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Book Details
Abstract
Lignin, an aromatic biopolymer found in plant cell walls, is a key component of lignocellulosic biomass and generally utilized for heat and power. However, lignin’s chemical composition makes it an attractive source for biological and catalytic conversion to fuels and chemicals. Bringing together experts from biology, catalysis, engineering, analytical chemistry, and techno-economic/life-cycle analysis, Lignin Valorization presents a comprehensive, interdisciplinary picture of how lignocellulosic biorefineries could potentially employ lignin valorization technologies.
Chapters will specifically focus on the production of fuels and chemicals from lignin and topics covered include (i) methods for isolating lignin in the context of the lignocellulosic biorefinery, (ii) thermal, chemo-catalytic, and biological methods for lignin depolymerization, (iii) chemo-catalytic and biological methods for upgrading lignin, (iv) characterization of lignin, and (v) techno-economic and life-cycle analysis of integrated processes to utilize lignin in an integrated biorefinery.
The book provides the latest breakthroughs and challenges in upgrading lignin to fuels and chemicals for graduate students and researchers in academia, governmental laboratories, and industry interested in biomass conversion.
Gregg T Beckham is a Senior Engineer in the National Bioenergy Center at the National Renewable Energy Laboratory, USA.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Contents | v | ||
| Chapter 1 A Brief Introduction to Lignin Structure | 1 | ||
| 1.1 Introduction | 1 | ||
| 1.2 Lignin Structure | 2 | ||
| 1.2.1 Side Chain Structure in the End-group | 4 | ||
| 1.2.2 Acylated End-groups | 6 | ||
| 1.2.3 Lignin Interunit Linkages | 8 | ||
| 1.2.4 Lignin Functional Groups | 11 | ||
| 1.2.5 Linkages between Lignin and Polysaccharides | 13 | ||
| 1.3 Scope of This Book | 15 | ||
| Acknowledgements | 15 | ||
| References | 15 | ||
| Chapter 2 Lignin Isolation Methodology for Biorefining, Pretreatment and Analysis | 21 | ||
| 2.1 Introduction | 21 | ||
| 2.2 Isolation of Lignin for Analysis | 22 | ||
| 2.2.1 Klason Lignin | 22 | ||
| 2.2.2 Dioxane Lignin (DL) | 23 | ||
| 2.2.3 Bjo¨rkman Lignin | 24 | ||
| 2.2.4 Cellulolytic Enzyme Lignin (CEL) | 24 | ||
| 2.2.5 Other Lignin Isolation Techniques | 25 | ||
| 2.3 Isolation of Lignin after its Removal from Biomass – Production within the Pulp and Paper Industry | 25 | ||
| 2.3.1 Kraft Process | 25 | ||
| 2.3.2 Sulfite Pulping and Lignosulfonates | 27 | ||
| 2.4 Lignin Isolation via Fractionation | 29 | ||
| 2.4.1 Organosolv Processes | 29 | ||
| 2.4.2 Ionic Liquid Fractionation | 35 | ||
| 2.4.3 Dilute Acid (DA) Pretreatment and Fractionation | 39 | ||
| 2.4.4 Steam Explosion | 43 | ||
| 2.4.5 Liquid Hot Water (LHW) | 44 | ||
| 2.4.6 Ammonia-based Fractionation and Pretreatment | 46 | ||
| 2.4.7 Thermochemical Conversion followed by Fractionation: Isolation of Pyrolytic Lignin | 47 | ||
| 2.5 Conclusions | 49 | ||
| References | 50 | ||
| Chapter 3 Lessons Learned from 150 Years of Pulping Wood | 62 | ||
| 3.1 History | 62 | ||
| 3.2 Chemistry | 65 | ||
| 3.2.1 Delignification Chemistry | 65 | ||
| 3.2.2 Alkaline Pulping Chemistry | 66 | ||
| 3.2.3 Neutral Pulping Chemistry | 67 | ||
