Production of Biofuels and Chemicals from Lignin (eBook)

Dr. Zhen Fang is Professor in Bioenergy, Leader and founder of biomass group, College of Engineering, Nanjing Agricultural University, China. Dr. Richard L Smith, Jr. is Professor of Chemical Engineering, Graduate School of Environmental Studies, Research Center of Supercritical Fluid Technology, Tohoku University, Japan. 

Preface 6
Acknowledgements 8
Contents 10
Contributors 12
Editors’ Biography 16
Part I: Lignin and Its Production 17
Chapter 1: Properties, Chemical Characteristics and Application of Lignin and Its Derivatives 18
1.1 Occurrence of Lignin in Biomass 18
1.1.1 Source, Monolignol Constituents and Sub-unit Structures 18
1.1.2 Distribution, Content and Chemical Structures of Lignin Sub-units 19
1.1.3 Biological Functions 22
1.1.4 Sources of Technical Lignin and Their Promise in Bio-­refining Process 23
1.2 Techniques for Determining Structural and Chemical Features of Lignin 24
1.2.1 Importance of Lignin Chemistry 24
1.2.2 Lignin Content 24
1.2.2.1 Wet Chemistry Methods 24
1.2.2.2 Spectroscopic Methods 25
1.2.3 Distribution of Lignin 25
1.2.3.1 Scanning Electron Microscopy and Atomic Force Microscopy Methods 25
1.2.3.2 Spectroscopy and Other Microscopy Methods 26
1.2.4 Molecular Weight and Polydispersity 26
1.2.5 Functional Side-Chain Groups 27
1.2.5.1 Nuclear Magnetic Resonance Methods 27
1.2.5.2 UV and GC-FID Methods 27
1.2.6 Content of Phenolic Units of Lignin 28
1.2.7 Content of Inter-molecular Linkages 28
1.2.7.1 13C- and 31P NMR Methods 28
1.2.7.2 FT-IR Spectroscopy Method 29
1.2.8 Lignin-Lignin Linkages and Macromolecular Assembly 29
1.2.8.1 Chemical Oxidation and GC-MS/FID Method 31
1.2.8.2 Pyrolysis Degradation and GC-MS/FID Method 31
1.2.8.3 Chemo-Thermo Degradation Method 32
1.2.8.4 Enzymatic Oxidization and Resonance Raman Spectroscopy Method 32
1.3 Derivatization and End-Use of Lignin and Lignin Derivatives 33
1.3.1 Sources of Lignocellulosic Biomass for Technical Lignin Derivatives 33
1.3.2 Application of Lignin and Lignin Derivatives 33
1.3.2.1 Energy 33
1.3.2.2 Renewable Chemicals 34
1.3.2.3 Materials and Additives 36
1.4 Conclusions and Future Outlook 38
References 39
Chapter 2: Extraction of Technical Lignins from Pulping Spent Liquors, Challenges and Opportunities 49
2.1 Introduction 49
2.2 Kraft Pulping Process 50
2.2.1 Properties of Black Liquor 50
2.2.2 Acidification 51
2.2.3 Membrane 53
2.2.4 Electrolysis 54
2.2.5 Solvent 55
2.3 Prehydrolysis Based Kraft Process 55
2.3.1 Properties of PHL 55
2.3.2 Acidification of PHL 56
2.3.3 Adsorption 57
2.3.4 Flocculation 57
2.3.5 In Situ Adsorption/Flocculation System 58
2.4 Spent Liquor of Sulfite Process 58
2.4.1 Properties of Spent Liquor 58
2.4.2 Membrane 59
2.4.3 Amine Extraction 60
2.4.4 Electrolysis 60
2.4.5 Ion Exchange Resin 61
2.5 Isolation of Lignosulfonate from Spent Liquor of NSSC Process 62
2.5.1 Properties of Spent Liquor in NSSC Process 62
2.5.2 Adsorption/Flocculation/Coagulation 62
2.5.3 Solvent Extraction 63
2.6 Conclusions and Future Outlook 64
References 64
