Covers the entire evolutionary spectrum of biomass, from its genetic modification and harvesting, to conversion technologies, life cycle analysis, and its value to the current global economy

This original textbook introduces readers to biomassa renewable resource derived from forest, agriculture, and organic-based materialswhich has attracted significant attention as a sustainable alternative to petrochemicals for large-scale production of fuels, materials, and chemicals. The current renaissance in the manipulation and uses of biomass has been so abrupt and focused, that very few educational textbooks actually cover these topics to any great extent. Thats why this interdisciplinary text is a welcome resource for those seeking a better understanding of this new discipline. It combines the underpinning science of biomass with technology applications and sustainability considerations to provide a broad focus to its readers.

Introduction to Renewable Biomaterials: First Principles and Concepts consists of eight chapters on the following topics: fundamental biochemical& biotechnological principles; principles and methodologies controlling plant growth and silviculture; fundamental science and engineering considerations; critical considerations and strategies for harvesting; first principles of pretreatment; conversion technologies; characterization methods and techniques; and life cycle analysis. Each chapter includes a glossary of terms, two to three problem sets, and boxes to highlight novel discoveries and instruments. Chapters also offer questions for further consideration and suggestions for further reading.

Introduction to Renewable Biomaterials: First Principles and Concepts is an ideal text for advanced academics and industry professionals involved with biomass and renewable resources, bioenergy, biorefining, biotechnology, materials science, sustainable chemistry, chemical engineering, crop science and technology, agriculture.

About the Editors

Ali S. Ayoub, PhD is an internationally recognized expert in the biopolymer science and engineering field and has successfully developed groundbreaking inventions in areas relevant to polymeric materials and the biorefinery concept. He is a senior scientist in the chemical industry, as well as an adjunct professor and associate graduate faculty member at North Carolina State University. He is associated with the United States Department of Interior and symposiums related to natural polymers within the American Chemical Society.

Lucian A. Lucia, PhD is an Associate Professor in Forest Biomaterials and Chemistry, North Carolina State University and an honorary Professor of Green Chemistry at Qilu University of Technology (China). He was the Principle Investigator for the acclaimedBioSUCCEED educational/research framework (BioProducts Sustainability, a University Cooperative Center for Excellence in Education). He has been elected Fellow to a number of prestigious organizations and is co-Founder and co-Editor of the international journalBioResources.

