Direct Thermochemical Liquefaction for Energy Applications

Description

Direct Thermochemical Liquefaction for Energy Applications presents the state-of-the-art of the value chains associated with these biomass conversion technologies. It covers multiple feedstock availability and feedstock composition impact on process chemistry and product quality and composition. Expert authors from around the world explore co-processing benefits, process parameters, implementation and scaling, upgrading to drop-in liquid biofuels or integration into existing petrochemical refinery infrastructure.

Finally, these topics are put into a sustainability perspective by establishing an LCA framework for this type of process. Its focus on implementation based on the most comprehensive knowledge makes this book particularly useful for researchers and graduate students from all sorts of background working in the field of biomass and biofuels. It is also a valuable reference for engineers working to commercialize DTL technologies, engineering specialists designing process equipment, refinery professionals and developers.

Focuses on implementation and scaling of direct thermochemical liquefaction technologies for biomass conversion into biofuels
Covers the state-of-the-art of the technologies, as well as technical and sustainability implementation aspects
Includes new approaches and concepts developed around the world within the different DTL technologies

Front Cover 2
Direct Thermochemical Liquefaction for Energy Applications 5
Copyright 6
Contents 7
List of contributors 11
Preface 13
- References 15
Part One Pyrolysis 17
- 1 Fast pyrolysis 19
  - 1.1 Introduction 19
    - 1.1.1 Background 19
    - 1.1.2 Process 19
  - 1.2 Fast pyrolysis products 24
    - 1.2.1 Bio-oil 24
      - 1.2.1.1 Bio-oil properties 25

Front Cover 2
Direct Thermochemical Liquefaction for Energy Applications 5
Copyright 6
Contents 7
List of contributors 11
Preface 13
- References 15
Part One Pyrolysis 17
- 1 Fast pyrolysis 19
  - 1.1 Introduction 19
    - 1.1.1 Background 19
    - 1.1.2 Process 19
  - 1.2 Fast pyrolysis products 24
    - 1.2.1 Bio-oil 24
      - 1.2.1.1 Bio-oil properties 25
      - 1.2.1.2 Application of bio-oil 26
    - 1.2.2 Char 27
    - 1.2.3 Gas 27
  - 1.3 Parameters affecting pyrolysis products 28
    - 1.3.1 Feedstock composition 28
      - 1.3.1.1 Water 28
      - 1.3.1.2 Cellulose, hemicellulose and lignin 28
      - 1.3.1.4 Inorganics 29
      - 1.3.1.3 Extractives 29
    - 1.3.2 Feedstock pretreatment 29
      - 1.3.2.1 Physical pretreatment 29
      - 1.3.2.2 Chemical pretreatment 30
      - 1.3.2.3 Thermal pretreatment 30
      - 1.3.2.4 Biological pretreatment 31
    - 1.3.3 Pyrolysis temperature 31
    - 1.3.5 Carrier gas 32
    - 1.3.6 Char separation 32
    - 1.3.4 Vapour residence time 32
  - 1.4 Bio-oil upgrading options 33
    - 1.4.1 Hot vapour filtration 33
    - 1.4.2 Solvent addition 33
    - 1.4.3 Catalytic upgrading 34
  - 1.5 Examples of plants/implementation 36
  - 1.6 Conclusions and recommendation 37
  - References 39
- 2 Catalytic pyrolysis 45
  - 2.1 Introduction 45
    - 2.1.1 Background 45
    - 2.1.2 Mode of catalysis 45
    - 2.1.3 Catalytic pyrolysis reactor 47
  - 2.2 Mechanism of catalytic reactions 49
  - 2.3 Effect of feedstock composition 50
    - 2.3.1 Cellulose, hemicellulose and lignin 50
    - 2.3.2 Inorganics 51
    - 2.3.3 Feedstock pretreatment 51
  - 2.4 Types of catalysts 52
    - 2.4.2 ZSM-5 based catalysts 53
    - 2.4.1 Zeolite 53
    - 2.4.3 Zeolite-like catalysts 56
    - 2.4.5 Natural minerals 59
    - 2.4.4 Metal oxides 59
  - 2.5 Catalyst properties 60
    - 2.5.1 Shape selectivity 60
    - 2.5.2 Acidity 61
    - 2.5.3 Pore size 62
    - 2.5.4 Catalyst pretreatment and calcination 63
    - 2.5.5 Catalyst deactivation 63
    - 2.5.6 Catalyst regeneration 65
  - 2.6 Effect of process parameters 65
    - 2.6.1 Efeect of catalyst position 65
    - 2.6.2 Catalyst temperature 66
    - 2.6.3 WHSV or catalyst contact time 67
    - 2.6.5 Environment or carrier gas 68
    - 2.6.4 Biomass-to-catalyst ratio 68
    - 2.6.6 Liquid collection 69
  - 2.7 Catalytic pyrolysis products 70
  - 2.8 Conclusions 71
  - References 71
- Part Two Hydrothermal Liquefaction 81
  - 3 Recent advances in energy recovery from wastewater sludge 83
    - 3.1 Introduction 83
      - 3.1.1 Wastewater sludge management 84
    - 3.2 Bio-oil production from wastewater sludge through HTL 86
      - 3.2.1 Fundamentals of HTL 86
      - 3.2.2 Effects operating conditions on HTL of biomass 88
        
