Iborra3.1 Introduction 573.2 Aldol Condensation 603.2.1 Aldol Condensation of Furanic Aldehydes 603.2.2 Self-Aldol Condensation of Acetone 633.2.3 Aldol Condensation Between Alcohols: Guerbet Coupling Reaction 643.3 Ketonization Reaction of Carboxylic Acids 653.4 Transesterification Reaction 683.4.1 Biodiesel Production 683.4.2 High Value-Added Chemicals from Transesterification Reactions 703.5 Conclusions and Perspectives 73References 744 Biomass Processing via Metal Catalysis 81Sofia Capelli and Alberto Villa4.1 Introduction 814.2 Synthetic Strategies for Supported Metal Nanoparticles 834.2.1 Impregnation 834.2.2 Precipitation 844.2.3 Sol Immobilization 854.3 Furfural 864.3.1 Furfural Hydrogenation 874.3.1.1 Furfural to Furfuryl Alcohol 874.3.1.2 Furfural to Tetrahydrofurfuryl Alcohol 884.3.1.3 Furfural to Pentanediols 894.3.1.4 Furfural to 2-Methylfuran 904.3.2 Furfural Oxidation 924.3.2.1 Furfural to Furoates 924.4 5-Hydroxymethylfurfural (HMF) 924.4.1 HMF Hydrogenation 934.4.1.1 HMF to 2,5-Dimethylfuran (DMF) 944.4.1.2 HMF to 2,5-Dihydroxymethyltetrahydrofuran (DHMTHF) 954.4.2 HMF Oxidation 964.4.2.1 HMF to 2,5-Furandicarboxylic Acid (FDCA) Using Monometallic Systems 964.4.2.2 HMF Oxidation over Bimetallic Catalysts 1004.5 Conclusions and Perspectives 103References 1035 Biomass Processing with Biocatalysis 113Roger A. Sheldon5.1 Introduction 1135.2 Generations of Renewable Biomass: Advantages and Limitations 1135.3 Advantages and Limitations of Biocatalysis 1165.4 Enzyme Discovery and Optimization of Enzyme Performance 1175.5 Enzyme Immobilization 1185.5.1 Enzyme Immobilization by Cross-linking Enzyme Molecules 1195.5.2 Advantages and Limitations of Cross-Linked Enzyme Aggregates (CLEAs) 1205.5.3 Magnetically Separable Immobilized Enzymes 1205.6 Enzymatic Hydrolysis of Starch to Glucose 1215.7 Enzymatic Depolymerization of Lignocellulose 1225.8 Enzymatic Hydrolysis of Cellulose and Hemicellulose 1235.8.1 Magnetizable Immobilized Enzymes in Lignocellulose Conversion 1245.9 Enzymatic Hydrolysis of 3rd Generation (3G) Polysaccharides 1245.10 Commodity Chemicals from Carbohydrates (Monosaccharides) 1265.10.1 Fermentative Production of Commodity Chemicals 1265.10.2 Deoxygenation via Dehydration of Carbohydrates to Furan Derivatives 1295.10.3 Polyethylene Furandicarboxylate (PEF) as a Renewable Alternative to PET 1295.10.4 Enzymatic Synthesis of Bio-based Polyesters 1315.11 Enzymatic Conversions of Triglycerides: Production of Biodiesel and Bulk Chemicals 1325.12 Conclusions and Perspectives 133References 133Section II Thermal Strategies 1476 Biomass Processing via Pyrolysis 149Daniele Fabbri, Yunchao Li and Shurong Wang6.1 Brief Introduction 1496.2 Chemicals from Cellulose Pyrolysis 1516.2.1 General Aspects 1516.2.2 Levoglucosan 1546.2.3 Levoglucosenone 1566.2.4 LAC,(1R,5S)-1-Hydroxy-3,6-Dioxabicydioxabicyclo-[3.2.1]octan-2-one 1576.3 Chemicals from Lignin Pyrolysis 1606.4 Pyrolysis of Biomass 1616.4.1 Levoglucosan 1616.4.1.1 Effects of Metal Oxides 1626.4.1.2 Effects of Alkali and Alkaline Earth Metals 1626.4.1.3 Effects of Acid Impregnation 