List of Contributors xiii

Preface xv

1 Fundamental Biochemical and Biotechnological Principles of Biomass Growth and Use 1Manfred Kircher

1.1 Learning Objectives 1

1.2 Comparison of Fossil-Based versus Bio-Based Raw Materials 2

1.2.1 The Nature of Fossil Raw Materials 2

1.2.2 Industrial Use 3

1.2.2.1 Energy 3

1.2.2.2 Chemicals 4

1.2.3 Expectancy of Resources 8

1.2.4 Green House Gas (GHG) Emission 8

1.2.5 Regional Pillars of Competitiveness 9

1.2.6 Questions for Further Consideration 11

1.3 The Nature of Bio-Based RawMaterials 11

1.3.1 Oil Crops 11

1.3.2 Sugar Crops 13

1.3.3 Starch Crops 14

1.3.4 Lignocellulosic Plants 15

1.3.5 Lignocellulosic Biomass 16

1.3.6 Algae 16

1.3.7 Plant Breeding 17

1.3.8 Basic Transformation Principles 17

1.3.8.1 First Generation 17

1.3.8.2 Second Generation 18

1.3.8.3 Third Generation 18

1.3.9 Industrial Use 18

1.3.9.1 Energy 18

1.3.9.2 Chemicals 20

1.3.9.3 Biocatalysts 22

1.3.9.4 Pharmaceuticals 23

1.3.9.5 Nutrition 24

1.3.9.6 Polymers 24

1.3.10 Expectancy of Resources 26

1.3.11 Green House Gas Emission 26

1.3.12 Regional Pillars of Competitiveness 27

1.3.13 Questions for Further Consideration 29

1.4 General Considerations Surrounding Bio-Based Raw Materials 29

1.4.1 Economical Challenges 29

1.4.2 Feedstock Demand Challenges 30

1.4.3 Ecological Considerations 31

1.4.4 Societal Considerations 31

1.4.4.1 Food Security 31

1.4.4.2 Public Acceptance 32

1.5 Research Advances Made Recently 32

1.5.1 First-Generation Processes and Products 32

1.5.2 Second-Generation Processes and Products 33

1.5.3 Third-Generation Processes and Products 33

1.6 Prominent ScientistsWorking in this Arena 34

1.7 Summary 35

1.8 Study Problems 35

1.9 Key References 36

References 36

2 Fundamental Science and Applications for Biomaterials 39Ali S. Ayoub and Lucian A. Lucia

2.1 Introduction 39

2.2 What are the Biopolymers that Encompass the Structure and Function of Lignocellulosics? 39

2.2.1 Cellulose 40

2.2.2 Heteropolysaccharides 43

2.2.3 Lignin 45

2.2.4 The Discovery of Cellulose and Lignin 47

2.3 Chemical Reactivity of Cellulose, Heteropolysaccharides, and Lignin 48

2.3.1 Cellulose Reactivity 48

2.3.1.1 ReactivityMeasurements 50

2.3.1.2 Dissolving-Grade Pulps 51

2.3.1.3 Converting Paper-Grade Pulps into Dissolving-Grade Pulps 51

2.3.2 Hemicellulose Reactivity 51

2.3.2.1 Structural Characterization of Hemicellulose 52

2.3.3 Lignin Reactivity 53

2.4 Composite as a Unique Application for Renewable Materials 53

2.4.1 Rationale and Significance 54

2.4.2 Starch-Based Materials 55

2.4.3 Starch-Based Plastics 56

2.4.3.1 Novamont 57

2.4.3.2 Cereplast 58

2.4.3.3 Ecobras 58

2.4.3.4 Biotec 58

2.4.3.5 Plantic 59

2.4.3.6 Biolice 59

2.4.3.7 KTM Industries 59

2.4.3.8 Cerestech, Inc. 59

2.4.3.9 Teknor Apex 60

2.5 Question for Further Consideration 60

References 60

3 Conversion Technologies 63Maurycy Daroch

3.1 Learning Objectives 63

3.2 Energy Scenario at Global Level 63

3.2.1 Why Our Energy is so Important? 63

3.2.2 Black Treasure Chest 64

3.2.3 Conventional Fossil Resources and their Alternatives 66

3.2.3.1 Light Crude Oil (Conventional Oil) 66

3.2.3.2 Coal 66

3.2.3.3 Natural Gas 66

3.2.3.4 Shale Oil (Tight Oil) 67

3.2.3.5 Oil Sands, Bitumen Extra Heavy Oil 67

3.2.3.6 Shale Gas 67

3.2.3.7 Methane (Gas) Hydrates 67

3.2.3.8 EROI How Much Fuel in Fuel? 68

3.2.3.9 Environmental Effects of Fossil Resource Utilisation 69

3.3 Biomass 71

3.3.1 Renewable Energy and Renewable Carbon 71

3.3.2 Why Different Types of Biomass have the Properties they Have? 73

3.4 Biomass Conversion Methods 75

3.4.1 Conversion of Biochemical Energy Perspective 75

3.4.2 Overview of Biomass Conversion Technologies 78

3.4.3 Thermochemical Conversion of Biomass 78

3.4.4 Biomass Combustion 80

3.4.5 Gasification 81

3.4.6 Pyrolysis 84

3.4.7 Conversion of Oily Feedstocks 86

