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Book Details
Abstract
Fast pyrolysis and related catalytic pyrolysis are of increasing interest as pathways to advanced biofuels that closely mimic traditional petroleum products. Research has moved from empirical investigations to more fundamental studies of pyrolysis mechanisms. Theories on the chemical and physical pathways from plant polymers to pyrolysis products have proliferated as a result.
This book brings together the latest developments in pyrolysis science and technology. It examines, reviews and challenges the unresolved and sometimes controversial questions about pyrolysis, helping advance the understanding of this important technology and stimulating discussion on the various competing theories of thermal deconstruction of plant polymers. Beginning with an introduction to the biomass-to-biofuels process via fast pyrolysis and catalytic pyrolysis, chapters address prominent questions such as whether free radicals or concerted reactions dominate deconstruction reactions. Finally, the book concludes with an economic analysis of fast pyrolysis versus catalytic pyrolysis.
This book will be of interest to advanced students and researchers interested in the science behind renewable fuel technology, and particularly the thermochemical processing of biomass.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Fast Pyrolysis of Biomass: Advances in Science and Technology | i | ||
| Acknowledgements | vii | ||
| Contents | ix | ||
| Chapter 1 - Prospects for Fast Pyrolysis of Biomass | 1 | ||
| 1.1 Introduction | 1 | ||
| 1.2 Biomass Fast Pyrolysis Technology | 3 | ||
| 1.2.1 Basic Concepts | 3 | ||
| 1.2.2 Fast Pyrolysis Feedstock | 3 | ||
| 1.2.3 Types of Fast Pyrolysis Reactors | 4 | ||
| 1.2.4 Bio-Oil from Fast Pyrolysis | 6 | ||
| 1.3 Recent Advances in Fast Pyrolysis Research and Development | 6 | ||
| 1.3.1 Reaction Chemistry of Fast Pyrolysis | 7 | ||
| 1.3.2 Computational Modeling of Fast Pyrolysis | 8 | ||
| 1.3.3 Utilization of Bio-Oil | 8 | ||
| 1.3.4 Catalytic Fast Pyrolysis | 9 | ||
| 1.3.5 Economics of Fast Pyrolysis | 10 | ||
| References | 10 | ||
| Chapter 2 - Primary Reactions of Cellulose Pyrolysis | 12 | ||
| 2.1 Introduction | 12 | ||
| 2.2 Thermal Conditions of Cellulose Pyrolysis4 | 13 | ||
| 2.2.1 Experimental and Conceptual Difficulties in the Accurate Knowledges of T and T′ | 13 | ||
| 2.2.2 Unclear Frontiers Between SP and FP | 14 | ||
| 2.2.3 Modeling of Solid Particle Pyrolysis | 14 | ||
| 2.2.4 Summary and Foreword | 15 | ||
| 2.3 Primary Cellulose Pyrolysis | 15 | ||
| 2.3.1 Research Prior to the Mid-1960s | 15 | ||
| 2.3.2 First Qualitative Evidence of the Formation of Liquid Products During Cellulose Pyrolysis Between the Mid-1960s and Mid-197... | 16 | ||
| 2.3.3 First Kinetic and Chemical Interpretations Published Before the Mid-1980s | 16 | ||
| 2.3.4 Developments from the Mid-1980s to Mid-1990s | 18 | ||
