Biofuels: Alternative Feedstocks and Conversion Processes

Table of Contents

Cover image

Front matter

Copyright

Preface

Contributors

Chapter 1. Principles of Biorefining

1. Introduction

2. From fossil to biomass raw materials

3. Biomass processing in biorefinery

4. Lignocellulosic molecular components and their derivatives

5. Biorefinery to replace existing fossil bulk chemicals

6. Biorefinery to produce alternative products

7. Next research outlook

Chapter 2. Life-Cycle Assessment of Biofuels

1. Introduction

2. The concept of LCA and its application to biofuels

3. Methodology and assumptions

4. Case study: bioethanol from wheat

5. Results

6. Conclusions

Chapter 3. Thermochemical Conversion of Biomass to Biofuels

1. Introduction

2. Feedstocks for biofuels

3. Composition of lignocellulosic biomass

4. Lignocellulosic biomass pretreatment techniques

5. Biotechnological conversion

6. Thermochemical conversion

7. Bio-refineries and biofuels

8. Typical issues for life-cycle analysis

9. Perspectives and challenges

Chapter 4. Biomass-derived Syngas Fermentation into Biofuels

1. Background

2. Fundamental aspects of syngas fermentation

3. Microbiology of syngas fermentation

4. Syngas characteristics

5. Current developments in syngas fermentation

6. Factors affecting syngas fermentation

7. Industrial-scale syngas fermentation

8. Challenges and future research directions

9. Summary

Chapter 5. Lignocellulosic Bioethanol

1. Introduction

2. First-generation fuel ethanol production: the feedstock and the process and their constraints

3. Second-generation ethanol production

4. Feasibility of lignocellulosic ethanol production

5. Concluding remarks

Chapter 6. Technoeconomic Analysis of Lignocellulosic Ethanol

1. Introduction

2. State of the art

3. Key drivers of the lignocellulosic ethanol production cost

4. Cost management system

5. Current economic evaluation of lignocellulosic bioethanol: some limitations

6. Conclusion

Chapter 7. Pretreatment Technologies for Lignocellulose-to-Bioethanol Conversion

1. Introduction

2. Toxic Compounds Generated During Pretreatment

3. Pretreatment processes

4. Biological pretreatments

5. Concluding remarks

Chapter 8. Production of Celluloytic Enzymes for the Hydrolysis of Lignocellulosic Biomass

1. Introduction

2. Cellulase: mode of action

3. Cellulase systems and the control of cellulase gene expression

4. Cellulase producers

5. Pretreatment

6. Bioprocesses for cellulase production

7. Applications of cellulases

8. Cellulase market scenario

9. Engineered/artificial cellulases

10. Future perspectives

11. Challenges

12. Conclusion

Chapter 9. Production of Hemicellulolytic Enzymes for Hydrolysis of Lignocellulosic Biomass

1. Introduction

2. Structure of hemicellulose

3. Hemicellulases

4. Endoxylanases

5. β-d-xylosidases

6. α-Arabinofuranosidases

7. Acetylxylan esterases

8. α-d-Glucuronidases

9. Mannanases

10. Methods for assay of hemicellulolytic activity

11. Domain organization of hemicellulases

12. Multiplicity of hemicellulases

13. Functional genomics approach for studying hemicellulases

14. Enzyme production

15. Applications of hemicellulases

Chapter 10. Hydrolysis of Lignocellulosic Biomass for Bioethanol Production

1. Introduction

2. Chemical hydrolysis

3. Enzymatic hydrolysis

4. Separate and simultaneous hydrolysis

5. Factors affecting enzymatic hydrolysis

6. Recycling of enzymes

7. Methods for improving enzymatic hydrolysis

8. Kinetic model for enzymatic hydrolysis of lignocelluloses

9. Conclusions

Chapter 11. Production of Bioethanol from Agroindustrial Residues as Feedstocks

1. Introduction

2. Lignocellulosic biomass

3. Pretreatment

4. Saccharification

5. Fermentation

6. Energy production using agroindustrial residues

7. Case studies

8. Conclusions

Chapter 12. Fermentation Inhibitors in Ethanol Processes and Different Strategies to Reduce Their Effects

1. Introduction

2. Common inhibitors for ethanol production

3. Formation of inhibitors in lignocelluloses hydrolyzates

4. Strategies for minimizing the effects of inhibitors

5. Conclusion

Chapter 13. Biotechnological Methods to Produce Biodiesel

List of Abbreviations

1. Introduction

2. Enzymatic transesterification

3. Enzymatic esterification

4. Hydroesterification

5. Reactor configurations

6. Economic evaluation of enzymatic biodiesel production

7. Conclusions

Chapter 14. Biodiesel Production in Supercritical Fluids

1. Introduction

2. Supercritical fluid reaction

3. Biodiesel production in non-catalytic supercritical fluid reaction

4. Conclusion

Chapter 15. Production of Biodiesel Using Palm Oil

1. Introduction

2. Palm biodiesel conversion technology

3. Conclusions

Chapter 16. Biodiesel Production from Waste Oils

1. Introduction

2. Biodiesel

3. Waste oils

4. Technical aspect of bd production from waste oils

5. Feasibility and economic analyses on bd production from waste oils

6. Concluding remarks and future prospects

Chapter 17. Production of Biodiesel from Algal Biomass

1. Introduction

2. Two approaches leading to lipid accumulation in microalgae

3. Efforts to further reduce costs of mass culture of heterotrophic microalgae in search for cheap substitutes of glucose