Chapter 3: Recovery of Low-Ash and Ultrapure Lignins from Alkaline Liquor By-Product Streams 69
3.1 Introduction and Background 69
3.1.1 Low-Ash Lignins from Alkaline Liquors 70
3.1.2 From Low-Ash to Ultrapure Lignins 71
3.2 Low-Ash Lignins via the SLRP Process 73
3.2.1 Procedure 73
3.2.1.1 Carbonation 73
3.2.1.2 Acidification 76
3.2.1.3 Filtration 76
3.2.1.4 Vent-Gas Capture 76
3.2.2 Properties of Liquid-Lignin Phase 77
3.2.3 Fractionating the Liquid-Lignin Phase via SLRP for Control of the Bulk and Molecular Properties of Lignin 80
3.3 Ultrapure Lignins via the ALPHA Process 83
3.3.1 Liquid–Liquid Equilibrium Phase Behavior for the Acetic Acid–Water–Lignin System 83
3.3.2 ALPHA as a Single-Stage, Batch Process 84
3.3.3 Two-Stage Batch ALPHA for Generating Ultrapure Lignins 87
3.3.4 ALPHA as a Continuous Process: Minimizing Residence Times and Maximizing Throughputs for Ultrapure Lignins 89
3.4 Conclusions and Future Outlook 90
References 91
Part II: Biological Conversion 93
Chapter 4: Lignin Degrading Fungal Enzymes 94
4.1 Introduction 94
4.2 Carbohydrate Active Enzyme Database (CAZy) 96
4.3 Fungal Oxidative Lignin Enzymes (FOLy) 97
4.4 Lignin Oxidizing Enzymes (LO) 98
4.4.1 Laccases (EC 1.10.3.2, Benzenediol: Oxygen Oxidoreductase) 98
4.4.2 Peroxidases (EC:1.11.1.x) 103
4.4.3 Lignin Peroxidases (E.C. 1.11.1.14) 103
4.4.4 Manganese Peroxidases (EC 1.11.1.13) 107
4.4.5 Versatile Peroxidases 110
4.5 Cellobiose Dehydrogenase 113
4.6 Lignin Degrading Auxiliary Enzymes (LDA) 115
4.6.1 Aryl Alcohol Oxidase 116
4.6.2 Vanillyl Alcohol Oxidase 119
4.6.3 Glyoxal Oxidase 121
4.6.4 Pyranose Oxidase 122
4.6.5 Galactose Oxidase 124
4.6.6 Glucose Oxidase 125
4.6.7 Benzoquinone Reductase 126
4.7 A Short Note on Genome Sequencing Studies of Lignin Degrading Fungi 128
4.8 Conclusion and Future Outlook 131
References 132
Chapter 5: Bacterial Enzymes for Lignin Oxidation and Conversion to Renewable Chemicals 144
5.1 Discovery of Lignin-Metabolising Bacteria 144
5.2 Bacterial Enzymes for Lignin Biotransformation 147
5.2.1 Dye-Decolorizing Peroxidases 147
5.2.2 Bacterial Laccases 149
5.2.3 Glutathione-Dependent ?-Etherase Enzymes 150
5.2.4 Other Lignin-Metabolising Enzymes 150
5.3 Metabolic Pathways for Lignin Metabolism in Bacteria 151
5.4 Use of Metabolic Engineering for Generation of Renewable Chemicals from Lignin 152
5.5 Conclusions and Future Outlook 156
References 156
Chapter 6: Lignin Biodegradation with Fungi, Bacteria and Enzymes for Producing Chemicals and Increasing Process Efficiency 160
6.1 Introduction 161
6.2 Fungal Degradation 161
6.2.1 Delignification 164
6.2.2 Waste Treatment 167
6.2.3 Chemical Production 167
6.2.4 Perspectives 170
6.3 Bacterial Degradation 170
6.3.1 Delignification 170
6.3.2 Chemical Production 171
6.3.3 Perspectives 175
6.4 Enzymatic Degradation 175
6.4.1 Laccases 176
6.4.2 Peroxidases 179
6.4.3 Cocktails 180
6.4.4 Bioinspired Enzyme-Like Synthetic Compounds 181
6.4.5 Perspectives 182
6.5 Conclusion and Future Outlook 183
References 184
Part III: Chemical Conversion 193
Chapter 7: Chemical Modification of Lignin for Renewable Polymers or Chemicals 194
7.1 Introduction 194