1626.4.1.4 Effects of Other Components 1636.4.2 Levoglucosenone 1636.4.2.1 Effects of Metal Chlorides 1636.4.2.2 Effects of Acid Catalysts 1636.4.2.3 Others 1646.4.3 Furfural 1646.4.4 Aromatic Hydrocarbons 1676.4.5 Phenolic Compounds 1696.5 Conclusions and Perspectives 170References 1717 Biomass Processing via Thermochemical–Biological Hybrid Processes 181Cristian Torri, Alessandro Girolamo Rombolà, Alisar Kiwan and Daniele Fabbri7.1 Introduction 1817.1.1 Hybrid Thermochemical/Biological Processing with Single-Strain Microorganisms 1837.1.2 Hybrid Thermochemical/Biological Processing with Microbial Mixed Consortia (MMC) 1837.2 Pyrolysis Products (PyP) from the Microorganism’s Standpoint 1857.2.1 What Pyrolysis Can Do for Microorganisms: Yields and Bioavailability of PyP 1867.2.2 Viable Pathways According to Thermodynamics Laws 1887.2.3 Rate of MMC Biological Conversions in Relationship with PyP Treatment 1917.2.4 Toxicity of PyP Toward MMC 1937.3 Conversion of PyP with MMC: Survey of Experimental Evidence 1987.3.1 Syngas Conversion to Methane 2037.3.2 Syngas Conversion to H2, Volatile Fatty Acids (VFA), and Alcohols 2037.3.3 Conversion of Condensable PyP to Methane 2057.3.4 Conversion of Condensable PyP to VFA and Other Intermediates 2067.4 Feasible Pathways for Producing Chemicals from PyP with MMC 2077.4.1 Hybrid Pyrolysis Fermentation and Extraction of Mixed VFA/Alcohols 2077.4.2 Alkaline Fermentation of Pyrolysis Products to VFA Salts, Ketonization, and Hydrogenation to C3–C6 Mixed Alcohols 2097.4.3 Alkaline Fermentation of Pyrolysis Products to VFA Salts and Polyhydroxyalkanoates (PHA) Production via Aerobic MMC 2117.4.4 Direct Alcohol Production by Means of Fermentation of PyP under High Hydrogen Pressure 2137.5 Conclusions and Perspectives 215References 216Section III Advanced/Unconventional Strategies 2258 Biomass Processing via Electrochemical Means 227Roman Latsuzbaia, Roel Johannes Martinus Bisselink, Marc Crockatt, Jan Cornelis van der Waal and Earl Lawrence Vincent Goetheer8.1 Introduction 2278.2 Electrochemical Conversion of Bio-Based Molecules 2288.3 Conversion of Sugars 2308.4 Conversion of Furanics 2348.4.1 5-(Hydroxymethyl)furfural (5-HMF) 2348.4.1.1 5-HMF Oxidation 2358.4.1.2 5-HMF Reduction 2388.4.2 Furfural 2408.5 Conversion of Levulinic Acid 2448.6 Conversion of Glycerol 2468.7 Lignin Depolymerization 2488.8 Scale-up of Electrosynthesis of Biomass-Derived Chemicals 2488.9 Conclusions and Perspectives 254References 2549 Biomass Processing via Photochemical Means 265Andrey Shatskiy and Markus D. Kärkäs9.1 Introduction 2659.2 Fundamental Aspects of Photoredox Catalysis 2669.3 Photochemical Valorization of Lignin 2679.3.1 Strategies for Cα—Cβ Bond Cleavage 2689.3.2 Strategies for Lignin Oxidation and Cβ—O Bond Cleavage 2729.3.3 Strategies for Ar—O Bond Cleavage 2789.4 Conclusions and Perspectives 281References 28210 Biomass Processing via Microwave Treatment 289Roberto Rosa, Giancarlo Cravotto and Cristina Leonelli10.1 Introduction 28910.2 Microwave–Matter Interaction: Advantages and Limitations in the Processing of Biomass 