Introduction to Renewable Biomaterials

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 acclaimed BioSUCCEED 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 journal BioResources.

• List of Contributors xiiiPreface xv1 Fundamental Biochemical and Biotechnological Principles of Biomass Growth and Use 1Manfred Kircher1.1 Learning Objectives 11.2 Comparison of Fossil-Based versus Bio-Based Raw Materials 21.2.1 The Nature of Fossil Raw Materials 21.2.2 Industrial Use 31.2.2.1 Energy 31.2.2.2 Chemicals 41.2.3 Expectancy of Resources 81.2.4 Green House Gas (GHG) Emission 81.2.5 Regional Pillars of Competitiveness 91.2.6 Questions for Further Consideration 111.3 TheNatureofBio-BasedRawMaterials 111.3.1 Oil Crops 111.3.2 Sugar Crops 131.3.3 Starch Crops 141.3.4 Lignocellulosic Plants 151.3.5 Lignocellulosic Biomass 161.3.6 Algae 161.3.7 Plant Breeding 171.3.8 Basic Transformation Principles 171.3.8.1 First Generation 171.3.8.2 Second Generation 181.3.8.3 Third Generation 181.3.9 Industrial Use 181.3.9.1 Energy 181.3.9.2 Chemicals 201.3.9.3 Biocatalysts 221.3.9.4 Pharmaceuticals 231.3.9.5 Nutrition 241.3.9.6 Polymers 241.3.10 Expectancy of Resources 261.3.11 Green House Gas Emission 261.3.12 Regional Pillars of Competitiveness 271.3.13 Questions for Further Consideration 291.4 General Considerations Surrounding Bio-Based Raw Materials 291.4.1 Economical Challenges 291.4.2 Feedstock Demand Challenges 301.4.3 Ecological Considerations 311.4.4 Societal Considerations 311.4.4.1 Food Security 311.4.4.2 Public Acceptance 321.5 Research Advances Made Recently 321.5.1 First-Generation Processes and Products 321.5.2 Second-Generation Processes and Products 331.5.3 Third-Generation Processes and Products 331.6 Prominent Scientists Working in this Arena 341.7 Summary 351.8 Study Problems 351.9 Key References 36References 362 Fundamental Science and Applications for Biomaterials 39Ali S. Ayoub and Lucian A. Lucia2.1 Introduction 392.2 What are the Biopolymers that Encompass the Structure and Function of Lignocellulosics? 392.2.1 Cellulose 402.2.2 Heteropolysaccharides 432.2.3 Lignin 452.2.4 The Discovery of Cellulose and Lignin 472.3 Chemical Reactivity of Cellulose, Heteropolysaccharides, and Lignin 482.3.1 Cellulose Reactivity 482.3.1.1 Reactivity Measurements 502.3.1.2 Dissolving-Grade Pulps 512.3.1.3 Converting Paper-Grade Pulps into Dissolving-Grade Pulps 512.3.2 Hemicellulose Reactivity 512.3.2.1 Structural Characterization of Hemicellulose 522.3.3 Lignin Reactivity 532.4 Composite as a Unique Application for Renewable Materials 532.4.1 Rationale and Significance 542.4.2 Starch-Based Materials 552.4.3 Starch-Based Plastics 562.4.3.1 Novamont 572.4.3.2 Cereplast 582.4.3.3 Ecobras 582.4.3.4 Biotec 582.4.3.5 Plantic 592.4.3.6 Biolice 592.4.3.7 KTM Industries 592.4.3.8 Cerestech, Inc. 592.4.3.9 Teknor Apex 602.5 Question for Further Consideration 60References 603 Conversion Technologies 63Maurycy Daroch3.1 Learning Objectives 633.2 Energy Scenario at Global Level 633.2.1 Why Our Energy is so Important? 633.2.2 Black Treasure Chest 643.2.3 Conventional Fossil Resources and their Alternatives 663.2.3.1 Light Crude Oil (Conventional Oil) 663.2.3.2 Coal 663.2.3.3 Natural Gas 663.2.3.4 Shale Oil (Tight Oil) 673.2.3.5 Oil Sands, Bitumen Extra Heavy Oil 673.2.3.6 Shale Gas 673.2.3.7 Methane (Gas) Hydrates 673.2.3.8 EROI – How Much Fuel in Fuel? 683.2.3.9 Environmental Effects of Fossil Resource Utilisation 693.3 Biomass 713.3.1 Renewable Energy and Renewable Carbon 713.3.2 Why Different Types of Biomass have the Properties they Have? 733.4 