4. The scaleup of heterotrophic microalgal biomass production

5. Progresses in lipid analysis

6. The conversion of algal biomass to biodiesel

7. The quality and economic analysis of algal biodiesel

8. Concluding remark and future perspectives

Chapter 18. Overview and Assessment of Algal Biofuels Production Technologies

1. Introduction

2. Autotrophic production technologies

3. Heterotrophic and mixotrophic production

4. Harvesting and processing of algal biomass

5. Challenges in large-scale cultivation of algae

6. Resource constraints for mass production of microalgae

7. Energy analysis

8. Life-cycle assessment

9. Future perspectives: challenges and opportunities

Chapter 19. Cultivation of Algae in Photobioreactors for Biodiesel Production

1. Introduction

2. Basic concepts of photobioreactor engineering

3. Modeling of microalgae cultivation systems

4. Productivity of microalgal cultivation systems

5. Engineering parameters governing photobioreactor productivity

6. Existing technology

Chapter 20. Production of Biohydrogen

1. Introduction

2. Feedstock

3. Economics of biohydrogen production

4. Future prospects and challenge

5. Conclusions

Chapter 21. Biohydrogen Production from Bio-oil

1. Introduction

2. Reforming of bio-oil

3. Water-gas shift reaction of syngas

4. Purification of biohydrogen and storage

5. Steam requirement for biohydrogen production

6. Harvesting and processing of forest biomass

7. Capital cost of bio-oil production plant

8. Operating cost of bio-oil plant

9. Production cost of bio-oil

10. Cost of bio-oil reforming

12. Bio-oil-based biohydrogen cost

Chapter 22. Biohydrogen Production from Industrial Effluents

1. Introduction

2. Biological routes of H2 production

3. Biocatalyst

4. Renewable wastewater

5. Factors influencing H2 production

6. Combined process efficiency

7. Process limitations

8. Strategies to enhance process efficiency

9. Future outlook

Chapter 23. Thermophilic Biohydrogen Production

1. Background

2. Thermodynamic aspects

3. Biochemical pathways and microbiology

4. effect of process conditions

5. Practical applications

6. Challenges, possibilities, and future perspectives

Chapter 24. Biohydrogen Production with High-Rate Bioreactors

1. Introduction

2. Integrated Continuously stirred tank reactors

3. Anaerobic fluidized-bed reactor

4. Packed-bed REACTORS

5. Upflow anaerobic sludge blanket reactors

6. Photobioreactors

7. Microbial electrolysis cells

8. Comparison of various biohydrogen reactor systems

9. Challenges and future implications

10. Conclusions

Chapter 25. Butanol Fuel from Biomass

1. Introduction

2. Butanol production by clostridia: the abe fermentation

3. Sporulation and solventogenesis: the scope for decoupling

4. Metabolic engineering approaches to improve abe fermentation

5. Fermentation technologies and downstream processing for abe fermentation

6. Conclusions

Chapter 26. Production of Green Liquid Hydrocarbon Fuels

1. Introduction

2. Desired characteristics of green liquid hydrocarbon fuels (GLHF)

3. Technologies for production of GLHF

4. Feedstock considerations for GLHF

5. Conclusion

Index

Front matter

BIOFUELS

Biofuels

Alternative Feedstocks and Conversion Processes

Edited by

Ashok Pandey

National Institute for Interdisciplinary Science and Technology, Council of Scientific and Industrial Research, Trivandrum, India

Christian Larroche

Biological Engineering Department, Chemical and Biochemical Engineering Laboratory, Polytech Clermont-Ferrand, Blaise Pascal University, France

Steven C Ricke

Food Science Department, Division of Agriculture, University of Arkansas, USA

Claude

-

Gilles Dussap

Laboratoire de Génie Chimique et Biochimique, Polytech Clermont-Ferrand, Blaise Pascal University, France

Edgard Gnansounou

Head, Bioenergy Group, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

Copyright

Academic Press is an imprint of Elsevier

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Library of Congress Cataloging-in-Publication Data

Biofuels : alternative feedstocks and conversion processes / edited by Ashok Pandey … [et al.] — 1st ed.

p. cm.

ISBN 978-0-12-385099-7

1. Biomass energy. I. Pandey, Ashok.

TP339.B539 2011

333.95′39—dc22

2011005287

British Library Cataloguing in Publication Data

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ISBN: 978-0-12-385099-7

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11 12 13 14 10 9 8 7 6 5 4 3 2 1

Preface

With the increasing demand of energy world over and depleting reserves of conventional fossil fuel, there has been growing global interest in developing alternative sources of energy. Also, there has been concern in growing economies with energy security. Biofuels offer much promise on these frontiers. In addition to above, they also offer benefits on environmental impact in comparison to fossil fuels. The present book provides state-of-the-art information on the status of the biofuel production and related aspects and also identifies the future R&D directions and perspectives.

The book has five sections. Section I is general and presents four chapters which deal with the principles of biorefineries, life cycle assessment of biofuels, thermochemical conversion of biomass to biofuels, and biomass-derived syngas fermentation into biofuels. Section II deals with different aspects of the production of second-generation bioethanol from lignocellulosic feedstocks. The first chapter in this section is introductory, giving state-of-the-art information on the status and perspectives; this is followed by a chapter on techno-economic analysis of lignocellulosic bioethanol. Subsequent chapters deal with the different aspects of bioconversion process such as the pretreatment of lignocellulosic biomass, production of cellulolytic and hemicellulolytic enzymes for the hydrolysis of lignocellulosic biomass, hydrolysis oflignocellulosic biomass, production of bioethanol from agro-industrial residues as feedstocks, and removal of inhibitory compounds from lignocellulosic hydrolyzates for bioethanol production. Section IIIA presents state-of-the-art information on the production of second-generation biodiesel from oilseeds. In this, the first chapter is introductory and presents current perspectives and future, followed by the biotechnological methods to produce biodiesel, biodiesel production in supercritical fluids, biodiesel production using palm oil, and biodiesel from waste oil. Section IIIB contains chapters dealing with the production of third-generation biofuels from algal sources. The first chapter in this section as usual presents the current perspectives and future, followed by life cycle assessment of algal biodiesel, and the cultivation of algae in photobioreactors.

Section IV is devoted on the fourth-generation biofuels, that is, biohydrogen. The section has five chapters and the first one gives general information with current perspectives and future. The other chapters are on biohydrogen production from bio-oils and industrial effluents, thermophilic biohydrogen production, and biohydrogen production with high-rate bioreactors. Section V provides two articles on the production of biobutanol and production of green liquid hydrocarbon fuels.

We thank the authors of all the chapters for their cooperation and also for their preparedness in revising the manuscripts in a time-framed manner. We also acknowledge the help from the reviewers, who in spite of their busy professional activities helped us by evaluating the manuscripts and gave their critical inputs to refine and improve the chapters. We warmly thank Dr. Marinakis Kostas and Dr. Anita Koch and the team of Elsevier for their cooperation and efforts in producing this book.

We sincerely hope that the current discourse on biofuels R&D would go a long way in bringing out the exciting technological possibilities and ushering the readers toward the frontiers of knowledge in the area of biofuels.

The text in all the chapters is supported by numerous clear, informative diagrams and tables. The book would be of great interest to the postgraduate students and researchers of applied biology, biotechnology, microbiology, biochemical, and chemical engineers working on biofuels.

Ashok Pandey, Christian Larroche, Steven Ricke, Claude-Gilles Dussap and Edgard Gnansounou

Editors

Contributors

Deepthy Alex

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

P. Alvira

CIEMAT, Renewable Energy Division, Biofuels Unit Av. Complutese 22, 28040 Madrid

Irini Angelidaki

Department of Environmental Engineering, Technical University of Denmark, Lyngby, Denmark

Amar Anumakonda

UOP LLC, 25 E. Algonquin Road, Des Plaines, IL 60616, USA

M. Ballestero

CIEMAT, Renewable Energy Division, Biofuels Unit Av. Complutese 22, 28040 Madrid

Thallada Bhaskar

Bio-Fuels Division (BFD), Indian Institute of Petroleum (IIP), Council of Scientific and Industrial Research (CSIR), Dehradun 248005, India

Balagurumurthy Bhavya

Bio-Fuels Division (BFD), Indian Institute of Petroleum (IIP), Council of Scientific and Industrial Research (CSIR), Dehradun 248005, India

Parameswaran Binod

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

Carlos A. Cardona

Departamento de Ingeniería Química, Universidad Nacional de Colombia Sede Manizales, Cra. 27 No. 64-60, Manizales, Colombia