3.4.8 Biochemical Conversion of Biomass 88

3.4.8.1 Aerobic and Anaerobic Metabolisms 88

3.4.8.2 Central Metabolic Pathway under Anaerobic Conditions 89

3.4.9 Harvesting Energy from Biochemical Processes 91

3.4.9.1 Ethanol Fermentation 91

3.4.9.2 ABE Fermentation 92

3.4.9.3 Biohydrogen 93

3.4.9.4 Biomethane 94

3.5 Metrics to Assist the Transition Towards Sustainable Production of Bioenergy and Biomaterials 95

3.5.1 EROI PrimaryMetrics of Energy Carrier Efficiency 95

3.5.2 LCA Sustainability Determinant 96

3.5.3 Environmental Assessment of Bioenergy Production Processes 97

3.5.3.1 Impacts Related to Land-Use Change 97

3.5.3.2 Impacts of Feedstock Cultivation 98

3.5.3.3 Impacts of Conversion Process 98

3.5.3.4 Impacts of Product Use 98

3.5.4 SustainabilityMetrics in Biomass and Bioenergy Policies 99

3.5.5 Renewable and Non-Renewable Carbon Taxation and Subsidies 99

3.6 Summary 102

3.7 Key References 102

References 103

4 Characterization Methods and Techniques 107Noppadon Sathitsuksanoh and Scott Renneckar

4.1 Philosophy Statement 107

4.2 Understanding the Characteristics of Biomass 107

4.3 Taking Precautions Prior to Setting Up Experiments for Biomass Analysis 108

4.4 Classifying Biomass Sizes for Proper Analysis 109

4.5 Moisture Content of Biomass and Importance of Drying Samples Prior to Analysis 110

4.6 When the Carbon is Burned 111

4.7 Structural CellWall Analysis, What To Look For 112

4.8 Hydrolyzing Biomass and Determining Its Composition 114

4.8.1 Analyzing Filtrate by HPLC for Monosaccharide Contents 115

4.8.2 Choosing the HPLC Column and Its Operating Conditions 115

4.9 Determining CellWall Structures Through Spectroscopy and Scattering 116

4.9.1 Probing the Chemical Structure of Biomass 116

4.9.1.1 X-Ray Diffraction (XRD) 118

4.9.1.2 Cross-polarization/Magic Angle Spinning (CP/MAS) 13CNMR 119

4.9.1.3 Fourier-Transform Infrared Spectroscopy (FTIR) 121

4.9.1.4 Raman Analysis 122

4.10 Examining the Size of the Biopolymers: MolecularWeight Analysis 123

4.11 Intricacies of Understanding Lignin Structure 125

4.11.1 13CNMR 126

4.11.2 31P NMR 126

4.11.3 2D HSQC 128

4.11.4 Methoxyl Content Determination 132

4.11.4.1 1HNMR 132

4.11.4.2 Hydriodic Acid 132

4.11.4.3 Direct Methanol 132

4.12 Questions for Further Consideration 132

References 132

5 Introduction to Life-Cycle Assessment and Decision Making Applied to Forest Biomaterials 141Jesse Daystar and Richard Venditti

5.1 Introduction 141

5.1.1 What is LCA? 141

5.1.1.1 History 142

5.1.2 LCA for Decision Making 142

5.1.2.1 Eco-labels 143

5.2 LCA Components Overview 144

5.2.1 Goal and Scope Definition 145

5.2.2 Inventory Analysis 145

5.2.3 Life-Cycle Impact Assessment 146

5.2.4 Interpretation 146

5.3 Life-Cycle Assessment Steps 146

5.3.1 Goal, Scope, System Boundaries 146

5.3.1.1 Goal Definition 146

5.3.1.2 Scope Definition 147

5.3.1.3 Functional Unit 148

5.3.1.4 Cutoff Criteria 148

5.3.1.5 Problems Set Goal and Scope Definition 148

5.3.2 Life-Cycle Inventory 150

5.3.2.1 Preparation of Data Collection Based on Goal and Scope 151

5.3.2.2 Data Collection 152

5.3.2.3 Data Quality 155

5.3.2.4 Coproduct Treatment Allocation 157

5.3.2.5 Relating Data to the Unit Process 158

5.3.2.6 Relating Data to the Functional Unit 159

5.3.2.7 Data Aggregation 159

5.3.2.8 LCI Data Interpretation 159

5.3.2.9 Problems Set Life-Cycle Inventory 160

5.3.2.10 Mandatory Elements 166

5.3.2.11 Classification 168

5.3.2.12 Characterization 169

5.3.2.13 Optional Elements 170

5.3.2.14 Life Cycle Impact Assessment Interpretation 173

5.3.2.15 Problems Set Life-Cycle Impact Assessment 173

5.4 LCA Tools for Forest Biomaterials 177

5.4.1 FICAT 177

5.4.2 GREET Model 178

References 178

6 First Principles of Pretreatment and Cracking Biomass to Fundamental Building Blocks 181Amir Daraei Garmakhany and Somayeh Sheykhnazari

