Biorefinery of Alternative Resources-Targeting Green Fuels and Platform

Sonil Nanda
Dai-Viet N. Vo
Prakash Kumar Sarangi Editors
Biorefinery
of Alternative
Resources:
Targeting Green
Fuels and Platform
Chemicals
Biorefinery of Alternative Resources:
Targeting Green Fuels
and Platform Chemicals
Sonil Nanda • Dai-Viet N. Vo •
Prakash Kumar Sarangi
Editors
Biorefinery of Alternative
Resources: Targeting
Green Fuels and Platform
Chemicals
Editors
Sonil Nanda Dai-Viet N. Vo
Department of Chemical and Biological Center of Excellence for Green Energy and
Engineering Environmental Nanomaterials
University of Saskatchewan Nguyễn Tất Thành University
Saskatoon, Saskatchewan, Canada Hồ Chí Minh City, Vietnam
Prakash Kumar Sarangi

Directorate of Research
Central Agricultural University
Imphal, Manipur, India
ISBN 978-981-15-1803-4 ISBN 978-981-15-1804-1 (eBook)

https://doi.org/10.1007/978-981-15-1804-1
© Springer Nature Singapore Pte Ltd. 2020

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Preface
The production and overwhelming usage of fossil fuels and petrochemicals have
resulted in several environmental concerns such as increased greenhouse gas emis-
sions, global warming and pollution. Moreover, the production and consumption of
fossil fuels and their derivatives are prodigiously increasing due to rapid urbaniza-
tion, industrialization, population growth and improvements in day-to-day lifestyle.
Due to the many adverse effects of fuels and chemicals derived from fossil resources
on the environment and ecosystems, it has become highly imperative to find alterna-
tives that are not only environmentally friendly but also fully or partially biodegrad-
able, cost-effective, feasible. Moreover, these green alternatives, usually referred to
biofuels, biochemical and biomaterials should be promising to make a paradigm shift
in the consumer market to replace the fossil fuels and petrochemicals.
Renewability, carbon neutrality, abundancy, reasonably priced as well as
non-competency to food, fodder and arable lands are other attributes of a potential
bioresource to generate biofuels and biochemicals. Some of such potential biore-
sources include lignocellulosic biomass (e.g., agricultural crop residues, forestry
residues and energy crops), microalgae, municipal solid wastes, industrial effluents,
cattle manure and other organic refuse. This book is a compilation of twenty
chapters, which discusses the potential of such bioresources to produce biofuels,
platform chemicals and other bio-based products. Several thermochemical and bio-
logical conversion technologies are described in terms of their conversion pathways
to biofuels and biochemical through biomass-to-liquid (e.g., pyrolysis, liquefaction,
fermentation and mechanical extraction), biomass-to-gas (gasification and anaero-
bic digestion) and gas-to-liquid (Fischer-Tropsch catalysis). This book provides the
up-to-date information on the production and utilization of biofuels and biochemi-
cal, biomass conversion routes (thermochemical, hydrothermal, biological, mechan-
ical and physicochemical), reforming technologies as well as techno-economic and
life-cycle assessment studies.
Chapter 1 by Arun and Dalai gives an overview of the opportunities, prospects
and challenges in the biofuel sector in the current market scenario. A detailed analy-
sis on the risk factors association with technological innovation in the biofuels
sector is the main objective of this chapter.
Chapter 2 by Pasin et al. describes the bioconversion potential of lignocellulosic bio-
mass to bioethanol. The composition of cellulose, hemicellulose and lignin as well as
their biosynthesis in different agricultural crop residues and hydrolysis are provided.
v
vi Preface
The pretreatment procedures, enzymatic hydrolysis and microbial fermentation of

biomass to second-generation bioethanol are described.
Chapter 3 by Rana and Parikh highlights the catalytic conversion of ethanol to
several value-added chemicals such as acetaldehyde, acetic acid, acetone, ethylene,
butanol, 1,3-butadiene and ethyl acetate. The role of catalysts, catalyst supports,
metal-support interactions, oxygen storage capacity, acidity and basicity of catalyst
in the conversion of ethanol to platform chemicals are described.
Chapter 4 by Phung and Busca summarizes the reaction pathways in bioethanol
conversion such as dehydration, oxidation, steam reforming, dehydrogenation and
Guerbet reaction to base chemicals and fuel derivatives. A highlight on different
catalysts, catalytic reactions and ethanol-derived products are made.
Chapter 5 by Nanda et al. throws light on butanol and propanol as the next-
generation biofuels. The fuel chemistry, production technologies from petrochemi-
cals and biomass as well as biotechnological developments in the fermentation of
lignocellulosic biomass to produce butanol and propanol are provided.
Chapter 6 by Sarangi et al. makes a review of the industrial applications and
production pathways of biomethanol as a biofuel and biochemical. The industrial
applications, technical challenges, future perspectives and several production path-
ways of biomethanol are summarized.
Chapter 7 by Naira et al. analyses various thermochemical and biological con-
version routes of lignocellulosic and algal feedstocks to produce biofuels and
biochemicals for use in energy, food, pharmaceutical, cosmetic and textile indus-
tries. The co-production technologies of biofuels and biochemicals from sugars
(pentose and hexose) and lignin as well as the generation of bioactive components
such as lipids, carbohydrates and proteins from algae have been described.
Chapter 8 by Koshin et al. discusses the main biorefining approaches and
concepts in the thermochemical and biological conversion of rice husk and nutshells
into valuable gaseous, liquid and solid biofuel products. The physicochemical prop-
erties and geographical distribution of rice husk and nutshells as well as their indus-
trial relevance of their fuel and chemical products are highlighted.
Chapter 9 by Singh et al. reviews the thermochemical (e.g., pyrolysis, liquefac-
tion, torrefaction and gasification) and biological (enzymatic saccharification and
fermentation) conversion technologies of Miscanthus as an energy crop to biofuels.
The value-added applications of Miscanthus, especially in pulp and papermaking,
biocomposites and biochemical production are also discussed. The physicochemi-
cal properties of bio-oil and biochar generated from Miscanthus are also described
for fuel and material applications.
Chapter 10 by Suryawanshi et al. reviews the challenges, opportunities, recent
developments and techno-economic feasibility of hydrothermal liquefaction and
pyrolysis of lignocellulosic biomass for bio-crude oil production. The scope of the
chapter also extends to bio-oil upgrading technologies, value-added chemical pro-
duction and application of novel catalysts in hydrothermal liquefaction and pyrolysis
of waste biomass.
Chapter 11 by Masoumi et al. described the production of biocrude oil via hydro-
thermal liquefaction of microalgae. Special attention is also given to the effects of
Preface vii
process parameters on hydrothermal liquefaction to improve the bio-oil yield.

Several bio-oil upgrading techniques are explored to remove the heteroatoms using
various heterogeneous acid catalysts.
Chapter 12 by Mahari et al. makes a review of the recent advancements in
co-pyrolysis as a next-generation conversion technology for energy and material
recovery from biomass. The chapter also includes a discussion on the impact of
process parameters on co-pyrolysis, technical challenges, opportunities, application
and combustion performance of the resulting synthetic liquid fuel products.
Chapter 13 by Volli et al. deals with the conversion of biomass and organic
residues to bio-oil through thermochemical technologies. The technical develop-
ments towards improving the bio-oil yields, fuel properties, influence of process
parameters and reactor configurations are discussed in details.
Chapter 14 by Trinh et al. reviews the pros and cons of biomass pyrolysis
technology along with opportunities for environmental benefits and circular

economy. The integration of molecular modeling with actual experiments has been
highlighted as a new paradigm for mechanistic studies to design hybrid catalysts
and enhance the bio-oil yield and upgrading processes. The chapter also introduces
the novel sonochemical technique in biomass treatment and conversion.
Chapter 15 by Samart et al. describes novel approaches in the conversion of
hydroxymethylfurfural using heterogeneous catalysts to advanced fuels and chemi-
cals. The chapter also discusses the synthesis of hydroxymethylfurfural from sugars
along with its conversion through oxidation, photocatalytic and electrochemical,
hydrogenation, Oxidative amidation and reductive amination and polycondensation
reactions.
Chapter 16 by Devi and Dalai provides the information about different pathways
available for the conversion of glycerol into specialty chemicals. Various approaches
and strategies have been discussed to investigate the effects of reaction parameters,
i.e., temperature, pressure, catalyst type, reaction time, type of solvent on glycerol
conversion and product selectivity.
Chapter 17 by Siang et al. summarizes the recent advances in catalytic steam
reforming of glycerol to produce syngas. The yield in terms of catalytic design
using various catalysts, supports and promoters, operating conditions are described.
The mechanistic pathways and kinetic models are provided to describe glycerol
reaction rates.
Chapter 18 by Minh et al. describes the thermodynamic aspect of biogas reform-
ing under different conditions. Some significant works related to catalyst design,
kinetic and mechanistic studies of biogas reforming processes are described.
Chapter 19 by Nayak et al. displays an extensive report on the opportunities and
challenges in biodiesel production and its compatibility in present diesel engines
without any engine modification. The experimental data quantifying the perfor-
mance, emissions and combustion analysis of biodiesel are also summarizes.
Chapter 20 by Bhatia et al. describes the progress in microbial fuel cells in
terms of structural modification, substrates utilization, modes of operation, sup-
plementation of different microbial communities, challenges and opportunities.
viii Preface
This chapter provides insights on the technological advancements and utilities of

the microbial fuel cells.
The editors are grateful to all the authors for contributing their scholarly materials
to develop this book. Our sincere thanks to Springer Nature for the editorial assistance
in preparing this book.
Saskatoon, Saskatchewan, Canada Sonil Nanda

Hồ Chí Minh City, Vietnam Dai-Viet N. Vo
Imphal, Manipur, India Prakash K. Sarangi
Contents
1 Growth of Biofuels Sector: Opportunities, Challenges,

and Outlook�� 1
Naveenji Arun and Ajay K. Dalai
2 Bioconversion of Agro-industrial Residues
to Second-Generation Bioethanol�� 23
Thiago Machado Pasin, Paula Zaghetto de Almeida,
Ana Sílvia de Almeida Scarcella, Juliana da Conceição Infante,
and Maria de Lourdes de Teixeira de Moraes Polizeli
3 Catalytic Transformation of Ethanol to Industrially
Relevant Fine Chemicals �� 49
Paresh H. Rana and Parimal A. Parikh
4 Selective Bioethanol Conversion to Chemicals and Fuels
via Advanced Catalytic Approaches �� 75
Thanh Khoa Phung and Guido Busca
5 A Spotlight on Butanol and Propanol as Next-Generation
Synthetic Fuels �� 105
Sonil Nanda, Rachita Rana, Dai-Viet N. Vo, Prakash K. Sarangi,
Trinh Duy Nguyen, Ajay K. Dalai, and Janusz A. Kozinski
6 Technological Advancements in the Production
and Application of Biomethanol �� 127
Prakash K. Sarangi, Sonil Nanda, and Dai-Viet N. Vo
7 Biorefinery Approaches for the Production of Fuels
and Chemicals from Lignocellulosic and Algal Feedstocks �� 141
Venkateswara R. Naira, R. Mahesh, Suraj K. Panda,
and Soumen K. Maiti
8 Conversion of Rice Husk and Nutshells into Gaseous,
Liquid, and Solid Biofuels �� 171
Anton P. Koskin, Inna V. Zibareva, and Aleksey A. Vedyagin
ix
x Contents
9 A Review of Thermochemical and Biochemical Conversion

of Miscanthus to Biofuels�� 195
Arshdeep Singh, Sonil Nanda, and Franco Berruti
10 Process Improvements and Techno-Economic Feasibility
of Hydrothermal Liquefaction and Pyrolysis of Biomass
for Biocrude Oil Production�� 221
Pravin G. Suryawanshi, Sutapa Das, Venu Babu Borugadda,
Vaibhav V. Goud, and Ajay K. Dalai
11 Biocrude Oil Production via Hydrothermal Liquefaction
of Algae and Upgradation Techniques to Liquid
Transportation Fuels�� 249
Shima Masoumi, Venu Babu Borugadda,
and Ajay K. Dalai
12 Co-pyrolysis of Lignocellulosic Biomass and Polymeric
Wastes for Liquid Oil Production�� 271
Wan Adibah Wan Mahari, Shin Ying Foong,
and Su Shiung Lam
13 Conversion of Waste Biomass to Bio-oils
and Upgradation by Hydrothermal Liquefaction,
Gasification, and Hydrodeoxygenation�� 285
Vikranth Volli, Anjani Ravi Kiran Gollakota,
Mihir Kumar Purkait, and Chi-Min Shu
14 Upgrading of Bio-oil from Biomass Pyrolysis:
Current Status and Future Development�� 317
Quang Thang Trinh, Arghya Banerjee, Khursheed B. Ansari,
Duy Quang Dao, Asmaa Drif, Nguyen Thanh Binh,
Dang Thanh Tung, Phan Minh Quoc Binh,
Prince Nana Amaniampong, Pham Thanh Huyen,
and Minh Thang Le
15 Heterogeneous Catalysis in Hydroxymethylfurfural
Conversion to Fuels and Chemicals�� 355
Chanatip Samart, Thi Tuong Vi Tran, Suwadee Kongparakul,
Surachai Karnjanakom, and Prasert Reubroycharoen
16 Conversion of Glycerol to Value-Added Products�� 371
Parmila Devi and Ajay K. Dalai
17 Recent Advances in Steam Reforming of Glycerol
for Syngas Production �� 399
Tan Ji Siang, Nurul Asmawati Roslan, Herma Dina Setiabudi,
Sumaiya Zainal Abidin, Trinh Duy Nguyen, Chin Kui Cheng,
Aishah Abdul Jalil, Minh Thang Le, Prakash K. Sarangi,
Sonil Nanda, and Dai-Viet N. Vo
Contents xi
18 Conversion of Biogas to Syngas via Catalytic Carbon Dioxide

Reforming Reactions: An Overview of Thermodynamic
Aspects, Catalytic Design, and Reaction Kinetics�� 427
Doan Pham Minh, Ahimee Hernandez Torres,
Bruna Rego de Vasconcelos, Tan Ji Siang, and Dai-Viet N. Vo
19 Opportunities for Biodiesel Compatibility as a Modern
Combustion Engine Fuel �� 457
Swarup Kumar Nayak, Purna Chandra Mishra, Sonil Nanda,
Biswajeet Nayak, and Muhamad Mat Noor
20 Current Advancements in Microbial Fuel Cell Technologies�� 477
Latika Bhatia, Prakash K. Sarangi, and Sonil Nanda
Editors and Contributors
About the Editors
Sonil Nanda is a Research Associate at the

University of Saskatchewan in Canada. He received
his Ph.D. degree in Biology from York University
in Toronto and has worked as a postdoctoral
researcher at York University and the University of
Western Ontario in Canada. His research areas are
related to advanced biofuels and biochemicals,
thermochemical and biological conversion tech-
nologies, generation of hydrothermal flames for
hazardous waste treatment, biochar-based agron-
omy, bioremediation, as well as carbon capture and
sequestration. He has published more than 80 peer-
reviewed journal articles, 25 book chapters and 80
conference proceedings. He is the editor of several
books published by Springer, Elsevier and CRC
Press. He is also the guest editor of several Special
Issues of esteemed journals, namely the
International Journal of Hydrogen Energy,
Chemical Engineering & Technology, Waste and
Biomass Valorization, SN Applied Sciences,
Biomass Conversion and Biorefinery, Chemical
Engineering Science and Topics in Catalysis.
xiii
xiv Editors and Contributors
Dai-Viet N. Vo is the Director of the Center of

Excellence for Green Energy and Environmental
Nanomaterials at Nguyen Tat Thanh University in
Vietnam. He received his Ph.D. degree in Chemical
Engineering from the University of New South
Wales in Australia and has worked as a postdoctoral
fellow at the University of New South Wales in
Sydney and Texas A&M University in Qatar. His
research interests include Fischer-Tropsch synthesis,
novel catalyst characterization, catalytic reforming
and other clean fuel technologies. He has published
more than 100 peer-reviewed journal articles, 8 book
chapters and 80 conference proceedings. He is the
editor of several books for Elsevier, Springer and
CRC Press as well as guest editor of Special Issues
of the International Journal of Hydrogen Energy,
Comptes Rendus Chimie, Arabian Journal of
Chemistry, Waste and Biomass Valorization, SN
Applied Sciences, Topics in Catalysis, Chemical
Engineering & Technology, Journal of Chemical
Technology & Biotechnology, Biomass Conversion
and Biorefinery, Chemical Engineering Science and
Frontiers in Energy Research.
Prakash K. Sarangi is a Scientist with specializa-

tion in Food Microbiology at the Central
Agricultural University in India. He received his
Ph.D. degree in Microbial Biotechnology from
Ravenshaw University in India. His research
focuses on bioprocess engineering, renewable
energy, biochemicals, biomaterials and rural devel-
opment. He has published more than 50 peer-
reviewed journal articles and 15 book chapters. He
is the editor of several books for Springer, CRC
Press and IK International Publishing House. He is
a fellow of the Society for Applied Biotechnology,
and a life member of the Biotech Research Society
of India; Society for Biotechnologists of India;
Association of Microbiologists of India; Orissa
Botanical Society; Medicinal and Aromatic Plants
Association of India; Indian Science Congress
Association; Forum of Scientists, Engineers &
Technologists; and International Association of
Academicians and Researchers.
Editors and Contributors xv
Contributors
Sumaiya Zainal Abidin Faculty of Chemical and Natural Resources Engineering,

Universiti Malaysia Pahang, Kuantan, Pahang, Malaysia
Prince Nana Amaniampong Institut de Chimie des Milieux et Matériaux de
Poitiers (IC2MP), Université de Poitiers, Poitiers, France
Khursheed B. Ansari Department of Chemical Engineering, Aligarh Muslim
University, Aligarh, Uttar Pradesh, India
Naveenji Arun Department of Chemical and Biological Engineering, University
of Saskatchewan, Saskatoon, Saskatchewan, Canada
Arghya Banerjee Department of Chemical Engineering, Birla Institute of
Technology and Science (BITS) Pilani, Pilani, Rajasthan, India
Franco Berruti Department of Chemical and Biochemical Engineering, University
of Western Ontario, London, Ontario, Canada
Latika Bhatia Department of Microbiology and Bioinformatics, Atal Bihari
Vajpayee University, Bilaspur, Chhattisgarh, India
Nguyen Thanh Binh Faculty of Chemistry, Vietnam National University, Cầu
Giấy, Hà Nội, Vietnam
Phan Minh Quoc Binh Vietnam Petroleum Institute, Vietnam National Oil & Gas
Group, Hà Nội, Vietnam
Venu Babu Borugadda Department of Chemical and Biological Engineering,
University of Saskatchewan, Saskatoon, Saskatchewan, Canada
Guido Busca Department of Civil, Chemical and Environmental Engineering,
University of Genova, Genova, Italy
Chin Kui Cheng Faculty of Chemical and Natural Resources Engineering,
Juliana da Conceição Infante Departamento de Bioquímica e Imunologia,
Universidade de São Paulo, Ribeirão Preto, São Paulo, Brazil
Ajay K. Dalai Department of Chemical and Biological Engineering, University of
Saskatchewan, Saskatoon, Saskatchewan, Canada
Duy Quang Dao Institute of Research and Development, Duy Tân University,
Thanh Khê, Đà Nẵng, Vietnam
Sutapa Das Department of Chemical Engineering, Indian Institute of Technology
Guwahati, Guwahati, Assam, India
Ana Sílvia de Almeida Scarcella Departamento de Bioquímica e Imunologia,
xvi Editors and Contributors
Paula Zaghetto de Almeida Departamento de Bioquímica e Imunologia,

Faculdade de Medicina de Ribeirão Preto, Universidade de São Paulo, Ribeirão
Preto, São Paulo, Brazil
Maria de Lourdes Teixeira de Moraes Polizeli Departamento de Bioquímica e
Imunologia, Faculdade de Medicina de Ribeirão Preto, Universidade de São Paulo,
Ribeirão Preto, São Paulo, Brazil
Bruna Rego de Vasconcelos Department of Chemical and Biotechnological
Engineering, Université de Sherbrooke, Sherbrooke, Québec, Canada
Parmila Devi Department of Chemical and Biological Engineering, University of
Asmaa Drif INCREASE, Université de Poitiers, Poitiers, France
Shin Ying Foong Pyrolysis Technology Research Group, School of Ocean
Engineering, Universiti Malaysia Terengganu, Kuala Terengganu, Terengganu,
Malaysia
Anjani Ravi Kiran Gollakota Department of Safety, Health and Environmental
Engineering, National Yunlin University of Science and Technology, Douliou,
Taiwan, Republic of China
Vaibhav V. Goud Department of Chemical Engineering, Indian Institute of
Technology Guwahati, Guwahati, Assam, India
Pham Thanh Huyen School of Chemical Engineering, Hanoi University of
Science and Technology, Hai Bà Trưng, Hà Nội, Vietnam
Aishah Abdul Jalil School of Chemical and Energy Engineering, Universiti
Teknologi Malaysia, Johor, Malaysia
Surachai Karnjanakom Department of Chemistry, Rangsit University,
Pathumthani, Thailand
Suwadee Kongparakul Department of Chemistry, Thammasat University,
Anton P. Koskin Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Janusz A. Kozinski Department of Chemical Engineering, University of Waterloo,
Waterloo, Ontario, Canada
Su Shiung Lam School of Ocean Engineering, Universiti Malaysia Terengganu,
Kuala Terengganu, Terengganu, Malaysia
Minh Thang Le School of Chemical Engineering, Hanoi University of Science
and Technology, Hai Bà Trưng, Hà Nội, Vietnam
Wan Adibah Wan Mahari School of Ocean Engineering, Universiti Malaysia
Terengganu, Kuala Terengganu, Terengganu, Malaysia
Editors and Contributors xvii
R. Mahesh Department of Biosciences and Bioengineering, Indian Institute of

Soumen K. Maiti Department of Biosciences and Bioengineering, Indian Institute
of Technology Guwahati, Guwahati, Assam, India
Shima Masoumi Department of Chemical and Biological Engineering, University
of Saskatchewan, Saskatoon, Saskatchewan, Canada
Doan Pham Minh Université de Toulouse, IMT Mines Albi, Centre RAPSODEE,
Albi, France
Purna Chandra Mishra School of Mechanical Engineering, Kalinga Institute of
Industrial Technology (KIIT University), Bhubaneswar, Odisha, India
Venkateswara R. Naira Department of Biosciences and Bioengineering, Indian
Institute of Technology Guwahati, Guwahati, Assam, India
Sonil Nanda Department of Chemical and Biological Engineering, University of
Biswajeet Nayak Department of Mechanical Engineering, Einstein Academy of
Technology and Management, Bhubaneswar, Odisha, India
Swarup Kumar Nayak School of Mechanical Engineering, Kalinga Institute of
Industrial Technology (KIIT University), Bhubaneswar, Odisha, India
Trinh Duy Nguyen Center of Excellence for Green Energy and Environmental
Nanomaterials, Nguyễn Tất Thành University, Hồ Chí Minh City, Vietnam
Muhamad Mat Noor Faculty of Mechanical Engineering, Universiti Malaysia
Pahang, Pekan, Pahang, Malaysia
Suraj K. Panda Department of Biosciences and Bioengineering, Indian Institute
of Technology Guwahati, Guwahati, Assam, India
Parimal A. Parikh Department of Chemical Engineering, Sardar Vallabhbhai
National Institute of Technology, Surat, Gujarat, India
Thiago Machado Pasin Departamento de Bioquímica e Imunologia, Universidade
de São Paulo, Ribeirão Preto, São Paulo, Brazil
Thanh Khoa Phung School of Biotechnology, International University, Vietnam
National University, Hồ Chí Minh City, Vietnam
Mihir Kumar Purkait Department of Chemical Engineering, Indian Institute of
Paresh H. Rana Department of Chemical Engineering, Government Engineering
College, Bhuj, Gujarat, India
Rachita Rana Department of Chemical and Biological Engineering, University of
Prasert Reubroycharoen Department of Chemical Technology, Chulalongkorn
University, Bangkok, Thailand
xviii Editors and Contributors
Nurul Asmawati Roslan Faculty of Chemical and Natural Resources Engineering,