Elisa d'Avila Cavalcanti-Oliveira

Universidade Federal do Rio de Janeiro, Instituto de Química, Av. Athos da Silveira Ramos, 149 - CT, Bloco A, lab. 549-1, CEP 21941-909 Rio de Janeiro, RJ, Brazil

Yi-Feng Chen

School of Life Sciences, Tsinghua University, Beijing 100084, People's Republic of China

Francesco Cherubini

Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway

Arnaud Dauriat

ENERS Energy Concept, P.O. Box 56, CH-1015 Lausanne, Switzerland

Joab Sampaio de Sousa

Universidade Federal do Rio de Janeiro, Instituto de Química, Av. Athos da Silveira Ramos, 149 - CT, Bloco A, lab. 549-1, CEP 21941-909 Rio de Janeiro, RJ, Brazil

Vincenza Faraco

Department of Organic Chemistry and Biochemistry, University of Naples Federico II, Complesso Universitario Monte S. Angelo, via Cintia 4 80126, Naples, Italy

Edgard Gnansounou

Bioenergy and Energy Planning Research Group (BPE), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

Lalitha Devi Gottumukkala

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology – CSIR, Trivandrum 695 019, India

Hari Bhagwan Goyal

Bio-Fuels division (BFD), Indian Institute of Petroleum (IIP), Council of Scientific and Industrial Research (CSIR), Dehradun 248005, India

Denise Maria Guimarães Freire

Universidade Federal do Rio de Janeiro, Instituto de Química, Av. Athos da Silveira Ramos, 149 - CT, Bloco A, lab. 549-1, CEP 21941-909 Rio de Janeiro, RJ, Brazil

Lien-Huong Huynh

Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 sec. 4, Keelung Road, Taipei 10607, Taiwan

K.U. Janu

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

Yi-Hsu Ju

Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 sec. 4, Keelung Road, Taipei 10607, Taiwan

Dimitar Karakashev

Department of Environmental Engineering, Technical University of Denmark, Lyngby, Denmark

Keikhosro Karimi

Chemical Engineering Department, Isfahan University of Technology, Iran

Susan Karp

Department of Bioprocess Engineering and Biotechnology, Federal University of Parana, P.O. Box 19011, Curitiba, Brazil

Novy S. Kasim

Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 sec. 4, Keelung Road, Taipei 10607, Taiwan

Samir Kumar Khanal

Department of Molecular Biosciences and Bioengineering (MBBE), University of Hawai'i at Mānoa, Agricultural Science Building 218, 1955 East-West Road, Honolulu, Hawaii 96822

Ajay Kumar

Bio-Fuels Division (BFD), Indian Institute of Petroleum (IIP), Council of Scientific and Industrial Research (CSIR), Dehradun 248005, India

Amit Kumar

Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta, Canada T6G 2G8

Man Kee Lam

School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia

Duu-Jong Lee

Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan

Keat Teong Lee

School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia

Wen-Wei Li

Department of Chemistry, University of Science and Technology of China, Hefei, 230026 China

S. Venkata Mohan

Bioengineering and Environmental Centre (BEEC), Indian Institute of Chemical Technology (IICT), Hyderabad-500007, India

G. Mohanakrishna

Bioengineering and Environmental Centre (BEEC), Indian Institute of Chemical Technology (IICT), Hyderabad-500007, India

Pradeep Chaminda Munasinghe

Department of Molecular Biosciences and Bioengineering (MBBE), University of Hawai'i at Mānoa, Agricultural Science Building 218, 1955 East-West Road, Honolulu, Hawaii 96822

Ganti S. Murthy

Biological and Ecological Engineering, Oregon State University, USA

Desavath Viswanath Naik

Bio-Fuels Division (BFD), Indian Institute of Petroleum (IIP), Council of Scientific and Industrial Research (CSIR), Dehradun 248005, India

M.J. Negro

CIEMAT, Renewable Energy Division, Biofuels Unit Av. Complutese 22, 28040 Madrid, Spain

Ashok Pandey

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

J. Pruvost

GEPEA, Université de Nantes, CNRS, UMR6144, boulevard de l'Université, CRTT – BP 406, 44602 Saint-Nazaire Cedex, France

Julián A. Quintero

Departamento de Ingeniería Química, Universidad Nacional de Colombia Sede Manizales, Cra. 27 No. 64-60, Manizales, Colombia

Kuniparambil Rajasree

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Industrial Estate PO, Trivandrum 695 019, India

Reeta Rani Singhania

Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

Anjan Ray

UOP India Pvt Ltd, 6th floor, Building 9B, Cyber City, DLF Phase III, Gurgaon-122002, India

Carlos Ricardo Soccol

Department of Bioprocess Engineering and Biotechnology, Federal University of Parana, P.O. Box 19011, Curitiba, Brazil

Luis E. Rincón

Departamento de Ingeniería Química, Universidad Nacional de Colombia Sede Manizales, Cra. 27 No. 64-60, Manizales, Colombia

Susanjib Sarkar

Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta, Canada T6G 2G8

Manju Sharma

Department of Microbiology, Guru Nanak Dev University, Amritsar-143 005, India

Kuan-Yeow Show

Department of Environmental Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman, Jalan University, Bandar Barat, 31900 Kampar, Perak, Malaysia

Ravindran Sindhu

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

Bhupinder Singh Chadha

Department of Microbiology, Guru Nanak Dev University, Amritsar-143 005, India

Rawel Singh

Bio-Fuels Division (BFD), Indian Institute of Petroleum (IIP), Council of Scientific and Industrial Research (CSIR), Dehradun 248005, India

S. Srikanth

Bioengineering and Environmental Centre (BEEC), Indian Institute of Chemical Technology (IICT), Hyderabad-500007, India

Anders H. Strømman

Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway

Rajeev K. Sukumaran

Centre for Biofuels, Biotechnology Division, National Institute for Interdisciplinary Science and Technology, CSIR, Trivandrum 695 019, India

Mohammad J. Taherzadeh

School of Engineering, University of Borås, Sweden

Kok Tat Tan

School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia

Vanete Thomaz-Soccol

Industrial Biotechnology Program, Positivo University, Curitiba, Brazil

E. Tomás-Pejó

CIEMAT, Renewable Energy Division, Biofuels Unit Av. Complutese 22, 28040 Madrid, Spain

Luciana P.S. Vandenberghe

Department of Bioprocess Engineering and Biotechnology, Federal University of Parana, P.O. Box 19011, Curitiba, Brazil

Adenise Woiciechowski

Department of Bioprocess Engineering and Biotechnology, Federal University of Parana, P.O. Box 19011, Curitiba, Brazil

Qingyu Wu

School of Life Sciences, Tsinghua University, Beijing 100084, People's Republic of China

Han-Qing Yu

Department of Chemistry, University of Science and Technology of China, Hefei, 230026 China

Zhen-Peng Zhang

Beijing Enterprises Water Group Limited, BLK 25, No. 3 Minzhuang Rd, Beijing, China

Chapter 1. Principles of Biorefining

Francesco Cherubini* (email: francesco.cherubini@ntnu.no) and Anders H. Strømman

Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway

*Corresponding author:

This chapter investigates the possibility to produce valuable chemical products from biomass. Similar to fossil refinery, in biorefinery, the three main components of lignocellulosic biomass are separated and depolymerized into the basic chemical structures, for example, glucose and xylose. These intermediates are then converted into bulk chemicals from which the different commodity chemicals required by our society can be produced. After an introduction to the biorefinery concept and an overview of the existing fossil refinery, the chemistry of the lignocellulosic biomass components cellulose, hemicelluloses, and lignin is described and the possible derivatives investigated. The exact replacement of fossil bulk chemicals with biochemicals shows limited possibilities, while the production of novel oxygenated bulk chemicals to be converted into innovative products appears as the most promising biomass utilization option.

