Biofuels and Biorefineries

Volume 8

Editor-in-Chief: Professor Zhen Fang, College of Engineering, Nanjing Agricultural University, Nanjing, China

Editorial Board Members: Professor Liang-shih Fan, Ohio State University, USA Professor John R. Grace, University of British Columbia, Canada Professor Yonghao Ni, University of New Brunswick, Canada Professor Norman R. Scott, Cornell University, USA Professor Richard L. Smith Jr., Tohoku University, Japan Aims and Scope of the Series The Biofuels and Biorefineries Series aims at being a comprehensive and integrated reference for biomass, bioenergy, biofuels, and bioproducts. The series provides leading global research advances and critical evaluations of methods for converting biomass to biofuels and chemicals. Scientific and engineering challenges inbiomass production and conversion are covered that show technological advances and approaches for creating new bio-economies in a format that is suitable for both industrialists and environmental policy decision-makers. The Biofuels and Biorefineries Series provides readers with clear and concisely written chapters that are peer-reviewed on significant topics in biomass production, biofuels, bioproducts, chemicals, catalysts, energy policy, economics, and processing technologies. The text covers major fields of plant science, green chemistry, economics and economy, biotechnology, microbiology, chemical engineering, mechanical engineering, and energy.

Series Description Annual global biomass production is about 220 billion dry tons or 4,500 EJ, equivalent to 8.3 times the world’s energy consumption in 2014 (543 EJ). On the other hand, world-proven oil reserves at the end of 2011 reached 1652.6 billion barrels, which can only meet just over 50 years of global production. Therefore, alternative resources are needed to both supplement and replace fossil oils as the raw material for transportation fuels, chemicals, and materials in petroleum-based industries. Renewable biomass is a likely candidate, because it is prevalent over the Earth and is readily converted to other products. Compared with coal, some of the advantages of biomass are (i) its carbon-neutral and sustainable nature when properly managed, (ii) its reactivity in biological conversion processes, (iii) its potential to produce bio-oil (ca. yields of 75%) by fast pyrolysis because of its high oxygen content, (iv) its low sulfur and lack of undesirable contaminants (e.g., metals, nitrogen content), (v) its wide geographical distribution, and (vi) its potential for creating jobs and industries in energy crop productions and conversion plants. Many researchers, governments, research institutions, and industries are developing projects for converting biomass including forest woody and herbaceous biomass into chemicals, biofuels, and materials, and the race is on for creating new “biorefinery” processes needed for future economies. The development of biorefineries will create remarkable opportunities for the forestry sector and biotechnology, materials, and chemical processing industry and stimulate advances in agriculture. It will help to create a sustainable society and industries that use renewable and carbon-neutral resources.

More information about this series at http://www.springer.com/series/11687 Zhen Fang • Richard L. Smith Jr. Hu Li Editors

Production of Biofuels and Chemicals with Bifunctional Catalysts Editors Zhen Fang Richard L. Smith Jr. College of Engineering Graduate School of Environmental Studies, Nanjing Agricultural University Research Center of Supercritical Fluid Nanjing, Jiangsu, China Technology Tohoku University Hu Li Sendai, Japan College of Engineering Nanjing Agricultural University Nanjing, Jiangsu, China

ISSN 2214-1537 ISSN 2214-1545 (electronic) Biofuels and Biorefineries ISBN 978-981-10-5136-4 ISBN 978-981-10-5137-1 (eBook) https://doi.org/10.1007/978-981-10-5137-1

Library of Congress Control Number: 2017961301

© Springer Nature Singapore Pte Ltd. 2017 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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This Springer imprint is published by Springer Nature The registered company is Springer Nature Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore Preface