| 2.3.5 New Results, Controversies and Models Published from the 1990s, Until the Beginning of the 2000s | 19 | ||
| 2.3.6 New Results Published After the Beginning of the 2000s | 23 | ||
| 2.4 Current Understanding of Cellulose Pyrolysis | 28 | ||
| 2.5 Conclusions | 30 | ||
| Glossary | 31 | ||
| References | 31 | ||
| Chapter 3 - Lignin Depolymerization/Deconstruction Reactions During Fast Pyrolysis | 37 | ||
| 3.1 Introduction | 37 | ||
| 3.2 Thermal Degradation Behavior of Various Lignins | 41 | ||
| 3.3 Lignin Depolymerization/Deconstruction by Analytical Pyrolysis | 43 | ||
| 3.4 Continuous Fast Pyrolysis of Lignin | 46 | ||
| 3.5 Chemical Properties of Lignin-Derived Oil | 49 | ||
| 3.6 Catalytic Pyrolysis of Lignin | 50 | ||
| 3.7 Conclusion | 53 | ||
| References | 54 | ||
| Chapter 4 - Transport and Secondary Reactions of Depolymerized/Deconstructed Species | 57 | ||
| 4.1 Introduction | 57 | ||
| 4.2 Transport and Secondary Reactions of Cellulose Pyrolysis Products | 58 | ||
| 4.3 Transport and Secondary Reactions of Lignin Pyrolysis Products | 64 | ||
| 4.4 Interactions Among Cellulose- and Lignin-Derived Pyrolysis Products | 68 | ||
| 4.5 Transport of Products During Biomass Pyrolysis | 70 | ||
| 4.6 Conclusion | 74 | ||
| References | 74 | ||
| Chapter 5 - Catalytic Biomass Pyrolysis with Reactive Gases | 78 | ||
| 5.1 Introduction | 78 | ||
| 5.2 Model Compound Studies | 80 | ||
| 5.2.1 Deoxygenation Reaction Pathways | 80 | ||
| 5.2.2 Catalyst Development | 81 | ||
| 5.3 Biomass Pyrolysis in Reactive Gases | 84 | ||
| 5.3.1 Batch Pyrolysis: Micro-Scale Py-GC-MS Studies | 84 | ||
| 5.3.2 Continuous Biomass Feed: Laboratory-Scale Reactor Studies | 86 | ||
| 5.4 Discussion | 89 | ||
| 5.5 Summary and Future Work | 91 | ||
| References | 92 | ||
| Chapter 6 - Characterization and Separation of Bio-Oil | 96 | ||
| 6.1 Introduction | 96 | ||
| 6.2 Bio-Oil Properties | 97 | ||
| 6.3 Characterization of the Bio-Oil | 99 | ||
| 6.4 Characterization of Bio-Oil After Separation | 104 | ||
| 6.4.1 Importance of Separation in the Bio-Oil Characterization | 104 | ||
| 6.4.2 Membrane Separation and Centrifugation | 105 | ||
| 6.4.3 Extraction and Column Chromatography | 105 | ||
| 6.4.4 Distillation | 109 | ||
| 6.5 Characterization of Bio-Oil After Derivatization | 111 | ||
| 6.5.1 Acetylation of Phenolic Compounds | 111 | ||
| 6.5.2 Trimethylsilylation of Sugars | 112 | ||
| 6.5.3 Other Derivatization Methods | 112 | ||
| 6.6 Conclusion | 112 | ||
| Acknowledgements | 113 | ||
| References | 113 | ||
| Chapter 7 - Role of Free Radicals in Fast Pyrolysis | 117 | ||
| 7.1 Introduction | 117 | ||
| 7.2 Free Radicals in General Organic Chemistry | 119 | ||
| 7.2.1 Stability of Free Radicals | 119 | ||
| 7.2.2 Elementary Radical Reactions | 119 | ||
| 7.2.3 Magnetic Properties of Radicals | 120 | ||
| 7.3 Free Radicals in Fast Pyrolysis of Biomass | 121 | ||