Keywords: biorefinery, biochemicals, biomass, oil refinery

1. Introduction

1.1. Background

Driven by the increase in industrialization and population, the global demand for energy and material products is steadily growing. Since the world primary sources for energy and chemicals are fossil fuels, this growth raises important issues at environmental, economic, and social levels. Petroleum is exploited at a much faster rate than its natural regeneration through the planet C cycle, and the larger part of petroleum and natural gas reserves is located within a small group of countries. This production and consumption pattern is unsustainable because of equity and environmental issues that have far-reaching implications. In addition, there is a common increasing perception that the end of the cheap fossil era is around the corner, and prices for crude oil, transportation fuels, and petroleum-derived chemicals are likely to steadily increase in the years to come (Bentley et al., 2007 and Greene, 2004). Climate experts widely agree that emissions of greenhouse gases (GHG), such as carbon dioxide (CO 2), methane (CH 4), and nitrous oxide (N 2O), arising from fossil fuel combustion and land-use change as a result of human activities, are perturbing the Earth's climate (Forster et al., 2007). Global warming and other issues can be mitigated by shifting from fossil sources to renewable energy resources, which are more evenly distributed than fossil resources and cause less environmental and social concerns.

Among the other energy sources, biomass resources are extremely promising since they are widespread and cheaply available in most of the countries. Today, biomass constitutes about 10% of the global primary energy demand, and it is mainly used in inefficient and traditional applications in developing countries (GBEP, 2007 and IEO, 2009). Modern uses of biomass are restricted to developed countries to produce space heating, power, transportation biofuels (mainly bioethanol and biodiesel), and few chemical products. Given the variety of applications for biomass sources, it is extremely important to select the most promising options under environmental, economic and resource perspectives. Electricity and heat can be provided by several renewable alternatives (wind, sun, water, biomass, and so on), while biomass is very likely to be the only viable alternative to fossil resources for production of transportation fuels and chemicals. Today, more than 90% of the fossil carbon is used only for its energy content (Marquardt et al., 2010). This pattern is not likely to be followed in the future for biomass because of the lower efficiency in converting biomass into energy and the lower energy density of biomass than fossils. Stemming from these considerations, some authors convincingly argued that electricity should be produced by an increasing share of renewable sources, and the use of biomass be restricted to the production of transportation biofuels and carbon-based chemical products (Agrawal and Singh, 2010; Marquardt et al., 2010).

1.2. The Biorefinery Concept

The sustainable use of bio-based carbon suggests integrated manufacturing in biorefineries to selectively transform the variety of molecular structures available in biomass into a range of products including transportation biofuels, chemicals, polymers, pharmaceuticals, pulp and paper, food, or cattle feed (Cherubini, 2009, Cherubini, 2010 and Kamm et al., 2006a).

The biorefinery concept embraces a wide range of technologies able to separate biomass resources (wood, grasses, corn, etc.) into their building blocks (carbohydrates, proteins, fats, etc.) which can be converted to value-added products, biofuels, and chemicals. A biorefinery is a facility (or network of facilities) that integrates biomass conversion processes and equipment to produce transportation biofuels, power, and chemicals from biomass. Figure 1 gives an overview of the possible conversion pathways to produce the desired energy and material products from different biomass feedstocks, through jointly applied technological processes (Cherubini et al., 2009). The biorefinery concept is analogous to today's petroleum refinery, which produces multiple fuels and products from petroleum.

Biomass is constituted of an enormous variety of plant species with varying morphology and chemical composition. However, regardless of the phenotype, five main biomass components can be identified worldwide: lipids, starch, cellulose, hemicelluloses, lignin, and proteins. The average biomass available in the world is reported in Figure 2. It clearly appears that lignocellulosic biomass components such as cellulose, hemicelluloses, and lignin are by far the most abundant. Since they can be even gathered from waste streams (e.g., crop residues, paper and wood industries), or directly harvested from forests or biomass stands through sustainable management, their price tend to be lower than other biomass sources which need a dedicated agricultural plot. For this reason, this chapter has a special focus on the possibility to produce commodity chemicals from lignocellulosic sources, which have the largest chances for a massive market penetration in the near future.

2. From fossil to biomass raw materials

The elemental and chemical structure of biorefinery raw materials differs from that on which the current fossil refinery and chemical industry is based. Chemical and elemental composition of petroleum is compared with some lignocellulosic biomass feedstocks in Table 1. Crude oil is a mixture of many different organic hydrocarbon compounds. The first step in oil refinery consists in the removal of water and impurities, and then distillation of the crude oil into its various fractions as gasoline, diesel fuel, naphtha, kerosene, lubricating oils, and asphalts is carried out. The relative volumes of the fractions formed depend on the processing conditions and the composition of the crude oil. The naphtha fraction is subsequently used as a feedstock for the production of just a few bulk chemicals from which all the major commodity chemicals are subsequently derived. An important characteristic of the naphtha feedstock is that, unlike biomass, it is very low in oxygen content. The most important chemical products currently derived from oil and natural gas refinery are shown in Figure 3.

This figure shows that today's chemical industry processes fossil resources into a limited number of bulk chemicals from which a wide spectrum of secondary commodity chemicals are produced. These commodity chemicals have many applications in almost all the sectors of our society as textiles, plastics, resins, food and feed additives, and others. The bulk chemicals from which the majority of commodity chemicals can be produced are ethylene, propylene, batanes/butadiene, and the aromatic benzene, toluene, and xylene (BTX).

The composition of biomass is less homogeneous than petroleum. The share of biomass components in the feedstock can change and the elemental composition is a mixture of C, H, and O (plus other minor components such as N, S, and other mineral compounds). If compared to petroleum, biomass generally has less hydrogen, more oxygen, and a lower fraction of carbon. The compositional variety in biomass feedstocks is both an advantage and a drawback. An advantage is that biorefineries can make more classes of products than can petroleum refineries and can rely on a wider range of raw materials. A drawback is that a relatively larger range of processing technologies is needed, and most of these technologies are still at a precommercial stage (Dale and Kim, 2006). Another difference with petroleum resources concerns the seasonal changes which biomass suppliers have to face, since harvesting is usually not possible throughout the year. A switch from crude oil to biomass may require a change in the capacity of chemical industries, with a requirement to generate the materials and chemicals in a seasonal time frame. Alternatively, biomass may have to be stabilized prior to long-term storage in order to ensure continuous, year-round operation of the biorefinery (Clark et al., 2009).