Chanatip Samart Department of Chemistry, Faculty of Science and Technology,
Thammasat University, Pathumthani, Thailand
Prakash K. Sarangi Directorate of Research, Central Agricultural University,
Imphal, Manipur, India
Herma Dina Setiabudi Faculty of Chemical and Natural Resources Engineering,
University Malaysia Pahang, Kuantan, Pahang, Malaysia
Chi-Min Shu Department of Safety, Health and Environmental Engineering,
National Yunlin University of Science and Technology, Douliou, Taiwan, Republic
of China
Tan Ji Siang School of Chemical and Energy Engineering, Universiti Teknologi
Malaysia, Johor, Malaysia
Arshdeep Singh Department of Chemical and Biochemical Engineering,
University of Western Ontario, London, Ontario, Canada
Pravin G. Suryawanshi Department of Chemical Engineering, Indian Institute of
Ahimee Hernandez Torres Université de Toulouse, IMT Mines Albi, Centre
RAPSODEE, Albi, France
Thi Tuong Vi Tran Department of Chemistry, Faculty of Science and Technology,
Thammasat University, Pathumthani, Thailand
Quang Thang Trinh Cambridge Centre for Advanced Research and Education in
Singapore (CARES), Campus for Research Excellence and Technological Enterprise
(CREATE), Singapore, Singapore
Dang Thanh Tung Vietnam Petroleum Institute, Vietnam National Oil & Gas
Group, Hà Nội, Vietnam
Aleksey A. Vedyagin Boreskov Institute of Catalysis SB RAS, Novosibirsk,
Russia
Dai-Viet N. Vo Center of Excellence for Green Energy and Environmental
Nanomaterials, Nguyễn Tất Thành University, Hồ Chí Minh City, Vietnam
Vikranth Volli Department of Safety, Health and Environmental Engineering,
National Yunlin University of Science and Technology, Douliou, Taiwan, Republic
of China
Inna V. Zibareva Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Growth of Biofuels Sector:
Opportunities, Challenges, and Outlook 1
Naveenji Arun and Ajay K. Dalai
Abstract
The demand for biofuels is increasing due to the uncertainties in the supply of
fossil fuels, increased pollution hazards, rural economic growth, and the neces-
sity to control carbon emissions. It is important to seek an alternate fuel resource
to curb the carbon emissions. The transition from fossil fuel refineries to sustain-
able biorefinery can be clearly noticed in the present era. The dependency on
food-based crops, which leads to the food versus fuel issue, has been addressed
with the search for alternative and sustainable nonfood feedstocks such as ligno-
cellulosic biomass. Until date, the methodology to unlock the full potential of
lignocellulosic biomass is still in infancy. The migration from food-based biofuel
feedstocks to lignocellulosic feedstocks and other organic wastes needs techno-
logical innovation and policies that could provide financial support. The detailed
analysis on the risk factors associated with technological innovation in the biofu-
els sector is relatively less, which is the main objective of this chapter.
Keywords
Biofuels · Lignocellulosic biomass · Biorefining
N. Arun · A. K. Dalai (*)

Department of Chemical and Biological Engineering, University of Saskatchewan,
Saskatoon, Saskatchewan, Canada
e-mail: [email protected]
© Springer Nature Singapore Pte Ltd. 2020 1

S. Nanda et al. (eds.), Biorefinery of Alternative Resources: Targeting Green
Fuels and Platform Chemicals, https://doi.org/10.1007/978-981-15-1804-1_1
2 N. Arun and A. K. Dalai
1.1 Introduction
Globally, the consumption of renewable and low-carbon biofuels is on rise owing to

the international policies that focus on decreasing the greenhouse gas (GHG) emis-
sions. Biofuels derived from lignocellulosic biomass, oil seeds, microalgae, and
other organic wastes such as municipal solid wastes, cattle manure, industrial efflu-
ents, and sewage sludge have tremendous potentials to meet the future clean energy
demands of the world (Nanda et al. 2015). Biofuels can be derived through the
thermochemical conversion (e.g., pyrolysis, liquefaction, and gasification) and bio-
chemical conversion (e.g., anaerobic digestion and fermentation) of organic wastes
(Nanda et al. 2014, 2017b). The usable forms of biofuels are mostly in the form of
liquid (e.g., bio-oil, biodiesel, microalgal oil, bioethanol, and biobutanol) and gas-
eous (e.g., syngas, producer gas, biohydrogen, and biomethane) forms (Nanda et al.
2016a). However, the bio-oils derived from the pyrolysis of biomass and organic
wastes require catalytic upgrading (hydrotreating) to be transformed into synthetic
transportation fuels (Arun et al. 2015, 2017).
The most commonly used classification of biofuels is presented in Fig. 1.1 (Raud
et al. 2019). Based on the production process, biofuels can be classified as primary
biofuels (from biomass in natural form) and secondary biofuels (from biomass in
processed form). The first-generation biofuels involve the usage of edible feed-
stocks, which create the “food versus fuel” argument worldwide (Nanda et al. 2018).
The second-generation biofuels addressed this issue as they are mostly produced
from nonedible biomass through thermochemical and biochemical processes. Algae
and other aquatic biomass are classified as third-generation biofuels and offer
advantages such as low land usage, high lipid content, and high atmospheric CO2
uptake capabilities (Correa et al. 2019). Genetic modification of third-generation
biofuels can lead to the forecasted fourth-generation biofuels, which are mostly
under research and developmental phase. Table 1.1 gives the examples of different
generations and categories of biofuels. The advantages of different generations of
biofuels are summarized in Table 1.2.
Fig. 1.1 Classification of biofuels according to processing technology and biomass type
(Reproduced with permission from Raud et al. 2019)
1 Growth of Biofuels Sector: Opportunities, Challenges, and Outlook 3
The sustainable biorefining of biomass can also result in the production of a

broad spectrum of marketable products such as biofuels, biochemicals, biomateri-
als, bioadditives for food and feed, as well as heat and power (Hassan et al. 2019;
Arun and Dalai 2019). During the Paris climate conference (COP21) in 2015, nearly
200 countries decided to limit global warming below 2 °C (Chen et al. 2016). Many
studies have reported about the “food versus fuel” debate, and a transition toward
cellulosic alcohols has gained equal attention as cellulosic ethanol has the potential
to lower the GHG emission by 90% in comparison to gasoline.
At the current population growth rate, it is estimated that the earth’s population
in 2030 will be around 8.5 billion people (Hassan et al. 2019). In 2016, the annual
GHG emission was measured at 51.9 gigatons of CO2 equivalent (GtCO2e), while
the target is to reduce the emissions by 11–13.5 GtCO2e per year by 2030. To con-
trol the catastrophic damages caused by anthropogenic activities, the United Nations
agreed on 17 sustainable development goals for 2030 (Hassan et al. 2019). Several
criteria considered for evaluating the socioeconomic and environmental benefits of
biofuel production systems are shown in Fig. 1.2.
According to the Food and Agriculture Organization (FAO), the total world con-
sumption of agricultural products will be 60% higher in 2050 in comparison to the
consumption in 2005. Another estimation by FAO indicates that by 2050, additional
70 million hectares of cultivated land will be required to meet the food demands of
the future generation. Hence, there is a clear indication of competition between
urbanization and agriculture. The urban expansion can potentially result in loss of
agricultural lands and it is estimated that the global loss of agricultural lands will be
1.8–2.4% by 2030.
The European Bioeconomy Strategy was launched by the European Commission
in 2012, which was themed on “Innovating for sustainable growth: A bioeconomy
for Europe” (European Environment Agency 2019). After assessment by the
European Union Commission in 2017, the scope of the current action plan was
found to be inadequate for the sustainable development of the biorefinery sector in
Table 1.1 Different generation and categories of biofuels (Reproduced from Kamani et al. 2019
with permission from The Royal Society of Chemistry)
Generation Source/substrate Product
Primary Firewood, wood chips, Used in unprocessed form, mainly for heating,
pellets, animal waste, cooking, and electricity purposes
forest, and crop residues
Secondary Seeds, grain, and sugars Bioethanol/biobutanol (by the fermentation of
starchy or sugar-rich crops), biodiesel (by the
transesterification of plant oils)
Secondary Lignocellulosic biomass Bioethanol/biobutanol (using enzymatic
hydrolysis), methanol, mixed alcohol, green diesel
(by thermochemical processes) and biomethane
(by anaerobic digestion)
Tertiary Algae and seaweed Biodiesel and bioethanol from algae and seaweeds,
hydrogen from microorganisms and green algae
4
Table 1.2 Advantages and disadvantages of different generations of biofuels (Reproduced with permission from Abdullah et al. 2019)
First-generation
Topic biofuel Second-generation biofuel Third-generation biofuel Fourth-generation biofuel
Competition with Made from edible oil No food-energy conflict No food-energy conflict No food-energy conflict
food crops and starch feedstock
Land footprint Requires arable land Require arable land or Non-arable land can be used for Non-arable land can be used for
forests cultivation cultivation
Conversion to Easy conversion Need sophisticated Easy conversion due to increased Easy conversion due to increased
biofuels downstream processing hydrolysis and/or fermentation hydrolysis and/or fermentation
technologies due to high efficiency efficiency
contents of hemicelluloses
and lignin
Water footprint Potable water is Potable water is required Waste, saline, and non-potable water Waste, saline, and non-potable
required for cultivation for cultivation also can be used water also can be used
Environment Using pesticides and No expenditure on fertilizer CO2 fixation, wastewater treatment, CO2 fixation and wastewater
friendliness fertilizers are of the or pesticides. Deforestation and no expenditure on fertilizer are treatment are the benefits, but
main concerns is a concern benefits. Ecological concerns such as release of genetically modified
marine eutrophication are a organisms is a main concern
disadvantage
Commercialization Commercially Commercially produced Insufficient biomass production for Insufficient biomass production for
produced commercialization commercialization
Sustainability Use of natural Does not preserve ecology Does not have favorable economics There are concerns about the
resources such as water due to deforestation release of genetically modified
and land is not concerns organisms to the environment and
conservative ecological risks
Nutrient Using pesticides and Does not require any Large carbon and nitrogen sources Large carbon and nitrogen sources
requirements fertilizers is of the fertilizer treatment are required. Solar energy is only are required. Solar energy is only
main concern available during daytime. Nutrients available during daytime. Nutrients
can be recycled in the process can be recycled in the process
N. Arun and A. K. Dalai
1
Harvesting Harvesting is done by Harvesting is done by hand Harvesting of microalgae is Harvesting of microalgae is
hand or machine or machine picking expensive and complicated expensive and complicated
picking
Regulation The regulations are The regulations are fairly No regulation is available for marine No regulation is available for
fairly clear clear cultivation marine cultivation. Furthermore,
strict regulation is for the intended
release of GM algae
Financial input The capital cost is The capital cost is fairly The initial cost for large-scale The initial cost for large-scale
fairly low low cultivation is too high cultivation is too high
Environmental Parameters such as Parameters such as Can be cultivated in harsh Can be cultivated in harsh
condition temperature and temperature and humidity environmental conditions such high environmental conditions such high
humidity must be must be within a suitable pH, salinity, and high light intensities pH, salinity, and high light
within a suitable range range intensities
Growth of Biofuels Sector: Opportunities, Challenges, and Outlook
5
Fig. 1.2 Criteria to be considered when evaluating the socioeconomic and environmental benefits
of biofuel production systems (Reproduced with permission from Correa et al. 2019)
the Europe. More recently, Brazil, the USA, Canada, the European Union, and
many Asian countries have started posing strict legal mandates for the usage of
biofuels on commercial scale.
According to International Energy Outlook (2016), the world’s energy consump-
tion is expected to increase by approximately 48% between 2012 and 2040. The
production of conventional biodiesel involves the usage of fertilizers, mechanical
equipments (which uses fossil fuels), and arable land. According to the Innovation
Outlook, Advanced Biofuels-IRENA, the basic energy input to produce conventional
biodiesel comes from fossil fuels. Therefore, the production cost for conventional
biodiesel is US $1.6 per liter in comparison to US $1.2 per liter for diesel. In European
Union, the annual turnover of current biofuel economy is €2.3 trillion and 18.5 mil-
lion people are employed in the biofuel sector (Hassan et al. 2019). The S2Biom
project supported by the European Commission indicates that the bio-based products
will have a market worth of €40 million by 2020 and are projected to have a 4%
annual growth rate. Many biofuel policies struggle to address the integrations
between company’s perspective and policy development. The success of biofuel
policies has been primarily based on climate change and community support. It is
estimated that nearly 67 biorefineries based on lignocellulosic biomass are in current
operation globally. Tables 1.3 and 1.4 illustrate the main products that can be obtained
by the hydrothermal conversion of lignocellulosic and non- lignocellulosic bio-
masses, respectively.
The commercialization of biofuels sector involves high capital expenditure
(CAPEX), and it is important to integrate the biochemical processes with the existing
Table 1.3 Summary of main structures and major compounds of lignocellulosic biomass
(Reproduced from Usman et al. 2019 with permission from The Royal Society of Chemistry)
Percentages of main structures
Lignocellulosic Cellulose Hemicellulose Lignin Major compounds into hydrothermal
biomass (wt%) (wt%) (wt%) conversion aqueous products
Crop straw and 29.2– 18.2–36.4 15.0– Volatile fatty acids, capronic acid,
husk 46.0 28.2 lactic acid, furfurals, sugars, alcohols,
and cyclopentenone
Newspaper 44.2 17.8 26.8 Volatile fatty acids, furfurals, sugars,
alcohols, and phenols
Orange 14.3 6.3 3.3 Acetic acid, 5-hydroxymethylfurfural,
pomace furfurals, ethanol, acetone, butanone,
and alkyl derivatives
Recycled paper 60.8 14.2 8.4 Volatile fatty acids, furfurals, sugars,
alcohols, and cyclopentenone
Spent grain 18.5 26.5 19.1 Cyclopentenones, carboxylic acids,
pyrazines, and ketones
Sugarcane 56.0 4.6 36.4 Volatile fatty acids, phenols, furfurals,
bagasse sugars, alcohols, and cyclopentenone
Switchgrass 32.8 23.7 18.2 Volatile fatty acids, phenols, furfurals,
sugars, alcohols, and cyclopentenone
Woody 38.6– 7.7–20.2 17.6– Phenols, furfurals, glycolic acid, acetic
biomass 63.6 32.7 acid, alcohols, and cyclopentenone
Table 1.4 Summary of main structures and major compounds of non-cellulosic biomass
(Reproduced from Usman et al. 2019 with permission from The Royal Society of Chemistry)
Non- Percentages of main structures
lignocellulosic Protein Carbohydrates Lipids Major compounds into hydrothermal
biomass (wt%) (wt%) (wt%) conversion aqueous products
Dried 42.2 35.0 22.4 Cyclopentenones, carboxylic acids,
distillers’ pyrazines, ketones, and oxygenated
grains aromatics
Food waste 15.0– 41.3–62.1 13.4– Volatile fatty acids,
25.2 30.2 5-hydroxymetgylfurfural, furfural,
ethanol, ketones, alkyl derivatives of
2-cyclopenten-1-one
Macroalgae 12.2– 54.3–83.6 0.9– Nitrogenous compounds, long-chain fatty
30.9 6.2 acids, glycerol, alcohols, and acetone
Microalgae 8.1– 4.2–57.1 2.4– Volatile fatty acids, phenols, pyrazines,
71.4 40.1 benzenes, alkanes, and fatty acids
Mixed cultural 27.2 17.9 5.7 Short-/long-chain organic acids, amino
algae acids, phenols, urea, N-heterocyclic
compounds, acetamide, and ketones
Sewage sludge 27.6– 3.3–4.0 6.6– Volatile fatty acids, benzene, acetic acid,
33.4 13.8 carbonic acid, alkenes, phenolic, and
aromatic compounds
8
Fig. 1.3 Schematic diagram showing differences between first- and second-generation lignocellulosic feedstocks, valorization processes, and end products
(Reproduced with permission from Hassan et al. 2019)
N. Arun and A. K. Dalai
refinery setup to produce biofuel products with minimum operational cost (Fig. 1.3).
In the future, it is imperative to consider the energy efficiency of biofuel blends and
the influence of carbon taxation policy, and they needed to be included in the analy-
sis. The policy makers should consider and analyze the risks involved in the com-
mercialization of technologies that produce advanced biofuels. The identified
potential risks are related to the management processes, market conditions, and prof-
itability. The developed policies should find a balance between the translation of
technology and business perspective. Most of the green energy innovation policies
have attempted to address the optimal balance between technological push and
supply-demand pull in green technologies. This chapter provides insights into the
present state of energy demand, search for novel feedstocks, and potential risks asso-
ciated in the commercialization of novel biofuels production technologies.
1.2 Biofuel Scenario in Canada and the World
After agreeing to the 2015 Paris Climate Conference (COP21), the Government of
Canada has taken initiatives to curb the greenhouse gas (GHG) emissions (Nanda
et al. 2016b). To achieve the Clean Fuel Standard and achieve the climate change
objectives, discussions with provincial and federal governments and indigenous
peoples and rural communities are in swift progress. According to the International
Energy Agency (IEA), to meet the Paris commitment of keeping the global warming
below 2 °C, the consumption level of biofuels should triple by 2030. On an average,
about 140–150 patents are filed annually and this clearly indicates a worldwide
hunger for advanced biofuel systems.
Owing to Canada’s extensive forestry and agricultural resources, the prospects
for advanced biofuels seem to be promising. In Canada, the Renewables Fuels
Regulations Act was enacted in August 2010. According to this act, the gasoline
pool must contain 5% by volume of renewable fuel, and in the diesel pool, the
renewable fuel content should be 2% by volume. With the depression of oil prices
in 2015 in Canada, the energy sector continued to account for 20% and 18% of the
gross domestic product of Alberta and Saskatchewan, respectively (Mondou et al.
2018). According to Dragojlovic and Einsiedel (2015), biofuels generated from
nonfood crops are recently gaining societal acceptance in the USA compared to
corn-based ethanol. Moreover, the communal perception on the climate change and
its associated risks and threat are the key predictor of the defiance toward biofuels
in the USA.
In Canada, the annual consumption of biodiesel has increased by 100% in com-
parison to 2010 (123 million liters). The Federal Renewable Fuels Regulations also
mandates the minimal blending of renewable fuels to decline the average lifecycle
carbon intensity (CI) of fuels over time. The energy density of ethanol is about 33%
lower than gasoline and it means that consumers must purchase more of ethanol to
meet the energy requirements. This also indicates greater distribution cost and
higher tax rates. It must be noted that blending ethanol (5–10 vol%) can increase the
energy efficiency of the vehicle by 1%. In addition, blending with ethanol also
permits refineries to produce gasoline blend stock with lower octane number, which
can potentially reduce the greenhouse gas intensity. In future, it is imperative to
consider the energy efficiency of biofuel blends and the influence of carbon taxation
policy and they needed to be included in the analysis.
Biomass from lignocellulosic materials (e.g., agricultural crop residues and
woody biomass), algae, and oilseed crops can be converted to biofuels through
applicable thermochemical and biochemical conversion routes. The oil extraction
from oilseed crops and algae undergoes transesterification to produce biodiesel. The
de-oiled algal biomass can undergo supercritical water gasification due to its high
moisture content to produce syngas (Reddy et al. 2014; Okolie et al. 2019; Yadav
et al. 2019). The syngas is further converted to refined fuels such as green diesel,
green kerosene, and other hydrocarbons through Fischer-Tropsch catalysis.
Fermentation of syngas using acidogenic bacteria can produce bioethanol.
Lignocellulosic biomass and de-oiled algae can also undergo pyrolysis to produce
bio-oil, biochar, and producer gas. The sugars in lignocellulosic biomass can be
recovered using enzymatic hydrolysis and fermentation to produce alcohols, e.g.,
bioethanol and biobutanol (Fig. 1.4), or through gasification and Fischer-Tropsch
catalysis to produce alcohols and hydrocarbon (Fig. 1.5) (Nanda et al. 2014, 2017a).
Algae-based biofuels seem to have the potential to offer a sustainable pathway
for bioenergy and bioproducts (Yadav et al. 2019). Alga is an energy density bio-
logical source and can accumulate lipids up to 50% of dry cell weight (U.S. DOE
2010). As a part of advanced biofuel systems, algal biofuels have gained attention.
The catalytic cracking process for the biofuels production from algal oil is energy
intensive and it is important to analyze the energy return on investment (EROI). In
chemical and enzymatic processes, reusability of catalyst is an important factor and
various studies have been done to develop a cost-effective catalyst for chemical and
enzymatic conversion. Algal biofuel production process possesses high productivity
(per acre) because it is not based on food resources and can be cultivated on open
ponds and wastewater. It is imperative to cultivate the specific type and strain of
algae (e.g., microalgae, macroalgae, and cyanobacteria) for the successful algae-
based biofuels production process. Although algal biofuels industry seems promis-
ing, it is limited by several factors such as biomass cultivation, availability of
advanced processing facilities, technical challenges, and logistic issues (Chen et al.
2016). There are many uncertainties in the availability and commercial usage of
fossil fuels after 2040. In the last two decades, the oil price had an average volatility
of 30% per year. According to the UK Production Capacity Outlook to 2030, the
design and development of cost-effective catalysts for fuel upgrading technologies
such as Fischer-Tropsch process, hydrotreating, or transesterification seem to be a
primary challenge in process commercialization.
As discussed earlier, biofuel feedstocks can be categorized into three categories
such as (a) biomass produced on marginal lands, (b) agricultural crop residues and
forestry biomass, and (c) cattle manure and organic wastes (Junginger et al. 2006).
It is globally estimated that these waste and biomass categories can supply bioen-
ergy accounting up to 200 EJ, 100 EJ, and 100 EJ, respectively. However, an access
to complete integrated biofuels process assessment is unavailable. The estimation
1
Growth of Biofuels Sector: Opportunities, Challenges, and Outlook
Fig. 1.4 The agricultural residues used for the production of bioethanol (Reproduced from Kamani et al. 2019 with permission from The Royal Society of
11
Chemistry)
Fig. 1.5 Production of biomethanol from carbohydrate biomass by gasification (Reproduced

from Usman et al. 2019 with permission from The Royal Society of Chemistry)
studies done by several international organizations such as USEPA, Stockholm

Environmental Institute, and the Intergovernmental Panel on Climate Change
(IPCC) provide different conclusions (100–500 EJ per year in 2050) on the reliabil-
ity of biomass to meet the future energy demands (Junginger et al. 2006). The major
difference in the analysis can be attributed to the uncertainty in land availability and
yield limits.
1.3 olicies and Their Impacts on the Success of Advanced

P
Biofuels: Scenario in Canada and the World
The governmental commitment to policies and the durability of the policies are of
concern for the commercialization of advanced biofuels market. The impact of pol-
icy changes is drastic on the venture capital companies in comparison to refineries
based on fossil fuels. For the deployment of futuristic biofuels production processes,
the uncertainties associated with the government policies need to be reduced. In
Canada, many private and federal organizations provide financial support for the
commercialization of biofuels sector. The Canadian Foundation for Innovation
(CFI) provides financial support for the development of research infrastructure.
The Sustainable Development Technology Canada (SDTC) is a foundation
funded by the government of Canada and it provides nonrepayable funds for the
development of novel processes and technologies (in the pre-commercial phase)
that focus to curb GHG emissions. Through the Next-generation Biofuels Fund
(NGBF), about $500 million was sanctioned to private research centers. Recently,
Canada’s Networks of Centers of Excellence funded a research initiative called
BioFuelNet Canada, which specifically focused on the Agriculture and Agri-Food
Canada, Canadian Forest Services, and Transport Canada. Like BioFuelNet Canada,
the Cellulosic Biofuel Network was initiated in 2010. The Renewable Industries
Canada (RIC) and the Advanced Biofuels Canada (ABC) are the two organizations
focusing on the advanced biofuels sector in Canada. The industries that produce
conventional biofuels are represented by Renewable Industries Canada, and indus-
tries in western Canada (which primarily produce biodiesel) are represented by
Advanced Biofuels Canada. Both these organizations have their own unique exper-
tise and policy capabilities. For practical implementation of low-carbon fuel stan-
dard (LCFS), skill set development of lifecycle analysis of GHG emissions of fuels
is important.
Decision-making step in the commercialization of novel biofuels technologies is
strongly dependent on the ability of the government and corporates to take risk
without developing aversion considering the challenges in getting higher returns
after commercial runs. Tables 1.5 and 1.6 summarize some notable biofuel projects
around the world and European Union, respectively. Scientifically, the term risk can
refer to challenges, barriers, or constraints and the source of risk can be external
(e.g., political, economic, social, and technological) and/or internal (management
and operations in an organization). The nontechnical challenges and biases usually
hinder the commercial development of bioenergy rather than technical issues
(McCormick and Kaberger 2007). The nontechnical risk factors are the factors
related to (a) policies; (b) supply, price, and demand of feedstocks; (c) fluctuations
in the prices of fossil fuels; (d) food versus fuel debate; and (e) lack of refinery to
process advanced feedstocks.
Pries et al. (2016) performed a detailed analysis on the different risks and their
influence on the commercialization of advanced biofuels technology. The risks
could be classified as political, economic, social, technological, primary, and sup-
port activities risks. The primary political risk arises from the support from the
Table 1.5 Main biofuel projects around the world (Reproduced with permission from Su et al.
2017)
Company or Cultivation
region method Technology Products and scale
LiveFuels (USA) Open ponds, Grows and harvests algae in Algal fuel
open water estuarine environments using
systems natural systems to keep cost
low. The company has
established pilot operations
across the USA
OriginOil Inc. Open ponds Developing a technology to Diesel, gasoline, jet
(USA) transform algae into true fuels, plastics, and
competitor to petroleum solvents
PetroSun Open ponds Extracting algae oil in the farm Algae oil (4.4
and transporting to biodiesel million gallons
refinery annually)
Neste Oil Open ponds It is the only company that Biofuels, plant oil,
(Europe) commercially produces and algae oil
high-value renewable fuels
with more than 10 raw
materials in which NEXBTL
yields renewable diesel at
about two million tons
annually
Seambiotic Open ponds Cooperating with power plant Food, chemicals, and
(Mediterranean) and cultivating algae with flue biofuels
gas in Israel
Aquaflow Open ponds Gaining feedstocks from algae Biocrude oil
Bionomics (New derived from wastewater
Zealand) purification
Biofuel System Producing biofuels with Biogasoline or
(UK) seaweed biodiesel
A2BE Carbon Closed systems Establishing carbon capture Biofuels
Capture (USA) cycle system. CO2 emitted
from industries is captured and
used in algae cultivation
GreenFuel Closed systems Cultivating microalgae with Drop-in biofuels
Technologies industrial waste gas
(USA)
Solazyme, Inc. Closed systems Cultivating microalgae in dark Biofuels
(USA) in large storage tank and
providing energy in growth
medium with sugar
(continued)
Table 1.5 (continued)