        3.2.2.1 Effects of type and composition of feedstock 88
        
        3.2.2.2 Effects of catalyst 90
        
        3.2.2.3 Effects of reaction temperature 91
        
        3.2.2.4 Effects of residence time 91
        
        3.2.2.5 Effects of water to biomass ratio 92
      - 3.2.3 HTL of wastewater sludge 92
      - 3.2.4 HTL of biomass in continuous operation processes 93
      - 3.2.5 HTL of biomass in pilot or demonstration scale 94
    - 3.3 Biogas production from wastewater sludge through anaerobic digestion 96
      - 3.3.1 Effects of thermal pre-treatment 99
      - 3.3.2 Effects of chemical pre-treatment 101
        
        3.3.2.2 Alkali pre-treatment 104
        
        3.3.2.1 Acid pre-treatment 104
        
        3.3.2.3 Ozonation 106
        
        3.3.2.4 Oxidation processes 106
      - 3.3.3 Combined thermal and chemical pre-treatment 106
      - 3.3.4 Mechanical pre-treatment 110
    - 3.4 Concluding remarks 110
    - Acknowledgements 111
    - References 111
  - 4 Hydrothermal liquefaction of aquatic Feedstocks 117
    - 4.1 Aquatic biomass in a hydrothermal liquefaction context 117
    - 4.2 Conversion characteristics, effect of process parameters on major product properties 120
      - 4.2.1 Aquatic HTL conceptual layout 120
      - 4.2.2 Process parameter optimisation 121
      - 4.2.3 Effect of species 124
      - 4.2.4 Catalysis 127
    - 4.3 Utilisation and composition of product streams 128
      - 4.3.1 Bio-crude 128
      - 4.3.2 Upgraded bio-crude 130
      - 4.3.3 Water phase 131
    - 4.4 Outlook and economic and environmental assessment 135
    - References 138
  - 5 Hydrothermal liquefaction of protein-containing feedstocks 143
    - 5.1 Pretreatment of feedstocks 143
    - 5.2 HTL process (yields, CHN & HHV, light oil fraction, functional groups) 147
      - 5.2.1 Feedstock type 147
      - 5.2.2 Process mode 153
      - 5.2.3 Process conditions 154
      - 5.2.4 Catalysis 157
      - 5.2.5 HTL products separation 159
    - 5.3 Characterization of HTL products 160
      - 5.3.1 Biocrude oil 160
        
        5.3.1.1 Elemental analyses and heating value 160
        
        5.3.1.2 TGA, Sim-Dist, GPC, and SEC analyses 162
        
        5.3.1.3 Chemical composition 163
        
        5.3.1.4 Potential value-added products 163
      - 5.3.2 Aqueous product 164
        
        5.3.2.1 Chemical composition 164
        
        5.3.2.2 Treatments on PHWW 167
      - 5.3.3 Gas products 168
      - 5.3.4 Solid residue 169
    - 5.4 HTL Reaction mechanism 169
    - 5.5 Upgrading of HTL biocrude 171
    - 5.6 Continuous HTL reactor development 172
    - References 175
    - Further reading 184
  - 6 Recipe-based co-HTL of biomass and organic waste 185
    - 6.1 Synergistic biomass mixing effects for continuous liquefaction 185
    - 6.2 Coliquefaction with algae 186
      - 6.2.1 Microalgae and lignocellulosic biomass 186
      - 6.2.2 Microalgae and macroalgae 189
      - 6.2.3 Microalgae and swine manure 191
    - 6.3 Coliquefaction with crude glycerol 194
      - 6.3.1 Crude glycerol and aspen wood 194
      - 6.3.2 Crude glycerol and straw 196
      - 6.3.3 Crude glycerol and swine manure 197
    - 6.4 Coliquefaction of lignocellulosic biomass with synthetic plastics 199
    - 6.5 Coliquefaction of various biomasses 201
      - 6.5.1 Pulp/paper-mill sludge and waste newspaper 201
      - 6.5.2 Spent coffee grounds with lignocellulosic biomass 201
    - References 204
  - Part Three Downstream processing 207
    - 7 Stabilisation of pyrolysis oils 209
      - 7.1 Introduction 209
        