More difficult is to adapt chemical processes to act on nonhomogeneous substrates, since the chemical industry has been built largely on the use of uniform and consistent raw materials (Hatti-Kaul, 2010). It is unlikely that this will change, so technologies will need to be developed to precondition biomass feedstocks to make their properties and reactivity patterns more stable, consistent, and uniform. One concept that may be of value is to separate the different biomass components early in biorefinery operations, so to make a distinction between those which are subject to energy uses (whose quality can be degraded) and those destined to chemical applications (which need high degree of purity and should be subject to milder process conditions to conserve the original structure).

3. Biomass processing in biorefinery

3.1. Basic Elemental Conversions in Biomass Processing

In order to be used for production of biofuels and chemicals, biomass needs to be depolymerized and deoxygenated. Deoxygenation is required because the presence of O in biofuels reduces the heat content of molecules and usually gives them high polarity, which hinders blending with existing fossil fuels (Lange, 2007). Chemical applications may require much less deoxygenation, since the presence of O often provides valuable physical and chemical properties to the product. Biomass feedstocks usually have an amount of carbon which must be retained throughout the value chain, few hydrogen, which must be added, and too much oxygen, which must be rejected along with other undesirable elements (such as nitrogen and sulfur). Hydrogen is usually added as water (H 2O), even if this implicates an addition of extra oxygen, which must be rejected. The addition of hydrogen as H 2 is more attractive and efficient (using proper metal catalysts) but underprivileged by the fact that elemental hydrogen is not present in nature and energy must be invested to produce it. Oxygen is rejected either as CO 2 or H 2O. In both cases, there are elemental issues: in the first case every mole of oxygen removes half a mole of carbon (thus reducing carbon efficiency), while in the second case 1 mol of oxygen removes 2 moles of hydrogen (which, contrarily, needs to be added). It would be most desirable to reject oxygen as O 2, but this is not a typical output of any biomass conversion process. The other undesired elements, sulfur and nitrogen, are usually rejected in their oxide forms (SO 2 and NO 2, respectively), thus contributing to rejection of excess oxygen.

3.2. Biomass Conversion Through Thermochemical or (Bio-)Chemical Processes

Biomass can be converted to chemicals through thermochemical or (bio-)chemical processes. The most promising thermochemical process is direct gasification of biomass, where the whole feedstock is kept at high temperature (>700 °C) with low oxygen levels to produce syngas, a mixture of H 2, CO, CO 2, and CH 4 (Gassner and Maréchal, 2009 and van Vliet et al., 2009). These C-1 building blocks are then reassembled into the desired functional molecules. Other common thermochemical processes are pyrolysis and combustion for heat and power. These thermochemical approaches do not consider the complex molecular structures synthesized by nature, since they destroy the original biomass structure, which should be rather used to the maximum possible extent (Marquardt et al., 2010). Contrarily, the target of (bio-)chemical processes is to access the rich molecular structure already available in biomass without significant degradation of the basic components. For this purpose, the pretreatment step of lignocellulosic biomass is particularly important, since the three main biomass components must be efficiently separated into independent flows, lignin, cellulose, and hemicellulose, to be further processed (Fernandes et al., 2009, Kaparaju and Felby, 2010 and Sun and Cheng, 2002). After pretreatment, these highly functionalized polymers have to be selectively depolymerized. Next, the resulting molecular structures need to be isolated and catalytically re-functionalized into target molecules. Such an advanced strategy offers the chance to establish conversion processes with higher carbon efficiency and lower entropic losses compared to conventional thermochemical processes. Although conceptually attractive, its implementation requires the tailoring of the industrial value chains to the nature of the bio-based raw materials. Preserving the natural molecular structures in the raw materials requires a shift from gas-phase reactions at high temperatures, prevalent in petroleum-based chemical engineering, to liquid-phase reactions at lower temperatures. Likewise, low-temperature separation technologies should be favored over classical distillation if possible. Higher viscosities of the process media and the management of large amounts of water are inevitable side effects offering their own challenges (Marquardt et al., 2010).

4. Lignocellulosic molecular components and their derivatives

4.1. Lignin

The structure of lignin (see Figure 4) is complex and changes with the type of biomass source. Lignin is composed of phenylpropenyl (C9) randomly branched units. The phenylpropenyl building blocks, like guaiacols and syringols, are connected through carbon-carbon and carbon-oxygen (ether) bonds. Trifunctionally linked units provide numerous branching sites and alternate ring units (Holladay et al., 2007). Lignin offers a significant opportunity for enhancing the operation of a lignocellulosic biorefinery. Today, lignin is used as a source of heat and power for the processing plant (e.g., pulp and paper industry), but this approach seems to be shortsighted: lignin's native structure suggests that it could play a central role as a new chemical feedstock, particularly in the formation of supramolecular materials and aromatic chemicals. All current commercial nonenergy uses of lignin, except combustion and production of synthetic vanillin and dimethylsulfoxide (DMSO), take advantage of lignin's polymer and polyelectrolyte properties. These are primarily applications targeted at dispersants, emulsifiers, binders, and sequestrants. Generally, lignin is used in these applications with little or no modification other than sulfonation or thio hydroxymethylation. These uses mainly represent relatively low value and limited volume growth applications. An economic study shows that when lignin is used for purposes other than power, the overall revenue improvement of a biorefinery concept is between $12 and $35 billion (Holladay et al., 2007). However, as will be shown hereinafter, significant technology developments are required to capture the lignin value benefit.

Besides the immediate opportunities for heat and power production, the specific types of products which can be produced from lignin can be grouped in two main categories:

1. Syngas-derived chemicals (near-term opportunity)

2. Aromatics (medium/long-term opportunity)

4.1.1. Syngas-Derived Chemicals

Gasification produces syngas, a mixture of H 2, CO, CH 4, and other light gases. Technology to produce methanol or dimethyl ether (DME) from syngas is well established (Li and Jiang, 1999, Peng, 2002 and Sai Prasad et al., 2008). These products can be used directly or may be further converted to green gasoline via the methanol to gasoline process or to olefins via the methanol to olefins process (Cui et al., 2006 and Lee, 1995). Because of the high degree of technology development in methanol and DME catalysts and processes, this conversion pathway is extremely promising. The main drawback for this technology is the purification of biomass-derived syngas, which is capital intensive, and demonstration that gasification can proceed smoothly with biorefinery lignin. Another promising use of syngas is the production of Fischer-Tropsch (FT) fuels (Wang et al., 2009). FT processes are well established but their application to biomass is still at a precommercial stage, due to the expensive purification of syngas streams and the need for catalyst and process improvements able to reduce unwanted side-products such as methane and higher molecular weight products such as waxes. Syngas can also be converted to mixed alcohols (like ethanol and other alcohol chemicals), but this technology has not been commercialized yet. Major challenges concern the catalyst and process improvements needed to increase the selectivity and consumption rate of the catalysts (Holladay et al., 2007). Finally, although syngas production via gasification is a well-developed technology for coal (and natural gas), there is continuing controversy over gasification economics at the scale needed for the lignocellulosic biorefinery.