Biomass Conversion Methods 753.4.1 Conversion of Biochemical Energy Perspective 753.4.2 Overview of Biomass Conversion Technologies 783.4.3 Thermochemical Conversion of Biomass 783.4.4 Biomass Combustion 803.4.5 Gasification 813.4.6 Pyrolysis 843.4.7 Conversion of Oily Feedstocks 863.4.8 Biochemical Conversion of Biomass 883.4.8.1 Aerobic and Anaerobic Metabolisms 883.4.8.2 Central Metabolic Pathway under Anaerobic Conditions 893.4.9 Harvesting Energy from Biochemical Processes 913.4.9.1 Ethanol Fermentation 913.4.9.2 ABE Fermentation 923.4.9.3 Biohydrogen 933.4.9.4 Biomethane 943.5 Metrics to Assist the Transition Towards Sustainable Production of Bioenergy and Biomaterials 953.5.1 EROI – Primary Metrics of Energy Carrier Efficiency 953.5.2 LCA – Sustainability Determinant 963.5.3 Environmental Assessment of Bioenergy Production Processes 973.5.3.1 Impacts Related to Land-Use Change 973.5.3.2 Impacts of Feedstock Cultivation 983.5.3.3 Impacts of Conversion Process 983.5.3.4 Impacts of Product Use 983.5.4 Sustainability Metrics in Biomass and Bioenergy Policies 993.5.5 Renewable and Non-Renewable Carbon – Taxation and Subsidies 993.6 Summary 1023.7 Key References 102References 1034 Characterization Methods and Techniques 107Noppadon Sathitsuksanoh and Scott Renneckar4.1 Philosophy Statement 1074.2 Understanding the Characteristics of Biomass 1074.3 Taking Precautions Prior to Setting Up Experiments for Biomass Analysis 1084.4 Classifying Biomass Sizes for Proper Analysis 1094.5 Moisture Content of Biomass and Importance of Drying Samples Prior to Analysis 1104.6 When the Carbon is Burned 1114.7 Structural Cell Wall Analysis, What To Look For 1124.8 Hydrolyzing Biomass and Determining Its Composition 1144.8.1 Analyzing Filtrate by HPLC for Monosaccharide Contents 1154.8.2 Choosing the HPLC Column and Its Operating Conditions 1154.9 Determining Cell Wall Structures Through Spectroscopy and Scattering 1164.9.1 Probing the Chemical Structure of Biomass 1164.9.1.1 X-Ray Diffraction (XRD) 1184.9.1.2 Cross-polarization/Magic Angle Spinning (CP/MAS) 13 CNMR 1194.9.1.3 Fourier-Transform Infrared Spectroscopy (FTIR) 1214.9.1.4 Raman Analysis 1224.10 Examining the Size of the Biopolymers: Molecular Weight Analysis 1234.11 Intricacies of Understanding Lignin Structure 1254.11.1 13 Cnmr 1264.11.2 31 Pnmr 1264.11.3 2d Hsqc 1284.11.4 Methoxyl Content Determination 1324.11.4.1 1 Hnmr 1324.11.4.2 Hydriodic Acid 1324.11.4.3 Direct Methanol 1324.12 Questions for Further Consideration 132References 1325 Introduction to Life-Cycle Assessment and Decision Making Applied to Forest Biomaterials 141Jesse Daystar and Richard Venditti5.1 Introduction 1415.1.1 What is LCA? 1415.1.1.1 History 1425.1.2 LCA for Decision Making 1425.1.2.1 Eco-labels 1435.2 LCA Components Overview 1445.2.1 Goal and Scope Definition 1455.2.2 Inventory Analysis 1455.2.3 Life-Cycle Impact Assessment 1465.2.4 Interpretation 1465.3 Life-Cycle Assessment Steps 1465.3.1 Goal, Scope, System Boundaries 1465.3.1.1 Goal Definition 1465.3.1.2 Scope Definition 1475.3.1.3 Functional Unit 1485.3.1.4 Cutoff Criteria 1485.3.1.5 Problems Set – Goal and Scope Definition 1485.3.2 Life-Cycle Inventory 1505.3.2.1 Preparation of Data Collection Based on Goal and Scope 1515.3.2.2 Data Collection 1525.3.2.3 Data Quality 1555.3.2.4 Coproduct Treatment – Allocation 1575.3.2.5 Relating Data to the Unit Process 1585.3.2.6 Relating Data to the Functional Unit 1595.3.2.7 Data Aggregation 1595.3.2.8 LCI Data Interpretation 1595.3.2.9 Problems Set – Life-Cycle Inventory 1605.3.2.10 Mandatory Elements 1665.3.2.11 Classification 1685.3.2.12 Characterization 1695.3.2.13 Optional Elements 1705.3.2.14 Life Cycle Impact Assessment Interpretation 1735.3.2.15 Problems Set –Life-Cycle Impact Assessment 1735.4 LCA Tools for Forest Biomaterials 1775.4.1 Ficat 1775.4.2 GREET Model 178References 1786 First Principles of Pretreatment and Cracking Biomass to Fundamental Building Blocks 181Amir Daraei Garmakhany and Somayeh Sheykhnazari6.1 Introduction 1816.1.1 What Is Lignocellulosic Material? 