Catalytic processes in multiple steps are typically required in the selective conversion of biomass derivatives into value-added chemicals and biofuels. Much effort has been made in the past decades toward the integration of different types of catalytic transformations with a bifunctional catalyst to improve reaction efficiency, enhance product selectivity, and promote specific reaction pathways. This text provides state-of-the-art reviews, current research, prospects, and challenges of production of platform chemicals (e.g., hexose, 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, furfural, and levulinic acid) and liquid biofuels (e.g., biodiesel, 2,5-dimethylfuran, 2-methylfuran, and γ-valerolactone) from sustainable biomass resources with cooperative catalytic processes that include heterogeneous bifunctional chemocatalysis (acid-base, Brønsted-Lewis acid, and metal-acid) and combined bio-/chemo-catalytic routes. Fundamentals of bifunctional catalysis and catalysts, characterization reaction mechanism/pathways, methods for heterogeneous catalysts, the impact of catalyst design on the reactivity, and catalytic process integration are introduced. The application of biomass-derived compounds for the synthesis of commodity chemicals and liquid transportation fuels via various catalytic routes is also covered. This book is the eighth book of the series entitled “Biofuels and Biorefineries,” and it contains 12 chapters contributed by leading experts in the field. The text is arranged into four key areas: Part I: Fundamentals (Chaps. 1 and 2) Part II: Bifunctional Chemocatalysis (Chaps. 3, 4, 5, 6, 7, 8 and 9) Part III: Production of Biodiesel (Chaps. 10 and 11) Part IV: Chemoenzymatic Catalysis (Chap. 12) Chapter 1 presents a brief introduction on the fundamentals of bifunctional catalysis to understand some of the specific roles in designing catalytic materials and a perspective outlook on bifunctional catalytic pathways for biomass transformations. Chapter 2 provides an introduction to characterization methods for heterogeneous catalysts for the general reader and an overview on the fundamentals of the solid acid, metal, and metal-acid bifunctional catalysts for cellulose conversion.

v vi Preface

Chapter 3 focuses on the application of Brønsted-Lewis bifunctional catalysts for efficient biomass conversion and emerging sustainable biorefining processes. Chapter 4 describes the pathways of biofuel production from lignocellulosic biomass and the processes involved in transforming lignocellulosic biomass to biosyn- gas, the research activities on converting syngas into biofuels over bifunctional Fischer-Tropsch synthesis catalysts, and some of the selectivity control strategies that can be adopted with bifunctional catalysts. Chapter 5 illustrates the effect of catalyst functions on product selectivity in the reductive conversion of furfurals in aqueous solutions using heterogeneous catalysts along with some studies on homo- geneous catalysts. Chapter 6 reviews key strategies used to convert biomass into polyols, with special emphasis on the emerging processes aimed to valorize biomass through a cascade approach. Chapter 7 introduces the impact of catalyst design on the activity and the selectivity to lactic acid transformation with particular attention to the production of specific and important products such as γ-valerolactone and valeric fuels. Chapter 8 provides state-of-the-art overview on furanic biofuel production from biomass with a brief description of the 2,5-dimethylfuran and 2-methylfuran production process. Chapter 9 provides an overview on the recent achievements made with bifunctional catalysts for the upgrading of biomass-derived furans via selective hydrogenation, selective oxidation, Diels-Alder reaction, and others, as well as accompanying reaction pathways and plausible reaction mechanisms. Chapter 10 describes the synthesis of biodiesel via simultaneous transesterification and esterification catalyzed by mixed metal oxides, acidic ionic liquids, carbon-based solid acids, magnetic solid acids, and hybrid solid acids, the advantages of heterogeneous catalytic reaction systems, and the guidance on improving the performance of heterogeneous acid catalyst for biodiesel production. Chapter 11 introduces the continuous production of biodiesel fuel from sunflower oil, noned- ible oil, and waste oil in a fixed-bed multiphase reactor packed with bifunctional heterogeneous catalyst. Chapter 12 highlights a series of combined bio-/chemo- catalytic routes that have the potential to facilitate the transition away from petroleum feedstock and toward sustainable and environmentally benign feeds. The text should be of interest to students, researchers, academicians, and industrialists who are working in the areas of catalysis, catalyst design, renewable energy, environmental and chemical sciences, engineering, resource development, biomass processing, sustainability, materials, biofuels, and chemical industries.

Nanjing, China Zhen Fang Sendai, Japan Richard L. Smith Jr. Nanjing, China Hu Li Acknowledgments

First and foremost, we would like to cordially thank all the contributing authors for their great efforts in writing and revising the chapters and ensuring the reliability of the information given in their chapters. Their contributions have really made this project realizable. Apart from the efforts of authors, we would also like to acknowledge the indi- viduals listed below for carefully reading the book chapters and giving many con- structive comments that significantly improved the quality of the chapters: Prof. Stefania Albonetti, Bologna University, Italy Dr. Christophe Bengoa, Universitat Rovira i Virgili, Spain Dr. Luis Francisco Bobadilla, Universidad de Sevilla, CSIC, Spain Dr. Giuseppe Bonura, Consiglio Nazionaledelle Ricerche, Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano,” CNR-ITAE, Italy Prof. Nicolas Brosse, Université de Lorraine, France Dr. Shih-Yuan Chen, National Institute of Advanced Industrial Science and Technology (AIST, Tsukuba), Japan Prof. Dr. Johannes G. de Vries, Leibniz Institute for Catalysis (LIKAT Rostock), Germany Dr. Nikolaos Dimitratos, Cardiff University, UK Dr. Paul-Henri Ducrot, INRA/AgroParisTech, France Dr. Lucía García, Universidad de Zaragoza, Spain Dr. Chao He, Nanyang Technological University, Singapore Prof. Juan Antonio Melero Hernández, Universidad Rey Juan Carlos, Madrid, Spain Dr. Masato Kouzu, Tokyo City University, Japan Prof. Pedro Jesús Maireles-Torres, University of Málaga, Spain Dr. Paivi Maki-Arvela, Åbo Akademi University, Finland Dr. Yoshinao Nakagawa, Tohoku University, Japan Dr. Manuel Fernando R. Pereira, University of Porto (FEUP), Portugal Dr. Martin Rebros, Slovak University of Technology, Slovakia Dr. S. Saravanamurugan, Center of Innovative and Applied Bioprocessing (CIAB), Punjab, India

