Editors’s Preface XXXIII

Foreword XXXVHenning Hopf

Foreword XXXVIIPaul T. Anastas

List of Contributors XXXIX

Volume 1

Part I Background and Outline – Principles and Fundamentals

1 Biorefinery Systems – An Overview 3Birgit Kamm, Michael Kamm, Patrick R. Gruber, and Stefan Kromus

1.1 Introduction 31.2 Historical Outline 41.2.1 Historical Technological Outline and Industrial Resources 41.2.2 The Beginning – A Digest 51.2.2.1 Sugar Production 51.2.2.2 Starch Hydrolysis 51.2.2.3 Wood Saccharification 51.2.2.4 Furfural 61.2.2.5 Cellulose and Pulp 61.2.2.6 Levulinic Acid 61.2.2.7 Lipids 71.2.2.8 Vanillin from Lignin 71.2.2.9 Lactic Acid 71.2.3 The Origins of Integrated Biobased Production 81.3 Situation 11

V

Biorefineries – Industrial Processes and Products. Status Quo and Future Directions.Edited by Birgit Kamm, Patrick R. Gruber, Michael KammCopyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-32953-3

Contents

1.3.1 Some Current Aspects of Biorefinery Researchand Development 11

1.3.2 Raw Material Biomass 121.3.3 National Vision and Goals and Plan for Biomass Technology

in the United States 141.3.4 Vision and Goals and Plan for Biomass Technology in the

European Union and Germany 151.4 Principles of Biorefineries 161.4.1 Fundamentals 161.4.2 Definition of the Term “Biorefinery” 191.4.3 The Role of Biotechnology 201.4.3.1 Guidelines of Fermentation Section within Glucose-product

Family Tree 211.4.4 Building Blocks, Chemicals and Potential Screening 221.5 Biorefinery Systems and Design 231.5.1 Introduction 231.5.2 Lignocellulosic Feedstock Biorefinery 241.5.3 Whole-crop Biorefinery 261.5.4 Green Biorefinery 291.5.5 Two-platform Concept and Syngas 311.6 Outlook and Perspectives 32

References 33

2 Biomass Refining Global Impact –The Biobased Economy of the 21st Century 41Bruce E. Dale and Seungdo Kim

2.1 Introduction 412.2 Historical Outline 422.2.1 Background and Development of the Fossil Carbon-processing

Industries 422.2.2 The Existing Biobased Economy: Renewable Carbon 432.2.3 Toward a Much Larger Biobased Economy 442.3 Supplying the Biorefinery 452.3.1 What Raw Materials do Biorefineries Require and What Products

Can They Make? 452.3.2 Comparing Biomass Feedstock Costs With Petroleum Costs 482.3.3 How Much Biomass Feedstock Can be Provided at What Cost? 502.4 How Will Biorefineries Develop Technologically? 532.4.1 Product Yield: The Dominant Technoeconomic Factor 532.4.2 Product Diversification: Using the Whole Barrel of Biomass 542.4.3 Process Development and a Technical Prerequisite

for Cellulosic Biorefineries 552.5 Sustainability of Integrated Biorefining Systems 562.5.1 Integrated Biorefining Systems: “All Biomass is Local” 56

ContentsVI

2.5.2 Agricultural/Forestry Ecosystem Modeling: New Tools for an Ageof Sustainability 57

2.5.3 Analyzing the Sustainability of Integrated Biorefining Systems:Some Results 60

2.6 Conclusions 64Acknowledgements 65References 65

3 Development of Biorefineries –Technical and Economic Considerations 67Bill Dean, Tim Dodge, Fernando Valle, and Gopal Chotani

3.1 Introduction 673.2 Overview: The Biorefinery Model 683.3 Feedstock and Conversion to Fermentable Sugar 683.3.1 Sucrose 703.3.2 Starch 703.3.3 Cellulose 713.4 Technical Challenges 743.4.1 Cellulase Enzymes 743.4.1.1 Improved Cellulase Production Economics 743.4.1.2 Improved Cellulase Enzyme Performance 763.4.2 Fermentation Organisms 773.4.2.1 Biomass Hydrolyzate as Fermentable Carbon Source 783.4.2.2 Production Process as a Whole 793.4.2.3 Emerging Solutions 803.5 Conclusions 81

Acknowledgments 82References 82

4 Biorefineries for the Chemical Industry –A Dutch Point of View 85Ed de Jong, René van Ree Rea, Robert van Tuil, and Wolter Elbersen

4.1 Introduction 854.2 Historical Outline – The Chemical Industry: Current Situation and

Perspectives 864.2.1 Overview of Products and Markets 864.2.2 Technological Pathways 874.2.3 Biomass-based Industrial Products 874.2.3.1 Carbohydrates 894.2.3.2 Fatty Acids 904.2.3.3 Other 914.2.4 International Perspectives 924.2.4.1 Production 924.2.4.2 Integration 924.2.4.3 Use and Re-use 93

Contents VII

4.3 Biomass: Technology and Sustainability 934.3.1 Transition to a Bio-based Industry: Sectoral Integration

in the Netherlands 934.3.2 Can Sustainability Drive Technology? 964.4 The Chemical Industry: Biomass Opportunities – Biorefineries 974.4.1 Biomass Opportunities 974.4.2 Biorefinery Concept 984.4.3 Biomass Availability 1004.4.4 Primary Refinery 1014.4.5 Secondary Thermochemical Refinery 1024.4.6 Secondary Biochemical Refinery – Fermentative Processes 1044.4.6.1 Feedstocks 1054.4.6.2 Product Spectrum 1054.4.6.3 Side Streams and Recycling 1064.5 Conclusions, Outlook, and Perspectives 1064.5.1 Biomass – Sustainability 1064.5.2 Biomass Refining and Pretreatment 1074.5.3 Conversion Technology 1084.5.4 Chemicals and Materials Design 1084.5.5 Dutch Energy Research Strategy (“EOS”) 109

References 109

Part II Biorefinery Systems

Lignocellulose Feedstock Biorefinery

5 The Lignocellulosic Biorefinery –A Strategy for Returning to a Sustainable Source of Fuelsand Industrial Organic Chemicals 115L. Davis Clements and Donald L. Van Dyne

5.1 The Situation 1155.2 The Strategy 1155.2.1 A Strategy Within a Strategy 1165.2.2 Environmental Benefits 1175.2.3 The Business Structure 1175.2.4 Cost Estimates 1185.3 Comparison of Petroleum and Biomass Chemistry 1185.3.1 Petroleum Resources 1185.3.2 Biomass Resources 1195.3.3 Saccharides and Polysaccharides 1215.3.4 Lignin 1215.3.5 Triacylglycerides (or Triglycerides) 1215.3.6 Proteins 1225.4 The Chemistry of the Lignocellulosic Biorefinery 1225.5 Examples of Integrated Biorefinery Applications 125