Algenol Biofuels Closed systems Located in desert. Cultivating Ethanol (yields
(USA) microalgae on large scale with amount to 9000
seawater and CO2 to produce gallon/acres in 2013)
ethanol. Cultivating blue-green
algae and blue algae
simultaneously based on
patent, fixing nitrogen, and
reducing cost
Sapphire Energy Closed systems The company’s molecular Green crude oil.
(USA) platform can convert sunlight Suitable for
and CO2 into renewable carbon infrastructures such
neutral fuels as automobile,
refinery, and pipeline
Inventure Closed systems The patented mixed Ethanol, butanol,
Chemical supercritical fluid processing triglycerides, fatty
Technology technology allows for the acids, dimethyl
(USA) direct conversion of a host of ether, and isoprene
waste biomass materials to
fuels, chemicals, and non-
gasification intermediates
Solena (USA) Closed systems Plasma techniques are used in Establishing a
gasification of algae and other 40 MW power plant
organic matters. It can generate in cooperation with
electricity from microalgae Sunflower Company
treated with gasification of Kanas
Solix Biosystems Closed systems The core of Solix’s intellectual Renewable
(USA) property consists of its chemicals and fuels,
proprietary AGS technology. personal care
AGS is an extended surface products, and
area culture system that nutritionals
incorporates Solix’s proprietary
Lumian™ photobioreactor
panels
XL Renewables Closed systems Patented algae production Biofuels and
(USA) technology—Simgae for bioproducts
simple algae. Phyco is
currently developing a
commercial production facility
near Phoenix, Arizona. XL
Renewable has formed Phyco
BioSciences, Inc. to
commercialize algae biomass
as a food and industrial crop
(continued)

Aurora Algae Open ponds Using genetically modified Eicosapentaenoic
algae to produce biodiesel acid, proteins,
based on patented techniques biodiesel, etc.
from UCB. The algae owned
by the company show light
color with light penetration for
the purpose of high yields.
Aurora Algae has developed
the world’s first commercial-
scale photosynthetic platform
for sustainable algae-based
product development
Cellena (USA) Photobioreactors Cellana’s patented ALDUO™ Biofuels, Omega-3
and open ponds system consists of a series of eicosapentaenoic
photobioreactors coupled with acid, and
open ponds. Cellena possesses docosahexaenoic
the techniques for oil acid and animal feed
extraction from seaweed
without chemicals or oil
extraction process. To date,
over 20 metric tons of whole
algae (dry weight) have been
produced. Since 2009, Cellana
has operated its Kona
Demonstration Facility, a
6-acres state-of-the-art
production and research
facility in Hawaii
LanzaTech Closed systems LanzaTech’s microbial gas Bioethanol, aviation
fermentation technology in biofuels, bioproducts
which microorganisms and
microalgae are cultivated in
captured CO and CO2 yields
fuels and chemicals
BioProcess Closed systems Applying biofilm techniques to Animal feed,
Algae cultivate microalgae possessing nutritionals, and
the Grower Harvester™ transportation fuels
harvesting methods based on
patented technology
Solix Closed The company’s production in Renewable chemical
Biosystems, Inc. photobioreactor algal growth system is seven products and fuels
panels times as much as that in open
ponds
(continued)

Heliae Closed systems Heliae possesses Volaris™ Biofuels and
and pond system commercial production bioproducts
platform, AMP™ strains rapid
screening system, and Helix™
algal strains cultivation system.
In 2010, Heliae built up a
20-acre microalgae cultivation
commercial demonstration
plant and invested 13 million
dollars in plant expansion
governing political parties and their proposed biofuel regulations. The economic
risk primarily originates from the feedstock market price. The technological risks
pose less threat in comparison to the other listed threats. The risk associated with
profitable operations is the most noted primary activities risk as analyzed.
1.4 Outlook for a Sustainable Future
Energy can be considered as the most influential commodity in supply-demand con-

cept worldwide. Over the last decade, the annual increase in global CO2 emission
was 2.5% and this has resulted in the increase in world’s temperature by 2 °C
(Friedlingstein et al. 2014). The consumption of renewable and low-carbon biofuels
is on the rise owing to the international policies that focus on decreasing the green-
house gas emissions. The land use patterns can vary among nations and different
lands such as marginal, degraded, agricultural, and pastureland should be integrated
to the current land use patterns. The introduction of biomass into the available lands
must happen gradually without affecting the agricultural productivity in any land.
The introduction of bioenergy production technologies must be able to provide
additional income in the rural regions.
For the growth of biofuel crops, the sustainability and carbon footprint involved
during the growth need attention. Canada is well positioned with resources and
availability of marginal lands to produce lignocellulosic biomass-based biofuels.
The first-generation and second-generation feedstocks are not substantial enough to
meet the present energy demands, and development of leading technology using
third-generation feedstocks is imperative. Due to the suboptimal climate in Canada,
photosynthetic microalgae cannot provide a complete solution for the futuristic
energy demand. Based on the current microalgae-based biofuels production tech-
nology, the net energy yield is 0.93. In other words, an input energy of 0.93 MJ is
required for every 1 MJ of energy produced using photosynthetic microalgae. The
usage of heterotrophic microalgae-based technology for biofuels production offers
several advantages such as higher productivity, reduction in capital investments, and
minimal operating cost. For the development of commercially viable process,
Table 1.6 The Bio-based Industries Joint Undertaking (BBI-JU) funded projects to support lig-
nocellulose biorefining industry in the European Union (Reproduced with permission from Hassan
et al. 2019)
BBI-JU
Start End contribution
Project and website date date (€) Focus
BIOFOREVER 2016 2019 9,937,998 Demonstrate the commercial
(https://www. viability of lignocellulosic
bioforever.org) biorefining (from woody biomass)
for the chemical industry
BIOSKOH (http:// 2016 2021 21,568,195 Demonstrate the first of a series of
bioskoh.eu) new second-generation
biorefineries in Europe
EUCALIVA (http:// 2017 2021 1,795,009 Create a whole value chain from
eucaliva.eu) lignin using Eucalyptus waste
GRACE (http://www. 2017 2022 12,324,632 Explore the potential of the
grace-bbi.eu) nonfood industrial crops as a
source of biomass for the
bioeconomy
GreenSolRes (http:// 2016 2021 7,451,945 Demonstrate the commercial
www.greensolres.eu) viability of converting
lignocellulosic biomass to levulinic
acid
HyperBioCoat (http:// 2016 2019 4,617,423 Develop biodegradable polymers
www.hyperbiocoat.eu) derived from food processing
by-products
iFermenter (https:// 2018 2022 3,997,825 Conversion of forestry sugar
ifermenter.eu) residual streams to antimicrobial
proteins by intelligent fermentation
LIBRE (http://www. 2016 2020 4,566,560 Lignin-based carbon fibers for
libre2020.eu) composites
LigniOx (http://www. 2017 2021 4,338,374 Lignin oxidation technology for
ligniox.eu) versatile lignin dispersants
LIGNOFLAG (http:// 2017 2022 24,738,840 Produce bioethanol involving a
www.lignoflag-project. bio-based value chain built on
eu) lignocellulosic feedstocks
PEFerence (http:// 2017 2022 24,999,610 Produce furan dicarboxylic acid, a
peference.eu) bio-based building block to
produce high-value products
SSUCHY (https:// 2017 2021 4,457,194 Produce sustainable structural and
www.ssuchy.eu) multifunctional biocomposites from
hybrid natural fibers and bio-based
polymers
SWEETWOODS 2018 2022 20,959,745 Produce and deploy high purity
(https://sweetwoods.eu) lignin and affordable platform
chemicals through wood-based
sugars
(continued)

BBI-JU
Start End contribution
Project and website date date (€) Focus
UNRAVEL (https:// 2018 2022 3,603,545 Develop advanced pretreatment,
www.bbi-europe.eu/ separation, and conversion
projects/unravel) technologies for complex
lignocellulosic biomass
US4Greenchem 2015 2019 3,457,602 Combined ultrasonic and enzyme
(https://www. treatment of lignocellulosic
us4greenchem.com) feedstock as substrate for sugar-
based biotechnological applications
VALCHEM (http:// 2015 2018 13,125,941 Value-added chemical building
www.valchem.eu) blocks and lignin from wood
WoodZymes (https:// 2018 2021 3,253,874 Extremozymes for wood-based
www.woodzymes.eu) building blocks: from pulp mill to
board and insulation products
ZELCOR (http://www. 2016 2020 5,256,993 Zero-waste lignocellulosic
zelcor.eu) biorefineries by integrated lignin
valorization
modification of cell metabolism may be essential. However, a risk-based assess-

ment is essential to understand the potential negative impact on local ecosystems.
The interaction of bioenergy sector with parameters such as CO2 sequestration,
food production for consumption, nature preservation, and biodiversity needs detailed
analysis. A detailed model illustrating this interaction will provide improved under-
standing on the growth of biofuels sector in future. The technological development
has direct influence on the capability of biofuels sector. The two main components of
technological development are production of final products (energy carriers) from
biomass and transport of these energy carriers. The usage of perennial crops such as
hybrid poplar, Miscanthus, and sugarcane should be promoted in comparison to
annual agricultural products due to the environmental and economic upper edge.
As mentioned by Scaife et al. (2015), some technological factors regarding bio-
fuels need to be addressed such as whether the optimal technology is regionally
specific or universal. Moreover, whether the technology be used to produce a broad
spectrum of biofuels and biochemicals is still questionable. Additionally, the use of
biological systems should address their utility based on photosynthetic or heterotro-
phic growth of microorganisms. The biomass harvesting processes, initial products
extraction, and biomass conversion into biofuels at a cost-effective and energy-
efficient manner are desirable.
1.5 Conclusions
The microalgae-based biofuels processes still need techno-economic analysis

before commercialization. The third-generation biofuels production technology is
still in research and developmental phase, and especially, microalgal biofuels are
generally overlooked owing to the limitations in availability of literature support-

ing the success of microalgal in other countries. The present economy is highly
fossil based and under the condition of fluctuations in oil prices. The dominance of
fossil fuels is based on various aspects primarily due to policies established in the
past, industrial infrastructure, and mind-set of customers to find fossil fuels more
reliable than advanced biofuels. Biofuels have promising potentials for a sustain-
able bioeconomy that can not only reduce greenhouse gas emissions but also
reduce the pollution problems and global warming. It is highly imperative to
explore more on the research and development of biofuel feedstocks and the con-
version technologies.
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Bioconversion of Agro-industrial
Residues to Second-Generation 2
Bioethanol
Thiago Machado Pasin, Paula Zaghetto de Almeida,

Ana Sílvia de Almeida Scarcella, Juliana da
Conceição Infante, and Maria de Lourdes de
Teixeira de Moraes Polizeli
Abstract
Bioenergy is the term used for energy produced from lignocellulosic biomass.
Most of the residues produced from agricultural and industrial activities present
high levels of lignocellulose. They are mostly formed by rigid structures mainly
containing hemicellulose and cellulose intermixed by lignin. These macromole-
cules are linked by covalent and hydrogen bonds, thus forming a complex archi-
tecture, which give a great resistance to their hydrolysis. This hampers the
subsequent production of fermentable sugars and their fermentation to produce
second-generation bioethanol. The technologies to obtain second-generation
bioethanol, independent of the plant source, involve the hydrolysis of polysac-
charides from the biomass in order to generate sugars that can be fermented by
yeasts. This chapter addresses the importance of biomass for the production of
green fuels. In this chapter, the potential of different lignocellulosic biomasses,
especially the agricultural crop residues, is described. The composition of the
main molecules forming the cell wall of different plants is provided. The enzymes
that are involved in the deconstruction of plant cell walls as well as the release of
fermentable sugars are discussed. The pretreatment and fermentation of biomass
for the second-generation ethanol production by yeasts are described. Some
T. M. Pasin · P. Z. de Almeida · A. S. de Almeida Scarcella · J. da Conceição Infante ·

M. L. T. M. Polizeli (*)
Departamento de Bioquímica e Imunologia, Faculdade de Medicina de Ribeirão Preto,

24 T. M. Pasin et al.
challenges concerning the technologies are considered, but, on the other hand,
some alternatives are also pointed out.
Keywords
Agro-industrial residues · Second-generation bioethanol · Biorefinery · Green
fuels · Enzymes · Saccharification
2.1 Introduction
Biomass refers to any matter of plant origin, which can be processed to provide
more elaborate bioenergetic and chemical forms suitable for end use. Around the
world, more than 146 billion tons of residues are annually available, but only a por-
tion (up to 100 million) of it is being used for energy and biofuel production (Ayres
2014). The rest of these residues is usually burnt or left behind, which may lead to
the worsening of the greenhouse effect. A few of the most biomass-producing coun-
tries in the world are Brazil, China, Indonesia, Russia, and the USA (Table 2.1).
Food, fiber, or wood production generates biomass, which could be useful for
energy production using mature technologies. Currently, the final biomass energy
produced is 50 EJ totaling 14% of the final energy used in the world, but it has a
potential to be increased up to 150 EJ by 2035. A total supply of 38–45% is esti-
mated to be originated from waste and residues from agriculture and the remaining
supply would be shared by the energy crops, forestry, and residual products (IRENA
2014). According to the World Bioenergy Association (WBA 2014), the estimated
potential of residues from agriculture in order to produce energy varies between 17
and 128 EJ. There is a high potential of using residues from agriculture, especially
in Asia and the Americas because of the different crops highly produced in these
regions. There is an enormous potential for exploiting the use of biomass in order to
produce larger quantities of products with high value.
Table 2.1 Comparative production of crops in different countries

Crop Country Production (million tons/year) References
Barley Russia 20.4 Worldatlas & Graphic Maps (2017)
Coffee Brazil 2.8 FAS (2018a)
Cotton China 5.9 FAS (2018b)
Maize USA 370.5 FAO (2017)
Oil palm Indonesia 40.5 Iskandar et al. (2018)
Potato China 99.0 FAO (2019)
Rice China 210.1 Muthayya et al. (2014)
Soybean USA 119.5 FAO (2017)
Sugarcane Brazil 758.5 FAO (2017)
Wheat China 134.4 Worldatlas & Graphic Maps (2019)
2 Bioconversion of Agro-industrial Residues to Second-Generation Bioethanol 25
Due to the various possible sources of lignocellulosic biomass, this chapter is

focused on describing the structure and characteristics of its major components,
such as cellulose, hemicellulose, pectin, and lignin present in the primary and sec-
ondary cell walls. The resins, fatty acids, phenols, tannins, nitrogenous compounds,
and mineral salts, e.g., calcium, potassium, and magnesium on a smaller scale, can
also be found, which depends on the plant species (Neureiter et al. 2002).
Subsequently, the chapter presents a description of different biomass sources that
can be used for the production of bioenergy, followed by the major enzymatic sys-
tems that can degrade plant cell walls and their mechanism of action on biomass,
especially in sugarcane, for the production of second-generation bioethanol.
2.2 Composition of Lignocellulosic Biomass
Cellulose (23–50 wt% of the dry matter of lignocellulosic biomass) is a linear

homopolymer containing up to 15,000 units of β-d-glucose bound by β-1,4-
glycosidic linkages (Nanda et al. 2015). It has reducing and nonreducing ends, and
it is extremely resistant to degradation (Michelin et al. 2013). The strength of cel-
lulose is due to many hydroxyl groups on the glucose structure that contribute to the
formation of massive intramolecular bounds (linkages among glucose units of the
same molecule) and intermolecular hydrogen bounds (among glucose units of adja-
cent molecules), which are responsible for stiffness. The intramolecular bonds are
responsible for the formation of fibrils, which are highly ordered structures.
According to the degree of organization of the bonds between the cellulose chains,
the structure can be crystalline (highly ordered) or amorphous (less ordered). The
amorphous regions can absorb water more easily and are more susceptible to enzy-
matic action.
Hemicellulose is a heteropolysaccharide (15–45 wt% of dry lignocellulosic
material) with branched chains of monosaccharides, mainly including aldopentoses
(xylose and arabinose) and aldohexoses (glucose, mannose, and galactose). This
macromolecule also contains deoxyhexoses and acids, such as β-d-galacturonic
acid, d-4-O-methylglucuronic acid, and β-d-glucuronic acid (Polizeli et al. 2005).
The variety of bonds and branching, as well as the presence of different monomeric
units, contributes to the complexity of the hemicellulosic structure and its different
conformations. Unlike cellulose, hemicellulose has low molecular mass (100–200
glycosidic units) and does not contain crystalline regions, which makes it easier to
hydrolyze in non-drastic conditions (Polizeli et al. 2005).
There are different types of hemicellulose, such as arabinoxylan, acetylglucuro-
noxylan, arabinan, arabinogalactan, xylan, galactomannan, xyloglucan, galacto-
glucomannan, and glucomannan. Hemicellulose is classified according to its sugar
chain composition. Thus, the term hemicellulose does not denote a defined chemi-
cal compound, rather, a set of polymeric components present in fibrous plants
where each component has different properties. The major hemicellulose constitu-
ent is the xylan, which is a xylose β-1,4-polymer with several branched residues
(Polizeli et al. 2005). The fermentation of pentoses is not yet as developed as the
processes involving glucose. Mannan is the second most abundant component of

the hemicellulosic fraction being widely found in woods (gymnosperms), tubers,
seeds, and grains in different compositions structure and complexity. The main
chain of mannan consists of mannose residues bound by β-1,4-linkages or a com-
bination of mannose and glucose residues associated by a same type linkage. In
addition, the major chain of mannan may have side chains attached to α-1,6-
galactose residues (De Marco et al. 2015).
Pectins are heterogeneous polysaccharides, which form the middle lamella
being the largest component inside it. These polysaccharides are adhesive materi-
als in the extracellular portion found in the higher plant cells located in the primary
walls. The structure consists of axial bonds with acid units of α-1,4-d-galacturonic
and contains molecules of galactose, arabinose, xylose, and l-rhamnose as the side
chains (Polizeli et al. 2013).
The biochemical structure of lignin (10–30 wt% of dry lignocellulosic mate-
rial) cannot be related to sugar molecules, and it is not suitable for bioconversion
or fermentative routes. However, this fraction plays a key role in the success of
hydrolysis technology, since it blocks the access to cellulose. The structure of
lignin has a three-dimensional polymeric structure formed by p-propylphenol
units with methoxy substituent on the aromatic ring joined by ether bonds that
crosslink each other. This macromolecule is originated through sinapyl, coumaric,
and coniferyl alcohols.
2.3 ommonly Available Agricultural Crop Residues

C
in the World
2.3.1 Barley and Coffee Residues
Barley (Hordeum vulgare) is one of the main cereal sources produced in the world
for humans and livestock consumption. Every year, an area of around 50 million
hectares is harvested, being the fourth major cereal produced in the world. The most
abundant staple crops cultivated in the world are wheat (~200 million hectares), rice
(~170 million hectares), and maize (~145 million hectares). Russia, Australia,
Ukraine, and Canada are the major barley-producing countries (WAP 2019). Barley
and beer residues are similar to other lignocellulosic materials being composed of
cellulose, hemicellulose, and lignin. It is reported that the percentage of cellulose
and hemicellulose in such materials is high (Table 2.2), which can be hydrolyzed
and fermented aiming the production of biofuels and biochemicals.
The coffee tree is a plant of permanent culture that belongs to the Rubiaceae
family and to the genus Coffea such as Coffea arabica and Coffea canephora.
Around 8.9 million tons of coffee are produced over an area of approximately 10.6
million hectares (FAO 2018). The major coffee producers in the world are Brazil,
Vietnam, and Colombia (Al-Abdulkader et al. 2018). One ton of bark is generated
per each ton of beans of coffee that are processed (Saenger et al. 2001). The coffee
pulp is the main residue originated in the wet processing of the mature coffee,
Table 2.2 Cellulose, hemicellulose, and lignin composition of some of the most widely found
lignocellulosic feedstocks in the world
Cellulose Hemicellulose Lignin
Residues (wt%) (wt%) (wt%) References
Barley bagasse 23.0 32.7 24.4 Tamanini and Hauly
(2004)
Coffee husks 22.7 14.7 12.4 Souza et al. (2001)
Cotton straw 40.7 10.5 15.4 Silanikove et al. (1988)
Corn cob 31.7 34.7 20.3 Tamanini and Hauly
(2004)
Oil palm fiber 41.9 29.5 30.0 Sudiyani et al. (2013)
Potato peels 55.2 11.7 14.2 Lenihan et al. (2010)
Rice straw 38.0 27.0 8.0 Santos et al. (2012)
Soybean 16.0 23.0 28.0 Heck et al. (2002)
fibrous
Sugarcane 43.0 26.0 22.0 Rocha et al. (2011)
bagasse
Wheat straw 35.0 24.0 25.0 Zhu et al. (2005)
representing approximately 40 wt% of the dry weight of the coffee bean, which is
rich in cellulose and hemicellulose (Table 2.2), proteins, minerals, and appreciable
amounts of tannins, caffeine, and potassium. Currently all these raw materials
could be used in developed processes to generate value-added and bulk chemicals
products such as active secondary metabolites, unicellular proteins, enzymes, and
organic acids (Pandey et al. 2000). Another alternative is the use of these wastes for
bioenergy production.
2.3.2 Sugarcane, Maize, Rice, and Wheat Residues
Sugarcane, maize, rice, and wheat residues generate most of the lignocellulosic resi-
dues in the world (Saini et al. 2015). One of the most famous plant being used nowa-
days is the sugarcane (Saccharum ssp.). It is a C4 crop that has been used for a long
time in the sugar production, but currently bioethanol and electricity have become
the most famous value-added energy products generated through bioconversion and
burning, respectively (Cotrim et al. 2018). The total harvested area for sugarcane in
the world is estimated to be around 26.7 million hectares and the major producers
are Brazil, India, and China. After the processing of the sugarcane, large quantities
of bagasse are generated what presents good amounts of cellulose and hemicellu-
lose. These factors make it an interesting, renewable, and cheap resource to produce
biochemicals and biofuels (Bhatia and Paliwal 2011).
There are several varieties of commercial sugarcane in the world. In Brazil, the
SP80-3280 variety is one of the most studied. The composition of the cell wall of
SP80-3280 variety sugarcane is reported having fundamental importance for under-
standing the enzymes necessary for its saccharification (De Souza et al. 2013). In
recent years, the search for sugarcane with high levels of sugars for first-generation
bioethanol and the accumulation of biomass for second-generation bioethanol pro-

