Catalytic Process Development for Renewable Materials

This handbook and ready reference is the first to combine the fields of high throughput experimentation and catalytic process development for biobased materials in industry. It describes the entire workflow from idea, approach, research, and process development, right up to commercialization by application of advanced methodologies and technologies. A large part of the book is devoted to the use of such advanced technologies as high throughput experimentation and equipment, as well as to reactor and process design models, with a wide selection of real life examples included at each stage. The contributions are from authors at leading companies, providing first-hand information and knowledge that is hard to find elsewhere.

Table of Contents:
The Next Feedstock Transition XIII Preface XV List of Contributors XVII 1 The Industrial Playing Field for the Conversion of Biomass to Renewable Fuels and Chemicals 1 Leo E. Manzer, Jan Cornelis van der Waal, and Pieter Imhof 1.1 Introduction 1 1.2 The Renewables Arena 2 1.3 Renewable Fuels 9 1.4 Renewable Chemicals 18 1.5 Conclusions 22 References 22 2 Selecting Targets 25 Gene Petersen, Joseph Bozell, and James White 2.1 Introduction 25 2.2 Target Selection Can Focus on Specifi c Structures or General Technologies 28 2.3 Previous Selection Efforts 29 2.4 Corroboration of the Value of Screening Studies 37 2.5 The Importance of Outcomes and Comparisons of Outcomes 38 2.6 Evaluation Processes Can be Comprised of a Variety of Criteria 40 2.6.1 Feedstock and Intermediate Availability 40 2.6.2 Existing Biorefining Infrastructure Dictates Chemical or Biochemical Processes to be Evaluated 41 2.6.3 Market Drivers 42 2.6.4 R&D Drivers 44 2.6.5 Other Screening Opportunities 44 2.6.6 Other Portfolio Opportunities - Biomass Produced Oils 45 2.7 Catalysis Aspects 46 2.8 Conclusions 48 References 48 3 The Development of Catalytic Processes from Terpenes to Chemicals 51 Derek McPhee 3.1 Introduction 51 3.2 Strain Engineering for the Production of Terpenes 52 3.3 Terpene Building Blocks of Commercial Interest 55 3.4 Sesquiterpenes as Chemical Building Blocks: beta-Farnesene 56 3.5 Polymers 58 3.5.1 Differential Scanning Calorimetry 63 3.5.2 Gel Permeation Chromatography 63 3.5.3 Thermal Gravimetric Analysis 64 3.5.4 Tensile Strength 65 3.6 Lubricants 66 3.7 Conclusions 75 References 76 4 Furan-Based Building Blocks from Carbohydrates 81 Robert-Jan van Putten, Ana Sousa Dias, and Ed de Jong 4.1 Importance of Furans as Building Blocks 81 4.2 Sources of Carbohydrates 82 4.2.1 Storage Carbohydrates 82 4.2.1.1 Sucrose 82 4.2.1.2 Starch 84 4.2.1.3 Inulin 84 4.2.2 Structural Carbohydrates 84 4.2.2.1 Cellulose 87 4.2.2.2 Hemicelluloses 87 4.2.3 Aquatic Carbohydrates 90 4.2.3.1 Macroalgae 91 4.2.3.2 Brown Macroalgae 91 4.2.3.3 Microalgae 91 4.2.3.4 Green Algae 92 4.2.4 Conclusions on Carbohydrate Feedstocks 92 4.3 Carbohydrate Dehydration 92 4.3.1 Introduction 92 4.3.2 Commercial Furfural Production and Applications 93 4.3.3 Furfural Formation from Pentose Feedstock 95 4.3.4 Production Systems of Furfural 99 4.3.5 Heterogeneous Catalysts 101 4.3.6 5-Hydroxymethylfurfural Formation from Hexose Feedstock 105 4.4 Conclusions and Further Perspectives 110 References 111 5 A Workflow for Process Design - Using Parallel Reactor Equipment Beyond Screening 119 Erik-Jan Ras 5.1 Introduction 119 5.2 The Evolution of Parallel Reactor Equipment 120 5.3 The Evolution of Research Methodology - Conceptual Process Design 