ContentsVIII

5.5.1 Production of Ethanol and Furfural from LignocellulosicFeedstocks 125

5.5.2 Management of Municipal Solid Waste 1255.5.3 Coupling MSW Management, Ethanol, and Biodiesel 1265.6 Summary 127

References 127

6 Lignocellulosic Feedstock Biorefinery:History and Plant Development for Biomass Hydrolysis 129Raphael Katzen and Daniel J. Schell

6.1 Introduction 1296.2 Hydrolysis of Biomass Materials 1296.2.1 Acid Conversion 1296.2.2 Enzymatic Conversion 1306.3 Acid Hydrolysis Processes 1306.3.1 Early Efforts to Produce Ethanol 1306.3.2 Other Products 1336.4 Enzymatic Hydrolysis Process 1346.4.1 Early History 1346.4.2 Enzyme-Based Plant Development 1346.4.3 Technology Development 1356.5 Conclusion 136

References 136

7 The Biofine Process – Production of Levulinic Acid, Furfural,and Formic Acid from Lignocellulosic Feedstocks 139Daniel J. Hayes, Steve Fitzpatrick, Michael H.B. Hayes,and Julian R.H. Ross

7.1 Introduction 1397.2 Lignocellulosic Fractionation 1397.2.1 Acid Hydrolysis of Polysaccharides 1417.2.2 Production of Levulinic Acid, Formic Acid and Furfural 1427.3 The Biofine Process 1447.3.1 Yields and Efficiencies of the Biofine Process 1457.3.2 Advantages over Conventional Lignocellulosic Technology 1467.3.3 Products of The Biofine Process 1477.3.3.1 Diphenolic Acid 1487.3.3.2 Succinic Acid and Derivatives 1497.3.3.3 Delta-aminolevulinic Acid 1497.3.3.4 Methyltetrahydrofuran 1507.3.3.5 Ethyl Levulinate 1527.3.3.6 Formic Acid 1537.3.3.7 Furfural 1547.3.4 Biofine Char 1557.3.5 Economics of The Biofine Process 158

Contents IX

7.4 Conclusion 161References 162

Whole Crop Biorefinery

8 A Whole Crop Biorefinery System:A Closed System for the Manufacture of Non-food Productsfrom Cereals 165Apostolis A. Koutinas, Rouhang Wang, Grant M. Campbell, and Colin Webb

8.1 Intro 1658.2 Biorefineries Based on Wheat 1678.2.1 Wheat Structure and Composition 1678.2.2 Secondary Processing of Wheat Flour Milling Byproducts 1698.2.3 Advanced Wheat Separation Processes for Food and Non-food

Applications 1738.2.3.1 Pearling as an Advanced Cereal Fractionation Technology 1738.2.3.2 Air Classification 1768.2.4 Biorefinery Based on Novel Dry Fractionation Processes

of Wheat 1768.2.4.1 Potential Value-added Byproducts from Wheat Bran-rich

Fractions 1788.2.4.2 Exploitation of the Pearled Wheat Kernel 1808.3 A Biorefinery Based on Oats 1838.3.1 Oat Structure and Composition 1838.3.2 Layout of a Potential Oat-based Fractionation Process 1838.3.2.1 Potential Value-added Byproducts from Oat Bran-rich Fractions 1858.4 Summary 187

References 187

Fuel-oriented Biorefineries

9 Iogen’s Demonstration Process for Producing Ethanolfrom Cellulosic Biomass 193Jeffrey S. Tolan

9.1 Introduction 1939.2 Process Overview 1939.3 Feedstock Selection 1949.3.1 Feedstock Composition 1949.3.2 Feedstock Selection 1969.3.3 Ethanol from Starch or Sucrose 1979.3.4 Advantages of Making Ethanol from Cellulosic Biomass 1979.4 Pretreatment 1989.4.1 Process 1989.4.2 Chemical Reactions 1989.4.3 Other Pretreatment Processes 199

ContentsX

9.5 Cellulase Enzyme Production 2019.5.1 Production of Cellulase Enzymes 2019.5.2 Enzyme Production on the Ethanol Plant Site 2029.5.3 Commercial Status of Cellulase 2029.6 Cellulose Hydrolysis 2029.6.1 Process Description 2029.6.2 Kinetics of Cellulose Hydrolysis 2039.6.3 Improvements in Enzymatic Hydrolysis 2059.7 Lignin Processing 2059.7.1 Process Description 2059.7.2 Alternative Uses for Lignin 2069.8 Sugar Fermentation and Ethanol Recovery 206

References 207

10 Sugar-based Biorefinery –Technology for Integrated Productionof Poly(3-hydroxybutyrate), Sugar, and Ethanol 209Carlos Eduardo Vaz Rossell, Paulo E. Mantelatto, José A.M. Agnelli,and Jefter Nascimento

10.1 Introduction 20910.2 Sugar Cane Agro Industry in Brazil – Historical Outline 20910.2.1 Sugar and Ethanol Production 20910.2.2 The Sugar Cane Agroindustry and the Green Cycle 21010.3 Biodegradable Plastics from Sugar Cane 21210.3.1 Poly(3-Hydroxybutyric Acid) 21210.3.1.1 Biodegradable Plastics and the Environment 21210.3.1.2 General Aspects of Biodegradability 21310.3.2 Poly(3-Hydroxybutyric Acid) Polymer 21410.3.2.1 General Characteristics of Poly(3-hydroxybutyric Acid)

and its Copolymer Poly(3-hydroxybutyric Acid-co-3-hydroxyvaleric Acid) 214

10.3.2.2 Processing of Poly(Hydroxybutyrates) 21510.4 Poly(3-Hydroxybutyric Acid) Production Process 21710.4.1 Sugar Fermentation to Poly(3-Hydroxybutyric Acid)

by Ralstonia eutropha 21710.4.2 Downstream Processing for Recovery and Purification of Intracellular