duction have increased. This sugarcane is known as energy cane, which presents the
particularity of having a higher fiber content, being distributed in the fractions of
lignin, cellulose, and hemicellulose. The energy cane comes from genetic improve-
ments of the sugarcane (Saccharum spontaneum) to increase the energy availability
and adaptation to different cultivation environments (Tew and Cobill 2008).
Maize (Zea mays) is a well-known cereal being considered the main input in
animal protein production, in human nutrition, and also in the biofuel production.
The total area harvested each year in the world is estimated to be around 145 million
hectares and the major maize producers in the world are the USA, China, and Brazil
(FAO 2018). From Table 2.2 it can be inferred that the maize residues have small
amounts of lignin, which makes it interesting for the use in the bioenergy and in the
production of chemicals.
Rice consists of two main species such as Oryza glaberrima and Oryza sativa.
It is a plant of the grass family and is among the products intended for human
consumption, being second in importance, only behind wheat. In some parts of
the world, especially in Asia, rice is staple food crop (CONAB 2018). It is har-
vested from over 163 million hectares in more than 100 countries (Laborte et al.
2017). The major rice producers are China, India, and Indonesia (FAO 2018).
During the rice cultivation, huge amounts of rice straw are generated along with
leaf blades, stems, leaf sheaths, and husks as the leftovers. These residues are one
of the largest lignocellulosic wastes in the world. Among the most rice straw pro-
ducers is Asia which alone generates 667.6 million tons of rice straw that consists
of 91.3% of the global rice production (Saini et al. 2015). This residue is also an
important source with similar contents of hemicellulose, lignin, and cellulose
when compared with other organic residues, which could be better used for the
production of biofuels and biochemicals.
Wheat is considered a staple food and cereal in all over the world (Shewry
2009; Balkovič et al. 2014). The common wheat, Triticum aestivum, is the most
widely grown in the world, over an arable land about 220.4 million hectares (FAO
2018). During the wheat harvesting process, straw is generated at a rate of 2.5–7.5
tons/hectare annually under rigorous farming conditions. Cellulose, hemicellu-
loses, and lignin make up the most part of the agricultural residues in a similar
rate. However, wheat straw presents pectin and proteins, whereas rice straw has
silica within its tissues (Sarkar et al. 2012).
2.3.3 Cotton
Cotton is a staple fiber found across the world. It belongs to the genus Gossypium
within the Malvaceae family. Cellulose is the main component of the cotton bolls.
It is estimated that 25 million tons of cotton are annually produced in the world
over an area that estimates about 2.5% of the total arable land at a global scale. The
cotton cultivation area in the world is accounted around 33.6 million hectares per
year and the major cotton producers are China, India, and the USA (Daisy et al.
2018). After harvesting the cotton, huge amounts of residues are left in the field,
such as side branches, stalks, bolls, seeds with adhering cotton lint, leaves, etc.
(Huang et al. 2012). The total amount of residues (e.g., cotton straw, cotton sticks,
cotton wood) generated from the cotton harvesting can range from 5 to 7 tons/
hectare. The quality of these materials that are generated from the cotton harvest-
ing presents a high variability as commonly observed in crop wastes. However,
these residues are also important sources of lignin, cellulose, and hemicellulose as
shown in Table 2.2.
2.3.4 Oil Palm Residues
Oil palm is a vegetable oil extracted from the mesocarp of Elaeis guineensis. Palm
oil is a common cooking ingredient in Brazil, Africa, and Asia. Oil palm trees pres-
ent a highly efficient land use with a large yield when compared with other crops
used for oil extraction. It is estimated that a total harvested area of about 17 million
hectares of mature oil palm plantation produces a total of 62.6 million tons of oil
palm per year. The major oil palm producers are Indonesia, Malaysia, and Nigeria
(EPOA 2018). Europe is the major importer of oil palm for using it as a precursor
for biodiesel production (Soeriaatmadja and Leong 2018). In addition to its massive
potentials for biodiesel production, all the oil palm residues generated after the oil
extraction could also be used to produce the bioethanol since it is composed of cel-
lulose, hemicellulose, and lignin (Table 2.2).
2.3.5 Potato Residues
Potato (Solanum tuberosum) is a staple food crop cultivated in most countries across
the world. Potatoes are considered the fifth largest crop for human consumption
after wheat, rice, maize, and barley. In 2016, the total world potato production and
harvested area were estimated at 376 million tons and 19 million hectares, respec-
tively (FAO 2018). The three largest potato producers in the world are China, India,
and Russia. Potato processing industry generates massive amounts of organic
wastes. It is estimated that one quarter of the total weight of potato is obtained as
wastes from the food processing plants. These wastes can be used, for example, as
a carbon source for yeast during alcohol fermentation to produce bioethanol. The
potato peel waste contains adequate amount of starch, hemicellulose, cellulose, lig-
nin (Table 2.2), and residual carbohydrates, which make potato peel a suitable feed-
stock for ethanol production (Ojewumi et al. 2018).
2.3.6 Soybean Residues
The soybean (Glycine max) is known to be widely cultivated because of its

comestible bean that presents several different uses. The worldwide soybean
production was estimated around 337 million tons in 2017–2018 (WASDE 2018).
The major producers of soybean in the world are the USA, Brazil, and Argentina.
Based on the global production, it is possible to affirm that these three countries
are responsible by approximately 85% of the total soybean production (FAO
2015). During the recovery of the protein from the soybean seeds, large amounts
of residues are generated. The residues generated are composed of 16 wt% cel-
lulose and 23 wt% hemicellulose (Table 2.2). Previous studies have estimated
that approximately 10,000 tons per year of these by-products are generated and
only a small portion is used for animal feeding, while the rest is mainly disposed
in the environment (Heck et al. 2002).
2.4 Enzymatic Saccharification of Lignocellulosic Residues
2.4.1 Cellulases
Cellulases are glycosyl hydrolases that act in the cleavage of cellulose and can be
classified into endoglucanases (EG), exoglucanases (CBH), and β-glucosidases
(BG) (Payne et al. 2015; Wei and Mcdonald 2016). Some cellulases are organized
in complexes called cellulosomes. These structures are produced by anaerobic bac-
teria (Artzi et al. 2017) and fungi (Haitjema et al. 2017) as a strategy to improve the
hydrolysis efficiency. They are composed of a complex scaffolding as structural
subunit and various enzymatic subunits. Many cellulases and hemicellulases are
attached to structures called carbohydrate binding module (CBM). These structures
have the property to attach the enzyme to the substrate. CBMs are not necessary to
the hydrolytic function and there is no evidence that they improve the action of cel-
lulases (Várnai et al. 2014).
Fig. 2.1 Cellulase action on cellulose crystalline and crystal structure. Endoglucanase (EG) in
blue at the amorphous region with a CBM attached to the crystalline region releasing smaller cel-
lulose chains. Cellobiohydrolase (CBH) in orange is attached to the crystalline terminal releasing
cellobiose. β-Glucosidase (BG) in yellow cleaves the cellobiose to glucose. Auxiliary activity 9
enzyme (AA9) in purple acts on the crystalline region leaving a rupture in the cellulose chain.
Swollenin (SWO) in pink acts between the cellulose chains resulting in a less crystalline
structure
Endo-β-1,4-glucanases (EC 3.2.1.4) hydrolyze the glycosidic bonds mainly at

the amorphous regions of cellulose (Fig. 2.1). They are distributed along 16 out of
134 glycoside hydrolase (GH) families and are characterized by shorter loops.
Thus, this feature enables the active site fissures to reach accessible sites of cel-
lulose chain. The endoglucanases act in the interior of cellulose, resulting in long-
chain oligomers. When compared with other cellulases, they have a faster
dissociation rate and show the best cellulose liquefaction results, thus decreasing
the chain length and consequently the viscosity (Badieyan et al. 2012; Boyce and
Walsh 2015; Juturu and Wu 2014).
Exoglucanases or cellobiohydrolases act in the end of crystalline cellulose chains
to release cellobiose (Fig. 2.1). They act efficiently in cellulose hydrolysis and are
divided into EC 3.2.1.91 (acting in the nonreducing ends) and EC 32.1.176 (acting
in the reducing ends). These enzymes have long loops usually forming tunnels
around the catalytic residues; thus the substrate is directed along these tunnels to
encounter the active site (Obeng et al. 2017; Wilson and Kostylev 2012).
β-Glucosidases (BGs, EC 3.2.1.21) break down cellobiose to glucose (Fig. 2.1).
Several β-glucosidases are also able to catalyze the reverse reaction by transglyco-
sylation in which glucose molecules are transferred to another glucose molecule or
cellobiose to yield different oligosaccharides. β-Glucosidases are susceptible to
product inhibition, especially at high-biomass conditions. Thus, it is one of the big-
gest bottlenecks for the total cellulose conversion to glucose. The addition of large
amounts of β-glucosidases in enzymatic cocktails has the extra goal to reduce the
product inhibition exhibited by cellobiose on cellobiohydrolases and endogluca-
nases (Andríc et al. 2010; Singhania et al. 2013).
The most reported cause to product inhibition on fungal β-glucosidases is via
competitive inhibition, but it is also described as one of the noncompetitive and
mixed mechanisms. The majority of β-glucosidases belong to the 1 and 3 GH
families, but they are also found in families 5, 9, and 30. The enzymes belonging
to family GH1 are 10 to 1000-fold more tolerant to glucose when compared to
GH3 β-glucosidases. The structural analysis shows that glucose tolerance is
strongly correlated with active site accessibility (Andríc et al. 2010; De Giuseppe
et al. 2014; Singhania et al. 2013).
2.4.2 Auxiliary Activity 9 Enzyme and Swollenin Protein
Auxiliary activity 9 (AA9) enzyme is a fungal lytic polysaccharide monooxygenase

(LPMO), a cooper-dependent enzyme that is added to the most commercial cock-
tails. AA9 boost the action of cellulases in lignocellulosic material hydrolysis. It
promotes the oxidative cleavage of glyosidic bounds of C1 or C4, thus disturbing
cellulose crystallinity and giving access to canonical cellulases, consequently
improving the overall hydrolysis yield (Fig. 2.1). The oxidation promoted by LPMO
is dependent on an electron donor, e.g., ascorbic acid, cellobiose dehydrogenase,
and lignin or photocatalytic systems. The oxidation occurs only in the presence of
O2 or H2O2 as the co-substrate (Bertini et al. 2018; Möllers et al. 2017; Müller et al.
2018; Walton and Davies 2016).
Swollenins (SWOs) are nonenzymatic proteins with high homology to plant
expansins. This class of proteins has the property to cause deagglomeration of
crystalline cellulose. SWOs act in the breakage of hydrogen bonds between
the cellulose chains, thus loosening the structure, increasing the accessibility
of canonical cellulases and enzymatic hydrolysis (Fig. 2.1). SWOs can also
disrupt hemicellulose, promoting a better solubilization and acting synergisti-
cally with hemicellulases (Cosgrove 2000; Gourlay et al. 2013; Kang et al.
2013; Kim et al. 2014; Santos et al. 2017).
2.4.3 Hemicellulases
Hemicellulases are classified as the class of enzymes responsible for depoly-

merizing the hemicellulose. In order to achieve the complete degradation of
hemicelluloses, the action of several enzymes belonging to GH families is
important. The most significant enzymes of these complex are discussed as fol-
lows (Polizeli et al. 2005; Saha 2003).
Xylan, a xylose β-1,4-polymer, is a major constituent of hemicellulose. For
the degradation of xylan, two main enzymes are necessary, namely, endo-β-
1,4-xylanase and β-1,4-xylosidase (Fig. 2.2). Endo-β-1,4-xylanases (EC
3.2.18) or endoxylanases catalyze the hydrolysis of xylan to xylooligosaccha-
rides. This enzyme acts in the internal backbone of xylan promoting the
COOH
Acetylxylan esterase O
Endoxylanase H3CO
HO
COCH3 OH α-glucuronidase COCH3
OH OH O O
O O HO O HO O HO
O O O O
O O O HO O HO O
O O O O O
OH O OH
OH O
Arabinofuranosidase
OH
CH2OH OH Feruloyl esterase
CH2
OH
O O β-xylanase
HO O O
HO O O O
OH HO OH HO
OH
OH
H3CO
OH
Fig. 2.2 Simplified structures of hemicelluloses with ramifications and the enzymes that act in
their hydrolysis. Acetyl substitutions cleaved by acetyl xylan esterase are shown in pink. Arabinan
removed from xylan chain by arabinofuranosidase is shown in yellow. Ferulic acid detached to
arabinan by feruloyl esterase is shown in green. 4-O-Methyl-d-glucuronic acid removed by
α-glucuronidase is shown in blue. The nonreductive end of an oligosaccharide cleaved by
β-xylanase to obtain xylose monomers is shown in purple. The xylan backbone cleaved in the
interior regions by endoxylanase releasing xylooligosaccharides is shown by the non-highlighted
region
hydrolysis of β-1,4-glycosidic linkages. Exo-β-1,4-xylosidase (EC 3.2.1.37) or

β-1,4-xylosidase acts in the nonreducing ends of xylan structure or xylooligo-
saccharides including xylobiose, thus releasing d-xylose monomers (Burlacu
et al. 2016; Heinen et al. 2018; Polizeli et al. 2005).
The removal of the ramifications attached to xylan chain is promoted by a com-
plex of enzymes. The most important enzymes are α-l-arabinofuranosidase,
α-glucuronidase, acetyl xylan esterase, and feruloyl esterase (Fig. 2.2). α-l-
Arabinofuranosidase (EC 3.2.1.55) or arabinofuranosidase cleaves the nonreductive
end of the arabinan in the positions O-2 or O-3 releasing oligomers (Juturu and Wu
2013). α-Glucuronidase (EC 3.2.1.139) hydrolyses the 1-2-glycosidic bound
between xylan and the side chain of 4-O-methyl-d-glucuronic acid, thus releasing
glucuronic acid (Shallom and Shoham 2003). Acetyl xylan esterase (EC3.1.1.72)
removes the acetyl substitutions attached on xylose releasing acetic acid (Tenkanen
et al. 1992). Feruloyl esterase (EC3.1.1.73) or feruloyl xylan esterase hydrolyses the
ester bond between ferulic acid and arabinose (Dilokpimol et al. 2016).
The mannan-degrading enzymes are β-mannosidase (EC 3.2.1.25), β-mannanase
(EC 3.2.1.78), and β-glucosidase (3.2.1.21). There are also additional enzymes such
as α-galactosidase (EC 3.2.1.22) and acetyl mannan esterase (EC 3.1.1.6) required
to remove side-chain substituents, thus creating more sites for enzymatic hydrolysis
(Fig. 2.3a–f) (Moreira and Filho 2008). According the Carbohydrate-Active
Enzymes Database (CAZy), the mannanases are classified into GH families 5, 26,
and 113 (Cantarel et al. 2009; Cruz 2013). These GH families have double-
displacement mechanism holding anomeric configuration (De Marco et al. 2015).
The complete hydrolysis of the mannan chain demands the synergy of exo-acting
and endo-acting hydrolases together with accessory enzymes to reach complete
hydrolysis. The heterosynergy is the synergistic action between main-chain and
side-chain enzymes (β-mannanase and α-galactosidase) and homosynergy between
two main-chain enzymes (β-mannosidase and β-mannanase) or between two side-
chain enzymes (acetyl mannan esterase and α-galactosidase) reported in the degra-
dation of mannan (Moreira and Filho 2008).
It is possible to visualize the presence and the size of the β-mannanase follow-
ing the molecular markers using the technique of sodium dodecyl sulfate-
polyacrylamide gel electrophoresis (SDS-PAGE) and zymography. Multiple bands
stained for β-mannanase activity (Fig. 2.3g, h) can be detected using these tech-
niques, which migrate at molecular masses ranging from 20 to 50 kDa. The variety
of forms is usually described for hemicellulases from bacteria and fungi as the
result of posttranslational modifications and differential messenger RNA (mRNA)
processing. These mannanases can be isozymes, allozymes, and products of differ-
ent alleles in the same gene or same molecules with different posttranscriptional
modifications (De Marco et al. 2015).
Fig. 2.3 Structures of mannans and pectins. Zymography of mannanase activity. (a) Mannan, (b)
glucomannan, (e) galactomannan, and (f) galactoglucomannan. The mannan is hydrolyzed by
2.4.4 Pectin-Degrading Enzyme System
Pectinases (EC 3.2.1.15) are a set of complex enzymes that degrade pectin in
plant cell wall (Fig. 2.3i–k). Pectin-degrading enzymes are capable of degrading
pectic substances per de-esterification (esterases) or depolymerization (lyases
and hydrolases) reactions (Tariq and Latif 2012) and include polygalacturonases
(PGs), pectinesterases (PEs), pectate lyases (PGLs), and pectin lyases (PLs)
(Ahlawat et al. 2009; Polizeli et al. 2013). Polygalacturonases (PGs) are hydro-
lases, which cleave α-1,4-glycosidic linkage in homopolygalacturon backbone.
They are classified into GH family 28 according to the Carbohydrate-Active
Enzymes Database (CAZy) classification.
Endopolygalacturonases (EC 3.2.1.15) randomly attack the α-1,4-glycosidic
bonds of the polysaccharide chain, thus releasing galacturonic acid oligomers. On
the other hand, exopolygalacturonase type I (EC 3.2.1.67) acts in the nonreducing
end and the d-galacturonic acid is hydrolyzed. Di-galacturonate is released as a
result of the action of exopolygalacturonase type II (EC 3.2.1.82) in the nonreduc-
ing end of polygalacturonic acid (Khan et al. 2013). Pectinesterases (EC 3.1.1.11)
are esterases that catalyze the methoxyl group of pectin forming pectic acid (Amin
et al. 2017). Endopectin lyases (EC 4.2.2.10) accomplish trans-elimination reaction
of pectin. Endopectate lyases (EC 4.2.2.2) and exopectate lyases (EC 4.2.2.9) cleave
internal and nonreducing end of α-1,4-polygalacturonic acid, respectively, via
β-elimination reaction (Yang et al. 2018).
2.4.5 Delignifying Enzymes
Delignifying enzymes are used for biomass pretreatment to remove lignin prior
to bioconversion of biomass. As the lignin is removed or ruptured, the hemicel-
lulose and cellulose fibrils become exposed. Thus, the glycoside hydrolases can
have a better access to the substrate. In addition, the delignifying enzymes can
remove some inhibitors (mainly phenolics), which interfere in the fermentation
process (Kudanga and Roes-Hill 2014).
The most important delignifying enzymes are the laccases (EC1.10.3.2). They
are multi-copper enzymes crucial to lignin degradation and the removal of pheno-
lics. They can be divided into different enzyme families according to Sirim et al.
Fig. 2.3 (continued) β-mannanase, while α-galactosidase releases galactose and acetyl mannan
esterase releases acetyl groups. The mannobiose and glucomannobiose are hydrolyzed by (c)
β-mannosidase and (d) β-glucosidase, to generate the monosaccharides mannose and glucose.
SDS-PAGE (12%) and zymography of mannanase activity in crude extract, stained with Coomassie
Brilliant Blue G-250 (g) and 0.1% Congo red (h). Molecular weight (MW), crude extract (CE) of
soybean husk, crude extract concentrated (C) tenfold 30.000 NMWC in the concentration system
QuixStand Benchtop (GE Healthcare), crude extract ultrafiltered (U) obtained by the same system
as above. (i) R = H (PG) and CH3 (PMG); (j) PE and (k) R = H (PGL) and CH3 (PL). The scissors
indicate the pectinases acting on the pectic substrates. Polygalacturonase (PG), polymethylgalac-
turonase (PMG), pectinesterase (PE), pectate lyase (PGL), and pectin lyase (PL)
Table 2.3 Classification of laccase families, sequences, and structures

Superfamily Homologous families Proteins Structures
A (Basidiomycete) 4 201 13
B (Ascomycete) 6 421 6
C (Insect) 8 168 0
G (Plant) 5 333 0
Reference: Sirim et al. (2011)
(2011) as shown in Table 2.3. Laccases act by promoting the oxidation of one elec-
tron in a wide variety of substrates, notably the lignin phenylpropanoids (Mate and
Alcalde 2017). Other important enzymes are the heme-peroxidases. They catalyze
hydrogen peroxide-dependent oxidative degradation of lignin of phenolic (as man-
ganese peroxidase-EC1.11.1.13) and in the non-phenolics (as lignin peroxidase-
EC1.11.1.14) substrates (Plácido and Capareda 2015).
2.5 ioconversion of Biomass to Second-Generation

B
Bioethanol
Among several alternative biomasses described in this chapter, the production of

bioethanol from sugarcane (Saccharum spp.) is very advantageous. Sugarcane is
rich in sucrose and allows the fermentation of this sugar by microorganisms result-
ing in first-generation (1G) bioethanol. On the other hand, the resulting lignocellu-
losic biomass (bagasse) can be used to produce second-generation (2G) bioethanol.
To improve each step of the 2G ethanol production, it is necessary to know the
composition of lignocellulosic residues.
Although the main targets for 2G ethanol production are sugarcane in Brazil
(Polizeli et al. 2011, 2016, 2017) and corn in the USA (Li et al. 2018), there are
studies reporting other biomasses, which were previously described in this chapter
such as barley (Yang et al. 2015) and coffee (Nguyen et al. 2019). The key elements
in the production of 2G bioethanol from sugarcane bagasse are shown in Fig. 2.4
and discussed below.
2.6 Pretreatment of Lignocellulosic Biomass
Pretreatment of biomass may contribute to enhance the cell wall hydrolysis. It alters
the chemical composition and physical structure of the substrates, since it aims to
separate the carbohydrates from the lignin matrix. This process of separation bene-
fits the enzymatic access to the cellulose and hemicellulose. The presence of lignin
allows the unproductive binding and inactivation of the cellulases, thus making the
high 2G ethanol yield practically impossible (Srinorakutara et al. 2013).
Some effects of the pretreatments are (a) breakage of the lignin structure and its con-
nection with cellulose and hemicellulose, (b) improvement in the access of cellulases to
Fig. 2.4 Scheme of the 2G bioethanol production process including pretreatment and bioconver-
sion of lignocellulosic biomass
cellulose due to the removal of hemicellulose and lignin, and (c) decrease in the degree
of polymerization of cellulose and its crystallinity (van Dyk and Pletschke 2012; Nanda
et al. 2014). According to Buckeridge et al. (2019), this step makes it possible to break
down several covalent bonds between lignin and cellulose or hemicellulose, thus mak-
ing the lignocellulosic biomass more accessible to the enzymatic attack.
There are broad ranges of pretreatments available, such as acidic, basic, or ther-
mal. The acid pretreatment consists of the use of concentrated or diluted acids,
associated with temperatures above 120 °C to decrease the rigidity of lignocellu-
losic biomass and increase the accessibility to the cellulose. In this type of pretreat-
ment, hemicellulose is removed. The alkaline pretreatment removes lignin from the
biomass and causes less damage to the sugars. Thermal pretreatment, also known as
autohydrolysis, uses water, high temperature, and high pressure to break the ligno-
cellulosic matrix (Michelin et al. 2014; Polizeli et al. 2015).
Each of these pretreatments has a different peculiarity, causing different chemi-
cal modifications as mentioned above. During pretreatment of the cellulosic resi-
dues, inhibitory compounds may be formed, such as furfural, hydroxymethylfurfural
(HMF), phenolic compounds, and organic acids. These compounds have an impact
on the action of hydrolytic enzymes, as well as on the microorganisms involved in
the fermentative process (Srinorakutara et al. 2013; van Dyk and Pletschke 2012).
The surfactants are used as additives in order to avoid the adsorption of
enzymes to their substrate in an unproductive way and to enhance the hydro-
lysis. The surface active agents are used in the bioconversion in the follow-
ing ways: (a) during pretreatment, (b) during enzymatic saccharification,
and (c) for the recycling of enzymes after plant cell wall degradation (Giese
et al. 2012; van Dyk and Pletschke 2012).
2.7 Obtaining an Enzymatic Consortium
In order to achieve a sustainable 2G bioethanol production, the key to increase the

efficiency of the saccharification is the thorough understanding of the plant cell wall
structure since enzymatic degradation of lignocellulosic biomass is required to yield
most of the fermentable sugars. According to Buckeridge and de Souza (2014),
plant cell walls show regions of polymers that relate with other polymer chains,
such as xyloglucan and cellulose. The interaction among the macromolecules of cell
walls of biomass makes its total hydrolysis impossible for endoglucanases to attack
glycosidic bonds of cellulose. Moreover, there is a need for the formulation of effi-
cient enzymatic cocktails with enzymes with endo/exo characters as well as branch-
ing and debranching feature. The synergism between the enzymes responsible for
cell wall hydrolysis considers that the structure of the polysaccharides present in the
lignocellulosic biomass may play an important role in the kinetic hydrolysis proper-
ties (Mohanram et al. 2013; De Souza et al. 2013; Buckeridge and de Souza 2014).
De Souza et al. (2013) proposed a theoretical scheme composed of the enzymes
necessary for the saccharification of the cell wall of sugarcane, which included hemi-
cellulases, cellulases, β-galactosidases, lichenases, and other accessory enzymes.
Commercial enzymatic cocktails available for the depolymerization of lignocellu-

losic materials are loosely defined as a complex mixture containing about 80–200
proteins, including hemicellulases, cellulases, and accessory enzymes (Mohanram
et al. 2013). To improve the performance of enzyme cocktails, it took years of bio-
prospecting studies, optimization of strains through genetic engineering for the pro-
duction of enzymes, and development of pretreatment strategies since these are the
major technical challenges in an efficient 2G ethanol production process.
The enzymes act in synergy for substrate degradation for ethanol production.
van Dyk and Pletschke (2012) as well as Li et al. (2014) have demonstrated that
the understanding of synergism is of fundamental importance to clarify the
mechanism of the action of the enzymes alone and the interaction between them.
The enzymatic saccharification is beneficial when compared to other methods
because it is a more specific and cleaner process besides the reduction of the
formation of inhibitory compounds. During the enzymatic hydrolysis of ligno-
cellulosic biomass, oligosaccharides, disaccharides, and monomers are formed.
They cause the inhibition of β-glucosidase and β-xylosidase associated with the
saccharification as previously mentioned in this chapter. High concentrations of
these sugars may have an impact on the hydrolytic efficiency of the lignocellu-
losic residue (van Dyk and Pletschke 2012).
For the bioconversion of lignocellulosic residue to fermentable sugars, it is
necessary to decrease the cost of enzymes, in addition to studies aiming to
enhance the efficiency of the enzymes used in the cell wall hydrolysis. In this
way, an effective tool to reduce the cost of the various hydrolytic enzymes
would be their immobilization. This process leads to an economy in the process
of producing biofuels besides allowing the recovery and reuse of the enzymes
(Borges et al. 2014; Maitan-Alfenas et al. 2015).
2.8 ermentation for the Production of Second-Generation