| 7.3.1 Free Radicals in Lignin Pyrolysis | 121 | ||
| 7.3.1.1 Study on Pyrolysis of Lignin Model Compounds | 121 | ||
| 7.3.1.2 Study on Pyrolysis of Lignin and Lignin-Derived Bio-Oil | 125 | ||
| 7.3.2 Study on Pyrolysis of Cellulose | 127 | ||
| 7.3.3 Study on Pyrolysis of Biomass and Bio-Oil Analysis | 128 | ||
| 7.3.4 Detection of Free Radicals in Biochar and Their Impact on Soil Application | 130 | ||
| 7.4 Potential Role of Free Radicals in Condensed-Phase Polymerization | 131 | ||
| 7.5 Free Radicals in Catalytic Pyrolysis | 133 | ||
| 7.6 Future Research and Opportunities | 134 | ||
| 7.7 Chapter Summary | 134 | ||
| References | 135 | ||
| Chapter 8 - Bio-Oil Stabilization | 138 | ||
| 8.1 Introduction | 138 | ||
| 8.2 Physico-Chemical Composition of Bio-Oil | 139 | ||
| 8.3 Aging | 139 | ||
| 8.4 Stability Indicators | 144 | ||
| 8.5 Phase Separation | 146 | ||
| 8.6 Stabilization | 147 | ||
| 8.6.1 Removal of Alkali Metals that Catalyse Aging Reactions | 148 | ||
| 8.6.1.1 Removal of Alkali Metals from Feedstock40–43 | 148 | ||
| 8.6.1.2 Removal of Alkali Metals by Hot Vapour Filtration9,10,15 | 148 | ||
| 8.6.1.3 Removal of Alkali Metals by Post-Processing | 149 | ||
| 8.6.2 Torrefaction | 149 | ||
| 8.6.3 Effect of Solvent Addition | 150 | ||
| 8.6.4 Esterification, Acetalization | 150 | ||
| 8.6.5 Stabilizing Bio-Oil with Antioxidants | 151 | ||
| 8.6.6 Transfer Hydrogenation | 152 | ||
| 8.6.7 Catalytic Hydrotreatment | 153 | ||
| 8.6.8 Miscellaneous | 154 | ||
| 8.7 Conclusion | 154 | ||
| References | 155 | ||
| Chapter 9 - Extraction of Value-Added Chemicals from Bio-Oil Products | 160 | ||
| 9.1 Introduction | 160 | ||
| 9.2 Equilibrium-Based Separation | 161 | ||
| 9.2.1 Distillation | 161 | ||
| 9.2.1.1 Ordinary Distillation | 161 | ||
| 9.2.1.2 Fractional Distillation | 161 | ||
| 9.2.1.3 Molecular Distillation (Short Path Distillation) | 162 | ||
| 9.2.1.4 Vacuum Distillation | 166 | ||
| 9.2.1.5 Azeotropic Distillation | 166 | ||
| 9.2.1.6 Extractive Distillation | 166 | ||
| 9.2.1.7 Steam Distillation | 167 | ||
| 9.2.2 Liquid–Liquid Extraction | 168 | ||
| 9.2.2.1 Introduction | 168 | ||
| 9.2.2.2 Polarity-Based Separations | 169 | ||
| 9.2.2.2.1\rExtraction with Organic Solvents and Liquid CO2.Extraction of whole bio-oil with solvents of different polarity is rarely descri... | 169 | ||
| 9.2.2.2.2\rExtraction with Water and Organic Solvents.Many of the solvent-based extraction methods first start with a separation into water... | 172 | ||
| 9.2.2.2.3\rExtraction with Supercritical CO2.Supercritical fluids, especially CO2, are widely used in the extraction of natural matter, suc... | 177 | ||
| 9.2.2.2.4\rExtraction with Switchable Hydrophilicity Solvents (SHS).Removal of solvents from products by distillation is a common industria... | 181 | ||
| 9.2.2.3 Separations Based Upon Salt Formation | 183 | ||
| 9.3 Affinity-Based Separation | 187 | ||