1836.1.1.1 Lignocellulosic Materials 1836.1.1.2 Cellulose 1836.1.1.3 Hemicellulose 1856.1.1.4 Lignin 1876.2 What Difference Should Be Considered Between Wood and Agricultural Biomass? 1896.2.1 Intrapolymeric Bonds 1906.2.2 Polymeric Inter Bonds 1906.2.3 Functional Groups and Chemical Characteristics of Lignocellulosic Biomass Components 1916.2.4 Aromatic Ring 1916.2.5 Hydroxyl Group 1926.2.6 Ether Bond 1926.2.7 Ester Bond 1926.2.8 Hydrogen Bond 1946.3 Define Pretreatment 1946.3.1 What Is the Purpose of Pretreatment? 1946.4 Steps of Production of Cellulosic Ethanol 1956.4.1 Pretreatment 1956.4.2 Hydrolysis 1956.4.3 What Are the Inhibitors for Biomass Carbohydrate Hydrolysis? 1956.4.4 Fermentation 1966.4.5 Formation of Fermentation Inhibitors 1966.4.6 Sugars Degradation Products 1966.4.7 Lignin Degradation Products 1976.4.8 Acetic Acid 1976.4.9 Inhibitory Extractives 1976.4.10 Heavy Metal Ions 1976.4.11 Separation 1976.5 What Are the Key Considerations for Making a Successful Pretreatment Technology? 1986.5.1 Effect of Pretreatment on Hydrolysis Process 1996.6 What Are the General Methods Used in Pretreatment? 1996.7 What Is Currently Being Done and What Are the Advances? 2006.7.1 Steam Explosion 2016.7.2 Hydrothermolysis 2046.7.3 High-Energy Irradiations 2056.7.4 Acid Pretreatment 2076.7.5 Mechanism of Acid Hydrolysis 2086.7.6 Alkaline Pretreatment 2086.7.7 Ammonia Pretreatment 2106.7.8 Ammonia Recycle Percolation (ARP) 2106.7.9 Ammonia Fiber Expansion (AFEX) 2106.7.10 Defects of AFEX Process 2106.7.11 Enzymatic Pretreatment 2106.7.12 Advantages of Biological Pretreatment 2116.7.13 Defects of Biological Pretreatment 2116.8 Summary 211References 2127 Green Route to Prepare Renewable Polyesters from Monomers: Enzymatic Polymerization 219Toufik Naolou7.1 Philosophic Statement 2197.2 Introduction 2197.3 Lipase-Catalyzed Ring-Opening Polymerizations of Cyclic Monomeric Esters (Lactones and Lactides) 2207.4 Lipase-Catalyzed Polycondensation 2237.4.1 Dicarboxylic Acid or Its Esters with Diols 2247.4.2 Dicarboxylic Acid or Its Esters with Polyols 2257.4.3 Polyesters from Fatty Acid-Based Monomers 2267.4.3.1 Lipase-Catalyzed Polycondensation of α, ω-Dicarboxylic Acids and Diols 2267.4.3.2 Lipase-Catalyzed Polycondensation of Hydroxy Fatty Acids 2277.4.3.3 Fatty Acids as Side Chains to Modify Functional Polyesters 2287.4.4 Polyester Using Furan as Building Block 2297.4.5 Conclusions and Remarks 2307.4.6 Questions for Further Consideration 230List of Abbreviations 230References 2318 Oil-Based and Bio-Derived Thermoplastic Polymer Blends and Composites 239Alessia Quitadamo, Valerie Massardier and Marco Valente8.1 Introduction 2398.2 Oil-Based and Bio-Derived Thermoplastic Polymer Blends 2408.2.1 Comparison Between Oil-Based and Bio-Derived Thermoplastic Polymers 2408.2.2 Thermoplastics Blends 2468.3 Thermoplastic Composites with Natural Fillers 2528.3.1 Wood–Plastic Composites 2548.3.2 Waste Paper as Filler in Thermoplastic Composites 2608.4 Conclusion 2638.5 Questions for Further Consideration 264References 264Index 269

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