F
Bioethanol
Alcoholic fermentation consists of the transformation of the sugars from the hydro-
lysate into ethanol, CO2, and energy due to the catalytic action of the yeast or
bacteria. There are two modes of operations for bioethanol production of lignocel-
lulosic biomass, namely, separate hydrolysis and fermentation (SHF) and simulta-
neous saccharification and fermentation (SSF) (Fig. 2.4b). Efforts at process
integration are still constrained by obstacles. There is a need of industrial microor-
ganisms capable to assimilate pentoses and hexoses as well as the control in the
formation and elimination of inhibitory compounds resulting from the whole pro-
cess. Another factor that must be studied is the standardization of the ideal condi-
tions for the integration of two or more processes to be simultaneously performed
in a single bioreactor (Ramos et al. 2015).
The pentoses are fermented by yeasts of the genus Candida, Komagataella, and
Meyerozyma, but studies with these yeasts are still limited. The hexoses are assimi-
lated by yeasts Saccharomyces cerevisiae, which have high fermentative efficiency.
This efficiency is due to the rapid growth of yeasts as well as the ability to metabo-
lize sugars. In addition, they have the ability to produce and consume ethanol and
are tolerant to high concentrations of this compound and resistant to low levels of
oxygen. Another bacterial producer of bioethanol, Zymomonas mobilis, has shown
promising results for the large-scale production of bioethanol.
2.9 Conclusions
The dependence on nonrenewable and highly polluting energy sources has led
to seek alternative fuel sources. Clean energy has the advantage to lower CO2
emissions, providing energy capable of reducing the production of greenhouse
gases, maintaining environmental sustainability, mitigating climate change, and
stimulating the global economy. Thus, the growing demand for biofuels has
motivated the use of biological materials, specifically photosynthetic organ-
isms, as the raw materials.
It is known that billions of tons of plant-based residues are obtained across the
world. However, only a small fraction of this organic waste is used for bioenergy
and bioproducts. Lignocellulosic biomass is mainly constituted by a polysaccharide-
lignin complex with varied composition depending on the plant variety. The decon-
struction of this intricate complex is one of the main bottlenecks in the conversion
of biomass to biofuels. The development of novel technologies is necessary to
make the hydrolysis and saccharification economically viable. Genetic modifica-
tions of plants resulting in a vegetal with increased content of biodegradable and
fermentable saccharides are some of the perspectives. Another focus in plants is to
increase the fiber content, as the energy cane, considering 2G ethanol production
from sugarcane.
Another problem confronted with 2G ethanol production is the biochemical
structure of the lignin because it blocks the access to cellulose. Various pretreat-
ments of biomass alter the chemical/physical structure of the plant cell walls, thus
separating the polysaccharides from lignin and allowing better enzymatic access to
cellulose, hemicellulose, and pectin. One of the problems of such pretreatments is
the formation of inhibitory compounds as furfural, hydroxymethylfurfural, phenolic
compounds, and organic acids, which inhibit enzymatic action and microbial activ-
ity during bioconversion. Hydrothermal pretreatment and steam explosion are alter-
native strategies to acid, alkaline, and other pretreatments. Delignifying enzymes
may contribute as a biomass pretreatment for bioethanol production since the
removal of lignin exposes hemicellulose and cellulose fibrils, and consequently,
glycoside hydrolase can have better access to the substrates.
In all cases, it is important to have an in-depth and detailed knowledge of
the structure of the biomass cell constituents and how they interact aiming at
the production of fermentable sugars. Immunofluorescence techniques using
antibodies against the macromolecules of the biomass cell wall have given
excellent know-h ow, and a glycolic code of sugarcane walls has also been
reported in the literature.
Enzymatic saccharification of raw or pretreated biomass for the liberation of fer-

mentable sugars by yeast is advantageous when compared to the chemical methods
because of being a selective, cleaner, and less energy-intensive process, which pro-
duces less amounts of inhibitory biological compounds. For this purpose, commer-
cial enzyme cocktails obtained from recombinant microorganisms, such as bacteria
and filamentous fungi, are used. Enzymatic hydrolysis process is largely successful
in many cases, but problems, such as the viability of the strain, mycotoxins, contami-
nation, genetic instability, reproducibility, inhibition of the enzyme by end products,
and other molecular complications, have been reported. Some proposed alternatives
include bioprospecting studies of mesophilic and thermophilic strains and optimiza-
tion of strains through genetic engineering for the production and thermostabiliza-
tion of enzymes.
Efficient enzymatic cocktails include the cellulases, hemicellulases, pectinases,
ligninases, and, accessory enzymes and proteins, such as auxiliary activity 9 and
swollenin. Synergism is expected between the hydrolitic enzymes, auxiliary activity
enzymes, and swollenins because they can act together favoring the oxidative cleav-
age of glycosidic bonds and deagglomeration of crystalline cellulose, thus giving
access to cellulases and facilitating enzymatic hydrolysis. Besides, the debranching
of hemicellulose is favored by the use of enzymatic cocktail. The addition of ligni-
nolytic enzymes in the cocktail helps in removing some phenolic compounds that
may interfere in the final fermentation process. Usually, the combinatory action of
enzymes reverts to higher levels of fermentable sugars. Thus, the understanding of
the synergic mechanisms between the hydrolytic enzymes is fundamental to
improve the saccharification process.
A perturbing factor for large-scale bioconversion studies, which still needs
attention, is the high cost of commercial hydrolytic enzymes. An alternative could
be the immobilization or co-immobilization of the enzymes. This process some-
times results in enzymatic hyperactivation and allows various reuses of the bio-
catalysts (enzyme and support). Furthermore, as may be concluded, various
studies must be developed aiming to achieve the total success of the lignocellu-
losic biomass conversion in fermentable sugars. Besides, it is a clean process with
many advantages that need recognition.
Acknowledgments The Laboratory of Microbiology and Cell Biology of Faculdade de Filosofia,

Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Brazil, has been supported by
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP 2014/50884-5 and 2018/07522-
6). Maria de Lourdes Teixeira de Moraes Polizeli is a research fellow of Conselho de
Desenvolvimento Científico e Tecnológico (CNPq, 301963/2017-7). Thiago Machado Pasin, Paula
Zaghetto de Almeida, Ana Sílvia de Almeida Scarcella, and Juliana da Conceição Infante are recip-
ients of the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Finance
Code 001) scholarship. We thank Mariana Cereia for the language review of the chapter.
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Catalytic Transformation of Ethanol
to Industrially Relevant Fine Chemicals 3
Paresh H. Rana and Parimal A. Parikh
Abstract
The industrial developments in the nineteenth century was due to coal energy,
while oil contributed majorly in the twentieth century. However, a question about
future energy source remains unanswered. With increased population, rapid indus-
trialization, and rising concerns for environment preventative measures, total
dependence on fossil fuel resources is not viable. Hence, immediate attention is
required to develop green and sustainable resource, thus stimulating research into
biomass as an alternative to conventional sources. After coal, oil, and gas, biomass
is world’s fourth largest energy source and is estimated to be equivalent about 14%
of global primary energy. There is a need to recognize a suitable species derived
from biomass, which can produce valuable chemicals in order to mitigate depen-
dency on fossil resources. Bioethanol is one of such biomass-derived platform
solvents with a potential to be used as a fuel and a sustainable feedstock of a variety
of chemicals. This chapter deals with the conversion of ethanol to many value-
added chemicals such as acetaldehyde, acetic acid, acetone, ethylene, butanol,
1,3-butadiene, and ethyl acetate through catalytic routes. It also discusses the role
of supports, metal–support interactions, oxygen storage capacity, acidity and basic-
ity of catalyst in the product distribution, and catalytic activity. The challenges and
prospects of ethanol conversion to different chemicals are also described.
Keywords
Biomass · Ethanol · Catalysts · Commodity chemicals
P. H. Rana (*)
Department of Chemical Engineering, Government Engineering College, Bhuj, Gujarat, India
P. A. Parikh
Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology,
Surat, Gujarat, India

50 P. H. Rana and P. A. Parikh
3.1 Introduction
Fossil fuels are used to meet the energy requirements and produce different chemi-
cals that make our lives comfortable. However, rampant utilization of fossil feed-
stocks led to their scarcity and global warming. To conquer these drawbacks with
fossil raw materials, in past decades constant efforts have been made to investigate
the sustainable route for synthesis of variety of chemicals starting with renewable
resources. In this regard, biomass can be considered a reliable alternative source to
replace fossil-based feedstocks for producing fuels and chemicals (Nanda et al.
2015). It is abundant, renewable, and readily available and causing less emission of
CO2 upon utilization. Thus, it has lower impact on the environment and synthesizes
chemicals via environmentally benign pathways (Huber et al. 2006).
Several potential platform chemicals such as levulinic acid, ethanol, sorbitol,
furfural, hydroxymethylfurfural, furans, and γ-valerolactone are derived from bio-
mass through various processes. Among them, ethanol is considered as valuable
molecules due to its numerous usages. It is well-known that bioethanol is obtained
from different edible biomass feedstocks via fermentation process. However, rising
concern towards the future food availability and ecological system leads to produce
ethanol from biomass-derived nonfood feedstocks. Presently, bioethanol contrib-
utes almost 90% of biofuel production and its annual production reached over 100
billion liters (Hu et al. 2018). Ethanol finds its major application in blending with
gasoline owing to high research octane number, low toxicity to environment, and
comparable energy content. Research shows that 5–27% petroleum can be saved via
blending of ethanol (Hu et al. 2018; Mika et al. 2018).
Apart from blending with gasoline, ethanol is used as a solvent for substances
including flavoring and coloring agents, perfumes, and medicines. Apart from these,
it can also be used in dyes and intermediates, as additives in paint industry, in
agricultural chemicals, and as odor agents as shown in Fig. 3.1 (Mika et al. 2018).
The blending of ethanol with gasoline is limited to 5–10%. Therefore, with higher
Fig. 3.1 Many industrial utilities of ethanol

3 Catalytic Transformation of Ethanol to Industrially Relevant Fine Chemicals 51
throughput and reduced price, it is expected that ethanol will be used for the synthe-
sis of industrially important chemicals such as acetaldehyde, acetic acid, ethylene,
1,3-butadiene, acetone, 1-butanol, diethyl ether, and propylene, which are currently
derived from nonrenewable resources (Angelici et al. 2013; Sun and Wang 2014).
For instance, acetaldehyde is commercially produced via catalytic oxidation of eth-
ylene in energy-intensive Wacker process, generating chlorinated wastes (Čičmanec
et al. 2018). Ethylene, an important compound for petrochemical industries, can be
obtained via dehydration of ethanol.
Catalytic transformation of ethanol to different value-added chemicals is dis-
cussed in this chapter. Different ethanol conversion technologies specifically to ace-
tic acid, acetaldehyde, acetone, 1,3-butadiene, and 1-butanol are discussed in this
chapter. The conversion of ethanol to hydrocarbons emphasizes on the advancement
of catalyst and conceptions about reaction mechanism were discussed. The chief
aim of this chapter is to provide basic idea about ethanol conversion and identifica-
tion of different reactions aiming future research.
3.2 Conversion of Ethanol to Small Oxygenates
Chemical building blocks can be produced using chemical or fermentation process.

Acetic acid is the only product which is commercially produced from fermentative
route and other chemicals produced via one- or two-step fermentation process
(Weusthuis et al. 2011). However, our focus is on conversion of ethanol to value-
added chemicals through chemical process. Rass-Hansen et al. (2007) have used
ethanol as a feedstock for intermediate chemicals such as ethylene, acetic acid, and
acetaldehyde. Furthermore, they argued that value-added chemicals from ethanol
would be more economical as compared to its use as a fuel additive.
This section discusses the direct conversion of ethanol to various intermediates
or by-products (Fig. 3.2) such as acetaldehyde (production projected to 1.4 million
tons by 2022) (Garbarino et al. 2019), acetic acid (12 × 106 ton per year) (Mostrou
et al. 2018), 1,3-butadiene (global demand of 10.5 million tons in 2010 and predi-
cated 3% increase in rate per year) (Baylon et al. 2016), ethyl acetate (global pro-
duction 2.6 million tons in 2010) (Men’shchikov et al. 2014), butanol (produced at
1.2 billion gallons per year) (Bharathiraja et al. 2017), and ethylene (annual produc-
tion of 140 million tons) (Hulea 2018).
3.2.1 Acetaldehyde
Acetaldehyde is a versatile chemical that can be used in the production of industrial

chemicals, such as acetic acid, ethyl acetate, acetic anhydride, n-butanol, crotonal-
dehyde, ethyl acetate, and many others (Ob-eye et al. 2019). Until the 1960s, acet-
aldehyde was produced by hydration of acetylene using sulfuric acid and mercuric
sulfate as catalyst. However, mercuric sulfate used in this process is toxic.
Furthermore, ethylene was used for the synthesis of acetaldehyde. In this process,
Fig. 3.2 Reaction network involved in ethanol transformations
ethylene is first hydrated to ethanol, which subsequently undergoes dehydrogena-

tion or partial oxidation to produce acetaldehyde in the presence of air using silver
gauze catalyst at 450 °C under 0.3 MPa pressure. Presently, acetaldehyde is com-
mercially produced from catalytic oxidation of ethylene using PdCl2/CuCl2 in water
in the presence of oxidants (Angelici et al. 2013; Ob-eye et al. 2019). This process
generates chlorinated wastes and consumes more energy to purify air and treat
wastewater, and also it requires expensive titanium in the reactor tubing (Čičmanec
et al. 2018). Dehydrogenation of ethanol with or without air is environmentally and
economically favorable for acetaldehyde production. In the past few years, intensive
studies have been carried out for this reaction over various types of catalysts.
Ethanol reaction was performed over Au/CeO2 surface using temperature pro-
grammed desorption (TPD), Fourier transform infrared (FTIR) spectroscopy, and in
steady-state catalytic conditions and observed that product selectivity changes sig-
nificantly with temperature. At 300 °C and 500 °C, acetaldehyde and acetone were
main product, respectively (Sheng et al. 2004). Takei et al. (2011) have studied Au
nanoparticles (Au NPs) supported on 23 metal oxides for gas phase oxidation,
which shows product distribution to be depending on nature of supports. Acid or
base metal oxides showed more than 95% selectivity towards acetaldehyde when
temperature was higher than 200 °C, while for less than 200 °C, complete oxidation
occurred to CO2 and H2O with p-type semi-conductive metal oxides such as MnO2,
Co3O4, and CeO2. Both acetaldehyde and acetic acid were obtained with n-type
semi-conductive metal oxides, e.g., ZnO and V2O5. In p-type semi-conductive metal
oxide supports, high availability of oxygen species at surface enables complete oxi-
dation of ethanol.
Zheng and Stucky (2006) employed Au/SiO2 for aerobic oxidation of ethanol
and studied effects of particle size on ethanol conversion and product selectivity at
200 °C. They observed that small Au nanoparticles of 3.5 nm did not revealed high
ethanol conversion as shown 6.3 nm Au nanoparticles. Lower ethanol conversions
of 24% and 22% were observed with 3.5 nm and 8.2 nm Au nanoparticles, respec-
tively. However, they exhibited high selectivity to acetaldehyde (90%) than that of
6.3 nm particles (75%). They also demonstrated that increased loading of Au on
SiO2 led to increased selectivity towards ethyl acetate (90%).
Guan and Hensen (2009) employed Au nanoparticles supported on mesoporous
and conventional silica for gas phase oxidation of ethanol. They checked effect of
both the size of Au nanoparticles and the structure of support with and without oxy-
gen. Irrespective of Au nanoparticle size, in oxidative conditions dehydrogenation
rate of ethanol was substantially higher as compared to non-oxidative conditions. In
the absence of oxygen, selectivity to acetaldehyde was near to 100% and above 90%
at 350 °C and 400 °C, respectively. Au nanoparticles with 4.9 and 5.8 nm supported
on SBA-15 and SBA-16, respectively, exhibited higher ethanol conversion (95%),
indicating optimal particle size for reaction. In oxidative conditions, with Au/MCM-
41 highest 20% ethanol conversion and 90% selectivity towards acetaldehyde were
obtained at 200 °C. However, no conversion was observed at same temperature in
non-oxidative conditions. The turnover frequency (TOF) study showed completely
different relation between TOF and Au nanoparticle size, where Au nanoparticles
with <7 nm size displayed almost similar activity and particle size >10 nm have a
higher activity per surface atom in the presence of oxygen. The results of this study
clearly demonstrated that catalytic performance relies on the nature of support and
particle size of Au.
Mielby et al. (2014) used encapsulated Au nanoparticles in zeolites silicate-1
(Au/Recryst-S1) for catalytic gas phase oxidation of bioethanol (10 wt%) and com-
pared its performance with other 3 Au/silicate-1, Au/meso-silicate-1 and Au/APS-
silicate-1 catalysts. They found that Au/Recryst-S1 was found better as compared to
other used catalysts and obtained ethanol conversion (50%) with 98% selectivity
towards acetaldehyde at 200 °C and has high site time yield of acetaldehyde. This
was ascribed to three-dimensional distribution and metal–support interfacial sites,
which played a vital role in the catalytic activity.
Zhang et al. (2015) demonstrated solvent-free synthesis of silicate-1 (S1) encap-
sulating Au–Pd bimetallic nanoparticles (Au–Pd@S1). They found that Au–Pd@
S1catalyst achieved higher ethanol conversion (92.8%) and outperformed the
reported Au/Recryst-S1 catalyst (Mielby et al. 2014). This can be due to higher
activity of bimetallic Au–Pd compared to Au nanoparticles in oxidation reactions.
They have also studied influence of water in bioethanol oxidation using Au–Pd@S1
and Au–Pd/S1 (prepared by conventional hydrothermal route) and reported that
Au–Pd@S1 catalyst exhibited higher catalytic activity (82% ethanol conversion) as
compared to conventionally prepared Au–Pd/S1 catalyst (2% ethanol conversion) in
the presence of 90% water. The activity of Au–Pd@S1 was due to the hydrophobic-
ity of the S1 zeolite, which enabled to efficiently separate the ethanol and water,
hindering access of water to the Au–Pd particles in the zeolites micropores.
Rana and Parikh (2017a) have used SiO2, CeO2, and ZrO2 as supports for Au and
Ag nanoparticles for ethanol (10 wt%) oxidation in the presence of air and evalu-
ated catalytic behavior between 200 °C and 350 °C and 5 atm with the gas hourly
space velocity (GHSV) of 18,000 mL/gcat/h. Among the used catalyst, Au sup-
ported on ZrO2 and CeO2 exhibited higher conversion of ethanol to 38% and 34%,
respectively, with 72% and 83% selectivity towards acetaldehyde, respectively,
than other catalysts. This can be attributed to strong interaction of Au nanoparticles
with supports. Ag/ZrO2 displayed lower ethanol conversion (27%) as compared to
Au/ZrO2 and Au/CeO2. This was due to oxidation of Ag0 under oxidative condition,
which may lead to deactivate Ag for reaction. Weaker interaction between Ag and
ZrO2 and non-transfer of electron charge were also responsible. In Au/ZrO2, the
presence of Au leads to reduce ZrO2 surface (Zr4+ to Zr3+) partially, thus creating
oxygen deficiencies on surface of ZrO2. This occurrence resulted into the increased
density of anionic vacancies on surface of ZrO2 and spillover of oxygen to Au from
ZrO2 surface. Higher availability of active oxygen atom resulted into enhanced
catalytic activity.
Rana and Parikh (2017b) further investigated ethanol oxidation with Ag/CeO2 as
catalyst describing importance of metal–support interactions. Ag/CeO2 catalyst
exhibited excellent results in terms of acetaldehyde selectivity (>90%) and time on
stream (>36 h) in comparison to reported catalytic systems at reaction conditions
(200–350 °C, 5 atm with GHSV of 18,000 mL/gcat/h). The presence of Ag reduces
CeO2 surface, thus creating crystal defects and activation of lattice oxygen of CeO2
support. Here Ag/CeO2 interface allows transfer of atomic oxygen from surface of
ceria to Ag particles. This intense interaction at interface resulted into reduced bond
energy of Ce–O in CeO2 and increased positive charge on Ag.
Rana and Parikh (2018) have extended ethanol oxidation with series of mixed
oxides CexZr1−xO2 (x = 0.25, 0.5 and 0.75) as supports for Au nanoparticles and
investigated role of oxygen supply/storage capacity for this reaction. Results dem-
onstrated that increased ethanol conversion was attributed to the insertion of Zr to
Ce framework, which led to enhance oxygen storage capacity (OSC) and thus
increases supply of oxygen to the reaction. The changes in lattice parameter and
defects in structure of Ce were observed with increased Zr content in ceria. This
changed in lattice parameter also shrinks cell volume; later stress induced by
decreased unit cell volume lowers activation energy for oxygen ion diffusion within
lattice and favors the reduction on Ce surface. As compared to Au/ZrO2 (Rana and
Parikh 2017a) catalyst which exhibited 72% selectivity towards acetaldehyde,
85–90% acetaldehyde selectivity was achieved with Au/CexZr1−xO2. This can be due
to high strength of basic sites of mixed oxide than bare ZrO2 and was also due to the
presence of water which blocked the Lewis acid site and resulting dehydrogenation
of ethanol (Rahman et al. 2016; Rana and Parikh 2017b, 2018).
Simakova et al. (2010) examined TiO2, SiO2, and Al2O3 on Au nanoparticle cata-
lysts for ethanol oxidation in gas phase and reported unusual behavior of Au/TiO2,
which showed double peak in temperature range of 80–280 °C. At 125 °C, active
oxygen species was formed at the catalytic sites, which was responsible for catalytic
activity at low temperature. In the presence of H2, active oxygen species was
generated under mild reaction conditions (Simakova et al. 2010; Sobolev et al.
2012). Active species recommended at lower temperature were surface O−, surface
O2−, anions, or peroxides (Sobolev et al. 2012; Sobolev and Koltunov 2015). At
higher temperatures, a sharp decrease in the activity was observed. This can be
ascribed to decay, desorption, or suppressed concentration of oxygen species
(Simakova et al. 2010; Sobolev et al. 2012). Oxygen is promoting dehydrogenation
reaction at high temperature for oxidative route. In contrast, Holz et al. (2014)
proposed that acetaldehyde formation followed a Mars–van Krevelen mechanism at
high temperature using Au/TiO2. Herein, the presence of highly dispersed Au
nanoparticles on TiO2 led to reduced TiO2, resulting in more oxygen vacancies, and
the created oxygen vacancies over TiO2 act as active sites for the reaction.
In the ethanol gas phase oxidation, vanadium oxide has been widely studied as
major catalyst. Metal oxides such as TiO2 (Jørgensen et al. 2009; Sobolev et al.
2013; Kaichev et al. 2016); hydrotalcite, Al2O3, TiO2, and SBA-15 (Hidalgo et al.
2016); and SiO2, Al2O3, and ZrO2 (Beck et al. 2012) have been used as supports for
V2O5. Among all, TiO2 was found to be better in demonstrating catalytic perfor-
mance. This can be attributed to several factors such as:
1. Ethanol oxidation mainly depends on the monolayer of the polymeric form of

vanadium and does not depend on the presence of the bulk form of V2O5 (Sobolev
et al. 2013).
2. Redox mechanism involved ethanol oxidation where the reactant oxidizes by the
oxidized surface of catalyst and this surface re-oxidized via oxygen of gas phase.
During the reaction on the V2O5/TiO2, Ti4+ state was maintained, whereas a
reversible reduction of V5+ cations resulted in V4+ and V3+ under reaction condi-
tions (Beck et al. 2012; Kaichev et al. 2016). Nearly 15 wt% V2O5/TiO2 catalyst
exhibited excellent catalytic performance, which produced higher than 90%
selectivity towards acetaldehyde and 95% ethanol conversion in oxidation of
aqueous ethanol (50 wt%) at 180–185 °C (Jørgensen et al. 2009). Furthermore, in
this reaction at 165 °C and with low gas velocity, above 80% selectivity towards
acetic acid was obtained.
Ob-eye et al. (2019) investigated a single-step synthesis of acetaldehyde through
dehydrogenation of ethanol with Cu, CE, Co, and Ni metal doped on commercially
activated carbon. Under specified reaction conditions, Cu/ACC (activated carbon
catalyst) exhibited 65% ethanol conversion and 96% acetaldehyde selectivity at
350 °C owing to its higher Lewis acidity than Ce, Co, and Ni doped on activated
carbon and confirmed that dehydrogenation of ethanol is favored in Lewis acid
sites. On the other hand, Ni/ACC catalyst was found potentially suitable to produce
ethylene via ethanol dehydration at 400 °C.
Garbarino et al. (2019) studied ethanol dehydrogenation over Cu/ZnAl2O4 cata-
lyst and observed that the presence of Cu over support surface was essential to
obtain higher selectivity towards acetaldehyde via suppressing the acidic/basic site
of support that favors formation of diethyl ether by ethanol dehydration. At higher
temperature (>400 °C), selectivity towards acetaldehyde decreased as more thermo-

dynamically stable products formed from acetaldehyde.
Synergetic effect of metal–support was investigated for oxidation of ethanol in
gas phase using M/MgCuCr2O4 (M = Au, Pd, Pt, Ag, and Cu). In aerobic conditions,
facile oxidation of Cu and Ag occurred, which resulted into their lower catalytic
activity. Pt/MgCuCr2O4 and Pd/MgCuCr2O4 were found to be more active for etha-
nol oxidation and less selective towards acetaldehyde. These can be ascertained to
cleavage of C–C bond of ethanol at moderately low temperature. The synergy
between Au0 and Cu+ in case of Au/MgCuCr2O4 catalyst plays a vital role. It
increased acetaldehyde selectivity up to 96% with 100% conversion of ethanol at
250 °C. The role of Cu+ is to activate O2, which facilitated cleavage of O–H bond in
the reaction. This indicates that the activation of O2 worked as the basic sites (Liu
et al. 2015). The performance of pertinent catalyst systems reported in literature is
shown in Table 3.1. Due to variations in reaction conditions, direct comparison of
catalytic activity cannot be made.
3.2.2 Acetic Acid and Ethyl Acetate
Carbonylation of methanol, which relies on fossil sources, is the only established

route to meet the current demands of acetic acid. Numerous heterogeneous catalysts
have been explored for its synthesis via aerobic ethanol oxidation in gas and liquid
phase. In majority of catalytic systems, pure oxygen or air is used as the oxidant.
Acetic acid generally produced in two steps from oxidation of ethanol. Ethanol is
first oxidized to acetaldehyde and subsequently to acetic acid.
Au, Pt and Pd supported MgAl2O4 catalyst for liquid phase oxidation of ethanol
(5 wt% in water) and found that all three catalyst exhibited similar activity but Au
nanoparticles were more selective towards acetic acid than Pt and Pd nanoparticles
at 150 °C and 3 MPa (Christensen et al. 2006). Further studies with supported Au
catalysts confirmed that the catalytic performance depends on the size of Au
nanoparticle (Sun et al. 2008) and nature of supports (Christensen et al. 2006;
Jørgensen et al. 2007; Tembe et al. 2009). For instance, Au nanoparticles supported
on TiO2 and ZnO displayed similar catalytic activity, while Au/Al2O3 showed poor
performance (Tembe et al. 2009).
Takei et al. (2015) used Au/NiO as the catalyst for ethanol oxidation and obtained
high conversion with NiO support in comparison to other oxides. They checked the
effects of different metal cations as dopant into NiO and found Cu to enhance semi-
conductivity, which resulted into higher selectivity to acetic acid and maintained
ethanol conversion. Moreover, Fe- and Co-doped catalyst exhibited lower ethanol
conversion, while acetic acid selectivity remained almost unchanged.
Gorbanev et al. (2012) studied the effects of different supports for Ru(OH)x for
aerobic oxidation of aqueous ethanol (2.5–50 wt%) at high temperatures and oxy-
gen pressure. There was little impact of ethanol concentration on the product distri-
bution at applied reaction conditions. On the other hand, to achieve a high yield of
acetic acid, temperature greater than 125 °C was essential, which depends on the
3
Table 3.1 Various catalysts reported for synthesis of acetaldehyde from oxidation of ethanol in gas phase
Time
Metal Ethanol Ethanol/O2/ Ethanol on
loading in feed Temperature Pressure carrier gas conversion Acetaldehyde stream GHSV
Catalyst (wt%) (%) (°C) (atm) (vol%) (%) selectivity (%) (h) (mLgcat−1 h−1) References
Ag/CeO2 1 10 350 5 0.02:20.99:78.99 36 87 36 18,000 Rana and
Parikh
(2017b)
Ag/ZrO2 2 99.9 250 – Inert atmosphere 24 31 6 W/F = 38 min Freitas et al.
(2016)
Au/ 1 10 350 5 0.02:20.99:78.99 46 90 36 18,000 Rana and
Ce0.25Zr0.75O2 Parikh
(2018)
Au/CeO2 1 100 200 1 1:2 (ethanol:O2) 31.8 56 – 257,120 Sheng et al.
(2004)
Au/ 0.5 100 250 – 1.5:3:95.5 92 90 10 100,000 Liu et al.
MgCuCr2O4 (2015)
Au/SiO2 1 10 350 – 9-10/0/90 8 90 – 12,000 Gazsi et al.
(2011)
Au/ZrO2 1 10 350 5 0.02:20.99:78.99 38 72 4 18,000 Rana and
Parikh
(2017a)
Cu/ 10 100 300 – N2 used as carrier 60 100 6 31.1 h−1 Petrolini
AlMgO-P gas (WHSV) et al. (2019)
Cu/ZnAl2O4 30 96 350 – N2 used as carrier 96 90 – 10,000 Garbarino
Catalytic Transformation of Ethanol to Industrially Relevant Fine Chemicals
gas et al. (2019)