Poly(3-Hydroxybutyric Acid) 21810.4.2.1 Processes for Extraction and Purification

of Poly(hydroxyalkanoates) 21810.4.2.2 Chemical Digestion 21810.4.2.3 Enzymatic Digestion 21910.4.2.4 Solvent Extraction 21910.4.3 Integration of Poly(3-Hydroxybutyric Acid) Production

in a Sugar Mill 221

Contents XI

10.4.4 Investment and Production Cost of Poly(3-Hydroxybutyric Acid)in a Sugar Mill 222

10.5 Outlook and Perspectives 223References 225

Biorefineries Based on Thermochemical Processing

11 Biomass Refineries Based on HybridThermochemical-Biological Processing – An Overview 227Robert C. Brown

11.1 Introduction 22711.2 Historical Outline 22811.2.1 Origins of Biorefineries Based on Syngas Fermentation 22811.2.2 Origins of Biorefineries Based on Fermentation of Bio-oils 22911.3 Gasification-Based Systems 23011.3.1 Fundamentals of Gasification 23011.3.2 Fermentation of Syngas 23311.3.2.1 Production of Organic Acids 23411.3.2.2 Production of Alcohols 23511.3.2.3 Production of Polyesters 23611.3.3 Biorefinery Based on Syngas Fermentation 23911.3.4 Enabling Technology 24011.4 Fast Pyrolysis-based Systems 24111.4.1 Fundamentals of Fast Pyrolysis 24111.4.2 Fermentation of Bio-oils 24411.4.3 Biorefineries Based on Fast Pyroylsis 24611.4.4 Enabling Technologies 24811.5 Outlook and Perspectives 249

References 250

Green Biorefineries

12 The Green Biorefiner Concept – Fundamentals and Potential 253Stefan Kromus, Birgit Kamm, Michael Kamm, Paul Fowler,and Michael Narodoslawsky

12.1 Introduction 25312.2 Historical Outline 25412.2.1 The Inceptions 25412.2.2 First Production of Leaf Protein Concentrate 25412.2.3 First Production of Leaf Dyes 25712.3 Green Biorefinery Raw Materials 25812.3.1 Raw Materials 25812.3.2 Availability of Grassland Feedstocks for Large-scale Green

Biorefineries 25912.3.3 Key Components of Green and Forage Grasses 260

ContentsXII

12.3.3.1 Structural Cell Wall Constituents 26012.3.3.2 Cell Contents 26512.4 Green Biorefinery Concept 26912.4.1 Fundamentals and Status Quo 26912.4.2 Wet Fractionation and Primary Refinery 27112.5 Processes and Products 27312.5.1 The Juice Fraction 27312.5.1.1 Green Juice 27312.5.2 GJ Drinks/Alternative Life 27512.5.2.1 Silage Juice 27612.5.3 Ingredients and Specialties 27712.5.3.1 Proteins/Polysacharides 27712.5.3.2 Cholesterol Mediation 27712.5.3.3 Antifeedants 27712.5.3.4 Silica 27712.5.3.5 Silicon Carbide 27812.5.3.6 Filter Aids 27812.5.3.7 Zeolites 27812.5.4 The Press-Cake (Fiber) Fraction 27812.5.4.1 Fibers 28012.5.4.2 Chemicals 28212.5.4.3 Residue Utilization 28312.6 Green Biorefinery – Economic and Ecological Aspects 28312.7 Outlook and Perspectives 285

Acknowledgment 285References 285

13 Plant Juice in the Biorefinery –Use of Plant Juice as Fermentation Medium 295Margrethe Andersen, Pauli Kiel, and Mette Hedegaard Thomsen

13.1 Introduction 29513.2 Historical Outline 29513.3 Biobased Poly(lactic Acid) 29613.3.1 Fermentation Processes 29613.3.2 The Green Biorefinery 29613.3.3 Lactic Acid Fermentation 29813.3.4 Brown Juice as a Fermentation Medium 29813.4 Materials and Methods 29913.4.1 Analytical Methods 29913.4.1.1 Sugar Analysis 29913.4.1.2 Analysis of Organic Acids 29913.4.1.3 Analysis of Minerals 29913.4.1.4 Analysis of Vitamins 29913.4.1.5 Analysis of Amino Acids 29913.4.1.6 Analysis of Protein 299

Contents XIII

13.4.2 Fed Batch Fermentation of Brown Juice with Lb. salivariusBC 1001 299

13.4.3 Pilot Scale Continuous Fermentation with Lb. salivariusBC 1001 300

13.4.4 Study of Potato Juice Quality During Aerobicand Anaerobic Storage 300

13.5 Brown Juice 30013.5.1 Chemical Composition 30013.5.2 Seasonal Variations 30213.5.3 Lactic Acid Fermentation of Brown Juice 30513.5.4 The Green Crop-drying Industry as a Lactic Acid Producer 30613.6 Potato Juice 30913.6.1 Potato Juice as Fermentation Medium 30913.6.2 The Potato Starch Industry as Lactic Acid Producer 31013.7 Carbohydrate Source 31113.8 Purification of Lactic Acid 31213.9 Conclusion and Outlook 313

Acknowledgments 313References 313

Part III Biomass Production and Primary Biorefineries

14 Biomass Commercialization and Agriculture Residue Collection 317James Hettenhaus

14.1 Introduction 31714.2 Historical Outline 31814.2.1 Case Study: Harlan, Iowa Corn Stover Collection Project 31914.2.2 Case Study: Bagasse Storage – Dry or Wet? 32114.2.2.1 Dry Storage 32114.2.2.2 Wet Storage 32314.3 Biomass Value 32414.3.1 Soil Quality 32414.3.2 Farmer Value 32514.3.3 Processor Value 32714.4 Sustainable Removal 32814.4.1 Soil Organic Material 32814.4.2 Soil Erosion Control 32914.4.3 Cover Crops 33114.5 Innovative Methods for Collection, Storage and Transport 33214.5.1 Collection 33214.5.1.1 Baling 33314.5.1.2 One-pass Collection 33314.5.2 Storage 33414.5.2.1 Density 33514.5.2.2 Storage Area 335

ContentsXIV

14.5.2.3 Storage Loss 33514.5.2.4 Foreign Matter and Solubles 33714.5.2.5 Storage Investment 33714.5.3 Transport 33714.5.3.1 Harvest Transport 33814.5.3.2 Biorefinery Supply 33814.6 Establishing Feedstock Supply 33914.6.1 Infrastructure 34014.6.1.1 Infrastructure Investment 34014.6.1.2 Organization Infrastructure 34014.7 Perspectives and Outlook 341

References 342

15 The Corn Wet Milling and Corn Dry Milling Industry –A Base for Biorefinery Technology Developments 345Donald L. Johnson

15.1 Introduction 34515.1.1 Corn – Wet and Dry Milling – Existing Biorefineries 34515.2 The Corn Refinery 34615.2.1 Wet Mill Refinery 34615.2.2 Dry Mill Refinery 34615.2.3 Waste Water Treatment 34715.3 The Modern Corn Refinery 34815.3.1 Background and Definition 34815.3.2 Technologies and Products 34815.3.3 Refinery Economy 35015.3.3.1 Refinery Economy of Scale and Location Considerations 35015.4 Carbohydrate Refining 35115.5 Outlook and Perspectives 352