29110.3 Microwave Pyrolysis 29610.4 Microwave-assisted Hydrolysis 29910.5 Microwave-assisted Extraction of Phytochemical Compounds 30310.6 Conclusions and Perspectives 306References 30711 Biomass Processing Assisted by Ultrasound 315Cezar A. Bizzi, Daniel Santos, Gabrielle D. Iop and Erico M. M. Flores11.1 Introduction 31511.2 Ultrasound Background 31611.3 Ultrasound-Assisted Biomass Pretreatments 31911.4 Ultrasound-Assisted Biomass Conversion 32211.4.1 Thermochemical Conversion Assisted by Ultrasound 32311.4.2 Biochemical Conversion Assisted by Ultrasound 32411.4.3 Chemical Conversion (Synthesis) Assisted by Ultrasound 32511.5 Ultrasound-Assisted Extraction of Value-Added Compounds 32611.5.1 Ultrasound Contribution to Biomass Extraction Processes 32611.5.2 Uses of Alternative Approaches for Biomass Extractions Assisted by Ultrasound 32811.6 Alternative Solvents 33111.7 Conclusions and Perspectives 332References 33312 Biomass Processing via Mechanochemical Means 343George Margoutidis and Francesca M. Kerton12.1 Overview and Introduction 34312.1.1 Background to the Method 34312.1.2 Properties of a Typical Laboratory Mixer/Mill 34612.2 Crystallinity Reduction in Biopolymers via Mechanochemistry 34812.3 Mechanochemical Transformations of Polysaccharides 35212.3.1 Cellulose Depolymerization 35212.3.2 Cellulose Modification Toward Composite Materials 35512.3.3 Transformations of Chitin 35512.4 Mechanochemical Transformations of Amino Acids, Nucleotides, and Related Materials 35712.5 Mechanochemical Treatment of Lignin 35912.6 Biominerals from Mechanochemical Processing of Biomass 36012.7 Conclusions and Perspectives 361References 361Section IV Closing Remarks 36713 Industrial Perspectives of Biomass Processing 369Tommaso Tabanelli and Fabrizio Cavani13.1 Replacing Existing Petrochemicals with Alternatives from Biomass: An Introduction 36913.2 Oleochemical Biorefinery: A Consolidated and Multifaceted Example of Biomass Processing 37113.2.1 Biofuels and Coproduced Chemicals from Oils and Fats 37113.2.2 Skeletal Isomerization of Unsaturated Fatty Acids for Isostearic Acid Production 37913.2.3 Bio-based Synthesis of Azelaic and Pelargonic Acids: A Renewable Route Toward Bio-based Polyesters and Cosmetics 38213.3 From Sugar to Bio-monomers: The Case of 2,5-Furandicarboxylic Acid (FDCA) 38513.4 From Bioethanol to Rubber: The Synthesis of Bio-butadiene 38813.5 Conclusions and Perspectives 391References 391Index 411

Davide Ravelli is Assistant Professor at the PhotoGreen Laboratory of the University of Pavia. His research focus is on photochemical reactions and their applications in various fields, especially sustainable organic synthesis.Chiara Samorì is Assistant Professor at the Green Chemistry Lab of the University of Bologna. She is primarily interested in the extraction of biomass using sustainable solvents for producing third generation biofuels, bioactive compounds, and bioplastics.