PdO/m-ZrO2 0.6 100 175 4 3.0:19.4:77.6 80 10 15 10,200 Letichevsky
et al. (2015)
V2O5/TiO2 15 50 215 2.7 3.3 (O2/ethanol 100 43 – 32,960 Jørgensen
molar ratio) et al. (2009)
57
type of supports. Over-oxidation of ethanol occurred at about 200 °C led to a

decreased selectivity towards acetic acid. Under the reaction conditions of 5 wt%
aqueous ethanol, 175 °C, 30 bar pressure, and 3 h of reaction time, an increased
order of ethanol conversion and selectivity to acetic acid followed the order:
Ru(OH)x/TiO2 < Ru(OH)x/Al2O3 < Ru(OH)x/MgAl2O4 < Ru(OH)x/CeO2. In the case
of Ru(OH)x/CeO2, increased loading of Ru on ceria surface resulted into larger par-
ticle sizes, which subsequently decreased the catalytic activity. PdO/Al2O3 and
PdO/m-ZrO2 catalysts employed for ethanol oxidation selectively produced acetic
acid. PdO/m-ZrO2 catalyst was found to be more active than PdO/Al2O3 owing to
the oxygenate species which are adsorbed and spillover from surface of m-ZrO2 to
PdO and vice versa (Letichevsky et al. 2015). Thus, atomic oxygen plays a vital role
in the ethanol conversion with reducible oxide (ZrO2). Similar observation was
made with Au-supported CeO2, ZrO2, and SiO2 catalysts for ethanol oxidation.
Moreover, Au/ZrO2 and Au/CeO2 exhibited higher activity owing to their reducibil-
ity (Rana and Parikh 2017a).
Li and Iglesia (2007) employed Mo0.61V0.31Nb0.08Ox/TiO2 catalyst, which yielded
more than 90% of acetic acid at complete ethanol conversion at 237 °C and 1.6 MPa
with aqueous ethanol and oxygen. They observed that water promotes the rate of
acetic acid formation via the sequential oxidation of acetaldehyde. The decreased
rate of acetaldehyde led to the production of stable acetic acid consequently pre-
venting its oxidation. Furthermore, MoV0.3Nb0.12Te0.23Ox mixed oxide was found to
be superior to Mo0.61V0.31Nb0.08Ox/TiO2 catalyst because it demonstrated higher syn-
thesis rate for acetic acid at 290 °C and atmospheric pressure. In contrast, Sobolev
and Koltunov (2011) argued that the presence of water is not essential for higher
selectivity of acetic acid.
Xiang et al. (2017) investigated the effects of different Cu content in CuCr cata-
lyst for acetic acid production from ethanol in the absence of oxygen and concluded
that reaction proceeds in two steps, such as (a) dehydrogenation of ethanol to acet-
aldehyde and (b) reaction of adsorbed aldehydes with surface hydroxyl groups to
produce acetic acid. Both the reactions are performed on the surface of Cu0 and/or
Cu+ species. The presence of Cr content enhanced the selectivity to acetic acid by
providing more surface oxygen.
Acetic acid was produced in liquid phase aerobic oxidation of bioethanol with
Au/CuM2O4 (M = Fe, Cr, Al) at 140 °C and 3 MPa, and the role of metal–support
interactions was investigated (Hu et al. 2018). Au/CuFe2O4 catalyst exhibited higher
ethanol conversion (63%) and selectivity towards acetic acid (81%) as compared to
other catalysts. This can be attributed to enhanced O2 activation and ethanol owing
to the existence of negatively charged Auδ- and redox active Fe+2 species in Au/
CuFe2O4 catalyst.
Ethyl acetate is mainly used as a solvent in a variety of industries. Industrially, it
is synthesized by several routes such as (a) esterification between ethanol and acetic
acid, (b) reaction of acetic acid with ethylene, and (c) disproportion of acetalde-
hydes through Tishchenko reaction. However, corrosiveness and toxicity of used
reagents are the major drawbacks for these methods. The production of ethyl acetate
from ethanol occurs in one-pot procedure. It is an alternative process and considered
as an environmentally and economically viable method. It is produced via an oxida-

tive route and a dehydrogenation route. In oxidative route, 2 mol of water molecules
are generated while hydrogen is produced in dehydrogenative route. Dehydrogenation
pathway has more commercial value as it produces hydrogen as the coproduct with-
out the use of oxygen, thus avoiding flammability of mixtures (Sánchez et al. 2011).
However, the separation of products from reaction mixture becomes a major issue
for both processes.
Inui et al. (2004) used Cu.Zn.Zr.AlO catalyst for the dehydrogenation of ethanol
to ethyl acetate. Catalyst (Cu:ZnO:ZrO2:Al2O3 = 12:1:2:2 molar ratio) showed about
84% ethyl acetate selectivity and 66% conversion of ethanol at 220 °C, thus favor-
ing the reaction mechanism by suppressing selectivity of methyl ethyl ketone to less
than 5%. It is considered as an undesirable by-product that forms azeotropic mix-
ture with ethyl acetate. In this case, coupling between ethanol and acetaldehyde
occurred at mixed metal oxide surface instead of Cu metal site.
Physically mixed Cu–ZnO–Al2O3 or PdO/m-ZrO2 anchored over m-ZrO2, t-ZrO2,
and a-ZrO2 catalyst was employed for the synthesis of ethyl acetate from ethanol
with and without oxygen (Gaspar et al. 2010). Three different phases of Zr oxide
(m-ZrO2, t-ZrO2, and a-ZrO2) with Cu–ZnO–Al2O3 were tested in the dehydrogena-
tive route, while PdO/m-ZrO2 was used in oxidative route. Among all the tested
catalysts, m-ZrO2 and t-ZrO2 exhibited similar catalytic activity in terms of ethanol
conversion and selectivity to acetaldehyde and ethyl acetate, while a-ZrO2 was
found to be less selective towards ethyl acetate due to its lower basicity. In both
oxidative and dehydrogenative routes, the condensation reaction between acetalde-
hyde and ethanol or ethoxide species occurred on the surface of Zr.
Sánchez et al. (2005) studied the conversion of ethanol to ethyl acetate using Pd
(1 wt%) supported on various oxides such as SiO2, Al2O3, ZnO, SnO2, and WO3–
ZrO2 at 250 °C and 1 MPa. Results showed that the catalytic activity and product
distribution change with the nature of support. Pd@ZnO and Pd@SnO2 were found
to be most efficient catalysts for the production of ethyl acetate at moderate ethanol
conversion. The reaction mechanism of dehydrogenative route studied with com-
mercial Cu/ZnO/Al2O3 (CZA) was physically mixed with ZrO2, CeO2, Al2O3, and
SiO2. The bare CZA catalyst exhibited lower ethanol conversion and produced acet-
aldehyde as the main product. The physical mixture of CZA and oxides showed
higher rate of ethanol consumption and increased selectivity to ethyl acetate when
compared to the bare CZA. Among the used catalysts, CZA with ZrO2 was found to
be superior in catalytic performance exhibiting higher rate of ethanol consumption
and ethyl acetate selectivity. This was attributed to the higher basic sites of ZrO2.
The proposed reaction mechanism involved (i) the formation of acetaldehyde on
bare CZA, (ii) the attack of ethoxide or ethanol to produce hemiacetal, and (iii) the
dehydrogenation of ethyl acetate. It was observed that the basicity of oxides plays a
vital role in the formation of ethoxide, which can be considered as the rate determin-
ing step (Zonetti et al. 2011).
Carotenuto et al. (2013) applied three commercial Cu-based catalysts for
dehydrogenative/oxidative route and evaluated the catalytic performance by vary-
ing the operating conditions. In the dehydrogenative route, at lower residence time
(about 0.15 gh mol−1), 300 °C, and atmospheric pressures, acetaldehyde was the
main product with 65% selectivity and around 85% ethanol conversion with
CuCrAl. However, addition of small amounts of O2 (O2/CH3CH2OH = 0.6) favored
higher selectivity towards acetaldehyde (90%) at temperatures less than 200 °C.
About 90% selectivity towards ethyl acetate and ethanol conversion around 45%
were observed when the reaction was carried out at higher pressure (20 bar), longer
residence time, and 220 °C by co-feeding 3.66 × 10−3 mol/h of H2 (25 cm3/min of a
mixture of 6% H2 in N2). Herein, the role of H2 was not only to inhibit the generation
of acetaldehyde by lowering its concentration but also to retain the catalyst in its
reduced form.
The literature relating to the oxidative route of ethyl acetate is very limited.
Gaspar et al. (2009) employed PdO/SiO2 catalyst for the synthesis of ethyl acetate
in oxidative route and observed that the reaction mechanism followed similar steps
as demonstrated by Inui et al. (2004). The oxidative dehydrogenation of ethanol
formed acetaldehyde, which reacted with ethanol or ethoxide species for producing
ethyl acetate. The results indicate almost similar reaction mechanism of oxidative
and dehydrogenative routes. However, the data generated by them does not clearly
indicate where the condensation reaction occurred. They also observed that the
change in ethanol consumption rate had influenced the formation of acetaldehyde
and ethyl acetate. Low ethanol consumption rate was the rate limiting step for
acetaldehyde, while high consumption rate was for condensation reaction (Gaspar
et al. 2009).
3.2.3 Acetone
Acetone is primarily used in the production of methyl methacrylate and meta acrylic
acid monomers, which are highly in demand nowadays in the manufacturing of
bisphenol-A (BPA polycarbonate) as the commercial solvent in the synthesis of
drugs and polymers and as thinner in paint industries. Currently, acetone is produced
either from cumene process or dehydrogenation of 2-propanol. These processes
derive their feedstock from fossil resources, which are associated with many environ-
mental issues. For example, benzene and propylene used in cumene process are con-
sidered as fossil raw materials. Acetone can be synthesized from ethanol as mentioned
in Eq. (3.1):
CH 3 CH 2 OH + H 2 O → CH 3 COCH3 + CO2 + 4H 2 (3.1)
Many heterogeneous catalytic systems are reported for synthesis of acetone from
ethanol. In this context, Murthy (1988) examined Fe2O3–ZnO, Fe2O3–CaO, and
Fe2O3–Mn and found that ZnO-promoted iron oxide catalyst exhibited better cata-
lytic activity and stability. Nakajima et al. (1994) employed 24 oxides for dehydra-
tion or dehydrogenation of ethanol in the presence of water. At 440 °C, complete
ethanol conversion and 94% acetone selectivity were achieved using Fe–Zn cata-
lyst. Furthermore, they observed that oxides having both acidic and basic properties
yielded higher acetone. Similarly, Cu/La2Zr2O7 catalyst having both acidic and
basic sites exhibited higher selectivity to acetone (70%) and complete ethanol con-
version at 400 °C. This indicates that the presence of both acidic and basic sites is
essential for the formation of acetone (Bussi et al. 1998).
Zinc–calcium oxide with different ratio is prepared by co-precipitation method
and investigated in vapor phase reaction of ethanol to acetone. With Zn:Ca = 9:1
ratio, highest ethanol conversion (100%) and selectivity towards acetone (86%)
were obtained at 425 °C. The increased amount of water (from 20% to 90%) in reac-
tion mixture resulted in higher ethanol conversion from 45% to 90% and increased
acetone selectivity from 15% to 74% at 450 °C. These results revealed that the pres-
ence of water had positive impact on ethanol conversion and selectivity for acetone
(Baghiyev et al. 2011). Liu et al. (2013) employed mixed oxide of ZnxZryOz for
isobutene production from ethanol and observed that acetone was a major product
at temperature range of 400–475 °C. A further increase in temperature (>475 °C)
resulted in a decreased selectivity of acetone, but the selectivity to isobutene
increased. It was suggested that acetone synthesis occurred via ethanol dehydroge-
nation and self-aldol condensation of acetaldehyde.
Iwamoto (2015) employed two catalysts (Sc/In2O3 and Y2O3–CeO2) and demon-
strated different reaction mechanism followed by the formation of acetone from
ethanol. In case of Sc/In2O3 catalyst, acetaldehyde was first oxidized by either water
or hydroxyl groups present on the surface of catalyst to produce acetic acid; subse-
quently ketonization takes place to generate acetone and CO2. The condensation of
acetaldehyde with Y2O3–CeO2 produced ethyl acetate, which decayed to give acetic
acid and ethene. Acetone formation was followed by same ketonization step as
reported with Sc/In2O3.
Rodrigues et al. (2013) proposed the reaction mechanism by employing Cu/ZnO/
Al2O3 (CZA) and ZrO2. ZrO2 and CZA surfaces generate ethoxide by the adsorption
of ethanol, which later generated ethoxide when the oxides surface migrated to
CZA and dehydrogenated to give acetaldehyde. Consecutively, the spillover or
sorption of acetaldehyde from CZA to ZrO2 surface and interaction with lattice
oxygen of ZrO2 induced acetate, which further converted to acetone, H2, and CO2.
Similar reaction mechanism was proposed by de Lima et al. (2017) with Ag–CeO2.
Insertion of Ag increased reducibility of CeO2; similar phenomenon was reported
by Rana and Parikh (2017b).
Further investigation of reaction mechanism and effect of acid–base properties of
catalyst were carried out with ZnxZr1-xO2-y catalysts by del Silva-Calpa et al. (2017).
They concluded that the inserted Zn led to an increased basicity of m-ZrO2. The
increased basicity of ZnxZr1-xO2-y mixed oxide resulted in higher selectivity towards
small oxygenate molecules compared to m-ZrO2. They also observed that in the
absence of water, acetone was not formed. Other works also supplemented that
water is essential for acetone formation (Nakajima et al. 1994; Baghiyev et al.
2011).
The reaction mechanism for acetone formation was similar to those proposed by
Rodrigues et al. (2013) and de Lima et al. (2017). Recently, Rodrigues et al. (2017)
employed different catalysts such as Ce0.75Zr0.25O2 (CZ), Cu/ZnO/Al2O3 (CZA),
ZrO2, CZA + CZ, and CZA + ZrO2 for this reaction and presented detailed mecha-
nism using analytical techniques such as thermal desorption spectroscopy (TPD),
temperature-programmed surface reaction (TPSR), and infrared mass spectrometry
(IR-MS). The obtained results showed that oxygen vacancies on oxide surface
increased reducibility and water dissociation activity of catalyst. This ultimately
resulted in higher acetone selectivity. The acidity of catalyst not only promoted the
adsorption of oxygenated species but also prevented the dehydration of ethoxide.
3.3 Conversion of Ethanol to Hydrocarbons
3.3.1 Ethylene
Ethylene is an important platform chemical used to produce polymers (e.g., poly-

ethylene, polyvinylchloride, and polystyrene), ethylene glycol, ethylene oxide,
ethyl benzene, and many other chemicals. It is mainly obtained from petroleum-
derived feedstocks through thermal cracking. The continuous depletion of fossil
fuel resources has led to an increased price of ethylene. With increased throughput
and decreased cost, bioethanol conversion to ethylene looks more attractive and
viable (Sun and Wang 2014). The typical reaction for the production of ethylene
through dehydration of ethanol is shown in Eq. (3.2):
(3.2)
CH CH OH → C H + H O
3 2 2 4 2
Thermodynamic conditions of the reaction favor the production of diethyl ether

as a by-product in lower temperature range. The generation of ethylene is endother-
mic and occurs in the temperature range of 200–450 °C. Hence, a major challenge
is to develop catalysts which are capable to selectively produce ethylene at lowest
possible temperature (Angelici et al. 2013). HZSM-5 (Phillips and Datta 1997) and
γ-Al2O3 (Phillips and Datta 1997; Zhang et al. 2008) were found to be prominent
catalysts in terms of activity and selectivity towards ethylene. HZSM-5 yielded
higher ethylene selectivity (95%) and ethanol conversion (>90%) at 300 °C in com-
parison to γ-Al2O3 that produced 80% selectivity towards ethylene and 85% conver-
sion of ethanol at 450 °C. It indicated that HZSM-5 worked efficiently at lower
temperature, while γ-Al2O3 required higher temperatures (Zhang et al. 2008). High
selectivity of ethylene with HZSM-5 attributed to its strong acid sites compared to
γ-Al2O3. Despite high activity of HZSM-5, alumina is a widely used catalyst in
chemical industries owing to its high stability, low price, and less coking.
Chen et al. (2007) employed TiO2/γ-Al2O3 catalyst for ethylene production from
catalytic dehydration of ethanol and studied effect of metal loading, ethanol concen-
tration, and reaction temperature. As the water concentration increased from 5% to
90% in the feed, a declining conversion of ethanol from 86% to 65% was observed.
In contrast, ethylene selectivity increased from 86% to 94% upon increased water
content. However, this impact of water on ethanol conversion was nullified at higher
temperature. It can be said that for alumina-based catalyst, higher reaction
temperature is required to achieve higher selectivity towards ethylene (Chen et al.

2007; Zhang et al. 2008).
Catalytic activity of Si–Al–phosphate (SAPO-11 and SAPO-34) and their modi-
fied forms with Mn and Zn were compared at 340 °C (Chen et al. 2010). The results
revealed that bare SAPO-11 exhibited higher ethanol conversion (97%) and ethyl-
ene selectivity (90%) when compared to Zn2+ and Mn2+ modified SAPO-11.
However, completely different catalytic performance was observed with modified
SAPO-34 as it exhibited higher ethanol conversion and high selectivity towards
ethylene when compared to bare SAPO-34. At 340 °C, 99.4% ethanol conversion
and 98.4% ethylene selectivity were obtained with Mn–SAPO-34 catalyst. This can
be correlated to its moderate acidic strength and high surface area.
Zhang et al. (2008) employed γ-Al2O3, HZSM-5 (Si/Al = 25), SAPO-34, and
Ni-SAPO-34 catalyst and evaluated their catalytic activity and stability in the dehy-
dration of ethanol to ethylene. Ethanol conversion and selectivity towards ethylene
in decreasing order as HZSM-5 > NiAPSO-34 > SAPO-34 > γ-Al2O3 at the reaction
condition: 300 °C for HZSM-5, 350 °C for SAPO-34 and NiAPSO-34, and 450 °C
for the γ-Al2O3 catalyst at LHSV 3 h−1. It was found that both HZSM-5 and
Ni-SAPO-34 achieved more than 90% yield of ethylene. SAPO-34 and Ni-SAPO-34
were found to have better stability (100 h). Hence, considering all aspect,
Ni-APSO-34 is evolved as a suitable catalyst in conversion of ethanol to ethylene.
Recently, Masih et al. (2019) used Rho–zeolite catalyst for the formation of eth-
ylene from ethanol in temperature range of 200–400 °C and compared the catalytic
activity against three different samples of γ-Al2O3 and ZSM-5. All γ-Al2O3 catalysts
showed poor catalytic activity to that of zeolites (Rho and ZSM-5). At 250 °C, Rho-
zeolite was found to be superior than ZSM-5 in terms of ethylene selectivity.
Moreover, Rho-zeolite exhibited excellent performance in terms of ethanol conver-
sion (100%) and selectivity towards ethylene (99%) at 350 °C with 65 h on stream
reaction. Herein, the concentration and strength of medium–strong acidic sites of
Rho-zeolite played vital roles in catalytic performance.
3.3.2 Propylene
Propylene is also considered as an important chemical in the petroleum industries.