References 352

Part IV Biomass Conversion: Processes and Technologies

16 Enzymes for Biorefineries 357Sarah A. Teter, Feng Xu, Glenn E. Nedwin, and Joel R. Cherry

16.1 Introduction 35716.2 Biomass as a Substrate 35916.2.1 Composition of Biomass 35916.2.1.1 Cellulose 35916.2.1.2 Hemicellulose 36016.2.1.3 Lignin 36016.2.1.4 Starch 36016.2.1.5 Protein 36116.2.1.6 Lipids and Other Extracts 36116.2.2 Biomass Pretreatment 361

Contents XV

16.2.2.1 Dilute Acid Pretreatment 36216.2.2.2 Ammonia Fiber Explosion 36216.2.2.3 Hot-wash Pretreatment 36216.2.2.4 Wet Oxidation 36316.3 Enzymes Involved in Biomass Biodegradation 36316.3.1 Glucanases or Cellulases 36416.3.2 Hemicellulases 36416.3.3 Nonhydrolytic Biomass-active Enzymes 36516.3.4 Synergism of Biomass-degrading Enzymes 36516.4 Cellulase Development for Biomass Conversion 36616.4.1 Optimization of the CBH-EG-BG System 36616.4.1.1 BG Supplement 36616.4.1.2 Novel Cellulases with Better Thermal Properties 36716.4.1.3 Structure–Function Relationship of EG 37016.4.2 Other Proteins Potentially Beneficial for Biomass Conversion 37116.4.2.1 Secretome of Cellulolytic Fungi 37116.4.2.2 Hydrolases 37316.4.2.3 Nonhydrolytic proteins 37416.5 Expression of Cellulases 37416.6 Range of Biobased Products 37516.6.1 Fuels 37616.6.2 Fine/Specialty Chemicals 37816.6.3 Fuel Cells 37816.7 Biorefineries: Outlook and Perspectives 38016.7.1 Potential of Biomass-based Material/Energy Sources 38016.7.2 Economic Drivers Toward Sustainability 381

References 382

17 Biocatalytic and Catalytic Routes for the Production of Bulk and FineChemicals from Renewable Resources 385Thomas Willke, Ulf Prüße, and Klaus-Dieter Vorlop

17.1 Introduction 38517.1.1 Renewable Resources 38517.1.2 Products 38617.1.2.1 Bulk Chemicals and Intermediates 38617.1.2.2 Fine Chemicals and Specialties 38617.2 Historical Outline 38717.3 Processes 38817.3.1 Immobilization 38917.3.2 Biocatalytic Routes from Renewable Resources to Solvents

or Fuels 39017.3.2.1 Ethanol Production with Bacteria or Yeasts? 39017.3.3 Biocatalytic Route from Glycerol to 1,3-Propanediol 39317.3.3.1 Introduction 39317.3.3.2 The Process 393

ContentsXVI

17.3.4 Biocatalytic Route from Inulin to Difructose Anhydride 39717.3.4.1 Introduction 39717.3.4.2 Enzyme Screening 39817.3.4.3 Genetic Engineering 39817.3.4.4 Fermentation of the Recombinant E. coli 39917.3.4.5 Enzyme Immobilization and Scale-up 40017.3.4.6 Summary 40117.3.5 Chemical Route from Sugars to Sugar Acids 40217.3.5.1 Introduction 40217.3.5.2 Gold Catalysts 40317.3.5.3 Summary 405

References 405

Volume 2

Part I Biobased Product Family Trees

Carbohydrate-based Product Lines

1 The Key Sugars of Biomass: Availability, Present Non-Food Uses andPotential Future Development Lines 3Frieder W. Lichtenthaler

1.1 Introduction 31.2 Availability of Mono- and Disaccharides 41.3 Current Non-Food Industrial Uses of Sugars 71.3.1 Ethanol 71.3.2 Furfural 81.3.3 D-Sorbitol (�D-Glucitol) 91.3.4 Lactic Acid�PolylacticAcid (PLA) 101.3.5 Sugar-based Surfactants 111.3.6 ‘Sorbitan’ Esters 111.3.7 N-Methyl-N-acyl-glucamides (NMGA) 121.3.8 Alkylpolyglucosides (APG) 121.3.9 Sucrose Fatty Acid Monoesters 131.3.10 Pharmaceuticals and Vitamins 141.4 Toward Further Sugar-based Chemicals:

Potential Development Lines 141.4.1 Furan Compounds 161.4.1.1 5-Hydroxymethylfurfural (HMF) 161.4.1.2 5-(Glucosyloxymethyl)furfural (GMF) 171.4.1.3 Furans with a Tetrahydroxybutyl Side-chain 191.4.2 Pyrones and Dihydropyranones 20

Contents XVII

1.4.3 Sugar-derived Unsaturated N-Heterocycles 241.4.1.4 Pyrroles 241.4.1.5 Pyrazoles 261.4.1.6 Imidazoles 271.4.1.7 3-Pyridinols 281.4.1.8 Quinoxalines 281.4.4 Toward Sugar-based Aromatic Chemicals 291.4.5 Microbial Conversion of Six-carbon Sugars into Simple Carboxylic

Acids and Alcohols 321.4.5.1 Carboxylic Acids 341.4.5.2 Potential Sugar-based Alcohol Commodities Obtained by Microbial

Conversions 361.4.6 Chemical Conversion of Sugars into Carboxylic Acids 371.4.7 Biopolymers from Polymerizable Sugar Derivatives 401.4.7.1 Synthetic Biopolyesters 411.4.7.2 Microbial Polyesters 441.4.7.3 Polyamides 451.4.7.4 Sugar-based Olefinic Polymers (“Polyvinylsaccharides”) 471.5 Conclusion 49

References 51

2 Industrial Starch Platform – Status quo of Production,Modification and Application 61Dietmar R. Grüll, Franz Jetzinger, Martin Kozich, Marnik M. Wastyn,and Robert Wittenberger

2.1 Introduction 612.1.1 History of Starch 612.1.2 History of Industrial Starch Production 622.1.3 History of Starch Modification 622.2 Raw Material for Starch Production 632.3 Industrial Production of Starch 652.3.1 Maize and Waxy Maize 662.3.2 Wheat 662.3.3 Potato 692.3.4 Tapioca 702.3.5 Other Starches 712.4 Properties of Commercial Starches 712.5 Modification of Starch Water 762.5.1 Modification Technology 762.5.1.1 Slurry Process (Heterogeneous Conditions) 762.5.1.2 Dry Reactions 772.5.1.3 Paste Reactions (Homogeneous Conditions) 772.5.1.4 Extrusion Cooking 772.5.2 Types of Starch Modification 782.5.2.1 Physical Modification 78