vii viii Acknowledgments

Dr. Takafumi Sato, Utsunomiya University, Japan Dr. Jesús Canales Vázquez, Universidad de Castilla-La Mancha, Spain Dr. Bin Wang, University of Oklahoma, USA Dr. Ziqiang Xu, Hubei University, China Dr. Aritomo Yamaguchi, National Institute of Advanced Industrial Science and Technology (AIST, Sendai), Japan Professor Hiromi Yamashita, Osaka University, Japan Dr. Ning Yan, National University of Singapore, Singapore Prof. Ji-Jun Zou, Tianjin University, China We are also grateful to Ms. Becky Zhao (senior editor) and Ms. Abbey Huang (editorial assistant) for their encouragement, assistance, and guidance during the preparation of the book. Finally, we would like to express our deepest gratitude toward our families for their love, understanding, and encouragement, which help us in the completion of this project.

Zhen Fang, August 25, 2017, in Nanjing (Zhen Fang)

Richard L. Smith, Jr., August 25, 2017, in Sendai (Richard L. Smith, Jr.)

Hu Li, August 25, 2017, in Nanjing (Hu Li) Contents

Part I Fundamentals 1 Fundamentals of Bifunctional Catalysis for Transforming Biomass-Related Compounds into Chemicals and Biofuels �� 3 Hu Li, Xiao Kong, Zhen Fang, and Richard L. Smith Jr. 2 Introduction to Characterization Methods for Heterogeneous Catalysts and Their Application to Cellulose Conversion Mechanisms �� 31 Xiao Kong, Yifeng Zhu, Hu Li, Zhen Fang, and Richard L. Smith Jr.

Part II Bifunctional Chemocatalysis 3 Brønsted-Lewis Acids for Efficient Conversion of Renewables �� 99 Zichun Wang and Jun Huang 4 Design of Bifunctional Solid Catalysts for Conversion of Biomass- Derived Syngas into Biofuels �� 137 Hao Wang, Yan Pei, Minghua Qiao, and Baoning Zong 5 Reductive Conversion of 5-Hydroxymethylfurfural in Aqueous Solutions by Furan Ring Opening and Rearrangement �� 159 Junya Ohyama and Atsushi Satsuma 6 Catalytic Cascade Transformations of Biomass into Polyols �� 187 Javier Fernández-Rodríguez, Xabier Erdocia, Pedro Luis de Hoyos, Ane Sequeiros, and Jalel Labidi

7 Production and Upgrading of γ-Valerolactone with Bifunctional Catalytic Processes �� 221 Laura Prati, Andrea Jouve, and Alberto Villa

ix x Contents

8 Production of Furanic Biofuels with Zeolite and Metal Oxide Bifunctional Catalysts for Energy-and Product-Driven Biorefineries �� 239 Jesús Requies, Ion Agirre, and Aitziber Iriondo 9 Upgrading of Biomass-Derived Furans into Value-Added Chemicals �� 273 Song Song, Guangjun Wu, Naijia Guan, and Landong Li

Part III Production of Biodiesel 10 Production of Biodiesel via Simultaneous Esterification and Transesterification �� 307 Hu Pan, Heng Zhang, and Song Yang 11 Biodiesel Production from Waste Oil in Multiphase Reactors with Bifunctional Catalyst for Sustainable Energy �� 327 M.E. Borges, J.C. Ruiz-Morales, P. Martín-Zarza, and P. Esparza

Part IV Chemoenzymatic Catalysis 12 Conversion of Biomass Using Simultaneous Chemo- and Bio-catalysis �� 347 Patrick J. Morgan, Fabio Lorenzini, and Andrew C. Marr