It is used for the production of polypropylene and propylene oxide. Owing to impor-
tant features such as comparable thermal and hydrothermal stability, acidity, pore
structure, and reactivity of HZSM-5, it has been widely used as a catalyst in various
reactions. The industrial transformation of methanol to olefins occurs in the pres-
ence of HZSM-5. In addition, it can be used as a catalyst in the conversion of etha-
nol to ethylene. Ethanol can be converted into a mixture of hydrocarbons containing
ethylene, light olefins (C3–C4), and C5+ long-chain hydrocarbons over zeolite cata-
lyst. The product distribution mainly depends on temperature, Si/Al ratio, surface
acidity, and water content in the feed. Surface acidity played crucial role in the
formation of propylene with H-ZSM-5 (Si/Al = 30, 80, and 280) (Song et al. 2009).
Lower acidity (Si/Al = 280) of HZSM-5 favored ethylene production, whereas C5+
hydrocarbons were dominant with higher acidity (Si/Al = 30), while moderate acid
strength (Si/Al = 80) was found to be optimum for propylene (Song et al. 2009).
Metal containing (Zr, P, and Sr) HZSM-5 catalysts exhibited superior yield of
propylene when compared to HZSM-5 catalyst at high temperatures. These addi-
tives were found to greatly reduce strong acid density while maintaining moderate
acid strength and improved propylene selectivity (31–32%) (Goto et al. 2010; Song
et al. 2009, 2010). Zr and P effectively prevented de-alumination of catalyst, thus
resulting in better stability. Similar activity in terms of stability was obtained by
tungsten-modified HZSM-11 (Si/Al = 120) catalyst. W-HZSM-11 exhibited highest
selectivity (25%) towards propylene 25% at 550 °C (Inoue et al. 2010). Gayubo
et al. (2010, 2011) conducted experimental and kinetic simulations studies and con-
cluded that 1 wt% Ni loading significantly suppressed acidity strength of ZSM-5
from 135 kJ to 125 kJ (mol of NH3)−1, which ultimately resulted in improved selec-
tivity of C3–C4.
Apart from zeolites, many transition metals and metal oxides have also been
reported for the production of propylene. Various catalytic systems for the conver-
sion of ethanol to propylene such as Ni ion-loaded mesoporous silica MCM-41
(Ni–M41) (Iwamoto et al. 2011), Sc-modified indium oxides (Sc/In2O3) (Mizuno
et al. 2012), yttrium-loaded zirconia (Y/ZrO2) (Xia et al. 2017), and many others
have been reported. Complete ethanol conversion and 16% yield of propylene have
been reported with Ni–MCM-41 (Si/Ni = 23) at 400 °C.
There are two different reaction pathways involved in the dehydration of ethanol
to ethylene, especially diethyl ether, as well as the formation of acetaldehyde and
ethyl acetate. Furthermore, dimerization, isomerization, and metathesis take place
to convert ethylene to propylene (Iwamoto et al. 2011). In contrast, reaction path-
ways recommended by Mizuno et al. (2012) were quite different. The reaction steps
were as follows:
1. Conversion of ethanol to acetaldehyde via dehydrogenation

2. Generation of acetone via condensation/ketonization of acetaldehyde
3. Hydrogenation–dehydration of intermediate acetone to propylene
Mizuno et al. (2012) also demonstrated that Sc/In2O3 catalyst exhibited higher
propylene yield (60% based on carbon balance) and 100% ethanol conversion at
550 °C in the presence of water and hydrogen. Herein, the role of water was to
reduce the deactivation of catalysts and hydrogen to promote the conversion of ace-
tone to propylene. Recently, Y/ZrO2 prepared by co-precipitation was employed for
this reaction. Maximum yield of propylene (44%) with 98% ethanol conversion at
450 °C was achieved with 3 wt% Y/ZrO2. It was observed that the conversion of
ethanol to ethylene takes place on acidic sites, while the transformation of ethanol
to propylene occurs via acetaldehyde and acetone on basic sites (Xia et al. 2017).
3.3.3 Butanol
Butanol is a versatile commodity chemical with applications as a feedstock for the

production of acrylic esters and acrylic acid. It is also used as a solvent and as an
additive in gasoline. Owing to its higher energy density, higher air-to-fuel ratio,
lower water solubility, and lower heat of vaporization, it is considered as a biofuel
(Ndou 2003; Nanda et al. 2017; Wu et al. 2018). Butanol is commercially produced
via oxo process in which the following steps are (a) hydroformylation of propylene
to generate butyraldehyde and (b) hydrogenation of butyraldehyde to yield butanol
(Angelici et al. 2013; Wu et al. 2018). There are few drawbacks of this process such
as difficulty in product separation, costly preparation of catalyst, and adverse envi-
ronmental impacts. Therefore, transformation of ethanol to butanol seems to be
more attractive. For the production of butanol, two different reaction pathways have
been proposed such as (a) direct dimerization of two molecules of ethanol and (b) a
multistep Guerbet process. In Guerbet process, ethanol is dehydrogenated to acetal-
dehyde followed by the formation of crotonaldehyde via self-aldol condensation of
acetaldehyde and subsequent hydrogenation of crotonaldehyde to butanol (Ndou
2003).
Tsuchida et al. (2006) investigated the influence of reaction temperature on cata-
lytic performance of hydroxyapatite (HAP) catalyst with Ca/P (molar ratio = 1.64).
At 300 °C, nearly 14.7% ethanol conversion and 76.3% selectivity to butanol were
obtained. Ethanol conversion increased from 14.7% to 95.3% by increasing the
temperature from 300 °C to 450 °C. On the other hand, the selectivity of n-butanol
drastically reduced to 6% from 76.3%. This indicated that lower temperature
(≤300 °C) was optimal to produce n-butanol.
Homogeneous Ru-bis(diphenylphosphanyl) methane catalyst exhibited exclu-
sive butanol selectivity (94%) and ethanol conversion (20%) at mild reaction tem-
perature of 150 °C. This was ascertained to the catalyst’s effective control over aldol
reaction of acetaldehyde, which mainly produced butanol rather than higher hydro-
carbons. It was observed that the catalytic activity decreased with time on stream.
This was due to the decomposition of catalyst over the time period and probably due
to weak water tolerance of ligands (Dowson et al. 2013). Wingad et al. (2015) also
reported Ru phosphine–amine (P–N) complex, which displayed 93% n-butanol
selectivity at 31% ethanol conversion with turnover number (TON) above 300. In
contrast to bis(diphenylphosphanyl) methane catalyst (Dowson et al. 2013), mixed
donor P–N ligands (Wingad et al. 2015) had improved water tolerance and assisted
deprotonation in hydrogen transfer reactions.
Marcu et al. (2013) demonstrated that acidic/basic site of catalyst plays a vital
role in product selectivity. They employed mixed oxides of M–Mg–Al–O (M = Cu,
Pd, Ag, Mn, Fe, Sm, and Yb) for ethanol conversion to butanol. Among the used
catalysts, Pd- and Sm-based catalysts exhibited higher selectivity towards butanol
such as 72.7% and 66.3%, respectively, at 200 °C for 5 h. In case of Cu-based cata-
lyst, an increase in Cu loading decreased the density of basic sites, which subse-
quently led to a decrease in the selectivity of n-butanol. This indicated that n-butanol
formation correlates with basic site of catalyst. In addition, the decreased basic sites
may raise acid sites strength, which could enhance the production of
1,1-diethoxyethane as the by-product.
Total thirteen different heterogeneous Al2O3-supported metal catalysts were
examined for liquid phase in a one-pot ethanol conversion to butanol (Riittonen
et al. 2012). Nearly 20 wt% Ni/Al2O3 (commercial catalyst) evolved as the best
catalyst in terms of ethanol conversion (25%) and butanol selectivity (80%) at
250 °C and 70 bar. The trend of metals in terms of butanol selectivity was
Ni > Pt > Au~Rh > Ru > > Ag. Furthermore, an increased hydrogen pressure
resulted in the decreased selectivity of butanol. This can be due to the presence of
hydrogen, which suppressed the dimerization of ethanol.
A similar research group carried out the same reaction with different metals
(Cu, Co, and Ni) supported on Al2O3 in a continuous fixed-bed reactor at 250 °C,
70 bar, and LHSV = 4.3 h−1 (Riittonen et al. 2015). Ni and Cu catalysts exhibited
better selectivity towards n-butanol and Co catalyst favored ethyl acetate as the
main product. This was due to the position of metal cations in the crystal struc-
ture. In the inverse spinel structure of metal aluminate, Ni and Cu were octahe-
drally coordinated, while Co was tetrahedrally occupied. Moreover, the acidic/
basic sites also played an important role in the product distributions. High acid
strength of catalyst resulted in higher butanol selectivity, while the basic site
favored ethyl acetate formation.
The effect of Cu and Ni dopant on porous metal oxides (PMOs) derived from
synthetic hydrotalcites was studied for the production of 1-butanol from ethanol via
Guerbet coupling (Sun et al. 2017). The results demonstrated that the incorporation
of Cu and Ni dopants not only enhanced the conversion of ethanol but also increased
the selectivity towards 1-butanol. An equimolar amount of Cu and Ni yielded 56%
ethanol conversion and 22% butanol at 320 °C for 6 h with space–time yield reach-
ing up to 704.6 kgcat-1 g−1. The structural characterization before and after the reac-
tion revealed that Ni–Cu alloy phase remained intact, which played a significant
role during the reaction.
3.3.4 1,3-Butadiene
1,3-Butadiene (butadiene or C4H6) is another important molecule that can be pro-

duced from ethanol. It is used in the production of a variety of synthetic rubbers,
resin, elastomers, and other polymeric materials. 1,3-Butadiene is a by-product of
steam crackers that used to produce ethylene. Ethanol conversion to 1,3-butadiene
was successfully implemented during World War II. Two different processes are
reported for 1,3-butadiene from ethanol, such as (a) a one-step catalytic process
known as Lebedev process and (b) a two-step process based on Ostromislenskiy
reaction. Both the processes are recognized to follow the same reaction pathway.
The following steps are believed to proceed in the reaction mechanism (Angelici
et al. 2013; Sun and Wang 2014; Pomalaza et al. 2016):
1. Ethanol dehydrogenated to produce acetaldehyde

2. Acetaldol (3-hydroxybutanal) formation by aldol condensation of acetaldehyde

3. Crotonaldehyde generated via dehydration of 3-hydroxybutanal
4. Crotyl alcohol and acetaldehyde produced through Meerwein–Ponndorf–Verley
(MPV) reaction of ethanol and crotonaldehyde
5. Crotyl alcohol dehydrated to 1,3-butadiene
The conversion of ethanol to 1,3-butadiene is a multistep reaction. Hence, it was

observed that strength of acidic and basic site or redox properties of catalysts played
important role in the reaction. As mentioned above, this reaction proceeds via dehy-
drogenation, condensation, and dehydration. The dehydrogenation step may occur
on the redox and basic sites, while condensation and dehydration may take place on
the acidic and basic sites (Sun and Wang 2014; Pomalaza et al. 2016). Considering
the complexity of reactions, catalyst with optimal functionality is desired to achieve
high productivity.
Niiyama et al. (1972) used Si–Mg oxide catalyst with varying ratio of MgO for
the conversion of ethanol to butadiene. They optimized that 85% MgO showed
high activity towards butadiene at the optimal reaction conditions and proved that
balance and control over acid and basic density were essential to gain the best
catalytic activity in terms of conversion and selectivity. Similar observation was
reported by Kvisle et al. (1988) in which high content of MgO in silica favored
high butadiene selectivity.
Jones et al. (2011) investigated several silica-impregnated bimetallic and tri-
metallic catalysts in ethanol transformation to butadiene. Zr–Zn catalyst with weight
ratio of 1.5/0.5 has emerged as the most efficient catalyst, which displayed highest
(66%) selectivity of butadiene when acetaldehyde and ethanol (feed ratio of 8:2) are
co-fed together in the reaction mixture. Improved catalytic activity was due to Lewis
acid sites of metals, while the presence of acetaldehyde in the co-fed enhanced
1,3-butadiene selectivity via aldol condensation reaction.
Various metal oxide dopants have been studied over MgO/SiO2 and the oxides
bearing Ag and Cu exhibited almost full ethanol conversion and 58.2% and 56.3%
yield of butadiene, respectively, at 350 °C with low ethanol concentration.
However, when the reaction was performed at higher temperature (400 °C) and at
higher ethanol concentration, lower ethanol conversion and reduced butadiene
yield were found. Moreover, it was observed that the acidic and basic component
ratio and redox property of promoters played crucial roles for improving butadi-
ene yield (Makshina et al. 2012).
Sushkevich et al. (2014) employed a multicomponent catalyst (M/MOx/SiO2) for
the synthesis of butadiene from ethanol in a one-step process. Herein, the metals
(M = Ag, Cu, and Ni) advocate the ethanol dehydrogenation, whereas the oxides
(MOx = ZrO2, MgO, Al2O3, Nb2O5, and TiO2) were active in aldol condensation and
Meerwein–Ponndorf–Verley reduction. Ag- and Cu-containing zirconia supported
on silica exhibited similar conversion and selectivity to butadiene at 320 °C. However,
Ag/ZrO2/SiO2 catalyst demonstrated higher stability with time on stream.
Sushkevich et al. (2015) also investigated the catalytic performance of
Ag-promoted Zr–BEA, Zr–MCM-41, and ZrO2/SiO2 in this reaction. Ag/Zr–BEA
(Si/Zr = 200) and Ag/Zr–MCM-41 (Si/Zr = 200) were found to be more active with
respect to Ag/ZrO2/SiO2 (Si/Zr = 200) at equal amounts of Ag and Zr. This activity
was ascertained to the isolation of highly concentrated Zr sites in Zr–BEA and Zr–
MCM-41 catalysts in comparison to SiO2 catalyst. In addition, all the catalyst dis-
played almost same the selectivity (about 65–66%) towards butadiene. This was
ascribed to Zr4+ sites located in the framework of molecular sieves and incorporated
in amorphous SiO2 resulting into similar selectivity. It was also observed that buta-
diene yield correlated with the amount of Lewis acid strength. The variation in by-
product distribution was mainly due to the nature and properties of the supports.
Angelici et al. (2014) investigated the effects of the addition of CuO to magne-
sia–silica materials. They synthesized the catalysts by different methods and found
that the synthesis method had effected morphology, acidity, and basicity. MgO–
SiO2 and 1 wt% CuO supported on MgO–SiO2 prepared using wet-kneaded process
exhibited 17% and 53% butadiene yield, respectively, under similar reaction condi-
tion. This increased activity in the later was attributed to the redox property of Cu,
which catalyzed ethanol dehydrogenation to acetaldehyde.
Catalytic performance of Na doping over the mixed metal oxides, i.e., ZnxZryOz,
was investigated (Baylon et al. 2016). It was observed that doping Na to ZnxZryOz
mixed oxide not only suppressed strong acidic sites but also minimized ethylene
selectivity and maximized acetaldehyde and butadiene selectivity. At 2000 ppm of
Na doping in Zn1Zr10Oz-H catalyst at 350 °C with the weight hourly space velocity
(WHSV) of 0.2 h−1, 97% conversion of ethanol with 47% butadiene selectivity and
15.9% ethylene selectivity were observed. At WHSV of 6.2 h−1, the catalyst
remained active and produced butadiene at a rate of 0.49 gbutadiene/gcat/h with 28%
butadiene selectivity and 54.4% ethanol conversion. Over a 60 h of time on stream,
a 20% drop in the ethanol conversion along with a minor decrease in butadiene
selectivity were observed.
Gao et al. (2018) examined ZrO2 supported on various silica oxides (nano-SiO2,
SBA-15, MCM-41, and SiO2) for the production of butadiene from feed mixture of
ethanol and acetaldehyde. The characterization results revealed that impregnated Zr
on silica support decreases the surface area. However, the average pore size for Zr/
nano-SiO2 and Zr/SiO2 increased, while that of Zr/SBA-15 and Zr/MCM-41
decreased. More importantly, larger pore size turned into increased butadiene selec-
tivity. The large pores of catalyst make it convenient for the in and out movement of
both reactant and product, thus providing more contact time. These results indicated
that pore size is also an important factor for determining the activity when catalyst
contains a balance of acidic and basic sites. With ZrO2/nano-SiO2 catalyst, about
91.4% selectivity to butadiene and 52.4% ethanol conversion at 320 °C with WHSV
of 1.8 h−1 were achieved. The catalyst also exhibited long-term stability (30 h) with-
out a decline in the ethanol conversion and butadiene selectivity, which indicated
better coke tolerance of catalyst.
3.4 Conclusions
Ethanol emerged as a prominent platform molecule to produce a variety of industri-

ally important chemicals. Substantial work has been done for the synthesis of vari-
ous value-added chemicals from ethanol in the past decades. It is observed that the
formation of small oxygenates such as acetaldehyde can take place at basic sites of
catalyst, while ethylene is generated on the acidic sites. Moderate acid strength is
required for propylene production, whereas bifunctional catalyst is required to pro-
duce acetone and multifunctional catalyst is desired to produce 1,3-butadiene
effectively.
The reaction mechanism for small oxygenates from ethanol is also well under-
stood. For instance, ethanol is dehydrogenated to produce acetaldehyde via break-
ing of C–H or O–H bonds, which subsequently oxidize to produce acetic acid. The
breaking of bonds generally depends on the nature of catalyst support. In the near
future, C2 or C3 products derived from ethanol may face economical challenge due
to the higher availability of low-cost shell gas in the USA. This has driven the inter-
est towards C–C bond-forming reactions to yield butanol or 1,3-butadiene. The
acidic, basic, and redox properties of catalysts are found to play significant roles in
the reaction mechanisms. Condensation and dehydrogenation reactions occur on the
basic sites, while acidic sites favor dehydration reaction.
Although extensive study has been carried out on the transformation of ethanol
to value-added compounds, still some challenges are there which are needed to be
addressed such as lower time on stream reported for the majority of catalytic sys-
tems. In the case of hydrocarbons, there is still some space to apply engineered cata-
lysts, which could enhance high carbon yield. For instance, reaction in which
product is highly active such as ethylene requires proper process design, instead of
catalyst. In case of unstable intermediates, the principles of catalyst design can be
applied to improve product yields. The development of optimal catalyst should
emphasize on the desired product selectivity. Finally, the usage of reaction chemis-
try can lead to prominent alternatives of fossil fuel resources, thus making the prod-
ucts more robust and cleaner, which are currently not accessible from conventional
resources.
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Selective Bioethanol Conversion
to Chemicals and Fuels via Advanced 4
Catalytic Approaches
Thanh Khoa Phung and Guido Busca
Abstract
Ethanol is one of the most important organic solvents used as a fuel, chemical,
and as an intermediate for organic chemical synthesis. However, its use as a fuel
has several drawbacks including corroding the engine, producing lower energy
than conventional fuel, and adsorbing water. Hence, it needs to upgrade into a
highly efficient fuel such as n-butanol. In addition, the demand for raw materials
increases due to the development of current industries such as plastic, solvent,
and surfactant industries. However, the fossil resources, the main sources for cur-
rent raw materials production, are limited and continuously depleted. As a result,
the conversion of low-cost biomaterials like bioethanol into high-value raw
materials for current industries is a promising perspective. In this chapter, some
potential reaction processes in bioethanol conversion including dehydration, oxi-
dation, steam reforming, dehydrogenation, and Guerbet reaction are summa-
rized. These catalytic reactions and ethanol-derived products are discussed to
elucidate the current picture of ethanol transformation.
Keywords
Ethanol · Dehydration · Oxidation · Dehydrogenation · Reforming · Guerbet
reaction
T. K. Phung (*)
School of Biotechnology, International University, Vietnam National University,
Hồ Chí Minh City, Vietnam
G. Busca
Department of Civil, Chemical and Environmental Engineering, University of Genova,
Genova, Italy

76 T. K. Phung and G. Busca
4.1 Introduction
The greenhouse effect and global warming are increasing in recent years, likely
due to the emissions associated with the consumption of fossil fuel. Additionally,
the demand for raw materials and current production from fossil resources are
increasing due to the development of industry and human being requirement.
However, the continuous depletion of fossil resources makes the exploitation of
alternative and renewable resources (Huber et al. 2006). Bioethanol generated
from lignocellulosic biomass (Fig. 4.1) is the most common biofuel, which can
substitute gasoline or blended with gasoline to be used as fuel of spark ignition
engines (Dowson et al. 2013; Patzek 2004). However, the use of ethanol as a fuel
results in a number of drawbacks including corroding the engine, producing
lower energy than conventional fuel, and adsorbing water (Chakraborty et al.
2015; Dziugan et al. 2015; Earley et al. 2015; Aitchison et al. 2016; Nanda et al.
2017a). However, ethanol could become a key primary intermediate in the frame
of a new organic chemical industry and fuels based on renewables (Phung et al.
2015c). Therefore, the transformation of ethanol into value-added chemicals and
advanced fuels is highly necessary.
Bioethanol is currently produced from biomass via the conventional fermenta-
tion process (Bulawayo et al. 1996; Olsson and Hahn-Hägerdal 1996; Birol et al.
1998; Huang et al. 2009). The global ethanol production is increasing rapidly and
over 117 million m3 in 2017 (Statista 2019). More than 90% of ethanol is used as
fuel and the rest is applied in beverages and industrial applications. However, the
ethanol demand is now lower than its world production. Therefore, the production
of raw chemicals and fuels from the available excess bioethanol could be necessary
in the biorefinery industry in the near future (Sun and Wang 2014).
Fig. 4.1 Applicable products from bioethanol produced from lignocellulosic biomass
4 Selective Bioethanol Conversion to Chemicals and Fuels via Advanced Catalytic… 77
Bioethanol can be used as a pure fuel or for blending with gasoline, mostly with
5–10 vol% (E5–E10) (Sun and Wang 2014; Nanda et al. 2014b). In Europe, the
maximum ethanol content in commercial motor gasoline is 10% (E10). Besides,
ethanol can be transformed into many value-added chemicals (Fig. 4.2). Ethanol
can be converted to hydrogen through steam reforming (Vaidya and Rodrigues
2006; Fatsikostas et al. 2001; Garbarino et al. 2013; Busca et al. 2010; Nanda et al.
2017b) or dehydrogenation (Autthanit et al. 2018; Campisano et al. 2018; Čičmanec
et al. 2018; Clarizia et al. 2019; Garbarino et al. 2019; Guan and Hensen 2013; Inui
et al. 2002a, b, 2004; Santacesaria et al. 2003; Shan et al. 2017; Tayrabekova et al.
2018; Tu and Chen 2001; Tu et al. 1994a, b; Weinstein et al. 2011). Dehydration of
ethanol generates diethyl ether and ethylene (Phung and Busca 2015a, b; Phung
et al. 2014a, b, 2015a, b) and other products such as aromatic and propylene (Bi
et al. 2011; Calsavara et al. 2008; Furumoto et al. 2011; Gayubo et al. 2010b; Inaba
et al. 2006, 2012; Phung et al. 2015c).
Ethylene oxide and acetic acid originate from the oxidation of ethanol or from
ethanol-derived ethylene and acetaldehyde, respectively (Chen et al. 2015;
Christensen et al. 2006; Kaichev et al. 2016; Li and Iglesia 2007; Lippits and
Nieuwenhuys 2010a, b; Snider et al. 1991). Ethyl acetate is produced from ethanol
through the esterification reaction with acetic acid, which can be made through
aldol condensation reaction. Additionally, acetaldehyde can be also produced from
Fig. 4.2 Possible chemicals generated from ethanol

ethanol followed by the catalytic conversion to acetic acid or 1,3-butadiene (Angelici

et al. 2014; Makshina et al. 2012). Besides, a high-value fuel, n-butanol, originating
from ethanol via Guerbet reaction could become a great biofuel in the near future
(Aitchison et al. 2016; Carvalho et al. 2012; Koda et al. 2009; Kozlowski and Davis
2013; Ogo et al. 2012; Nanda et al. 2014a).
These abovementioned ethanol-derived chemicals can be used as the intermedi-
ates in the biorefinery industry (Sun and Wang 2014). Ethylene and propylene are
the widely used compounds in the polymer industry where 1,3-butadiene is also
largely applied (Makshina et al. 2012). Ethylene oxide, diethyl ether, acetone, ethyl
acetate, and acetaldehyde are industrial solvents and chemical intermediates
(Fleischmann et al. 2000; Rebsdat and Mayer 2011; Riemenschneider and Bolt
2005; Sakuth et al. 2010; Sifniades et al. 2011). Moreover, ethanol-derived aromat-
ics and n-butanol can be applied as fuels or blended with gasoline (Hahn et al. 2010;
Sun and Wang 2014). In this chapter, all the current catalytic processes of ethanol
conversion to chemicals and fuels are summarized. An all-inclusive scenario of
catalysts used in the ethanol conversion processes is also discussed.
4.2 Dehydration of Ethanol
4.2.1 Diethyl Ether Production
Diethyl ether (C2H5OC2H5) is a simple and colorless ether and a flammable liquid.
It has a low solubility in water and low boiling point (34.6 °C); also its melting point
is extremely low (−116.3 °C) (Sakuth et al. 2010). Diethyl ether has many applica-
tions in the chemical industry such as a solvent in several chemical synthesis pro-
cesses. Diethyl ether can also be used as a fuel additive for both diesel and gasoline
fuels due to its high cetane number (>125) and octane number (>110) (Doğu and
Varişli 2007; Erwin and Moulton 1996; Kito-Borsa et al. 1998). However, diethyl
ether also has certain drawbacks including low lubricity, easy peroxidation in stor-
age, high volatility, and anesthetic effects to human beings. Diethyl ether can be
produced from ethanol, in which ethanol is dehydrated into ethylene and diethyl
ether according to the following reactions:
C H OH C2 H 4 H 2 O H 298 44.9 kJ / mol (4.1)