4.1.2. Aromatics

Lignin is the most abundant renewable source which has aromatic units in its structure. As shown in Figure 3, the world demand for aromatics is consistent and increasing over the years. The possibility to establish a direct and efficient conversion of lignin to high-volume, low-molecular weight aromatic molecules is therefore extremely attractive. However, there are important technological barriers which must be overcome, given the resistant and robust lignin structure.

The basic chemical units of lignin shows very high potential for making BTX chemicals (Figure 5). Technologies able to efficiently depolymerize the polymer by breaking the C–C and C–O bonds are necessary. An aggressive, nonselective, depolymerization would bring to a mixture of BTX, phenols, and aliphatic fractions (C1-C3). These chemicals should be suitable for being directly used by the conventional petrochemical processes which convert the bulk aromatics into nylons, resins, polymers, and others. Development of the required aggressive and nonselective chemistries is part of the long-term opportunity but is likely to be achievable sooner than highly selective depolymerizations (presented below; Holladay et al., 2007).

A related technological challenge for the production of chemicals from lignin is the elaboration of proper separation techniques for the mixture intermediates from which the aromatic chemicals are to be isolated (Huang et al., 2008).

4.2. Cellulose and Hemicellulose

Carbohydrates are obtained from lignocellulosic resources after depolymerization of cellulose and hemicelluloses. Glucose (a sugar containing six carbons) is produced via hydrolysis of cellulose, whereas xylose and mannose are the main products obtained by hydrolysis of hemicellulose.

Carbohydrates have the possibility to be converted to a wide spectrum of products by means of biochemical (e.g., fermentation) or chemical transformations. Fermentation of sugars to ethanol is already established in the market: nowadays more than 90% of the world ethanol production is derived from biomass feedstocks, while the remaining 10% is produced from oil or gas refinery (Patel, 2006). Further promising sugar derivatives through fermentation are organic acids like succinic, fumaric, malic, glutamic, aspartic, and others (Werpy and Petersen, 2004). Because of their functional groups, organic acids are extremely useful as starting materials for the chemical industry and may act as intermediate to production of fine chemicals. For many organic acids, the actual market is small, but an economical production process will create new markets by providing new opportunities for the chemical industry (Sauer et al., 2008). For example, succinic, fumaric, and malic acid could replace the petroleum-derived commodity chemical maleic anhydride in its applications. The market for maleic anhydride is huge, whereas the current market for the organic acids mentioned is small owing to price limitations. Once a competitive microbial production process for one of these acids is established, the market for that acid is expected to consistently increase. The technological barriers which keep these conversion routes at a precommercial stage concern microbial biocatalysts, which need to be improved to simultaneously reduce formation of byproducts and increase yields and selectivity. Issues of scale-up and system integration are also to be addressed (Werpy and Petersen, 2004).

In addition to microbial conversions, there are several catalytic transformations for carbohydrates, like oxidations, dehydration, hydrogenations, alkylations, among others, which are industrially feasible. Oxidation leads to valuable intermediates like gluconic acid, which is used for synthesis of pharmaceuticals, food additives, cleaning agents, and others (van Bekkum, 1998). Dehydration of sugars is a promising option for producing important platform chemicals like levulinic acid (LA; from glucose) and furfural (from xylose) which can be converted into a large portfolio of chemicals having many applications in the chemical industry and transportation sector (i.e., fuel additives; Bozell et al., 2000 and Hayes et al., 2006). The technical barriers for this pathway concern the necessity to increase yields through more selective dehydration processes, perhaps supported by the development of new catalysts. Catalytic hydrogenation of sugars gives sugar alcohols, such as xylitol and sorbitol. Sorbitol is used as a sweetener as well as an intermediate for synthesis of vitamin C, food additives, and C4-C6 polyols for synthesis of alkyds (Blanc et al., 2000). Alkyds are polyesters formed via esterification between polyhydric alcohols and di- or poly-basic carboxylic acids or their anhydrides (Mäki-Arvela et al., 2007). These reaction pathways have a larger degree of development than fermentation routes, and some of them are already at a commercial stage. For instance, the production of sorbitol is practiced by several companies and has a production volume on the order of 0.1 million tons/years (Werpy and Petersen, 2004). These productions are usually based on batch technology, and the only technical development needed would be the use of a continuous process.

5. Biorefinery to replace existing fossil bulk chemicals

Over the last decade, prices of fossil fuel feedstocks have increased, whereas prices of biomass resources have slowly and steadily decreased. This situation makes the possibility to produce the existing bulk chemicals from biomass rather than fossils an attractive option. In the following paragraphs, the current state of the art in the production of the bulk chemicals previously highlighted is investigated. The possible reaction pathways are summarized in Figure 6.

5.1. Ethylene

The production of this chemical from biomass sources can be achieved through dehydration of ethanol. This dehydration is favored at high temperatures (300-600 °C) and can be carried out over a wide variety of heterogeneous catalysts (Arenamnarta and Trakarnpruk, 2006 and Takahara et al., 2005). There are no technological barriers to be faced for the production of ethene from ethanol at a commercial scale; this production is initially most likely to happen in regions with cheap and easy access to bioethanol (Haveren et al., 2008).

5.2. Propylene

Direct production of propene from sugars can be carried out via fermentation (Fukuda et al., 1987). Product yields are very low: the productivity needs to be improved by orders of magnitude to make this process economically viable (Haveren et al., 2008). An alternative production pathway consists in the dehydration of 2-propanol, which is produced by reduction of acetone. The latter can be obtained via the acetone, butanol, ethanol (ABE) fermentation process, which is largely studied in the scientific and industrial community (Ezeji et al., 2007). In addition, propene can be produced from dehydration of 1,2-propanediol (either called propene glycol). This glycol can be effectively produced from reduced sugars as sorbitol and xylitol or lactic acid, and such conversion routes have strong commercial potential (Haveren et al., 2008).

5.3. Butane and Butadiene

Starting from biomass, butadiene potentially can be produced from ethanol: ethanol is firstly dehydrogenated to acetaldehyde, which is then followed by aldol condensation and dehydration over a catalyst to form butadiene, with an overall yield of 70% (Weissermel and Arpe, 2003). Butadiene can subsequently be converted to butane by reduction.

5.4. Aromatics (BTX)

If the conversion of carbohydrates to oxygen-containing chemicals has been largely investigated, the replacement of bulk aromatic petrochemical compounds has received so far relatively little attention and limited success. Fermentation of glucose to a number of aromatic structures has been described in the patent literature. However, these aromatic structures themselves were neither bulk products nor the desired end product of the fermentation process (adipic acid; Haveren et al., 2008).