| 3.2.4 Acidic Pulping Chemistry | 67 | ||
| 3.3 Paper Industry Attempts to Get More Than Energy out of Lignin | 68 | ||
| 3.3.1 Lignin Sulfonate | 68 | ||
| 3.3.2 Vanillin Production | 68 | ||
| 3.3.3 Kraft Lignin Recovery | 69 | ||
| 3.3.4 Black Liquor Gasification | 70 | ||
| 3.4 Conclusions | 71 | ||
| References | 71 | ||
| Chapter 4 Thermal and Solvolytic Depolymerization Approaches for Lignin Depolymerization and Upgrading | 74 | ||
| 4.1 Lignin Refining | 74 | ||
| 4.1.1 Liquefaction | 75 | ||
| 4.1.2 Direct Liquefaction of Coal and Lignin | 77 | ||
| 4.1.3 Lignin Liquefaction Chemistry | 81 | ||
| 4.2 Solvent Effects | 84 | ||
| 4.2.1 Base Catalyzed Depolymerization | 84 | ||
| 4.2.2 Hydrothermal Liquefaction (HTL) | 88 | ||
| 4.2.3 Polar Organic Media | 94 | ||
| 4.2.4 Hydrogen Donating Solvents | 99 | ||
| 4.3 Conclusion | 100 | ||
| References | 101 | ||
| Chapter 5 Early-stage Conversion of Lignin over Hydrogenation Catalysts | 108 | ||
| 5.1 Introduction | 108 | ||
| 5.2 Early-stage and Late-stage Catalytic Conversion of Lignin | 109 | ||
| 5.3 Deconstruction of Lignocellulose Based on ECCL | 111 | ||
| 5.4 Processes Taking Place in the Lignocellulosic Matrix | 113 | ||
| 5.5 Processes Occurring on Lignin Dissolved in the Liquor | 115 | ||
| 5.6 Catalytic Processes Involving the Lignin Species Dissolved in the Liquor | 119 | ||
| 5.7 Outlook | 122 | ||
| Acknowledgements | 123 | ||
| References | 124 | ||
| Chapter 6 Oxidative Valorization of Lignin | 128 | ||
| 6.1 Introduction | 128 | ||
| 6.2 Electron Flux through the Lignin Biosynthesis Pathway | 129 | ||
| 6.2.1 Electron Flux through the Shikimate Pathway and Phenyl propanoid Pathway | 130 | ||
| 6.2.2 Electron Flux through the Polymerization Process | 134 | ||
| 6.3 Rationale for Employing an Oxidative Approach | 135 | ||
| 6.4 Recent Advances in Catalytic Oxidation of Biorefinery Lignin | 136 | ||
| 6.5 Oxidative Cleavage of Inter-unit Linkages | 138 | ||
| 6.6 Oxidative Modification of Lignin Side-chain | 141 | ||
| 6.7 Oxidation of the Aromatic Ring and Ring Cleavage Reactions | 144 | ||
| 6.8 Conclusions and Future Perspective | 147 | ||
| References | 148 | ||
| Chapter 7 Catalytic Conversion of Lignin-derived Aromatic Compounds into Chemicals | 159 | ||
| 7.1 General Introduction | 159 | ||
| 7.1.1 Lignocellulosic Biomass in the Bioeconomy | 159 | ||
| 7.1.2 The Need for Lignin Valorization | 160 | ||
| 7.1.3 Lignin as a Source of Aromatics | 161 | ||
| 7.1.4 Lignin Biosynthesis, Structure and Considerations | 162 | ||
| 7.1.5 Challenges in Lignin-derived Aromatic Chemicals | 162 | ||
| 7.2 Catalytic Processing of Monomers from the Selective Depolymerization of Lignin | 165 | ||
| 7.2.1 Introduction – Simple Mixtures of Mono-aromatic Chemicals from Lignin | 165 | ||
| 7.2.2 4-(1-Propenyl)phenols | 167 | ||
| 7.2.3 4-Methylphenols | 169 | ||
| 7.2.4 4-Propylphenols | 172 | ||
| 7.2.5 3-Hydroxy-1-aryl-propanones | 174 | ||
| 7.2.6 Vanillin and Syringaldehyde | 177 | ||
| 7.2.7 Guaiacol and Syringol | 179 | ||
| 7.3 Lignin Pendent and End-groups as a Source of Renewable Aromatics | 180 | ||
| 7.3.1 Monolignol Plasticity in Lignification | 180 | ||
| 7.3.2 p-Hydroxybenzoates | 182 | ||
| 7.3.3 p-Coumaric Acid | 185 | ||
| 7.3.4 Tricin | 186 | ||
| 7.3.5 Non-aromatic Building Blocks: Muconic Acid and Its Derivatives | 187 | ||