| 9.3.1 Adsorption – Desorption | 187 | ||
| 9.3.1.1 Introduction | 187 | ||
| 9.3.1.2 Open-Column Chromatography (Sequential Elution by Solvents Chromatography, SESC) | 187 | ||
| 9.3.1.3 Solid-Phase Extraction | 190 | ||
| 9.4 Fractional Condensation | 191 | ||
| 9.5 Industrial Processes | 193 | ||
| 9.6 Conclusions | 195 | ||
| References | 195 | ||
| Chapter 10 - Catalytic Fast Pyrolysis Over Zeolites† | 200 | ||
| 10.1 Introduction | 200 | ||
| 10.2 Process Conditions for CFP of Biomass | 205 | ||
| 10.2.1 Choice of the Biomass Feedstock | 205 | ||
| 10.2.2 Key Process Parameters | 206 | ||
| 10.2.2.1 Temperature | 206 | ||
| 10.2.2.2 Heating Rate and Residence Time of Biomass | 206 | ||
| 10.2.2.3 Catalyst-to-Biomass Ratio | 207 | ||
| 10.2.2.4 Vapor Residence Time | 207 | ||
| 10.2.2.5 In situ vs. Ex situ Catalytic Pyrolysis | 208 | ||
| 10.2.3 Reactors and Setups Used for CFP of Biomass | 209 | ||
| 10.2.3.1 Analytical Reactors (µg- and mg-Scale) | 209 | ||
| 10.2.3.2 Bench- and Pilot-Scale Reactors (g to kg Scale) | 210 | ||
| 10.2.3.3 PDU’s and (Semi-)Commercial Process Units (kg to t Scale) | 212 | ||
| 10.2.4 Catalysts Used in CFP of Biomass | 213 | ||
| 10.3 Reported Results of Continuous CFP of Woody Biomass Over Zeolites | 214 | ||
| 10.4 Discussion and Further Outlook | 224 | ||
| References | 226 | ||
| Chapter 11 - Simulating Biomass Fast Pyrolysis at the Single Particle Scale | 231 | ||
| 11.1 Introduction | 231 | ||
| 11.2 Overview of Biomass Structure | 233 | ||
| 11.3 Representing the Microstructure, Morphology, and Material Properties of Biomass in Particle Models | 235 | ||
| 11.4 Simulating Intra-Particle Transport Phenomena | 238 | ||
| 11.4.1 Governing Equations for Transport | 238 | ||
| 11.4.2 Finite Element Simulations | 239 | ||
| 11.5 Simulating Particle-Scale Reactions | 240 | ||
| 11.6 Approaches for Low-Order Particle Models | 246 | ||
| 11.6.1 1-D Heat Transfer Approximations | 246 | ||
| 11.6.2 Combining 1-D Heat Transfer and Reaction | 248 | ||
| 11.7 Current Limitations in Particle-Scale Modeling | 248 | ||
| 11.8 Conclusions | 250 | ||
| References | 251 | ||
| Chapter 12 - Economic Comparison of Various Pathways to Pyrolysis-Based Fuels | 254 | ||
| 12.1 Introduction | 254 | ||
| 12.2 Pathway Economics | 256 | ||
| 12.2.1 Fast Pyrolysis and Fluidized Catalytic Cracking of Bio-Oil | 256 | ||
| 12.2.2 Fast Pyrolysis and ex situ Vapor-Phase Catalytic Upgrading | 257 | ||
| 12.2.3 Fast Pyrolysis and Bio-Oil Hydroprocessing | 258 | ||
| 12.2.4 In situ Catalytic Pyrolysis and Bio-Oil Hydroprocessing | 260 | ||
| 12.2.5 Hydropyrolysis and Vapor-Phase Hydroprocessing | 261 | ||
| 12.2.6 Slow Pyrolysis and Syngas Upgrading | 262 | ||
| 12.2.7 Gasification of Bio-Oil and Syngas Upgrading | 262 | ||
| 12.3 Pathway Comparisons | 263 | ||
| 12.4 Deterministic versus Stochastic Analyses | 266 | ||
| 12.5 Conclusions | 269 | ||
| References | 270 | ||
| Subject Index | 273 |