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• Foreword xiPreface xiii1 Role of Biomass in the Production of Chemicals 1Layla Filiciotto, Evan Pfab and Rafael Luque1.1 Introduction 11.2 Biomass Valorization 31.3 Lignocellulosic Biomass 51.4 Key Biomolecules 61.5 Solvents 101.6 Pretreatment of Lignocelluloses 121.7 Conclusions and Perspectives 15References 15Section I Catalytic Strategies 232 Biomass Processing via Acid Catalysis 25Iurii Bodachivskyi, Unnikrishnan Kuzhiumparambil and D. Bradley G. Williams2.1 Introduction 252.1.1 Is an Acid the Best Catalyst? 262.2 Acid-Catalyzed Processing of Cellulosic Polysaccharides 292.3 Acid-Catalyzed Processing of Lignin 442.4 Conclusions and Perspectives 47References 473 Biomass Processing via Base Catalysis 57Lichen Liu, Maria J. Climent and Sara Iborra3.1 Introduction 573.2 Aldol Condensation 603.2.1 Aldol Condensation of Furanic Aldehydes 603.2.2 Self-Aldol Condensation of Acetone 633.2.3 Aldol Condensation Between Alcohols: Guerbet Coupling Reaction 643.3 Ketonization Reaction of Carboxylic Acids 653.4 Transesterification Reaction 683.4.1 Biodiesel Production 683.4.2 High Value-Added Chemicals from Transesterification Reactions 703.5 Conclusions and Perspectives 73References 744 Biomass Processing via Metal Catalysis 81Sofia Capelli and Alberto Villa4.1 Introduction 814.2 Synthetic Strategies for Supported Metal Nanoparticles 834.2.1 Impregnation 834.2.2 Precipitation 844.2.3 Sol Immobilization 854.3 Furfural 864.3.1 Furfural Hydrogenation 874.3.1.1 Furfural to Furfuryl Alcohol 874.3.1.2 Furfural to Tetrahydrofurfuryl Alcohol 884.3.1.3 Furfural to Pentanediols 894.3.1.4 Furfural to 2-Methylfuran 904.3.2 Furfural Oxidation 924.3.2.1 Furfural to Furoates 924.4 5-Hydroxymethylfurfural (HMF) 924.4.1 HMF Hydrogenation 934.4.1.1 HMF to 2,5-Dimethylfuran (DMF) 944.4.1.2 HMF to 2,5-Dihydroxymethyltetrahydrofuran (DHMTHF) 954.4.2 HMF Oxidation 964.4.2.1 HMF to 2,5-Furandicarboxylic Acid (FDCA) Using Monometallic Systems 964.4.2.2 HMF Oxidation over Bimetallic Catalysts 1004.5 Conclusions and Perspectives 103References 1035 Biomass Processing with Biocatalysis 113Roger A. Sheldon5.1 Introduction 1135.2 Generations of Renewable Biomass: Advantages and Limitations 1135.3 Advantages and Limitations of Biocatalysis 1165.4 Enzyme Discovery and Optimization of Enzyme Performance 1175.5 Enzyme Immobilization 1185.5.1 Enzyme Immobilization by Cross-linking Enzyme Molecules 1195.5.2 Advantages and Limitations of Cross-Linked Enzyme Aggregates (CLEAs) 1205.5.3 Magnetically Separable Immobilized Enzymes 1205.6 Enzymatic Hydrolysis of Starch to Glucose 1215.7 Enzymatic Depolymerization of Lignocellulose 1225.8 Enzymatic Hydrolysis of Cellulose and Hemicellulose 1235.8.1 Magnetizable Immobilized Enzymes in Lignocellulose Conversion 1245.9 Enzymatic Hydrolysis of 3rd Generation (3G) Polysaccharides 1245.10 Commodity Chemicals from Carbohydrates (Monosaccharides) 1265.10.1 Fermentative Production of Commodity Chemicals 1265.10.2 Deoxygenation via Dehydration of Carbohydrates to Furan Derivatives 1295.10.3 Polyethylene Furandicarboxylate (PEF) as a Renewable Alternative to PET 1295.10.4 Enzymatic Synthesis of Bio-based Polyesters 1315.11 Enzymatic Conversions of Triglycerides: Production of Biodiesel and Bulk Chemicals 1325.12 Conclusions and Perspectives 133References 133Section II Thermal Strategies 1476 Biomass Processing via Pyrolysis 149Daniele Fabbri, Yunchao Li and Shurong Wang6.1 Brief Introduction 1496.2 Chemicals from Cellulose Pyrolysis 1516.2.1 General Aspects 1516.2.2 Levoglucosan 1546.2.3 Levoglucosenone 1566.2.4 LAC,(1R,5S)-1-Hydroxy-3,6-Dioxabicydioxabicyclo-[3.2.1]octan-2-one 1576.3 Chemicals from Lignin Pyrolysis 1606.4 Pyrolysis of Biomass 1616.4.1 Levoglucosan 1616.4.1.1 Effects of Metal Oxides 1626.4.1.2 Effects of Alkali and Alkaline Earth Metals 1626.4.1.3 Effects of Acid Impregnation 1626.4.1.4 Effects of Other Components 1636.4.2 Levoglucosenone 1636.4.2.1 Effects of Metal Chlorides 1636.4.2.2 Effects of Acid Catalysts 1636.4.2.3 Others 1646.4.3 Furfural 1646.4.4 Aromatic Hydrocarbons 1676.4.5 Phenolic Compounds 1696.5 Conclusions and Perspectives 170References 1717 Biomass Processing via Thermochemical–Biological Hybrid Processes 181Cristian Torri, Alessandro Girolamo Rombolà, Alisar Kiwan and Daniele Fabbri7.1 Introduction 1817.1.1 Hybrid Thermochemical/Biological Processing with Single-Strain Microorganisms 1837.1.2 Hybrid Thermochemical/Biological Processing with Microbial Mixed Consortia (MMC) 1837.2 Pyrolysis Products (PyP) from the Microorganism’s Standpoint 1857.2.1 What Pyrolysis Can Do for Microorganisms: Yields and Bioavailability of PyP 1867.2.2 Viable Pathways According to Thermodynamics Laws 1887.2.3 Rate of MMC Biological Conversions in Relationship with PyP Treatment 1917.2.4 Toxicity of PyP Toward MMC 1937.3 Conversion of PyP with MMC: Survey of Experimental Evidence 1987.3.1 Syngas Conversion to Methane 2037.3.2 Syngas Conversion to H2, Volatile Fatty Acids (VFA), and Alcohols 2037.3.3 Conversion of Condensable PyP to Methane 2057.3.4 Conversion of Condensable PyP to VFA and Other Intermediates 2067.4 Feasible Pathways for Producing Chemicals from PyP with MMC 2077.4.1 Hybrid Pyrolysis Fermentation and Extraction of Mixed VFA/Alcohols 2077.4.2 Alkaline Fermentation of Pyrolysis Products to VFA Salts, Ketonization, and Hydrogenation to C3–C6 Mixed Alcohols 2097.4.3 Alkaline Fermentation of Pyrolysis Products to VFA Salts and Polyhydroxyalkanoates (PHA) Production via Aerobic MMC 2117.4.4 Direct Alcohol Production by Means of Fermentation of PyP under High Hydrogen Pressure 2137.5 Conclusions and Perspectives 215References 216Section III Advanced/Unconventional Strategies 2258 Biomass Processing via Electrochemical Means 227Roman Latsuzbaia, Roel Johannes Martinus Bisselink, Marc Crockatt, Jan Cornelis van der Waal and Earl Lawrence Vincent Goetheer8.1 Introduction 2278.2 Electrochemical Conversion of Bio-Based Molecules 2288.3 Conversion of Sugars 2308.4 Conversion of Furanics 2348.4.1 5-(Hydroxymethyl)furfural (5-HMF) 2348.4.1.1 5-HMF Oxidation 2358.4.1.2 5-HMF Reduction 2388.4.2 Furfural 2408.5 Conversion of Levulinic Acid 2448.6 Conversion of Glycerol 2468.7 Lignin Depolymerization 2488.8 Scale-up of Electrosynthesis of Biomass-Derived Chemicals 2488.9 Conclusions