| 7.3.6 Yields of Monomers Obtainable from Pendent Groups | 187 | ||
| 7.4 Conclusions | 188 | ||
| 7.4.1 Summary | 188 | ||
| 7.4.2 Product Functionality | 188 | ||
| 7.4.3 Challenges | 189 | ||
| 7.4.4 Outlook | 191 | ||
| Acknowledgements | 191 | ||
| References | 191 | ||
| Chapter 8 Biological Lignin Degradation | 199 | ||
| 8.1 Historical Perspective for Lignin Biodegradation Studies | 199 | ||
| 8.2 Fungal Degradation of Lignin: A Complex Multi-enzymatic Process | 200 | ||
| 8.3 Long-range Electron Transfer (LRET) Characterizes Ligninolytic Peroxidases | 205 | ||
| 8.4 Indirect Degradation of Lignin by Other Fungal Oxidoreductases | 207 | ||
| 8.5 Key Enzymes in Lignin Degradation as Revealed by Genomic Analyses | 208 | ||
| 8.6 Enzymatic Degradation of Lignin and Lignin Products by Bacteria | 209 | ||
| 8.7 Bacterial DyPs and Lignin Degradation | 210 | ||
| 8.8 Stereoselectivity in Lignin Decay: The Exception that Proves the Rule | 212 | ||
| 8.9 Lignin-degrading Enzymes in Lignocellulose Biorefineries | 213 | ||
| 8.10 Conclusion | 215 | ||
| Acknowledgements | 216 | ||
| References | 216 | ||
| Chapter 9 Bacterial Enzymes for the Cleavage of Lignin β-Aryl Ether Bonds: Properties and Applications | 226 | ||
| 9.1 Introduction | 226 | ||
| 9.2 Catabolic Pathway and Enzyme Genes for the Cleavage of β-Aryl Ether in Sphingobium sp. Strain SYK-6 | 228 | ||
| 9.3 Functions and Structures of β-Etherases | 233 | ||
| 9.4 Functions and Structures of Glutathione-removing Enzymes | 238 | ||
| 9.5 Functions and Structures of Ca-dehydrogenases | 239 | ||
| 9.6 β-Aryl Ether Catabolic Genes found in Recently Isolated Bacteria | 241 | ||
| 9.7 Applications of the β-Aryl Ether Catabolic System | 245 | ||
| 9.8 Concluding Remarks | 246 | ||
| References | 247 | ||
| Chapter 10 Using Aerobic Pathways for Aromatic Compound Degradation to Engineer Lignin Metabolism | 252 | ||
| 10.1 Pathway Discovery and Principles: A Historical Perspective | 252 | ||
| 10.1.1 The Devil in the Detail | 254 | ||
| 10.2 Lower-pathway Basics: Ortho (Intradiol), Meta (Extradiol), and Other Types of Ring Cleavage | 255 | ||
| 10.2.1 Catechol | 255 | ||
| 10.2.2 Protocatechuate | 258 | ||
| 10.2.3 Gallate | 261 | ||
| 10.2.4 3-O-Methylgallate | 261 | ||
| 10.2.5 Additional Entry Points to Lower Pathways | 262 | ||
| 10.3 Upper-pathway Diversity: Vastly Different Compounds Can be Funneled into the Lower Pathways | 263 | ||
| 10.3.1 What Are the Upper Pathways Most Relevant to Lignin Metabolism? | 264 | ||
| 10.3.2 Small Lignin Oligomers | 265 | ||
| 10.3.3 Syringaldehyde, Syringate, Vanillin, Vanillate, and Veratryl Alcohol | 266 | ||
| 10.3.4 Hydroxycinnamates: Ferulate, p-Coumarate, and Caffeate | 268 | ||
| 10.3.5 Guaiacol, Benzoate, and Phenol | 269 | ||
| 10.4 Transport | 269 | ||
| 10.4.1 ATP-binding Cassette Transport Systems | 270 | ||
| 10.4.2 Major Facilitator Superfamily Transporters | 270 | ||
| 10.4.3 Additional Proteins Involved in the Uptake of Aromatic Compounds | 271 | ||
| 10.5 Genetic Organization and Regulatory Control | 272 | ||
| 10.5.1 Genomic Clustering of Catabolic Genes | 272 | ||
| 10.5.2 Mobile Genetic Elements | 273 | ||
| 10.5.3 Transcriptional Regulation | 274 | ||
| 10.5.4 Global Control and Hierarchical Substrate Utilization | 275 | ||