121 5.4 Essential Workfl ow Elements 126 5.4.1 Catalyst Testing Equipment 126 5.4.2 Kinetics and Pseudo-Kinetics 129 5.4.3 Statistical Design of Experiments 130 5.4.4 Data Analysis 136 5.4.5 Example of PCA Applied to Catalysis 137 5.4.6 Example of PLS Applied to Diesel Properties 141 5.5 Other Examples of Parallel Reactor Equipment Applied Beyond Screening - Long-Term Catalyst Performance 143 5.6 Concluding Remarks 147 References 147 6 Braskem's Ethanol to Polyethylene Process Development 149 Paulo Luiz de Andrade Coutinho, Augusto Teruo Morita, Luis F. Cassinelli, Antonio Morschbacker, and Roberto Werneck Do Carmo 6.1 Introduction 149 6.1.1 Overview of Braskem Activities and History 149 6.1.2 Why Renewable Polymers and Why Green Polyethylene? 149 6.2 Ethanol and Brazil 150 6.3 Commercial Plants for Ethanol Dehydration 152 6.3.1 Salgema 100 kty Plant 152 6.3.2 Triunfo 200 kty Plant 153 6.3.3 MEG Plants 154 6.3.4 Announced Renewable Polymer Projects 155 6.4 Legislation and Certifi cation 155 6.4.1 Ethanol Suppliers Code of Conduct 155 6.5 Process Description 156 6.5.1 Reaction 156 6.5.1.1 Catalysts 157 6.5.1.2 Side Reactions 158 6.5.1.3 Fixed Bed, Isothermal Reaction 159 6.5.1.4 Fixed Bed, Adiabatic Reaction 159 6.5.1.5 Fluidized Bed Reaction 160 6.5.2 Removal of Impurities 161 6.5.2.1 Unreacted Ethanol and Oxygenates 161 6.5.2.2 CO2 and Acids 161 6.5.3 Ethylene Purification 161 6.6 Polymerization 162 6.7 Conclusion 162 Acknowledgments 162 References 163 7 Fats and Oils as Raw Material for the Chemical Industry 167 Aalbert (Bart) Zwijnenburg 7.1 Introduction - Setting the Scene, Definitions 167 7.2 Why Fats and Oils Need Catalytic Transformation 168 7.2.1 Carboxylic Acids 168 7.2.2 Alcohols 168 7.2.3 Amines and Amides 168 7.2.4 Esters 168 7.3 Catalytic Process Development - Conceptual 171 7.3.1 Biology or Chemical Routes? 171 7.3.2 How to Select between Slurry and Fixed-Bed Operations? 172 7.3.3 How to Choose between Nickel and Palladium? 174 7.4 Fatty Alcohols: Then and Now, a Case Study 175 7.4.1 Catalyst Selection 176 7.4.2 Slurry versus Fixed-Bed Processes 177 7.5 Conclusion and Outlook: Development Challenges for the Future 178 References 179 8 Production of Aromatic Chemicals from Biobased Feedstock 183 David Dodds and Bob Humphreys 8.1 Introduction 183 8.2 Chemical Routes to Aromatic Chemicals from Biomass 184 8.2.1 Process Chemistry 186 8.2.1.1 Pyrolysis 186 8.2.1.2 Hydrogenation and Hydrogenolysis 186 8.2.1.3 Catalytic Reforming 188 8.2.1.4 Zeolite Treatment 188 8.2.2 Technology Examples 189 8.2.2.1 Conversion of Biomass-Derived Sugars to Aromatics including BTX 189 8.2.2.2 Pyrolysis of Solid Biomass to Aromatic Chemicals 190 8.2.2.3 Upgrading Bio-Oils to Aromatics 192 8.2.2.4 Aromatic Chemicals from Other Renewable Raw Materials 192 8.2.3 Summary 193 8.3 Biological Routes to Specifi c Aromatic Chemicals 194 8.3.1 PTA via PX 194 8.3.1.1 PX via Isobutanol and Isobutylene 194 8.3.1.2 Valine Pathway to Isobutylene 194 8.3.1.3 Direct Biological Isobutylene Production 196 8.3.1.4 Biological Oxidation of PX to PTA 198 8.3.2 Aromatics via HMF Production 198 8.3.2.1 Preparation of PTA via HMF 200 8.3.2.2 Yield Summary of HMF Routes to PTA 202 8.3.3 Limonene to PTA 203 8.3.4 The Common Aromatic Pathway 203 8.3.4.1 Background 203 8.3.4.2 Other Aromatic Compounds from the Common Aromatic Pathway 210 8.3.5 Other Routes to Aromatic Compounds 215 8.3.5.1 Tetrahydroxybenzene and Pyrogallol 215 8.3.5.2 Phloroglucinol 217 8.3.5.3 Chalcones, Stilbenes, Vanillin and Lignans 217 8.4 