7.1.1 Lignin: An Important Renewable Resource 194
7.1.2 Possible Uses of Lignin 194
7.1.3 The Types of Chemical Modifications Carried Out on Lignin 196
7.1.3.1 Alkylation and Oxidation 196
7.1.3.2 Alkylation and Thioacidolysis 197
7.1.3.3 Halogenation 198
7.1.3.4 Nitration 198
7.1.3.5 Amination 198
7.1.3.6 Phosphitylation 199
7.1.3.7 Other Chemical Modifications of Lignin 199
7.2 Depolymerization of Modified Lignin 199
7.2.1 Sequential Lignin Modification Applied to Lignin Structural Analysis 200
7.2.2 Benzylic Oxidations Followed by Cleavage as a Route to Chemicals 202
7.3 Lignin Modification Leading to Novel Polymeric Materials 206
7.3.1 Overview 206
7.3.2 Reaction with Mono-functional Monomers 207
7.3.2.1 ‘Grafting Onto’ Approach 207
7.3.2.2 ‘Grafting From’ Approach 209
7.3.3 Reaction with Multi-functional Monomers 210
7.3.3.1 Phenol Formaldehyde Thermoset Materials 210
7.3.3.2 Polyurethanes 213
7.3.4 Polymer Blending 214
7.3.5 Smart Lignin Materials 216
7.4 Concluding Remarks & Future Outlook
References 220
Chapter 8: Carbon Materials from Lignin and Their Applications 228
8.1 Introduction 228
8.2 Activated Carbons from Lignin 229
8.2.1 Physical Activation 230
8.2.2 Chemical Activation 236
8.2.3 Applications of Lignin-Derived Activated Carbons 244
8.2.3.1 Applications in Adsorption 245
8.2.3.2 Applications in Catalysis 247
8.3 Lignin-Based Carbon Fibers 249
8.3.1 Lignin-Based CFs by Melt-Spinning Methods 250
8.3.2 Electrospinning 252
8.3.3 Oxidative Thermostabilization of Lignin Fibers 254
8.3.4 Potential Applications of Lignin-Based Carbon Fibers 255
8.3.4.1 CFs for Structural Applications 256
8.3.4.2 CFs for Functional Applications 257
8.4 Templated Carbons from Lignin 258
8.5 Lignin Graphitization 259
8.6 Conclusions and Future Outlook 264
References 265
Chapter 9: Biofuels and Chemicals from Lignin Based on Pyrolysis 274
9.1 Introduction 274
9.2 Fundamentals of Lignin Pyrolysis 276
9.2.1 Lignin Structures Related to Complexity of Pyrolysis 276
9.2.2 Pyrolysis Kinetics of Lignin 276
9.2.3 Py-GC/MS of Lignin 277
9.2.4 Factors Affecting Lignin Pyrolysis 280
9.3 Pyrolysis of Technical Lignin 284
9.3.1 Pyrolysis of Lignin in Lab-Scale Reactors 284
9.3.2 Properties of Lignin Pyrolysis Oil 287
9.4 Catalytic Upgrading of Lignin 289
9.4.1 Catalytic Upgrading of Pyrolysis Vapor of Lignin 289
9.4.2 Catalytic Upgrading of Phenolic Oil 291
9.5 Application of Lignin Pyrolysis Products 292
9.6 Conclusions and Future Outlook 294
References 295
Chapter 10: Lignin Depolymerization (LDP) with Solvolysis for Selective Production of Renewable Aromatic Chemicals 299
10.1 Introduction 299
10.2 Lignin in Conventional Heating 301
10.2.1 Hydrogenolysis 301
10.2.2 Hydrogen-Donor Solvent System 304
10.2.3 Hydrogen-Involved System 311
10.2.4 Oxidativelysis 314
10.2.5 Organometallic Catalysts 315
10.2.6 Metal-Free-Organic Catalysts 317
10.2.7 Acid/Base Catalysts 317
10.2.8 Metal Salt Catalysts 318
10.2.9 Two-Step LDP 318
10.3 LDP Assisted by microwave Heating 320
10.3.1 Hydrogenolysis 320
10.3.2 Oxidativelysis 325
10.4 Conclusions and Future Outlook 326
References 326