Utilization of specific terpenes could offer potential for the production of aromatic compounds such as, for example, substituted phenols or terephthalic acid and fine and specialty chemicals to be applied in the chemical or pharmaceutical industry (Costantino et al., 2009). However, current production volumes of terpenes are rather in the range of hundreds of thousands of tons instead of the million tons needed to substitute a significant amount of aromatics production.

Thanks to its original structure, the most promising feedstock for production of aromatics from biomass is lignin. The ideal conversion pathway would include the possibility to efficiently and selectively depolymerize lignin and separate from the resulting mixture the components of interest (e.g., BTX). Prior to be able to isolate aromatics and phenols from lignin, major technological improvements are needed. Another long term possibility to synthesize aromatics from biomass is the Diels-Alder cyclo-addiction of butadiene over a catalyst. Clearly, this route relies on an economic production pathway to butadiene prior being industrially taken into consideration.

5.5. N-containing Chemicals

The production of N-containing bulk chemicals from biomass is at a later stage of development than oxygenated chemicals. Genetically modified plants may produce elevated levels of amino acids, like lysine, which can be converted to caprolactam (a precursor of nylon), while fermentation of glucose can lead to N-containing compounds like glutamic acid and aspartic acid (see Figure 7). Other nitrogen-based chemicals could be produced by using protein waste streams from bioethanol and biodiesel production chains. Aspartic acid is an amino acid that can be produced by reaction of ammonia with fumaric acid, which can be theoretically produced from glucose fermentation. In order to be produced on a large scale, a direct fermentation route from glucose to aspartic acid is fundamental. Aspartic acid has large potential to be converted into a wide spectrum of N-containing chemicals (aspartic anhydride, pyrrolydone, and others).

Fermentation of sugars may even lead to the N-containing chemical glutamic acid. Glutamic acid is a five-carbon amino acid and has the potential to be a novel building block for five carbon polymers. The building block and its derivatives have the potential to build similar polymers but with new functionality to derivatives of the petrochemicals derived from maleic anhydride (Werpy and Petersen, 2004). These polymers could include polyesters and polyamides. The major technical hurdles for the development of glutamic acid as a building block include the development of very low-cost fermentation routes. There are currently several fermentation routes for the production of sodium glutamate. One of the major challenges for the development of a low-cost fermentation is to develop an organism that can produce glutamic acid as the free acid.

In general, there is a midterm potential for production of acrylic acid and other N-containing bulk chemicals like acrylonitrile, acrylamide, and caprolactam. The production of N-based chemicals from biomass is expected to become competitive in the market when large quantities of proteins (as a byproduct of biofuel production chains) will be available at affordable prices.

6. Biorefinery to produce alternative products

In the previous section, the possibility to replace existing bulk chemicals from fossil refinery with the same bulk chemicals from oil refinery has been investigated. Unlike few cases, possible market penetration of biochemicals in the near term is limited and major technological barriers exist, especially in the production of aromatics. Rather than a head-to-head substitution of petrochemicals with biochemicals, biomass resources can be used to produce platform chemicals which better reflect the initial biomass composition and are easier to be achieved. At the same time, the products must ensure to meet the same functional properties expected by the consumers. The head-to-head substitution of petrochemicals with biochemicals is consistently disadvantaged by the presence of large quantity of oxygen in the biomass feedstock. Future product trees should accommodate the native oxygen content of biomass to reduce the need for deoxygenation. These considerations imply the need for a radical shift from petroleum-based to biomass-based chemical engineering aiming at new value chains with a new range of oxygenated products, novel production routes, and integrated biorefineries built from intensified unit operations which operate at moderate conditions (Marquardt et al., 2010).

6.1. New Bulk Chemicals from Lignin

Lignin has potential for a very selective depolymerization leading to a wide spectrum of oxygen-containing aromatics which are difficult to make via existing petrochemical routes (see Figure 8). These products preserve the lignin monomer structure and can be highly desirable if produced in reasonable quantity with an economic process. The major barrier of this conversion concerns the development of a technology that would allow highly selective bond scissions to maintain the monomeric lignin block structures (Holladay et al., 2007). In addition, proper markets and industrial applications for those aromatics which are related to the original lignin building blocks need to be established. Figure 9 shows the potential reaction products from the decomposition of lignin via high temperature thermal processes (Haveren et al., 2008). This cracking of lignin results in a complex mixture of polyhydroxylated and alkylated phenol compounds, where the abundance and type of products are influenced by reaction conditions. Clearly, improved separation techniques for aromatic lignin monomers must be achieved.

6.2. New Bulk Chemicals from Carbohydrates

Figure 10 shows the selected new bulk chemicals and derivatives which can be produced from biomass. A total of 13 intermediates are identified as potential bulk chemicals from which a wide spectrum of products can be obtained. They are specified according to the number of C atoms:

• C2: ethanol

• C3: acetone, lactic acid, 3-Hydroxypropionic acid (HPA)

• C4: succinic acid

• C5: furfural, itaconic acid, xylytol, and LA.

• C6: sorbitol, HMF, 2,5-Furan dicarboxylic acid (FDCA), and gluconic acid.

6.2.1. C2 Bulk Chemicals

Besides its uses as transportation biofuel, ethanol also has interesting applications as bulk chemical from which C2 derivatives can be produced. In particular, ethanol can be converted via dehydration to ethene, one of the bulk petrochemicals, which has a world production of 107 million tons/year. Once produced from bioethanol, ethene can be then used for the production of other important chemicals like 1,2-dichloroethane (world production of 20 million tons/year), vinyl chloride, butadiene, and others.

6.2.2. C3 Bulk Chemicals

Acetone is an important chemical compound with a market volume of 3 million tons/year. As already mentioned, it is possible to produce acetone via the ABE fermentation process. This process is widely studied and is expected to be competitive in the market within the next 5-10 years (Bos et al., 2010). Acetone can be a valuable bulk chemical for the production of propene, whose production from fossil refinery is large (50 million tons/year) due to its wide applications (mainly as polypropylene).

Lactic acid is a promising bulk chemical which can lead to many derivatives (in particular polymers), thanks to two reactive sites, the carboxylic group and the hydroxyl group. The production of lactic acid from biomass (fermentation of sugars) is already established in the market, with an annual production around 0.26 million tons and a 10% annual growth (Jem et al., 2010). Major applications are in the food sector, industrial uses, and personal care. Important derivatives which can be produced from lactic acid are acrylic acid via dehydration (current global market of 2 million tons/year) and 1,2-propanediol by reduction (1.5 million tons/year).

3-HPA has the potential to be a key bulk chemical for deriving both commodity and specialty chemicals. The basic chemistry of 3-HPA is not represented by a current petrochemically derived technology (Werpy and Petersen, 2004). Its production from biomass depends on the development of low-cost fermentation routes, since this conversion pathway should in principle have the same yields of that leading to lactic acid. The potential derivatives are similar to those produced from lactic acid, since they have identical reactive sites. In both cases, the development of new catalysts able to directly reduce the carboxylic acid groups to alcohols is required. The esterification of the carboxylic group to an ester, and then reduce the ester, is technically easier, but the process is more expensive. The dehydration of 3-HPA to acrylic acid and acrylamide will require the development of new acid catalyst systems that afford high selectivity (Werpy and Petersen, 2004).