        7.1.2 Background 209
        
        7.1.1 Motivation 209
        
        7.1.3 Status 210
        
        7.1.3.1 Bio-oil history 210
        
        7.1.3.2 Processes 213
        
        7.1.3.3 Applications 215
        
        7.1.4 Bio-oil instability and the challenge of stabilisation 215
        
        7.1.5 Reference stability of conventional fuels 217
      - 7.2 Stability relevant properties of pyrolysis oils 219
        
        7.2.1 General introduction 219
        
        7.2.2 Analysis 220
        
        7.2.2.2 Water content 221
        
        7.2.2.1 Chemical composition 221
        
        7.2.2.3 Oxygen content 222
        
        7.2.2.4 Viscosity 222
        
        7.2.2.7 Acidity 223
        
        7.2.2.5 Aromatics and average molecular weight (ave-Mr) 223
        
        7.2.2.8 Heating value 223
        
        7.2.2.6 Carbonyls 223
        
        7.2.2.10 Flash point 224
        
        7.2.2.11 Ash content 224
        
        7.2.2.9 Pour point 224
        
        7.2.2.12 Char content 225
        
        7.3 Chemistry of bio-oil self-transformations 225
        
        7.3.2 Detailing chemistry of bio-oil instability 225
        
        7.3.2.1 General behaviour 225
        
        7.3.2.2 Specific reactions 229
        
        7.3.2.2.1 Off gases 230
        
        7.3.2.2.4 Aldehyde homopolymerization 230
        
        7.3.2.2.2 Esterification 230
        
        7.3.2.2.5 Hydration 230
        
        7.3.2.2.3 Transesterification 230
        
        7.3.2.2.6 Hemiacetal formation 231
        
        7.3.2.2.7 Transacetalization 231
        
        7.3.2.2.8 Phenol/aldehyde reactions and resins 231
        
        7.3.2.2.9 Polymerisation of furan derivatives 232
        
        7.3.2.2.12 Condensation of olefinics 232
        
        7.3.2.2.10 Sulphur containing compounds 232
        
        7.3.2.2.13 Air oxidation 232
        
        7.3.2.2.11 Alcohol addition 232
        
        7.3.2.2.14 Gas forming reactions 233
        
        7.3.2.2.15 Hydrogen 233
        
        7.3.2.3 Stability issues 233
        
        7.3.2.3.1 Oxidative bio-oil stability 234
        
        7.3.2.3.2 Accelerated ageing studies 234
        
        7.4 Stabilisation methods 236
        
        7.4.1 General 236
        
        7.4.2 Chemical (Reactive) stabilisation 236
        
        7.4.2.1 Esterification 236
        
        7.4.2.2 Catalytic cracking 238
        
        7.4.2.3 Hydrotreatment (HT) 240
        
        7.4.2.4 Hybrid methods 242
        
        7.4.3 Thermal stabilisation 243
        
        7.4.3.1 Pyrolysis optimization schemes (Noncatalytic) 243
        
        7.4.3.2 Supercritical (H2O, CO2, alcohols) 244
        
        7.4.3.3 Biomass co-pyrolysis 247
        
        7.4.3.4 High-pressure homogenization (HPH) 248
        
        7.4.4 Physical (Nonreactive) stabilisation 248
        
        7.4.4.1 Introduction 248
        
        7.4.4.2 Addition of solvents and chemicals 249
        
        7.4.4.3 Antioxidants 250
        
        7.4.4.4 Char and inorganics removal 250
        
        7.4.4.5 Emulsification 251
        
        7.4.4.6 Fractionation 251
        
        7.4.4.7 Filtration 252
        
        7.4.4.8 Microwave and Plasma 253
        
        7.5 Conclusions and outlook 253
        
        7.5.1 Hybrid solutions 254
        
        7.5.2 Hydrogen 254
        
        7.5.3 Integration strategies 254
        
        7.5.4 Catalytic solutions 255
        
        References 255
        
        Further reading 263
        
        8 Recent developments in the catalytic hydrotreatment of pyrolysis liquids 265
        
        8.1 Introduction 265
        
        8.2 Fast pyrolysis technology 267
        
        8.3 The composition of PLs 269
        
        8.4 Properties of PLs 271
        
        8.4.1 Acidity of PLs 271
        
        8.4.2 Heating value of PLs 273
        