| 10.6 Current and Future Directions for Aerobic Aromatic Compound Metabolism in Lignin Valorization | 276 | ||
| 10.6.1 Discovering New Metabolic Enzymes and Pathways in Nature | 277 | ||
| 10.6.2 Engineering, Design, and Evolution of New Pathways | 278 | ||
| 10.6.3 Enzyme Substrate Specificity and Catalytic Efficiency | 279 | ||
| 10.6.4 Choice of Platform Strain | 280 | ||
| Acknowledgements | 281 | ||
| References | 281 | ||
| Chapter 11 Biological Funneling as a Means of Transforming Lignin-derived Aromatic Compounds into Value-added Chemicals | 290 | ||
| 11.1 Introduction | 290 | ||
| 11.2 Applicability of Biological Funneling | 293 | ||
| 11.3 Convergent Catabolism of Aromatic Compounds | 294 | ||
| 11.4 Transport | 298 | ||
| 11.5 Bacterial Ligninases | 299 | ||
| 11.6 Chassis for Lignin-transforming Biocatalysts | 301 | ||
| 11.7 Biological Funneling | 302 | ||
| 11.8 Modeling Metabolism | 305 | ||
| 11.9 Genome-editing Tools | 307 | ||
| 11.10 Bioprospecting for New Activities | 307 | ||
| 11.11 Conclusion | 308 | ||
| References | 308 | ||
| Chapter 12 Systems Biology Analyses of Lignin Conversion | 314 | ||
| 12.1 Introduction | 314 | ||
| 12.2 Chemical Characteristics, Biodegradation, and Bioconversion of Lignin | 316 | ||
| 12.3 Genomics | 319 | ||
| 12.4 Transcriptomics | 323 | ||
| 12.5 Proteomics | 325 | ||
| 12.6 Metabolomics | 327 | ||
| 12.7 Concluding Remarks | 328 | ||
| Acknowledgements | 329 | ||
| References | 329 | ||
| Chapter 13 Anaerobic Pathways for the Catabolism of Aromatic Compounds | 333 | ||
| 13.1 Introduction | 333 | ||
| 13.2 Benzoyl-CoA Central Pathway | 337 | ||
| 13.2.1 Upper Benzoyl-CoA Pathway | 338 | ||
| 13.2.2 Lower Benzoyl-CoA Pathway | 343 | ||
| 13.3 Central Pathways for Degradation of Substituted Benzoyl-CoA Analogs | 344 | ||
| 13.3.1 3-Hydroxybenzoyl-CoA Catabolism | 344 | ||
| 13.3.2 3-Methylbenzoyl-CoA Catabolism | 345 | ||
| 13.3.3 4-Methylbenzoyl-CoA Catabolism | 345 | ||
| 13.4 Peripheral Pathways for the Anaerobic Catabolism of Aromatic Compounds | 347 | ||
| 13.4.1 Catabolism of Hydroxybenzoates | 347 | ||
| 13.4.2 Catabolism of Halobenzoates | 351 | ||
| 13.4.3 Catabolism of Aminobenzoates | 351 | ||
| 13.4.4 Catabolism of Phenylalanine/Phenylacetate | 352 | ||
| 13.4.5 Catabolism of Tyrosine/4-Hydroxyphenylacetate | 353 | ||
| 13.4.6 Catabolism of Tryptophan/Indoleacetate | 353 | ||
| 13.4.7 Catabolism of Phenylpropanoids | 355 | ||
| 13.4.8 Catabolism of Aromatic Alcohols | 356 | ||
| 13.4.9 Catabolism of Phenolic Compounds | 357 | ||
| 13.4.10 Catabolism of Phthalates | 360 | ||
| 13.4.11 Catabolism of Aromatic Hydrocarbons | 361 | ||
| 13.5 Anaerobic Degradation of Aromatic Compounds with meta-Positioned Hydroxyl Groups | 369 | ||
| 13.5.1 Catabolism of Resorcinol and Resorcylates | 369 | ||
| 13.5.2 Catabolism of Trihydroxybenzenes: Pyrogallol, Phloroglucinol, and HHQ | 372 | ||
| 13.6 Systems Biology View of the Anaerobic Catabolism of Aromatic Compounds | 372 | ||
| 13.6.1 The Metabolic Response | 373 | ||
| 13.6.2 The Stress Response | 375 | ||
| 13.6.3 The Social Response | 377 | ||
| 13.7 Applications Derived from the Anaerobic Catabolism of Aromatic Compounds | 378 | ||
| 13.7.1 Molecular Biomarkers | 378 | ||
| 13.7.2 Bioreporter Strains | 379 | ||
| 13.7.3 Bioremediation and Bioconversion Processes | 379 | ||