and Perspectives 254References 2549 Biomass Processing via Photochemical Means 265Andrey Shatskiy and Markus D. Kärkäs9.1 Introduction 2659.2 Fundamental Aspects of Photoredox Catalysis 2669.3 Photochemical Valorization of Lignin 2679.3.1 Strategies for Cα—Cβ Bond Cleavage 2689.3.2 Strategies for Lignin Oxidation and Cβ—O Bond Cleavage 2729.3.3 Strategies for Ar—O Bond Cleavage 2789.4 Conclusions and Perspectives 281References 28210 Biomass Processing via Microwave Treatment 289Roberto Rosa, Giancarlo Cravotto and Cristina Leonelli10.1 Introduction 28910.2 Microwave–Matter Interaction: Advantages and Limitations in the Processing of Biomass 29110.3 Microwave Pyrolysis 29610.4 Microwave-assisted Hydrolysis 29910.5 Microwave-assisted Extraction of Phytochemical Compounds 30310.6 Conclusions and Perspectives 306References 30711 Biomass Processing Assisted by Ultrasound 315Cezar A. Bizzi, Daniel Santos, Gabrielle D. Iop and Erico M. M. Flores11.1 Introduction 31511.2 Ultrasound Background 31611.3 Ultrasound-Assisted Biomass Pretreatments 31911.4 Ultrasound-Assisted Biomass Conversion 32211.4.1 Thermochemical Conversion Assisted by Ultrasound 32311.4.2 Biochemical Conversion Assisted by Ultrasound 32411.4.3 Chemical Conversion (Synthesis) Assisted by Ultrasound 32511.5 Ultrasound-Assisted Extraction of Value-Added Compounds 32611.5.1 Ultrasound Contribution to Biomass Extraction Processes 32611.5.2 Uses of Alternative Approaches for Biomass Extractions Assisted by Ultrasound 32811.6 Alternative Solvents 33111.7 Conclusions and Perspectives 332References 33312 Biomass Processing via Mechanochemical Means 343George Margoutidis and Francesca M. Kerton12.1 Overview and Introduction 34312.1.1 Background to the Method 34312.1.2 Properties of a Typical Laboratory Mixer/Mill 34612.2 Crystallinity Reduction in Biopolymers via Mechanochemistry 34812.3 Mechanochemical Transformations of Polysaccharides 35212.3.1 Cellulose Depolymerization 35212.3.2 Cellulose Modification Toward Composite Materials 35512.3.3 Transformations of Chitin 35512.4 Mechanochemical Transformations of Amino Acids, Nucleotides, and Related Materials 35712.5 Mechanochemical Treatment of Lignin 35912.6 Biominerals from Mechanochemical Processing of Biomass 36012.7 Conclusions and Perspectives 361References 361Section IV Closing Remarks 36713 Industrial Perspectives of Biomass Processing 369Tommaso Tabanelli and Fabrizio Cavani13.1 Replacing Existing Petrochemicals with Alternatives from Biomass: An Introduction 36913.2 Oleochemical Biorefinery: A Consolidated and Multifaceted Example of Biomass Processing 37113.2.1 Biofuels and Coproduced Chemicals from Oils and Fats 37113.2.2 Skeletal Isomerization of Unsaturated Fatty Acids for Isostearic Acid Production 37913.2.3 Bio-based Synthesis of Azelaic and Pelargonic Acids: A Renewable Route Toward Bio-based Polyesters and Cosmetics 38213.3 From Sugar to Bio-monomers: The Case of 2,5-Furandicarboxylic Acid (FDCA) 38513.4 From Bioethanol to Rubber: The Synthesis of Bio-butadiene 38813.5 Conclusions and Perspectives 391References 391Index 411