        8.4.3 Stability of PLs 275
        
        8.5 Characterisation of PLs by solvent fractionation 276
        
        8.6 Biorefinery concepts for PLs 277
        
        8.7 Catalytic hydrotreatment 279
        
        8.8.1 Reactor configurations 280
        
        8.7.2 Chemical reactions during catalytic hydrotreatment 282
        
        8.7.3 Reactivity of various component classes in PLs 284
        
        8.7.4 Application of product oils from catalytic hydrotreatment reactions 284
        
        8.8 Catalysts development for the catalytic hydrotreatment of PLs 286
        
        8.8.1 Noble metal based catalysts 286
        
        8.8.1.1 Studies in batch set-ups 287
        
        8.8.1.2 Studies in continuous set-ups 291
        
        8.8.2 Nonnoble-metal based catalysts 292
        
        8.8.3 Catalytic hydrotreatment of PLs in solvents 296
        
        8.8.3.1 Reactions in batch 298
        
        8.8.3.2 Studies in continuous set-ups 302
        
        8.9 Conclusions 302
        
        References 303
        
        Further Reading 308
        
        9 Coprocessing of pyrolysis oil in refineries 309
        
        9.1 Introduction 309
        
        9.1.1 The coprocessing approach: Integration in the existing refineries 310
        
        9.2 Coprocessing in fluid catalytic crackers (co-FCC) 312
        
        9.2.1 Catalytic deoxygenation and synergetic effects 314
        
        9.2.2 Co-FCC of different types of bio-oils 316
        
        9.2.2.1 Hydrodeoxygenated oil (HDO) 316
        
        9.2.2.2 Catalytic pyrolysis oil (CPO) 319
        
        9.2.2.3 Thermal fast pyrolysis oil (FPO) 321
        
        9.2.3 The amount of renewable carbon in the co-FCC product 323
        
        9.3 Cohydrotreating 325
        
        9.3.1 Process understanding: Tests with model compounds 326
        
        9.3.2 Cohydrotreating of pyrolysis oil 327
        
        9.4 Challenges and perspectives 328
        
        9.4.1 The extent of pretreatment 328
        
        9.4.2 Enhancing the production of middle distillates 329
        
        9.4.3 The potential of hydrothermal liquefaction oils 330
        
        9.5 Conclusions 330
        
        References 331
        
        Further reading 333
        
        10 Hydrofaction™ of forestry residues to drop-in renewable transportation fuels 335
        
        10.1 Introduction 335
        
        10.1.1 Forestry residues as feedstock 336
        
        10.2 The Hydrofaction™ process 337
        
        10.2.1 Supercritical HTL (first stage) 338
        
        10.2.1.1 Feed preparation 339
        
        10.2.1.2 Pressurization and heating 339
        
        10.2.1.5 Separation and water treatment 341
        
        10.2.1.3 Reactors 341
        
        10.2.1.6 Summary of HTL pilot operation data (first stage) 341
        
        10.2.1.4 Cooling and pressure reduction 341
        
        10.2.1.7 Effect of feedstock on renewable crude oil quality (first stage) 342
        
        10.2.2 Upgrading to drop-in biofuels (second stage) 345
        
        10.2.2.1 Experimental procedure, Hydrotreating studies (second stage) 346
        
        10.2.2.2 Continuous reactor system 346
        
        10.2.2.5 Nonsulphided catalysts 347
        
        10.2.2.3 Batch reactor system 347
        
        10.2.2.6 Results: Hydrotreatment using a sulphided catalyst (second stage) 347
        
        10.2.2.4 Sulphided catalysts 347
        
        10.2.2.7 Results: Two-zone upgrading using nonsulphided catalyst (second stage) 351
        
        10.3 Life cycle GHG emissions of Hydrofaction™ 353
        
        10.4 Conclusion 358
        
        Acknowledgements 358
        
        References 359
        
        Index 363
        
        Back Cover 373
        
        7.3.1 General introduction 225

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