ContentsXVIII

2.5.2.2 Degraded Starches 792.5.2.3 Chemical Modification 802.6 Application of Starch and Starch Derivatives 822.6.1 The Paper and Corrugating Industries 832.6.1.1 Use of Starch in the Paper Industry 832.6.1.2 Use of Starch in the Corrugating Industry 852.6.2 The Textile Industry 852.6.2.1 Sizing Agents 852.6.2.2 Textile-printing Thickeners 862.6.2.3 Finishing Agents 862.6.3 Adhesives 872.6.4 Building Chemistry 872.6.5 Pharmaceuticals and Cosmetics 882.6.6 Laundry Starches 892.6.7 Bioconversion of Starch 892.6.8 Other Applications of Starch 912.7 Future Trends and Developments 922.7.1 Tailor-made Starches by Use of Biotechnological Tools 922.7.2 New Modification Technologies for New Properties 932.7.3 New Fields of Application 94

Bibliography 95

3 Lignocellulose-based Chemical Productsand Product Family Trees 97Birgit Kamm, Michael Kamm, Matthias Schmidt, Thomas Hirth,and Margit Schulze

3.1 Introduction 973.2 Historical Outline of Chemical and Technical Aspects of Utilization

Lignocellulose in the 19th and 20th Century 983.2.1 From the Beginnings of Lignocellulose Chemistry Until 1800 983.2.2 Lignocellulose Chemistry in the Eighteenth Century 993.2.2.1 Cellulose Saccharification 993.2.2.2 Oxalic Acid 993.2.2.3 Xyloidin and Nitrocellulose 993.2.2.4 Cellulose 1003.2.2.5 Levulinic Acid 1003.2.2.6 Lignin 1013.2.2.7 Hemicellulose (Polyoses) and Furfural 1013.2.2.8 Lignocellulose 1023.2.3 Industrial Lignocellulose Utilization in the 19th and Beginning

of the 20th Century 1023.3 Lignocellulosic Raw Material 1033.3.1 Definition 1033.3.2 Sources and Composition 1053.3.2.1 Sources 105

Contents XIX

3.3.2.2 Chemical Composition of Lignocelluloses 1063.3.2.3 Carbohydrates in Lignocelluloses 1083.4 Lignocelluloses in Biorefineries 1103.4.1 Background 1103.4.1.1 Example 1 1103.4.1.2 Example 2 1103.4.2 LCF Biorefinery 1113.4.3 LCF Conversion Methods 1133.4.3.1 Pretreatment Methods 1133.4.3.2 Chemical Pulping Methods 1143.4.3.3 Enzymatic Methods 1153.5 Lignin-based Product Lines 1163.5.1 Isolation and Application Areas 1163.5.2 A Lignin-based Product Family Tree 1173.6 Hemicellulose-based Product Lines 1193.6.1 Isolation and Application Areas 1193.6.2 A Hemicellulose-based Product Family Tree 1193.6.2.1 Mannan/Mannose Product Lines 1193.6.2.2 Xylan/Xylose Product Line 1203.6.3 Furfural and Furfural-based Products 1223.6.3.1 Furfural 1223.6.3.2 A Furfural-based Family Tree 1273.7 Cellulose-based Product Lines 1273.7.1 Isolation, Fractionation and Application Areas 1273.7.2 Cellulose-based Key Chemicals 1283.7.2.1 Glucose 1283.7.2.2 Sorbitol 1293.7.2.3 Glucosides 1303.7.2.4 Fructose 1313.7.2.5 Ethanol 1323.7.2.6 Hydroxymethylfurfural 1333.7.2.7 Levulinic Acid 1343.7.3 An HMF and Levulinic Acid-based Family Tree 1353.8 Outlook and Perspectives 138

References 139

Lignin Line and Lignin-based Product Family Trees

4 Lignin Chemistry and its Role in Biomass Conversion 151Gösta Brunow

4.1 Introduction 1514.2 Historical Overview 1524.3 The Structure of Lignin 1524.3.1 Definition 1524.3.2 The Bonding of the Phenylpropane Units 153

ContentsXX

4.3.3 Bonding Patterns and Functional Groups 1564.3.3.1 General 1564.3.3.2 Survey of Different Types of Lignin Unit 1564.4 Role of Lignin in Biomass Conversion 1594.4.1 Introduction 1594.4.2 Low-molecular-weight Chemicals from Lignin 1604.4.3 Polymeric Products 1604.4.4 Biodegradation 160

References 160

5 Industrial Lignin Production and Applications 165E. Kendall Pye

5.1 Introduction 1655.2 Historical Outline of Lignin Production and Applications 1685.2.1 Lignosulfonates from the Sulfite Pulping Industry 1685.2.2 Lignin from the Kraft Pulping Industry 1695.2.3 Lignin from the Soda Pulping Industry 1705.3 Existing Industrial Lignin Products 1725.3.1 Lignosulfonates 1725.3.1.1 Chemical Characteristics of Lignosulfonates 1725.3.1.2 Lignosulfonate Producers 1735.3.1.3 Markets for Lignosulfonates 1745.3.2 Kraft Pulping and Kraft Lignin Recovery 1755.3.2.1 Producers of Kraft Lignin 1755.3.2.2 Markets for Kraft Lignin 1755.3.3 Lignins Produced from the Soda Process 1765.3.4 Lignin from Other Biomass Processing Operations 1765.3.5 Comparisons of the Physical and Chemical Properties

of Commercially Available Lignins 1765.4 Lignin from Biorefineries 1775.4.1 Advantages of Lignin and Hemicellulose Removal on Saccharification

and Fermentation of Cellulose 1775.4.2 Lignin from an Organosolv Biorefinery 1795.5 Applications and Markets for Lignin 1815.5.1 Phenol–Formaldehyde Resin Applications 1815.5.2 The Potential Use of Biorefinery Lignin in Phenolic Resins 1815.5.3 Panelboard Adhesives 1835.5.4 Thermoset Resins for Molded Products 1845.5.5 Friction Materials 1845.5.6 Foundry Resins 1845.5.7 Insulation Materials 1855.5.8 Decorative Laminates 1855.5.9 Panel and Door Binders 1855.5.10 Rubber Processing 186