6.1 Introduction 181

6.1.1 What Is Lignocellulosic Material? 183

6.1.1.1 Lignocellulosic Materials 183

6.1.1.2 Cellulose 183

6.1.1.3 Hemicellulose 185

6.1.1.4 Lignin 187

6.2 What Difference Should Be Considered BetweenWood and Agricultural Biomass? 189

6.2.1 Intrapolymeric Bonds 190

6.2.2 Polymeric Inter Bonds 190

6.2.3 Functional Groups and Chemical Characteristics of Lignocellulosic Biomass Components 191

6.2.4 Aromatic Ring 191

6.2.5 Hydroxyl Group 192

6.2.6 Ether Bond 192

6.2.7 Ester Bond 192

6.2.8 Hydrogen Bond 194

6.3 Define Pretreatment 194

6.3.1 What Is the Purpose of Pretreatment? 194

6.4 Steps of Production of Cellulosic Ethanol 195

6.4.1 Pretreatment 195

6.4.2 Hydrolysis 195

6.4.3 What Are the Inhibitors for Biomass Carbohydrate Hydrolysis? 195

6.4.4 Fermentation 196

6.4.5 Formation of Fermentation Inhibitors 196

6.4.6 Sugars Degradation Products 196

6.4.7 Lignin Degradation Products 197

6.4.8 Acetic Acid 197

6.4.9 Inhibitory Extractives 197

6.4.10 Heavy Metal Ions 197

6.4.11 Separation 197

6.5 What Are the Key Considerations for Making a Successful Pretreatment Technology? 198

6.5.1 Effect of Pretreatment on Hydrolysis Process 199

6.6 What Are the GeneralMethods Used in Pretreatment? 199

6.7 What Is Currently Being Done and What Are the Advances? 200

6.7.1 Steam Explosion 201

6.7.2 Hydrothermolysis 204

6.7.3 High-Energy Irradiations 205

6.7.4 Acid Pretreatment 207

6.7.5 Mechanism of Acid Hydrolysis 208

6.7.6 Alkaline Pretreatment 208

6.7.7 Ammonia Pretreatment 210

6.7.8 Ammonia Recycle Percolation (ARP) 210

6.7.9 Ammonia Fiber Expansion (AFEX) 210

6.7.10 Defects of AFEX Process 210

6.7.11 Enzymatic Pretreatment 210

6.7.12 Advantages of Biological Pretreatment 211

6.7.13 Defects of Biological Pretreatment 211

6.8 Summary 211

References 212

7 Green Route to Prepare Renewable Polyesters fromMonomers: Enzymatic Polymerization 219Toufik Naolou

7.1 Philosophic Statement 219

7.2 Introduction 219

7.3 Lipase-Catalyzed Ring-Opening Polymerizations of Cyclic Monomeric Esters (Lactones and Lactides) 220

7.4 Lipase-Catalyzed Polycondensation 223

7.4.1 Dicarboxylic Acid or Its Esters with Diols 224

7.4.2 Dicarboxylic Acid or Its Esters with Polyols 225

7.4.3 Polyesters from Fatty Acid-Based Monomers 226

7.4.3.1 Lipase-Catalyzed Polycondensation of , -Dicarboxylic Acids and Diols 226

7.4.3.2 Lipase-Catalyzed Polycondensation of Hydroxy Fatty Acids 227

7.4.3.3 Fatty Acids as Side Chains to Modify Functional Polyesters 228

7.4.4 Polyester Using Furan as Building Block 229

7.4.5 Conclusions and Remarks 230

7.4.6 Questions for Further Consideration 230

List of Abbreviations 230

References 231

8 Oil-Based and Bio-Derived Thermoplastic Polymer Blends and Composites 239Alessia Quitadamo, ValerieMassardier and Marco Valente

8.1 Introduction 239

8.2 Oil-Based and Bio-Derived Thermoplastic Polymer Blends 240

8.2.1 Comparison Between Oil-Based and Bio-DerivedThermoplastic Polymers 240

8.2.2 Thermoplastics Blends 246

8.3 Thermoplastic Composites with Natural Fillers 252

8.3.1 WoodPlastic Composites 254

8.3.2 Waste Paper as Filler inThermoplastic Composites 260

8.4 Conclusion 263

8.5 Questions for Further Consideration 264

References 264

Index 269