Chapter 11: Molecular Mechanisms in the Thermochemical Conversion of Lignins into Bio-Oil/Chemicals and Biofuels 331
11.1 Introduction 331
11.2 Lignin Devolatilization Temperature 332
11.3 Pyrolysis Products and Effects of Temperature 333
11.4 Primary Pyrolysis Reactions 335
11.4.1 Model Compound Reactivity 335
11.4.2 Ether Cleavage Mechanisms 337
11.4.3 Radical Chain Reactions 343
11.4.4 Re-polymerization and Side Chain Conversion 345
11.4.5 Side-Chain Conversion Mechanism 348
11.4.6 Role of Cinnamyl Alcohol in Lignin Primary Pyrolysis 350
11.5 Secondary Reactions 353
11.5.1 Homolysis and Rearrangement of Methoxyl Groups 354
11.5.2 Coke and Polyaromatic Hydrocarbon Formation 355
11.5.3 Dealkylation 357
11.5.4 Gasification 357
11.5.5 Interaction Between Lignin and Polysaccharide Pyrolysis 358
11.6 Conclusions and Future Outlook 359
References 360
Chapter 12: Depolymerization Mechanisms and Product Formation Rules for Understanding Lignin Pyrolysis 364
12.1 Introduction 364
12.2 Experimentation and Computational Calculation 366
12.2.1 Materials and Characterization 366
12.2.2 Pyrolysis and Product Analysis 367
12.2.3 Theoretical Study of Bond Dissociation Energies 368
12.3 Results and Discussion 368
12.3.1 Characterization of EMAL 368
12.3.2 Thermal Analysis 371
12.3.3 Pyrolysis Products of EMAL 373
12.3.4 Products Distribution 376
12.3.5 Bond Dissociation Energies of Lignin Model Compounds 379
12.3.6 Pyrolysis Mechanism of EMAL 381
12.4 Conclusions and Future Outlook 381
References 383
Part IV: Techno-economics 385
Chapter 13: Integrated Lignin-Kraft Pulp Biorefinery for the Production of Lignin and Its Derivatives: Economic Assessment and LCA-Based Environmental Footprint 386
13.1 Introduction 386
13.2 Process Descriptions: Lignin Recovery and Production of Derivatives 388
13.2.1 LignoBoost™ Process 388
13.2.2 LignoForce System™ 389
13.2.3 Sequential Liquid-Lignin Recovery and Purification (SLRP™) 391
13.2.4 Other Lignin Isolation Methods: Ultrafiltration, Electrolysis, and Electrodialysis Membranes 391
13.2.5 Molecular Structure of Lignin 393
13.2.6 Emerging Innovative Applications of Lignin 394
13.2.6.1 Lignin-Based Polyols for Polyurethanes 395
13.2.6.2 Lignin-Based Precursor for Carbon Fibers 397
13.3 Multi-criteria Analysis Methodology: Technical, Economic, and Environmental Assessments 398
13.3.1 Foundations of Multi-criteria Analysis 398
13.3.2 Technical Assessment 399
13.3.3 Economic Assessment 400
13.3.3.1 Total Product Cost 400
13.3.3.2 Total Capital Investment 400
13.3.3.3 Economic Metrics 401
13.3.4 Environmental Assessment Methodology 403
13.4 Industrial Case Study Description 406
13.4.1 Host Mill for Lignin Recovery Processes 406
13.4.2 Lignin Recovery 406
13.4.3 Lignin Derivatives 408
13.5 Process Impacts, Economic and Environmental Assessment 409
13.5.1 Economic Assessment Result of Lignin Recovery 410
13.5.2 Environmental Assessment Results 414
13.5.3 Economic Assessment for Lignin Derivative Production 416
13.5.3.1 Economic Results for the Implementation Scenario 419
13.6 Conclusion and Future Outlook 421
References 422
Index 426