Nanoporous Catalysts for Biomass Conversion

A comprehensive introduction to the design, synthesis, characterization, and catalytic properties of nanoporous catalysts for the biomass conversion 

With the specter of peak oil demand looming on the horizon, and mounting concerns over the environmental impact of greenhouse gas emissions, biomass has taken on a prominent role as a sustainable alternative fuel source. One critical aspect of the biomass challenge is the development of novel catalytic materials for effective and controllable biomass conversion. Edited by two scientists recognized internationally for their pioneering work in the field, this book focuses on nanoporous catalysts, the most promising class of catalytic materials for the conversion of biomass into fuel and other products.

Although various catalysts have been used in the conversion of biomass-derived feedstocks, nanoporous catalysts exhibit high catalytic activities and/or unique product selectivities due to their large surface area, open nanopores, and highly dispersed active sites. This book covers an array of nanoporous catalysts currently in use for biomass conversion, including resins, metal oxides, carbons, mesoporous silicates, polydivinylbenzene, and zeolites. The authors summarize the design, synthesis, characterization and catalytic properties of these nanoporous catalysts for biomass conversions, discussing the features of these catalysts and considering future opportunities for developing more efficient catalysts. Topics covered include:

• Resins for biomass conversion
• Supported metal oxides/sulfides for biomass oxidation and hydrogenation
• Nanoporous metal oxides
• Ordered mesoporous silica-based catalysts
• Sulfonated carbon catalysts
• Porous polydivinylbenzene
• Aluminosilicate zeolites for bio-oil upgrading
• Rice straw Hydrogenation for sugar conversion
• Lignin depolymerization

Timely, authoritative, and comprehensive, Nanoporous Catalysts for Biomass Conversion is a valuable working resource for academic researchers, industrial scientists and graduate students working in the fields of biomass conversion, catalysis, materials science, green and sustainable chemistry, and chemical/process engineering.

Edited by

Feng-Shou Xiao, Zhejiang University, Hangzhou, China

Liang Wang, Zhejiang University, Hangzhou, China

Series Editor

Christian Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium

List of Contributors xiii

Series Preface xvii

Acknowledgements xix

1 Nanoporous Organic Frameworks for Biomass Conversion 1
Xiang Zhu, Chi-Linh Do-Thanh, and Sheng Dai

1.1 Introduction 1

1.2 Nanoporous Crystalline Organic Frameworks 4

1.2.1 Metal–Organic Frameworks 4

1.2.2 Covalent Organic Frameworks 10

1.3 Nanoporous Organic Sulfonated Resins 11

1.3.1 Amberlyst Resins 11

1.3.2 Nafion Resins 11

1.4 Conclusions and Perspective 13

References 13

2 Activated Carbon and Ordered Mesoporous Carbon-Based Catalysts for Biomass Conversion 17
Xiaochen Zhao, Jifeng Pang, Guangyi Li, Fei Liu, Jinming Xu, Mingyuan Zheng, Ning Li, Changzhi Li, Aiqin Wang, and Tao Zhang

2.1 Introduction 17

2.2 Activated Carbon and Mesoporous Carbon 18

2.2.1 Preparation of Activated Carbon and Mesoporous Carbon 18

2.2.2 Properties of Carbon in Catalysis 19

2.2.3 Functionalization of Carbon Materials 20

2.3 Cellulose Conversion 21

2.3.1 Cellulose Hydrolysis 21

2.3.2 Conversion of Cellulose to Hexitols 27

2.3.3 Conversion of Cellulose to Glycols 30

2.3.4 Conversion of Cellulose to Other Important Chemicals 32

2.4 Lignin Conversion 33

2.4.1 Hydrogenolysis (Hydrocracking) 34

2.4.2 Hydrodeoxygenation (HDO) 35

2.4.3 Hydrogenation and Ethanolysis 38

2.5 Synthesis of Biofuel (Diesel or Jet Fuel) from Lignocellulose 39

2.5.1 C–C Coupling Reactions 40

2.5.2 Hydrodeoxygenation (HDO) 42

2.6 Summary 46

References 46

3 Nanoporous Carbon/Nitrogen Materials and their Hybrids for Biomass Conversion 55
Hui Su, Hong-Hui Wang, Tian-Jian Zhao, and Xin-Hao Li