6.2.3. C4 Bulk Chemicals

In fossil refinery, succinic acid is currently produced from butane/butadiene via maleic acid and has a production volume of 30-50 kilotons/year (Bos et al., 2010). This process is relatively expensive and the existing market for succinic acid is limited. However, if a more economic production route could be established, it has a potential market of hundreds to thousands tons, thanks to its many possible derivatives (Sauer et al., 2008). Succinic acid can be efficiently produced from fermentation of sugars, on condition that low-cost fermentation routes are established. The basic chemistry of succinic acid is similar to that of the petrochemically derived maleic acid/anhydride. These compounds can be converted via hydrogenation/reduction to butanediol, tetrahydrofuran, and gamma-butyrolactone. In the case of succinic acid, the technical challenge is the development of catalysts that would not be affected by impurities in the fermentation. Noteworthy is the possibility to produce pyrrolidinones, so addressing a large solvent market (Werpy and Petersen, 2004).

6.2.4. C5 Bulk Chemicals

Furfural is the starting material for industrial production of furan compounds and today it is completely produced from biomass feedstocks rich in C5 sugars. The market volume is 0.2-0.3 million ton/year. It is obtained from hydrolysis of C5 sugars along with other degradation products. Removal of these impurities is expensive and industrial uses of furfural will benefit of an optimization of the furfural production process (Patel, 2006). Many valuable chemicals can be derived from furfural (e.g., maleic anhydride, furfuryl alcohol, etc.), and the chemistry for the conversions is well developed (Kamm et al., 2006b).

Itaconic acid has a chemistry similar to the fossil-derived chemicals maleic acid and maleic anhydride, which are used as monomers in the production of acrylate-based polymers and thermoset resins in oil refinery (Bos et al., 2010). Itaconic acid is currently produced via fungal fermentation and is used primarily as a specialty monomer. The major applications include the use as a copolymer with acrylic acid and in styrene-butadiene systems. The major technical hurdles for the development of itaconic acid as a bulk chemical include the development of very low-cost fermentation routes. The primary elements of improved fermentation include increasing the fermentation rate, improving the final titer, and potentially increasing the yield from sugar. Besides important chemical derivatives, itaconic acid can also undergo polymerization, but the properties of polyitaconic polymers need to be ascertained in order to evaluate its use as a polymer (Werpy and Petersen, 2004).

Xylitol is commercially produced from hydrogenation of xylose, the most abundant C5 sugar in hemicellulose. At the moment, there is limited commercial production of xylitol, but once a cheaper production route is established a large potential for production of ethylene glycol and 1,2-propanediol via hydrogenation is expected.

Another promising C5 bulk chemical is LA. It is produced from dehydration by means of acid treatment of C6 sugars like glucose and fructose. LA is one of the most important building blocks available from carbohydrates and has attracted interest from a number of large chemical industry firms: it has frequently been suggested as a starting material for a wide number of compounds (Bozell et al., 2000, Hayes et al., 2006, Kamm et al., 2006b and Werpy and Petersen, 2004). The technical barriers for this option include improvement of the process for LA production itself, even if the LA yield is already at 70% (Hayes et al., 2006). The family of chemical compounds available from LA is quite broad, and addresses a number of large volume chemical markets. Besides chemicals, LA shows promising efficiency in the conversion to methyltetrahydrofuran and ethyl levulinate, two fuel additives which can be blended up to 20% with gasoline and diesel (without requiring any modification of the engine).

6.2.5. C6 Bulk Chemicals

Sorbitol is produced by catalytic hydrogenation of glucose on a large industrial scale (1.1 million tons/year; Patel, 2006). Besides the food industry, it can be used for production of surfactants and polyurethanes. Sorbitol has potential for the production of isosorbide at low costs (if higher yields are achieved through optimization of process conditions and dehydration catalysts). Isosorbide is a very effective monomer for raising the glass transition temperature of polymers. The major applications are as a copolymer with PET for the use in bottle production. Hydrogenolysis of sorbitol leads to glycols, while direct polymerization forms polyesters for the resin market, whose characteristics need to be properly tested.

2,5-FDCA is formed by an oxidative dehydration of glucose, where side reactions still need to be minimized. FDCA has a large potential as a replacement for terephthalic acid, a widely used component in various polyesters, such as polyethylene terephthalate (PET) and polybutyleneterephthalate (PBT). This bulk chemical has high versatility in production of derivatives through simple chemical reactions: selective reduction leads to partially or fully hydrogenated products (with applications as new polyesters), combination with diamines produces new nylons, etc. (Werpy and Petersen, 2004). Like the other sugar-derived products, the primary technical barriers to production and use of FDCA include development of effective and selective dehydration processes for sugars.

Glucaric acid is the product of catalytic oxidation (with nitric acid, which should be replaced by oxygen) of glucose. Glucaric acid can serve as starting point for the production of a wide range of products with applicability in high volume markets, like new nylons (e.g., polyhydroxypolyamides) or new surfactants.

7. Next research outlook

The success of the chemical industry in biomass conversion to chemical products is highly dependent on the development of new catalysts. Since the original molecular structure of biomass components is supposed to be preserved, the focus of catalysis research will have to shift from building functional structures out of simple building blocks to the re-functionalization of complex molecular structures (Marquardt et al., 2010). A crucial role is played by the next research achievements for basic chemical reactions like dehydration, condensation, hydrogenation, and so on, which require high selectivity to be implemented at commercial scale. Enzymatic or whole-cell biocatalysts are often high-performance alternatives resulting in high selectivity and yield (Stephanopoulos, 2007). Hybrid catalysts, combining enzymes with chemocatalysts in a complex molecular or nanoparticulate structure, constitute even more sophisticated options (Marquardt et al., 2010). In particular, the specific developments needed in the main conversion reactions are:

• Hydrogenation/reduction: this reaction is generally used to add hydrogen, e.g. to an acid functional group to form alcohols. Research developments should ensure the possibility to operate at milder conditions (pressure, temperature, etc.) giving high selectivity, by means of the improvements in catalyst performances. Catalysts should also improve their tolerance to inhibitory compounds and lifetime.

• Oxidation: this reaction oxidizes carbon and converts alcohols into acid functional groups. In future biorefineries, mineral oxidants like sulfuric acid and nitric acid should be replaced by air, molecular oxygen, dilute hydrogen peroxide, and others. Tolerance to inhibitory components of biomass processing streams should also be enhanced.

• Dehydration: this reaction removes oxygen from the substrate and it is fundamental for biomass processing. It requires improvements in the selectivity, needed to avoid side reactions. New heterogeneous catalysts (solid acid catalysts) are preferred over liquid catalysts.

• Fermentation: fermentation processes convert sugars into valuable products. In general, an improvement of microbial biocatalysts to reduce acetic acid coproducts and increase yields is needed. Lower costs to recover the products are necessary to scale-up.

• Polymerization: it is usually done through esterification to produce innovative polymers, whose applications