Contents XXI

5.5.11 The Opportunity for Lignin in Phenol–Formaldehyde ResinMarkets 187

5.6 Lignin as an Antioxidant 1875.6.1 Antioxidants in Animal Feed Supplements 1885.6.2 Antioxidants in the Rubber Industry 1885.6.3 Antioxidants in the Lubricants Industry 1885.7 Applications for Water-soluble, Derivatized Lignins 1895.7.1 Concrete Admixtures 1895.7.2 Dye Dispersants 1905.7.3 Asphalt Emulsifiers 1925.7.4 Agricultural Applications 1925.7.5 Dispersants for Herbicides, Pesticides and Fungicides 1935.8 New and Emerging Markets for Lignin 1945.8.1 Printed Circuit Board Resins 1945.8.2 Animal Health Applications 1955.8.3 Animal Feed Supplement 1965.8.4 Carbon Fibers for Mass-produced Vehicles 1965.9 Conclusions and Perspectives 198

References 199

Protein Line and Amino Acid-based Product Family Trees

6 Towards Integration of Biorefinery and Microbial Amino AcidProduction 201Achim Marx, Volker F. Wendisch, Ralf Kelle, and Stefan Buchholz

6.1 Introduction 2016.2 Present State of the Industry 2026.2.1 Microbial Amino Acid Production 2026.2.2 Biorefinery and the Building-block Concept 2026.2.3 Metabolic Engineering and the Building-block Concept 2046.3 Environmental and Commercial Consideration of Microbial

Amino Acid Production Integrated in a Biorefinery 2056.4 Technical Constraints for Integration of Microbial Amino Acid

Fermentation into a Biorefinery 2096.4.1 Mono-septic Operation 2096.4.2 Carbon Sources 2096.4.3 Nitrogen Source 2116.4.4 Phosphorus Source 2116.4.5 Mixing and Oxygen Supply 2126.4.6 Toxicity 2126.4.7 Cultivation Temperature 2136.5 Outlook and Perspectives 213

Acknowledgment 214References 215

ContentsXXII

7 Protein-based Polymers:Mechanistic Foundations for Bioproduction and Engineering 217Dan W. Urry

7.1 Introduction 2177.1.1 Definitions 2177.1.1.1 Proteins and Protein-based Polymers 2177.1.1.2 Two Basic Principles for Protein-based Polymer Engineering 2177.1.2 Proteins in Aqueous Media 2187.1.3 Thermodynamics of Proteins in Water 2187.1.3.1 Exothermic Hydration of Apolar Groups 2187.1.3.2 The Change in Gibbs Free Energy of Hydrophobic Association 2187.1.3.3 The Apolar–Polar Repulsive Free Energy of Hydration, �G�ap 2187.1.4 The Inverse Temperature Transition for Hydrophobic

Association 2197.1.5 The Role of Elasticity in the Engineering of Protein-based

Polymers 2197.1.5.1 Near Ideal Elasticity Provides for Efficient Energy Conversion 2197.1.5.2 Mechanism of Near Ideal Elasticity 2207.1.6 Many of the Advantages of Protein-based Polymeric Materials 2207.2 Historical Outline 2217.2.1 Historical Beginnings of (Elastic) Protein-based Polymer

Development 2217.2.2 Mechanistic Foundations: Fundamental Engineering Principles 2227.2.2.1 The Hydrophobic Consilient Mechanism 2227.2.2.2 The Elastic Consilient Mechanism 2237.2.3 Highlights of Bioproduction 2237.3 Bioproduction 2247.3.1 Gene Construction using Recombinant DNA Technology 2257.3.1.1 Preparation of Monomer Genes and the PCR Technique 2257.3.1.2 Transformation, Monomer Gene Production and Sequence

Verification 2267.3.1.3 Monomer Gene Concatenation Produces Multimer Genes

of Monomer 2267.3.2 E. coli Transformation for Protein-based Polymer Expression 2277.3.3 Fermentation using Transformed E. coli 2277.4 Purification of Protein-based Polymers 2277.4.1 Use of the Inverse Temperature Transition as a Method

of Purification 2287.4.1.1 Purification by Phase Separation as Demonstrated

by SDS–PAGE 2287.4.1.2 Purification by Phase Separation Shown by Carbon-14-labeled

E. coli 2287.4.2 Physical Characterization and Verification of Product Integrity 2297.4.2.1 Gross Visualization of the Phase Separated Product 229

Contents XXIII

7.4.2.2 Sequence Integrity and Purity Evaluated by Nuclear MagneticResonance 229

7.4.2.3 Mass Spectra Reaffirm Size of Expressed Polymer 2297.4.3 Biocompatibility 2307.4.3.1 The Challenge of Using E. coli-produced Protein

as a Biomaterial 2307.4.3.2 Removal of Endotoxins and Determination of Levels 2307.4.3.3 Western Immunoblot Technique to Demonstrate Level

of Purity 2307.4.3.4 Western Immunodotblot Technique to Demonstrate

Medical Grade Purity 2317.4.3.5 Subcutaneous Injection in the Guinea-pig 2317.4.3.6 ASTM Tests 2327.5 Mechanistic Foundations for Engineering Protein-based

Polymers 2327.5.1 Phenomenological Axioms 2327.5.2 The Change in Gibbs Free Energy for Hydrophobic Association,

�GHA 2327.5.2.1 The Change in Gibbs Free Energy Attending a Phase Transition,

��Gt(�) 2347.5.2.2 The �GHA-based Hydrophobicity Scale for Amino Acid

Residues 2347.5.2.3 �G�HA-based Hydrophobicity Scale of Prosthetic Groups, etc. 2357.5.2.4 Comprehensive Hydrophobic Effect: �GHA Responds

to all Variables 2377.5.2.5 The Apolar–Polar Repulsive Free Energy of Hydration, �Gap 2377.5.3 The Coupling of Hydrophobic and Elastic Mechanisms 2377.6 Examples of Applications 2387.6.1 Soft Tissue Restoration 2387.6.1.1 Prevention of Post-surgical Adhesions 2387.6.1.2 Soft Tissue Augmentation 2387.6.1.3 Soft Tissue Reconstruction: The Concept of Temporary Functional