Index �� 379 Contributors

Ion Agirre Engineering Faculty of Bilbao, University of Basque Country (UPV/ EHU), Bilbao, Spain M.E. Borges Chemical Engineering Department, University of La Laguna, Tenerife, Spain Pedro Luis de Hoyos Chemical and Environmental Engineering Department, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain Xabier Erdocia Chemical and Environmental Engineering Department, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain P. Esparza Inorganic Chemistry Department, University of La Laguna, Tenerife, Spain Zhen Fang College of Engineering, Nanjing Agricultural University, Nanjing, Jiangsu, China Javier Fernández-Rodríguez Chemical and Environmental Engineering Department, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain Naijia Guan School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, People’s Republic of China Jun Huang Laboratory for Catalysis Engineering, University of Sydney, Sydney, NSW, Australia Aitziber Iriondo Engineering Faculty of Bilbao, University of Basque Country (UPV/EHU), Bilbao, Spain Andrea Jouve Dipartimento di Chimica, Università degli Studi di Milano, Milan, Italy Xiao Kong Biomass Group, College of Engineering, Nanjing Agricultural University, Nanjing, Jiangsu, China

xi xii Contributors

Jalel Labidi Chemical and Environmental Engineering Department, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain Hu Li College of Engineering, Nanjing Agricultural University, Nanjing, Jiangsu, China Landong Li School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, People’s Republic of China Fabio Lorenzini School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast, UK Andrew C. Marr School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast, UK P. Martín-Zarza Inorganic Chemistry Department, University of La Laguna, Tenerife, Spain Patrick J. Morgan School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast, UK Junya Ohyama Materials Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan Hu Pan State-Local Joint Engineering Lab for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, China Yan Pei Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, People’s Republic of China Laura Prati Dipartimento di Chimica, Università degli Studi di Milano, Milan, Italy Minghua Qiao Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, People’s Republic of China Jesús Requies Engineering Faculty of Bilbao, University of Basque Country (UPV/EHU), Bilbao, Spain J.C. Ruiz-Morales Inorganic Chemistry Department, University of La Laguna, Tenerife, Spain Atsushi Satsuma Materials Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan Ane Sequeiros Chemical and Environmental Engineering Department, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain Contributors xiii

Richard L. Smith Jr. Graduate School of Environmental Studies, Research Center of Supercritical Fluid Technology, Tohoku University, Sendai, Japan Song Song School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, People’s Republic of China Alberto Villa Dipartimento di Chimica, Università degli Studi di Milano, Milan, Italy Hao Wang Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, People’s Republic of China Zichun Wang Laboratory for Catalysis Engineering, University of Sydney, Sydney, NSW, Australia Guangjun Wu School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, People’s Republic of China Song Yang State-Local Joint Engineering Lab for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, China Heng Zhang State-Local Joint Engineering Lab for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, China Yifeng Zhu State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China Baoning Zong State Key Laboratory of Catalytic Materials and Chemical Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing, People’s Republic of China About the Editors

Zhen Fang is professor and leader of the biomass group at Nanjing Agricultural University. He is the inventor of the “fast hydrolysis” process. He is listed in the “Most Cited Chinese Researchers” in energy for 2014, 2015, and 2016 (Elsevier-Scopus). Professor Fang specializes in thermal/biochemical conversion of biomass, nanocatalyst synthesis and its applications, and pretreatment of biomass for biorefineries. He obtained his PhDs from China Agricultural University (biological and agricultural engineering, Beijing) and McGill University (materials engineering, Montreal). Professor Fang is associate editor of Biotechnology for Biofuels and is serving on editorial boards of major international journals in energy.

Richard L. Smith Jr. is professor of chemical engineering at the Graduate School of Environmental Studies, Research Center of Supercritical Fluid Technology, Tohoku University, Japan. Professor Smith has a strong background in physical properties and sepa- rations and obtained his PhD in chemical engineering from the Georgia Institute of Technology (USA). His research focuses on developing green chemical processes especially those that use water and carbon dioxide as the solvents in their supercritical state. He has exper- tise in physical property measurements and in separation techniques with ionic liquids and has published more than 200 scientific papers, patents, and reports in the field of chemical engineering. Professor Smith is the Asia regional editor for the Journal of Supercritical Fluids and has served on editorial boards of major international journals associated with properties and energy.

xv xvi About the Editors

Hu Li is a researcher of agricultural engineering in the group of Professor Zhen Fang at Nanjing Agricultural University, China. Dr. Li obtained his PhD from Guizhou University (China). His research focuses on the catalytic conversion of biomass into chemicals and biofuels with functional catalytic materials. Dr. Li has coauthored more than 50 peer-reviewed papers on biomass valorization and is a guest editor of Current Organic Chemistry.