| 13.7.4 Molecular Evolution Studies and Development of New Regulatory Circuits | 380 | ||
| 13.8 Outlook | 381 | ||
| Acknowledgements | 383 | ||
| References | 383 | ||
| Chapter 14 Biogas Production from Lignin via Anaerobic Digestion | 391 | ||
| 14.1 Introduction | 391 | ||
| 14.1.1 Biorefineries and Lignin-rich Residues | 391 | ||
| 14.1.2 Anaerobic Digestion | 392 | ||
| 14.2 Biogas from Lignin Building Blocks | 399 | ||
| 14.3 Biogas from Polymeric and Oligomeric Lignin | 400 | ||
| 14.4 Methods for Enhancing Biogas Production from Lignin | 401 | ||
| 14.5 Inhibitory effect of Lignin-derived Aromatic Compounds on Microbial Community | 405 | ||
| 14.6 Conclusion | 406 | ||
| Acknowledgements | 407 | ||
| References | 407 | ||
| Chapter 15 Lignin Analytics | 413 | ||
| 15.1 Introduction | 413 | ||
| 15.1.1 General Aspects of Lignin Formationand Function In Planta, Lignin Structure and Lignin Analytics | 414 | ||
| 15.2 Analysis of Non-isolated Lignins | 419 | ||
| 15.2.1 Current Mainstream Analyses | 419 | ||
| 15.3 Analysis of Isolated Lignins | 423 | ||
| 15.3.1 Types of Isolated Lignins | 423 | ||
| 15.3.2 Analysis of Isolated Lignins | 426 | ||
| 15.4 Fractionated and Depolymerized Lignins | 450 | ||
| 15.4.1 Strategies for Lignin Fractionation | 451 | ||
| 15.4.2 Strategies for Lignin Depolymerization | 451 | ||
| 15.4.3 Analysis Methods for Depolymerized Lignins | 454 | ||
| 15.5 In Silico Considerations Regarding Isolated and Non-isolated Lignins | 454 | ||
| 15.6 Conclusion | 455 | ||
| Conflicts of Interest | 456 | ||
| References | 456 | ||
| Chapter 16 Lignin Visualization: Advanced Microscopy Techniques for Lignin Characterization | 477 | ||
| 16.1 Background | 477 | ||
| 16.1.1 Lignin's Multifaceted Role in Plant Cell Walls | 477 | ||
| 16.1.2 Models of Lignin Distribution and Interactions with Other CellWall Polymers | 478 | ||
| 16.1.3 Tracking the Fate of Lignin Biomass Conversion | 479 | ||
| 16.2 Current Tools for Lignin Visualization and Localization | 481 | ||
| 16.2.1 Cytochemical Stains Used to LocalizeLignin for Visualization by Optical Microscopy | 482 | ||
| 16.2.2 Antibodies for Immuno-localization of Lignin Epitopes | 483 | ||
| 16.2.3 Direct Fluorescent Labeling Monolignols and Chemical Reporter Approaches | 485 | ||
| 16.2.4 Spectroscopic Tools for Detecting Lignins | 487 | ||
| 16.3 Challenges and Future Prospects | 490 | ||
| 16.3.1 3D Microscopy | 491 | ||
| 16.3.2 Imaging Mass Spectroscopy | 493 | ||
| 16.3.3 Label-free Super Resolution Microscopy | 493 | ||
| 16.4 Conclusions | 494 | ||
| Acknowledgements | 494 | ||
| References | 494 | ||
| Chapter 17 Adding Value to the Biorefinery with Lignin: An Engineer's Perspective | 499 | ||
| 17.1 Introduction | 499 | ||
| 17.2 Techno-economic Analyses: The Motivation and Approach | 501 | ||
| 17.3 Lignin Utilization | 504 | ||
| 17.3.1 Conversion of Lignin into Steam and Electricity: Challenges and Opportunities | 504 | ||
| 17.3.2 Conversion of Lignin into Solid Fuels: Challenges and Opportunities | 506 | ||
| 17.3.3 Conversion of Lignin into Value Added Products: Challenges and Opportunities | 506 | ||
| 17.4 Case Study: Illustrative TEA for the Conversion of Lignin into Adipic Acid | 508 | ||
| 17.5 Summary | 513 | ||
| Acknowledgements | 513 | ||
| References | 514 | ||
| Subject Index | 519 |