Scaffoldings 2397.6.2 Controlled Release Devices for Amphiphilic Drugs

and Therapeutics 2407.6.2.1 The Use of �Gap in the Design of Controlled-release Devices 2407.6.2.2 Prevention of Pressure Ulcers by Means of Elastic Patches

for Drug Delivery 2407.6.3 Fibers of Improved Elastic Moduli and Break Stresses and Strains 2417.6.4 Programmably Biodegradable Thermoplastics 2417.6.5 Acoustic Absorption 2427.7 Outlook and Perspectives 2427.7.1 List of Gene Constructions and Expressed Protein-based Polymers 2427.7.2 Efforts Toward Low-cost Production in other Microbes

and in Plants 242

ContentsXXIV

7.8 Patents 2457.8.1 Patents of D.W. Urry on Protein-based Polymers 2457.8.2 Result of Ex Parte Patent Reexamination Request

to the USPTO 245Acknowledgment 249References 249

Biobased Fats (Lipids) and Oils

8 New Syntheses with Oils and Fats as RenewableRaw Materials for the Chemical Industry 253Ursula Biermann, Wolfgang Friedt, Siegmund Lang, Wilfried Lühs,Guido Machmüller, Jürgen O. Metzger, Mark Rüsch gen. Klaas,Hans J. Schäfer, Manfred P. Schneider

8.1 Introduction 2538.2 Reactions of Unsaturated Fatty Compounds 2548.2.1 Oxidations 2548.2.1.1 New Methods for the Epoxidation of Unsaturated Fatty Acids 2548.2.1.2 Oxidation to vic-Dihydroxy Fatty Acids 2578.2.1.3 Oxidative Cleavage 2588.2.2 Transition Metal-Catalyzed Syntheses of Aromatic Compounds 2598.2.3 Olefin Metathesis 2598.2.4 Pericyclic Reactions 2608.2.5 Radical Additions 2618.2.5.1 Solvent-Free, Copper-Initiated Additions of 2-Halocarboxylates 2628.2.5.2 Addition of Perfluoroalkyl Iodides 2638.2.5.3 Thermal Addition of Alkanes 2648.2.6 Lewis Acid-Induced Cationic Addition 2648.2.7 Nucleophilic Addition to Reversed-Polarity Unsaturated Fatty

Acids 2658.3 Reactions of Saturated Fatty Compounds 2668.3.1 Radical C–C Coupling 2668.3.1.1 Oxidative Coupling of C2 Anions of Fatty Acids 2668.3.1.2 Anodic Homo- and Heterocoupling of Fatty Acids

(Kolbe Electrolysis) 2678.3.2 Functionalization of C–H Bonds 2698.3.2.1 Oxidation of Nonactivated C–H Bonds 2698.3.2.2 Oxidation of Allylic C–H Bonds 2698.4 Enzymatic Reactions 2708.4.1 Lipase Catalyzed Transformations 2708.4.1.1 Lipase-Catalyzed Syntheses of Monoglycerides and Diglycerides 2708.4.1.2 Lipase-Catalyzed Syntheses of Carbohydrate Esters 2728.4.2 Microbial Transformations 2728.4.2.1 Microbial Hydration of Unsaturated Fatty Acids 2728.4.2.2 Microbial �- and �-Oxidation of Fatty Acids 273

Contents XXV

8.4.3 Microbial Conversion of Oils/Fats and Glucose into Glycolipids 2748.5 Improvement in Natural Oils and Fats by Plant Breeding 2758.5.1 Gene Technology as an Extension of the Methodological Repertoire

of Plant Breeding 2758.5.2 New Oil Qualities by Oil Designed with Available Agricultural

Varieties 2768.5.3 Overview of Renewable Raw Materials Optimized by Breeding 2778.5.3.1 Soybean 2778.5.3.2 Rapeseed 2778.5.3.3 Sunflower 2808.5.3.4 Peanut 2818.5.3.5 Linseed 2818.5.4 Concluding Remarks on the Use of Gene Technology 2818.6 Future Prospects 282

Acknowledgments 282References 282

9 Industrial Development and Application of BiobasedOleochemicals 291Karlheinz Hill

9.1 Introduction 2919.2 The Raw Materials 2929.3 Ecological Compatibility 2939.4 Examples of Products 2949.4.1 Oleochemicals for Polymer Applications 2959.4.1.1 Dimerdiols Based on Dimer Acid 2979.4.1.2 Polyols Based on Epoxides 2989.4.2 Biodegradable Fatty Acid Esters for Lubricants 2999.4.3 Surfactants and Emulsifiers Derived from Vegetable Oil 3019.4.3.1 Fatty Alcohol Sulfate (FAS) 3039.4.3.2 Acylated Proteins and Amino Acids (Protein–Fatty Acid

Condensates) 3049.4.3.3 Carbohydrate-based Surfactants – Alkyl Polyglycosides 3059.4.3.4 Alkyl Polyglycoside Carboxylate 3079.4.3.5 Polyol Esters 3079.4.3.6 Multifunctional Care Additives for Skin and Hair 3099.4.4 Emollients 3109.4.4.1 Introduction 3109.4.4.2 Dialkyl Carbonate 3119.4.4.3 Guerbet Alcohols 3119.5 Perspectives 3129.6 Trademarks 312

References 312

ContentsXXVI

Special Ingredients and Subsequent Products

10 Phytochemicals, Dyes, and Pigments in the Biorefinery Context 315George A. Kraus

10.1 Introduction 31510.2 Historical Outline 31610.3 Phytochemicals from Corn and Soybeans 31710.3.1 Phytosterols 31710.3.2 Lecithin 31810.3.3 Tocopherols 31910.3.4 Carotenoids 32010.3.5 Phytoestrogens 32110.3.6 Saponins 32110.3.7 Protease Inhibitors 32210.4 Outlook and Perspectives 323

References 323

11 Adding Color to Green Chemistry?An Overview of the Fundamentals and Potential of Chlorophylls 325Mathias O. Senge and Julia Richter

11.1 Introduction 32511.2 Historical Outline 32511.3 Chlorophyll Fundamentals 32611.3.1 Occurrence and Basic Structures 32611.3.2 Principles of Chlorophyll Chemistry 32711.3.3 Isolation of Chlorophylls 32811.4 Chlorophyll Breakdown and Chemical Transformations 33011.4.1 Biological Chlorophyll Catabolism 33011.4.2 Geological Chlorophyll Degradation – Petroporphyrins 33111.4.3 Chemical Degradation of Chlorophylls 33311.5 Industrial Uses of Chlorophyll Derivatives 33511.6 A Look at “Green” Chlorophyll Chemistry 33711.7 Outlook and Perspectives 339

Acknowledgment 341References and Notes 341

Part II Biobased Industrial Products, Materials and Consumer Products

12 Industrial Chemicals from Biomass – Industrial Concepts 347Johan Thoen and Rainer Busch

12.1 Introduction 34712.2 Historical Outline 34712.3 Basic Principles 34912.3.1 Primary Conversion Technologies of Biomass 35012.3.1.1 Gasification 350