3.1 Introduction 55

3.2 Dehydrogenation of Formic Acid 57

3.2.1 Mono-Metallic Nanoparticle/Carbon–Nitrogen Nanocomposites: Metal-Support Effect 57

3.2.2 Bimetallic Nanoparticle/Carbon–Nitrogen Nanocomposites 59

3.2.3 Trimetallic Nanoparticle/Carbon–Nitrogen Nanocomposites 59

3.2.4 Core–Shell Nanostructure/Carbon–Nitrogen Nanocomposites 60

3.2.5 Reduction of Carbon Dioxide to Formic Acid Using Carbon/Nitrogen Materials 61

3.3 Transfer Hydrogenation of Unsaturated Compounds from Formic Acid 64

3.4 Synthesis of High-Value-Added Chemicals from Biomass 67

3.5 Metal-Free Catalyst: Graphene Oxide for the Conversion of Fructose 71

3.6 Conclusions and Outlook 72

References 73

4 Recent Developments in the Use of Porous Carbon Materials for Cellulose Conversion 79
Abhijit Shrotri, Hirokazu Kobayashi, and Atsushi Fukuoka

4.1 Introduction 79

4.2 Overview of Catalytic Cellulose Hydrolysis 81

4.3 Functionalized Carbon Catalyst for Cellulose Hydrolysis 84

4.3.1 Synthesis and Properties of Carbon Catalysts 84

4.3.2 Sulfonated Carbon Catalyst for Cellulose Hydrolysis 85

4.3.3 Oxygenated Carbon Catalyst for Cellulose Hydrolysis 87

4.3.4 Mechanistic Aspects of Carbon-Catalyzed Cellulose Hydrolysis 90

4.4 Summary and Outlook 93

References 94

5 Ordered Mesoporous Silica-Based Catalysts for Biomass Conversion 99
Liang Wang, Shaodan Xu, Xiangju Meng, and Feng-Shou Xiao

5.1 Introduction 99

5.2 Sulfated Ordered Mesoporous Silicas 100

5.2.1 Conversion of Levulinic Acid to Valerate Esters 100

5.2.2 One-Pot Conversion of Cellulose into Chemicals 101

5.2.3 Dehydration of Xylose to Furfural 104

5.3 Ordered Mesoporous Silica-Supported Polyoxometalates and Sulfated Metal Oxides 106

5.4 Heteroatom-Doped Ordered Mesoporous Silica 108

5.4.1 Al-Doped Mesoporous Silica 108

5.4.2 Sn-Doped Mesoporous Silica 108

5.5 Ordered Mesoporous Silica-Supported Metal Nanoparticles 109

5.5.1 Mesoporous Silica-Supported Pd Nanoparticles 110

5.5.2 Mesoporous Silica-Supported Pt Nanoparticles 111

5.5.3 Mesoporous Silica-Supported Ni Nanoparticles 111

5.6 Overall Summary and Outlook 113

References 115

6 Porous Polydivinylbenzene-Based Solid Catalysts for Biomass Transformation Reactions 127
Fujian Liu and Yao Lin

6.1 Introduction 127

6.2 Synthesis of Porous PDVB-Based Solid Acids and Investigation of their Catalytic Performances 129

6.2.1 Sulfonic Group-Functionalized Porous PDVB 129

6.2.2 Sulfonic Group-Functionalized Porous PDVB-SO3HSO2CF3 132

6.2.3 PDVB-Based Porous Solid Bases for Biomass Transformation 133

6.2.4 Strong Acid Ionic Liquid-Functionalized PDVB-Based Catalysts 135

6.2.5 Cooperative Effects in Applying both PDVB-Based Solid Acids and Solid Bases for Biomass Transformation 141

6.3 Perspectives of PDVB-Based Solid Catalysts and their Application for Biomass Transformations 144

Acknowledgments 144

References 145

7 Designing Zeolite Catalysts to Convert Glycerol, Rice Straw, and Bio-Syngas 149
Chuang Xing, Guohui Yang, Ruiqin Yang, and Noritatsu Tsubaki