Lignin - The Last Frontier 220 8.5 Considerations for Scale-Up and Commercialization 222 8.6 Conclusion 224 References 224 9 Organosolv Biorefining: Creating Higher Value from Biomass 239 E. Kendall Pye and Michael Rushton 9.1 Introduction 239 9.2 Concepts and Principles of Biorefinery Technologies 241 9.2.1 Types of Biorefineries for Biomass Processing 241 9.2.1.1 Biorefineries Employing Thermochemical Treatment of Biomass 242 9.2.1.2 Biorefineries Using Physical and Chemical Pretreatment with Biochemical Processing 243 9.3 Catalytic Processes Employed in Biorefi ning 245 9.3.1 Catalysis in Biorefineries Employing Gasifi cation and Pyrolysis 245 9.3.2 Catalysts in Anaerobic Digestion Biorefineries 246 9.3.2.1 Catalysts in Non-Thermochemical Biorefineries 246 9.4 An Organosolv Biorefinery Process for High-Value Products 247 9.4.1 Guiding Principles of the Lignol Organosolv Biorefinery 250 9.4.2 Applications and Markets for Organosolv Biorefinery Products 251 9.4.2.1 Native Lignin - Its Properties and Composition 251 9.4.2.2 Lignin from Other Processes 251 9.4.2.3 HP-L(TM) Lignin - Organosolv Lignin from the Lignol Biorefinery 252 9.4.2.4 Lignin Derivatives 252 9.4.3 HP-L Lignin Properties 253 9.4.4 Current Applications and Market Opportunities for HP-L Lignin 253 9.4.4.1 New Product Opportunities for Lignin Derivatives 254 9.4.4.2 Market Drivers for Commercial Use of HP-L Lignin and Other Bio-Products 256 9.4.4.3 Application Strategies for the Lignol Biorefinery Process 257 9.4.4.4 Development of the Lignol Biorefinery Process 258 9.5 Conclusions 260 References 261 10 Biomass-to-Liquids by the Fischer-Tropsch Process 265 Erling Rytter, Esther Ochoa-Fernandez, and Adil Fahmi 10.1 Basics of Fischer-Tropsch Chemistry and BTL 265 10.1.1 The FT History and Drivers 265 10.1.2 Reactions 266 10.1.3 Mechanisms and Kinetics 268 10.1.4 Products 269 10.1.5 Fischer-Tropsch Metals 270 10.1.6 The Biomass-to-Liquid FT Concept 271 10.2 Cobalt Fischer-Tropsch Catalysis 272 10.2.1 Catalyst Preparation and Activation 272 10.2.2 Catalyst Activity 274 10.2.3 Selectivity 275 10.2.4 Activity Loss 276 10.2.5 Commercial Formulations 277 10.3 Fischer-Tropsch Reactors 279 10.3.1 Reactor Selection 279 10.3.2 Tubular Fixed-Bed 279 10.3.3 Slurry Bubble Column 280 10.4 Biomass Pretreatment and Gasification 282 10.4.1 Pretreatment of Biomass 282 10.4.2 Biomass Gasifi cation 284 10.4.3 Entrained-Flow Gasifi er 286 10.4.4 Fluidized-Bed Gasifi er 287 10.4.5 Plasma Gasifi er 288 10.4.6 Gasification Pilot and Demonstration Projects 288 10.4.6.1 Entrained-Flow Gasifiers 290 10.4.6.2 Fluidized-Bed Gasifiers 291 10.4.6.3 Plasma Gasifiers 291 10.4.6.4 Steam Reforming 292 10.4.7 Syngas Composition 292 10.5 Biomass-to-Liquids Process Concepts 293 10.5.1 Example of Process Flow-Sheet 293 10.5.2 Gas Conditioning and Clean-Up 294 10.5.3 BTL Mass and Energy Balance 295 10.5.4 CO2 Management 298 10.5.5 Upgrading and Products 299 10.5.6 Production Cost 300 10.6 BTL Pilot and Demonstration Plants 301 10.7 XTL Energy and Carbon Efficiencies 303 10.8 BTL Summary and Outlook 304 References 305 11 Catalytic Transformation of Extractives 309 Paivi Maki-Arvela, Irina L. Simakova, Tapio Salmi, and Dmitry Yu. Murzin 11.1 Introduction 309 11.2 Fine and Special Chemicals from Crude Tall Oil Compounds 313 11.2.1 Sitosterol Hydrogenation and Its Application in Food as a Cholesterol-Suppressing Agent 313 11.3 Fine and Special Chemicals from Turpentine Compounds 317 11.3.1 Isomerization of Monoterpenes and Their Derivatives 317 11.3.2 