Contents XXVII

12.3.1.2 Hydrothermolysis 35112.3.1.3 Fermentation to Ethanol 35112.4 Current Status 35112.4.1 Europe 35112.4.2 United States 35212.4.3 Products 35312.5 Industrial Concepts 35412.5.1 Introduction 35412.5.2 Biorefinery Concepts 35512.5.3 Classes of Bioproduct 35612.5.4 Opportunities for Industrial Bioproducts 35712.5.5 Product Categories Based on C6-Carbon Sugars to Bioproducts 35812.5.6 Product Categories Based on C5-Carbon Sugars to Bioproducts 35812.5.7 Thermochemical Conversion of Sugars to Bioproducts 36012.5.8 Thermochemical Conversion of Oils and Lipid Based

Bioproducts 36112.5.9 Bioproducts via Gasification 36112.5.10 Bioproducts via Pyrolysis 36212.5.11 Biocomposites 36212.6 Outlook and Perspectives 362

References 364

13 Succinic Acid – A Model Building Block for Chemical Productionfrom Renewable Resources 367Todd Werpy, John Frye, and John Holladay

13.1 Introduction 36713.2 Economics of Feedstock Supply 36813.3 Succinic Acid Fermentation 36913.4 Succinic Acid Catalytic Transformations 37213.5 Current Petrochemical Technology 37313.5.1 1,4-BDO, THF, GBL, and NMP 37313.6 Current Biobased Technology 37513.6.1 1,4-BDO, GBL, and NMP 37513.6.2 Derivatives of Diammonium Succinate 37613.7 Conclusions 378

References 378

14 Polylactic Acid from Renewable ResourcesPatrick Gruber, David E. Henton, and Jack Starr 381

14.1 Introduction 38114.2 Lactic Acid 38214.2.1 Lactic Acid Production Routes 38214.2.1.1 Chemical Synthesis 38214.2.1.2 Fermentation 38314.2.2 Production by Fermentation 384

ContentsXXVIII

14.2.2.1 Microorganisms 38414.2.2.2 Sugar Feedstock 38514.2.2.3 Nutrients 38514.2.2.4 Neutralizing Agent 38514.2.3 Acidification 38614.2.3.1 Strong Acid Addition 38614.2.3.2 Salt Splitting Technology 38714.2.4 Purification 38814.2.4.1 Cell Removal 38814.2.4.2 Separation of Residual Sugars, Nutrients and Fermentation

By-products 38814.3 PLA Production 39014.3.1 Polymerization of Lactide 39214.4 Control of Crystalline Melting Point 39414.5 Rheology Control by Molecular Weight and Branching 39614.5.1 Melt Rheology of Linear PLA 39714.5.2 Melt Rheology of Branched PLA 39714.5.3 Branching Technology 39814.5.3.1 Multi-functional Polymerization Initiators 39814.5.3.2 Hydroxy Cyclic Ester and/or Carbonate Polymerization

Initiators 39814.5.3.3 Multi-cyclic Ester, Multi-cyclic Carbonate and/or Multi-cyclic Epoxy

Comonomers 39814.5.3.4 Free Radical Cross-linking 39914.6 Melt Stability 39914.7 Applications and Performance 40014.8 PLA Stereocomplex 40114.9 Fossil Resource Use and Green House Gases 40214.10 Summary 402

Abbreviations 403References 404

15 Biobased Consumer Products for Cosmetics 409Thomas C. Kripp

15.1 Introduction and Historical Outline 40915.1.1 Cosmetics Past and Present 40915.1.2 Bionics: Learning from Nature 41015.2 Betaine, The Conditioner Made from Sugar Beet 41015.2.1 Occurrence 41015.2.2 Chemical Properties 41115.2.3 Production 41115.2.4 Use and Fields of Application 41215.2.5 Innovation Through Combination: Betaine Esters 41415.2.6 Summary and Prospects 41515.3 Chitosan, Hair-setting Agent from the Ocean 415

Contents XXIX

15.3.1 Chitin, a Precursor of Chitosan 41515.3.2 Occurrence of Chitin 41515.3.3 Production 41615.3.3.1 Purification of Chitin 41615.3.3.2 Production of Chitosan 41715.3.4 Chitosan in cosmetic products 41915.3.5 Summary and Prospect 42115.4 From Energy Reserve to Shampoo Bottle: Biopol 42215.4.1 Biodegradable Packages 42215.4.2 What is “Biopol”? 42315.4.3 Biodegradability of Biopol 42415.4.4 The Long Way to the Shampoo Bottle 42615.4.4.1 Product Development 42615.4.4.2 Market Launch 42715.4.5 Quo vadis, Biopol? 42815.5 Natural Apple-peel Wax: Protection for Hair and Skin 42915.5.1 Raw Material Source 42915.5.2 Apple-peel Wax 43015.5.3 Observations 43015.5.4 Production of Apple-peel Wax 43215.5.5 Chemical Composition 43315.5.6 Mode of Action and Uses 43315.5.6.1 Skin Cosmetics 43415.5.6.2 Hair Care 43415.5.7 Market Launch 43615.5.8 Summary and Prospects 43615.6 Ilex Resin: From Shiny Leaves to Shiny Hair 43715.6.1 Holly 43715.6.2 Extraction of a Resin Fraction 43815.6.3 Effects in Cosmetics 43915.6.3.1 Skin Care 43915.6.3.2 Hair Care 43915.6.3.3 Styling 44015.6.4 Summary and Prospects 440

References 441

Part III Biobased Industry:Economy, Commercialization and Sustainability

16 Industrial Biotech –Setting Conditions to Capitalize on the Economic Potential 445Rolf Bachmann and Jens Riese

16.1 Introduction 44516.2 Time to Exploit the Potential 44616.2.1 How Far Can it Go? 446

ContentsXXX

16.2.2 Better Technology, Faster Results 44716.2.3 Environmentally and Balance-sheet Friendly 44816.2.4 Rekindling Chemicals Innovation 45016.2.5 Increasing Corporate Action in all Segments 45116.3 The Importance of Residual Biomass 45216.3.1 Why Waste Biomass Works 45216.3.2 Economic Benefits and Regulation 45216.3.3 Still a Long Way to Go 45416.3.4 Collaboration Will Push Biomass Conversion Forward 45416.4 Overcoming the Challenges Ahead 45516.4.1 Internal Obstacles 45516.4.2 External Challenges 45616.5 Overcoming Challenges 45716.5.1 Case 1: Building a Biotech Strategy 45716.5.2 Case 2: Identifying the Right Opportunities 45816.5.3 Case 3: Managing Uncertainties 45916.5.4 Case 4: Preparing the Launch and Market Development 46016.5.5 Case 5: Building a Favorable External Environment 46116.6 More Needs to be Done 461

Subject Index 463

Contents XXXI