7.1 Glycerol Conversion to Propanediols 149

7.1.1 Introduction 149

7.1.2 Mechanisms of Propanediol Synthesis 151

7.1.3 Zeolite Catalysts for Propanediol Synthesis 152

7.1.4 Conclusions and Outlook 156

7.2 Rice Straw Hydrogenation 156

7.2.1 Introduction 156

7.2.2 Direct Conversion of Rice Straw into Sugar Alcohol Through In-Situ Hydrogen 157

7.2.3 Conclusions and Outlook 159

7.3 Bio-Gasoline Direct Synthesis from Bio-Syngas 159

7.3.1 Introduction 159

7.3.2 Biomass Gasification to Bio-Syngas 160

7.3.3 Representative FT Gasoline Synthesis System 161

7.3.4 FT Gasoline Synthesis Catalysts 163

7.3.5 Conclusions and Outlook 168

References 169

8 Depolymerization of Lignin with Nanoporous Catalysts 177
Zhicheng Luo, Jiechen Kong, Liubi Wu, and Chen Zhao

8.1 Introduction 177

8.2 Developed Techniques for Lignin Depolymerization 178

8.2.1 Heterogeneous Noble Metal Catalyst System in the Presence of Hydrogen 178

8.2.2 Heterogeneous Transition Metal Catalyst System in the Presence of Hydrogen 183

8.2.3 Homogeneous Catalyst System for Lignin Depolymerization in the Presence of H2 187

8.2.4 Cleavage of C–O Bonds in Lignin with Metals and Hydrogen-Donor Solvents in the Absence of Hydrogen 188

8.3 Oxidative Depolymerization of Lignin 190

8.3.1 Metal-Supported Oxide Catalysts 191

8.3.2 Polyoxometalate Catalysts 195

8.3.3 Organometallic Catalysts 196

8.3.4 Ionic Liquid Catalysts 197

8.4 Hydrolysis of Lignin with Base and Acid Catalysts 198

8.5 Other Depolymerization Techniques (Cracking, Photocatalysis, Electrocatalysis, and Biocatalysis) 200

8.6 Conclusions 202

Acknowledgments 203

References 203

9 Mesoporous Zeolite for Biomass Conversion 209
Liang Wang, Shaodan Xu, Xiangju Meng, and Feng-Shou Xiao

9.1 Introduction 209

9.2 Production of Biofuels 210

9.2.1 Pyrolysis of Biomass 210

9.2.2 Upgrading of Pyrolysis Oil 211

9.2.3 Conversion of Lipids into Alkane Oil 217

9.2.4 Synthesis of Ethyl Levulinate Biofuel 218

9.3 Conversion of Glycerol 220

9.3.1 Dehydration of Glycerol 220

9.3.2 Etherification of Glycerol 221

9.3.3 Aromatization of Glycerol 223

9.4 Overall Summary and Outlook 224

References 225

10 Lignin Depolymerization Over Porous Copper-Based Mixed-Oxide Catalysts in Supercritical Ethanol 231
Xiaoming Huang, Tamás I. Korányi, and Emiel J. M. Hensen

10.1 Introduction 231

10.1.1 Hydrotalcites 231

10.1.2 Lignin Depolymerization 233

10.2 Lignin Depolymerization by CuMgAl Mixed-Oxide Catalysts in Supercritical Ethanol 234

10.2.1 Effect of Catalyst and Ethanol Solvent 236

10.2.2 Influence of Reaction Parameters and Lignin Source 240

10.2.3 Effect of Catalyst Composition 242

10.3 Conclusions 246

References 248

11 Niobium-Based Catalysts for Biomass Conversion 253
Qineng Xia and Yanqin Wang

11.1 Introduction 253

11.2 Hydrolysis 255

11.3 Dehydration 257

11.3.1 Sorbitol Dehydration 257

11.3.2 Carbohydrate Dehydration 258

11.3.3 Glycerol Dehydration 261

11.4 HMF Hydration to Levulinic Acid 265

11.5 Hydrodeoxygenation 266

11.6 C–C Coupling Reactions 272

11.7 Esterification/Transesterification 272

11.8 Other Reactions in Biomass Conversion 273

11.8.1 Delignification 273

11.8.2 Ring-Opening of GVL 273

11.8.3 Steam Reforming Reaction 274

11.8.4 Ketalization 274

11.9 Summary and Outlook 274

References 275

12 Towards More Sustainable Chemical Synthesis, Using Formic Acid as a Renewable Feedstock 283
Shu-Shuang Li, Lei Tao, Yong-Mei Liu, and Yong Cao

12.1 Introduction 283

12.2 General Properties of FA and Implications for Green Synthesis 285

12.3 Transformation of Bio-Based Platform Chemicals 286

12.3.1 Reductive Transformation Using FA as a Hydrogen Source 286

12.3.2 Tandem Transformation Using FA as a Versatile Reagent 291

12.4 FA-Mediated Depolymerization of Lignin or Chitin 292

12.4.1 Lignin Depolymerization using FA 292

12.4.2 Chitin Depolymerization using FA 295

12.5 Upgrading of Bio-Oil and Related Model Compounds 296

12.6 FA as the Direct Feedstock for Bulk Chemical Synthesis 297

12.7 Conclusions and Outlook 300

References 300

Index 307

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