Oxidation of Monoterpenes 327 11.3.3 Hydrogenation of Monoterpenes 329 11.3.4 Epoxidation of Monoterpenes 330 11.3.5 Hydration of Monoterpenes 332 11.3.6 Esterification and Etherification of Monoterpenes 333 11.3.7 Aldol Condensation of Monoterpene Derivatives 334 11.4 Conclusions 335 11.5 Acknowledgment 336 References 336 12 Environmental Assessment of Novel Catalytic Processes Based on Renewable Raw Materials - Case Study for Furanics 341 Martin K. Patel, Aloysius J.J.E. Eerhart, and Deger Saygin 12.1 Introduction 341 12.2 Energy Savings by Catalytic Processes 343 12.3 LCA Methodology 346 12.4 Case Study: Energy Analysis and GHG Balance of Polyethylene Furandicarboxylate (PEF) as a Potential Replacement for Polyethylene Terephthalate (PET) 348 12.5 Discussion and Conclusions 352 References 352 13 Carbon Dioxide: A Valuable Source of Carbon for Chemicals, Fuels and Materials 355 Michele Aresta and Angela Dibenedetto 13.1 Introduction 355 13.2 The Conditions for Industrial Use of CO2 356 13.2.1 Environmental Issue 356 13.2.2 Energy Issues 357 13.2.3 Economic Issues 359 13.3 Carbon Dioxide Conversion 359 13.3.1 Carbonates 359 13.3.1.1 Organic Molecular Compounds 360 13.3.1.2 Synthesis of Acyclic Carbonates via Carboxylation of Alcohols 361 13.3.1.3 Synthesis of Carbonates via Transesterifi cation or Alcoholysis of Urea 364 13.3.1.4 Synthesis of Cyclic Carbonates and Polymers 365 13.3.2 Carbamates and Polyurethanes 366 13.3.2.1 Synthesis of Molecular Carbamates 366 13.3.2.2 Indirect Synthesis of Carbamates 369 13.4 Energy Products from CO2 371 13.5 Production of Inorganic Carbonates 373 13.6 Enhanced Fixation of CO2 into Aquatic Biomass 374 13.7 Conclusion and Future Outlook 378 References 379 Index 387

About the Author :
Dr. Pieter Imhof is currently VP Strategic Account Management at Avantium Chemicals B.V., after having held several positions in Research and Development, Technical Service, Marketing and Product Development both at Akzo Nobel Catalysts and Albemarle. Within Avantium, Pieter has been responsible for Global Business Development, Sales and Marketing for high throughput services and systems in both Chemical and Pharmaceutical Industry. Pieter obtained his M.Sc. and Ph.D degrees in Organometallic and Coordination Chemistry at the University of Amsterdam. He has published and contributed to over 100 scientific and conference papers and patents. Dr. Jan Cornelis van der Waal is Principal Scientist at Avantium Chemicals B.V. He studied Chemical Engineering at the Delft University of Technology (1987-1993) and received his Ph.D. at the same institute in 1998. After a postdoctoral assignment at the Royal Dutch Shell research and technology centre in Amsterdam for 2 years, he was involved in the foundation of Avantium Chemicals in 2000 and has since then worked for Avantium Technologies. Currently he is Principal Scientist Catalysts covering the area of biorenewable feedstocks conversion, in particular of oxygenates such as sugars, syn gas chemistries such as Fischer-Tropsch, Methanol and Ethanol synthesis, as well as selective oxidations and hydrogenations. He has published over 60 scientific and conference papers and patents.

Review :
"Overall, especially for an edited book, this is a well organized book showing the overall story, rather than giving only pieces of a puzzle ... It makes for an entertaining read. The book is certainly more suited to researchers in the field or at least with some background information." (Green Processing and Synthesis, 1 August 2013)