2 5
2C2 H 5 OH C2 H 5 OC2 H 5 H 2 O H 298 25.1 kJ / mol (4.2)
Ethanol dehydration is well studied using most acid catalysts such as alumina
and zeolites in the gas phase or sulfuric acid in the liquid phase (Chaichana et al.
2019; de Oliveira et al. 2018; Phung and Busca 2015b; Phung et al. 2015b; Sakuth
et al. 2010). It is also a byproduct of the ethylene hydration process into ethanol
(Kosaric et al. 2011). For the dehydration of ethanol, acid catalysts favor this reac-
tion than the basic catalysts (Phung et al. 2015a). Several oxides including alumina,
titania, and zirconia are the most catalysts used as well as ZSM-5 which is a com-
mon catalyst for ethanol dehydration (Chaichana et al. 2019; de Oliveira et al. 2018;
Phung and Busca 2015b; Phung et al. 2014a, b, 2015a, b). Additionally, the polyacid
catalysts are also used for this reaction (Lee et al. 1992; Varisli et al. 2007).
In parallel with experimental studies, some computational studies and mecha-
nism are also well investigated. The reaction represented in Eq. (4.1) occurs with an
E2 concerted elimination mechanism and the mechanism of reaction represented in
Eq. (4.2) is an SN2 bimolecular from a protonated and non-protonated form of etha-
nol (Christiansen et al. 2013; Brown et al. 2014). The mechanism of ethanol dehy-
dration is also confirmed by the density functional theory (DFT) computational
studies. However, Eqs. (4.1) and (4.2) are parallel reactions, in which the bimolecu-
lar and unimolecular mechanisms are the mechanism in the production of diethyl
ether and ethylene, respectively (DeWilde et al. 2013; Roca et al. 1969). Recently,
several authors (Phung and Busca 2015a, b; Garbarino et al. 2018) concluded that
the parallel-successive path is very active. In fact, diethyl ether can be produced
from the reaction of ethoxide group on the surface of catalyst with an adsorbed etha-
nol molecule (Knözinger 1968) or the reaction of two ethoxide groups (Arai et al.
1967). Moreover, diethyl ether is possibly as an intermediate in the ethylene produc-
tion from ethanol dehydration (Bokade and Yadav 2011; Christiansen et al. 2013;
Ciftci et al. 2012; Kagyrmanova et al. 2011; Yasunaga et al. 2010).
4.2.2 Ethylene Production
Ethylene (C2H4) is the simplest alkene and a colorless flammable gas. It has a faint
“sweet and musky” odor. Ethylene is soluble in diethyl ether and poorly soluble
in water (2.9 mg/L) and in ethanol (4.22 mg/L). Its boiling point is −103.7 °C and
melting point is −169.2 °C (Zimmermann and Walzl 2009). Ethylene is one of the
largely produced materials in the petrochemical industry with its annual global
production of about 150 million metric tons (Lewandowski 2016). North America,
Western Europe, Middle East and North East Asia are the main ethylene produc-
tion regions (Lewandowski 2016). Ethylene has many applications in the produc-
tion of chemicals and polymers such as polyethylene, ethylene dichloride, and
ethylene oxide production (Fan et al. 2013). It was first produced from coke oven
gas and Line was the first company commercializing ethylene production plant in
the 1930s with the thermal cracking process patent of Standard Oil in 1913. Later
in 1941, the first steam cracker was developed by Standard Jersey, and in the
1950s, ethylene became a largest intermediate for the synthesis of organic com-
pounds as the replacement for acetylene as an intermediate (Zimmermann and
Walzl 2009).
Nowadays, ethylene is produced commercially from crude oil through steam
cracking of paraffinic hydrocarbons process and as a byproduct of fluid catalytic
cracking of heavy oils. However, those processes consume high amount of energy
as well as emit enormous amounts of greenhouse gas. To reduce the greenhouse
gas emissions, bioethylene is produced from bioethanol via dehydration. Ethylene

production from ethanol through dehydration has been industrially applied until
the 1960s using alumina-based catalysts (Hu 1993). Le Van Mao et al. (1989)
developed the bioethanol-to-ethylene (BETE) pathway using zeolites as the cata-
lyst in the 1980s.
The literature indicates high catalytic activities over H-ZSM-5, HBEA, HFAU,
HFER, and HMOR zeolites for ethanol dehydration (De las Pozas et al. 1993;
Oudejans et al. 1982; Ouyang et al. 2009; Phillips and Datta 1997; Ramesh et al.
2009; Takahara et al. 2005, 2007; Zhang et al. 2008). Those zeolites can be
applied to produce ethylene from bioethanol industrially (Fan et al. 2013), but
Zhang and Yu (2013) reported that these might be unstable for the dehydration of
ethanol. Moreover, the mechanism of this reaction over zeolites has been pub-
lished with some disagreements between the respective conclusions (Chiang and
Bhan 2010; Kondo et al. 2005; Lee et al. 1997; Nguyen et al. 2010; Wang et al.
2005; Zecchina et al. 1996). Currently, bioethylene is commercially produced
from ethanol using Syndol catalyst based on MgO-Al2O3/SiO2 catalysts (Syndol
catalyst, Halcon SD) through the process of Chematur (Fan et al. 2013). The
process is performed at a higher temperature (450 °C) giving 99% ethanol con-
version with high selectivity of ethylene (96.8%).
4.2.3 Propylene Production
Propylene (C3H6) is the second simplest alkene and has one double bond. Propylene
has poor solubility in water (0.61 g/m3) and its boiling point and melting point are
−47.6 °C and −185.2 °C, respectively (Eisele and Killpack 2011). Propylene is also
the second largest petrochemical after ethylene with many applications in plastics
and solvent industries. Due to its wide usage, the global demand for propylene has
increased significantly with the global increase forecast of roughly 4.5% (52 billion
lbs) by 2020 (Wattanakarunwong 2015).
Propylene is a byproduct from the petrochemical processes involving ethylene
and gasoline production (Thinnes 2010; Wattanakarunwong 2015). It is also pro-
duced using technologies such as propane dehydrogenation (PDH) and ethylene/
butene metathesis. New chemical processes for on-purpose propylene production
using low-cost and nonpetroleum source materials such as methanol-to-olefin
(MTO) (Chen et al. 2005; Pujadó and Andersen 2006) and methanol-to-propylene
(MTP) (Jasper and El-Halwagi 2015; Liebner 2005) have been commercialized.
The methanol-to-olefin (MTO) process (UOP/Hydro MTO) uses the MTO-100
(silicoaluminophosphate)-based catalyst, while the MTPROP (ZSM-5-based cata-
lyst, Süd-Chemie) is used for Lurgi’s MTP (methanol-to-propylene) process
(Koempel and Liebner 2007). Both the processes are based on the methanol obtained
in large-scale quantities from natural gas (steam reforming and synthesis) or coal
(gasification and synthesis).
Bioethanol is also a suitable choice as a starting chemical for producing biopropyl-
ene (Posada et al. 2013). A number of studies on the conversion of ethanol to propylene
have been published using zeolite-based catalysts (Aguayo et al. 2002a, b; Arias et al.
1997; Brandão et al. 2002; Gayubo et al. 2010a, 2011; Inaba et al. 2007; Oikawa et al.
2006; Phillips and Datta 1997; Phung et al. 2015c; Song et al. 2009, 2010; Takahara
et al. 2005, 2007) and metal oxide catalysts (Bakoyannakis et al. 2001; Carrasco-Marín
et al. 1998; Doheim and El-Shobaky 2002; Golay et al. 1999; Phung and Busca 2015b;
Phung et al. 2014b, 2015a; Tsuchida et al. 2008; Varisli et al. 2007; Zaki 2005).
Currently, the Brazilian chemical company Braskem, who is the leader in the
manufacturing of biopolyethylene, announced to use bioethanol to produce biopro-
pylene (Tullo 2010) for further converting it into biopolypropylene. In this technol-
ogy, the first step is the fermentation process converting sugars into ethanol followed
by the conversion of ethanol into ethylene on one route and dimerized to butene on
another route. In the next step, biopropylene is produced by metathesis of bioethyl-
ene and biobutene (Eq. 4.3) (Gotro 2013).
CH 2 CH 2 CH 3 CH CHCH3 2CH 3 CH CH 2 (4.3)

The mechanism of transformation from ethanol to propylene is still debated.
There are many reaction pathways to generate propylene via ethylene (Inaba et al.
2006; Iwamoto 2015; Murata et al. 2008; Takahashi et al. 2012) or acetaldehyde
(Hayashi et al. 2014). Hayashi et al. (2014) suggested that ethanol can dehydroge-
nate to acetaldehyde and transform to acetone by reacting with water on the surface
of yttrium-modified ceria catalysts, finally converting into propylene by the hydro-
genation reaction (Fig. 4.3a). Moreover, ethanol can also transform directly to
propylene.
A few other authors also indicate that propylene can be produced from ethanol
via ethylene (Bhadra et al. 2018; Ghashghaee and Shirvani 2019; Khan et al. 2019;
Kim et al. 2017; Sarker et al. 2019). However, the reaction mechanism to generate
propylene from ethylene can occur via different pathways. Ethanol dehydrates to
form ethylene, which trimerizes to give hexane followed by the production of pro-
pylene by β-fission (Murata et al. 2008; Oikawa et al. 2006) (Fig. 4.3b). Iwamoto
(2015) suggested that propylene production could take place via ethylene and
diethyl ether as the immediate. However, ethylene dimerizes to form 1-butene,
Fig. 4.3 Reaction pathways of ethanol decomposition into propylene

which transforms to 2-butene followed by the reaction of 2-butene with ethylene to

produce propylene (Fig. 4.3c).
4.3 Oxidation of Ethanol
4.3.1 Ethylene Oxide Production
Ethylene oxide (C2H4O) is a flammable gas and the simplest epoxide. It is a three-
membered ring ether with two carbon atoms and one oxygen atom. Therefore, it is
easy to open the rings in the addition reactions. Ethylene oxide is miscible with
water and has a low boiling point (10.4 °C) and melting point (−112.5 °C) (Rebsdat
and Mayer 2011). Ethylene oxide is an important intermediate for many organic
syntheses (Salmi et al. 2012). It is commonly utilized for the production of ethylene
glycol and polyesters in the fabricating beverage bottles (Bac and Avci 2018; Liu
et al. 2017). Additionally, glycols from ethylene oxide can be used in the production
of coolants, detergents, polyester fibers, heat transfer fluids, surfactants, polyure-
thanes, plasticizers, and solvents (Bac and Avci 2018; Liu et al. 2017; Mendes et al.
2007). Polyethylene glycol is used as an important component in the cosmetic,
pharmaceutical, lubricant, plasticizer, and solvent industries (Bac and Avci 2018;
Liu et al. 2017; Mendes et al. 2007). Ethylene oxide is also utilized to produce eth-
ylene glycol ethers, ethanolamine, and ethoxylates (Bac and Avci 2018; Liu et al.
2017; Mendes et al. 2007).
Ethylene oxide is mainly produced from ethylene as a product from dehydration
of ethanol. The studies on the direct oxidation of ethanol into ethylene oxide are
relatively scarce. The process mostly involves two reactions of dehydration of etha-
nol to ethylene and oxidizing the ethylene into ethylene oxide (Coupard and
Plennevaux 2014). Copper-, silver-, and gold-based catalysts are the main active
sites for the oxidation of ethanol to ethylene oxide (Chen et al. 2015; Lippits and
Nieuwenhuys 2010a, b). Catalyst support is also important to enhance the catalytic
activity. ZSM-5 (Chen et al. 2015) and Li2O/Al2O3 (Lippits and Nieuwenhuys
2010a, b) showed the best activities as supports of catalysts in terms of the selectiv-
ity to ethylene oxide. The literature also reported that the presence of oxygen allows
to prevent carbon deposition (Lippits and Nieuwenhuys 2010b). Tuning oxygen
concentration and Li2O doping boost the selectivity of ethylene oxide over silver-
based catalysts (Lippits and Nieuwenhuys 2010a). In the case of the ceria support,
it can make extra oxygen available to the catalytic reaction (Lippits and Nieuwenhuys
2010b).
4.3.2 Acetic Acid Production
Acetic acid (CH3COOH) is a simple carboxylic acid and a colorless liquid at room
temperature. Its melting point and boiling points are 16–17 °C and 118–119 °C,
respectively. In addition, it is a main component of vinegar, an additive used in food
and salads for its sour taste (Le Berre et al. 2014). Vinegar is one of the most ancient
applications of acetic acid in the world. Acetic acid also has many applications
including vinyl acetate monomer, ester production, acetic anhydride, solvents, and
in medical use (Le Berre et al. 2014). Vinyl acetate monomer is used as wood glue
as well as synthetic fibers and fabrics (Roscher 2000). Other esters arising from
acetic acid such as ethyl acetate, propyl acetate, isobutyl acetate, and n-butyl acetate
are commonly applied in paints, coatings, and inks as solvents (Riemenschneider
and Bolt 2005). Acetic anhydride is an acetylation agent, which is used to produce
cellulose acetate (Held et al. 2000). Moreover, acetic acid can be involved as a sol-
vent in Friedel-Crafts alkylation reaction or terephthalic acid production. It is also
used in medical research such as for the treatment for otitis externa and part of
cervical cancer screening (Le Berre et al. 2014).
C2 H 5 OH O2 CH 3 COOH H 2 O (4.4)
Oxidation of ethanol to acetic acid (Eq. 4.4) was performed in both gas phase
(Kaichev et al. 2016; Li and Iglesia 2007) and liquid phase (Christensen et al. 2006;
Snider et al. 1991). Palladium-, platinum-, and gold-based catalysts have received
attention as suitable catalysts for this reaction (Bianchini et al. 2009; Christensen
et al. 2006; Tarnowski and Korzeniewski 1997). In the liquid phase, Au/MgAl2O4
was selective for ethanol oxidation to acetic acid with a selectivity of 86% at 180 °C
(Christensen et al. 2006). Gold-based catalysts with other supports including TiO2,
SiO2, ZnO, Al2O3, and NiO were also optimal catalysts giving high conversion and
high acetic acid selectivity (Jørgensen et al. 2007; Sun et al. 2008; Takei et al. 2011).
Li and Iglesia (2007) reported that Mo0.61V0.31Nb0.08Ox/TiO2 showed high acetic acid
selectivity of 95% with complete ethanol conversion at 237 °C.
The selectivity to acetic acid decreased at high temperature (>200 °C) in the gas
phase due to the formation of other products (Kaichev et al. 2016). However, at low
temperature (100–150 °C), the main compound was acetaldehyde, which shifted the
reaction toward acetic acid at higher temperatures (Kaichev et al. 2016). In mono-
layer V2O5/TiO2 catalysts, the oxidation of ethanol reaction involved reversible
reduction of V5+ cation, whereas titanium cations remained in the Ti4+ state (Kaichev
et al. 2016). In this case, acetic acid selectivity reached 60% at 200 °C, while it
achieved 68% selectivity with 60% ethanol conversion at 150 °C using Ce-meso
TiO2 (Eguchi et al. 2008). According to some authors, ethanol is oxidized into acet-
aldehyde intermediate and transformed into acetic acid in the second step in both
gas and liquid phase (Takei et al. 2011). Instead, other authors conclude that the
selectivity of acetic acid increases in the presence of water because the oxidation to
acetic acid is favored than acetaldehyde production (Li and Iglesia 2007).
4.4 Steam Reforming of Ethanol and Dehydrogenation
4.4.1 Steam Reforming of Ethanol to Hydrogen
Hydrogen has wide applications in energy and chemical industry including manu-
facture of chemicals (e.g., ammonia and methanol production, upgrading heavy
oils), as a coolant, an energy carrier, and in the semiconductor sectors. Hydrogen is
considered as a clean energy and mostly used for fuel cell systems to generate elec-
tricity. Hydrogen is a highly efficient energy carrier (143 MJ/kg) with respect to that
of liquid hydrocarbon-based fuels (Häussinger et al. 2000). Hydrogen is currently
produced by several processes including hydrocarbon steam reforming, water elec-
trolysis, and photocatalytic methods (Häussinger et al. 2000; Marone et al. 2014; Ni
et al. 2007b; Taboada et al. 2014). Among them, steam reforming of organic com-
pounds is the most common process to produce hydrogen (Faria et al. 2014; Nahar
and Dupont 2014). However, using natural gas or oil-derived hydrocarbons, it is not
a clean process and causes greenhouse gas emissions. Therefore, hydrogen produc-
tion through steam reforming of ethanol, arising from renewable biomass, is a clean
process to reduce the environmental problems (Nanda et al. 2017b).
Ethanol steam reforming may produce up to six hydrogen molecules per ethanol
molecule converted (Eq. 4.5). However, the amount of hydrogen produced is low-
ered if CO is produced instead of CO2 (Eq. 4.6) and other side reactions producing
methane as a byproduct. Other reactions include dehydration of ethanol to ethylene
(Eq. 4.1), hydrogenation of ethanol (Eq. 4.7), dehydrogenation (Eq. 4.8), acetalde-
hyde decomposition (Eq. 4.9), steam reforming of acetaldehyde (Eq. 4.10), and
water-gas shift reaction (Eq. 4.11).
C2 H 5 OH 3H 2 O 2CO2 6H 2 (4.5)
C2 H 5 OH H 2 O 2CO 4H 2 (4.6)
C2 H 5 OH 2H 2 2CH 4 H 2 O (4.7)
C2 H 5 OH CH 3 CHO H 2 (4.8)
CH 3 CHO CH 4 CO (4.9)
CH 3 CHO H 2 O 2CO 3H 2 (4.10)
CO H 2 O CO2 H 2 (4.11)
Steam reforming of ethanol may be realized on both noble metal catalysts and
non-noble catalysts (Table 4.1), which has an important role in obtaining maximum
hydrogen yield and complete ethanol conversion. However, the highest hydrogen
yield is also controlled by the reaction temperature, feed composition, and residence
time (Hou et al. 2015). Being an endothermic reaction, high reaction temperature,
high stream-to-ethanol ratio, and long residence time are required to enhance
Table 4.1 Summary of catalysts used for ethanol steam reforming

H2O/
Metal C2H5OH Ethanol Hydrogen
loading Temperature (molar conversion selectivity
Catalyst (wt%) (°C) ratio) (%) (%) References
Rh/CeO2 2 300 8/1 58.5 102.1 Diagne
et al. (2004)
400 100 66.3
450 100 69.1
Rh/ZrO2 300 100 59.6
450 100 71.7
Ru/CeO2 1 450 – 57 35 Erdohelyi
(20 min) et al. (2006)
25 23
(100 min)
Rh/CeO2 1 80 84
(20 min)
56 72
(80 min)
Ru/Al2O3 6 630 1/1 100 67 Chiu et al.
(2013)
Rh/Al2O3 6 100 72
Pd/Al2O3 6 100 60
Pt/Al2O3 6 100 58
Rh/MgO 3 650 2.1/1 99 (10 h) 91 Frusteri
et al. (2004)
Pd/MgO 3 10 (10 h) 70
Ni/MgO 21 42 (10 h) 97
Co/MgO 21 55 (10 h) 92
Ru/Al2O3 1 800 3/1 42 55 Liguras
et al. (2003)
5 100 96
Rh/Al2O3 1 100 95
2 100 96
Pd/Al2O3 1 55 50
Pt/Al2O3 1 60 65
Co/ZnO 10 350 4/1 100 (75 h) 73.4 Llorca et al.
(2003)
Co/ZnO 10 400 13/1 100 72.1 Llorca et al.
(0.06 wt% (2004)
Na)
Co/ZnO 10 100 73.4
(0.23 wt%
Na)
(continued)

H2O/
Co/ZnO 10 100 74.2
(0.78 wt%
Na)
Co/Al2O3 8 400 3/1 74 60–70 Batista
et al. (2004)
18 99 63–70
Co/SiO2 8 89 62–70
18 97 69–72
Co/ 10 420 21/1 100 93 Machocki
CeO2-nano et al. (2010)
Co/ 420 100 76
CeO2-micro
Co/ZrO2-nano 420 100 85
Co/ 420 100 77
ZrO2-micro
Co/ZnO 20 600 13/1 95 71 Da
Costa-Serra
et al. (2010)
Ni/ZnO 20 600 12/1 100 67
Ni/Y2O3 20.6 250 3/1 81.9 43.1 Sun et al.
(2005)
Ni/Al2O3 16.1 76 44
Ni/La2O3 15.3 80.7 49.5
Ni/La2O3 10 350 12/1 38 55 Liu et al.
(2010)
24 350 84 64
45 350 100 70
Ni/ 10 400 10/1 100 83 Furtado
Ce0.6Zr0.4O2 et al. (2009)
Cu/Al2O3 1 400 10/1 100 71
Ni/γ-Al2O3 35 500 6/1 100 91 Comas
et al. (2004)
Ni/Al2O3 3.8 450 3/1 96.6 61.5
(pretreatment
at 550 °C)
650 100 89.0
Ni/Al2O3 450 100 0
(pretreatment
at 700 °C)
550 99.2 67.3
650 100 87.4
(continued)

H2O/
Ni/CeO2-ZrO2 10 600 3/1 100 75 Ebiad et al.
(2012)
24 600 3/1 100 70
Ni/ 7 650 8/1 95 70 Galetti
ZnAl2O4- et al. (2011)
CeO2
Ni/γ-Al2O3 10 650 8/1 100 78.2 Akande
et al. (2005)
Ni/MgO 100 82.2
Ni/La2O3 100 89.3
Ni/ZnO 100 89.1
Ni/La2O3 20 500 3/1 35 70 Fatsikostas
and
Verykios
(2004)
800 ~100 95
Ni/Al2O3 700 77 87
800 100 96
hydrogen yields (Piscina and Homs 2008). Besides, high reaction temperature also
prevents methane formation (Piscina and Homs 2008), while an increase of space-
time favors hydrogen selectivity causing a decrease of intermediates (da Silva et al.
2010).
It is well-known that noble metal catalysts are very active for catalytic ethanol
steam reforming. A number of studies reported that Ru, Rh, Pd, and Pt are excel-
lent catalysts for ethanol steam reforming (Auprêtre et al. 2002; Chiu et al. 2013;
Diagne et al. 2004; Erdohelyi et al. 2006; Frusteri et al. 2004; Liguras et al. 2003).
Rh and Ru are competitive catalysts depending on the catalyst loading (Chiu et al.
2013; Diagne et al. 2004; Frusteri et al. 2004). Rhodium has very high activity at
low catalyst loading (0–5 wt%), while Ru gave high catalytic activity but with
greater catalyst loading (Chiu et al. 2013; Diagne et al. 2004; Frusteri et al. 2004).
The supports and dispersion of metal catalysts on support also play important roles
for this reaction (Hou et al. 2015).
Lewis acid γ-Al2O3 is remarkably used for steam reforming of ethanol as a sup-
port (Auprêtre et al. 2002; Chiu et al. 2013; Liguras et al. 2003), while basic oxides
such as La2O3, MgO, ZnO, and CeO2 are also frequently employed as the supports
(Diagne et al. 2004; Erdohelyi et al. 2006; Frusteri et al. 2004; Liu et al. 2010;
Llorca et al. 2004). The support γ-Al2O3 is reported to enhance the ethanol conver-
sion with respect to that of basic supports (Hou et al. 2015). However, acid supports
favor ethanol dehydration into ethylene, which can be transformed into coke at high
temperatures (Hou et al. 2015; Phung et al. 2015a, b). In fact, 1.0 wt% Rh/γ-Al2O3
showed complete ethanol conversion with approximately 95% of hydrogen selectiv-
ity at 800 °C with steam:ethanol molar ratio of 3:1 (Liguras et al. 2003).
With high loading of Rh (5 wt%), ethanol conversion was complete at the begin-
ning of the experiment at 650 °C but decreased at the longer times on stream with-
out oxygen addition (43% conversion at 100 h) due to coke formation on the surface
of catalysts (Cavallaro et al. 2003). The coke formation also reduces the selectivity
of hydrogen (Cavallaro et al. 2003). In contrast, basic supports such as MgO and
Mg/Al-based spinel oxide reduce the coke formation rate due to the lower surface
acidity, thereby enhancing the stability of the catalysts (Frusteri et al. 2004).
However, the deactivation was found mainly due to the sintering of metal (Frusteri
et al. 2004). Interestingly, basic MgO support also showed complete ethanol conver-
sion and high stability of catalyst over 3 wt% Rh at 650 °C (Frusteri et al. 2004). In
the same support, higher catalyst loading (21 wt%) of Ni and Co gave high hydro-
gen selectivity (Table 4.1), but they lowered ethanol conversion after 10 h of reac-
tion time (42% conversion for Ni and 55% conversion for Co) (Frusteri et al. 2004).
As mentioned earlier, the catalyst activity increases with an increase in the dis-
persion of metals on the support. In fact, well dispersion of Ni-Rh bimetallic cata-
lyst on smaller crystals of CeO2 enhanced the ethanol conversion (Kugai et al.
2006), while the formation of Pd-Zn alloy from the co-deposits of Pd and Zn on
ZnO support favored side reactions instead of sufficient steam supply reaction
(Casanovas et al. 2006), resulting in a decrease in hydrogen yield. Besides, the reac-
tion mechanism of ethanol steam reforming is less studied. The surface chemistry
requires intensive studies to better understand the interactions between the chemical
species and the catalyst surface (Hou et al. 2015; Ni et al. 2007a).
Steam reforming normally employs noble metals as the catalysts, but it also uti-
lizes low-cost non-noble metal catalysts (Table 4.1). Nickel is one of the most metal
catalysts used with different supports such as Al2O3, La2O3, and CeO2-ZrO2 for
steam reforming reaction (Akande et al. 2005; Comas et al. 2004; Ebiad et al. 2012;
Fatsikostas and Verykios 2004; Furtado et al. 2009; Galetti et al. 2011; Garbarino
et al. 2015; Liu et al. 2010; Sun et al. 2005). Cobalt and copper are also employed
for this reaction. Co/CeO2-nano (XC2H5OH, 100%; SH2, 93%) is comparable with Ni/
Al2O3 (XC2H5OH, 100%; SH2, 95%) (Machocki et al. 2010; Fatsikostas and Verykios
2004). However, Co achieved high catalytic activity and hydrogen selectivity at
lower temperature (420 °C) than that of Ni (800 °C).
Acid support such as Al2O3 is still an excellent support for ethanol steam
reforming (Comas et al. 2004; Fatsikostas and Verykios 2004). Moreover, La2O3,
ZnO, and CeO2-nano are also good support candidates (Akande et al. 2005;
Fatsikostas and Verykios 2004; Machocki et al. 2010). In the same support and
metal catalysts, the reaction temperature enhanced both ethanol conversion and
hydrogen selectivity (Comas et al. 2004; Fatsikostas and Verykios 2004). In
fact, higher temperature improved ethanol decomposition by both catalyst and
thermal conversions. Additionally, it prevented the formation of methane, result-
ing in an increase in hydrogen production (Ni et al. 2007a). Interestingly, cobalt
metal nanoparticles are also active as a catalyst for steam reforming even when
nonsupported (Riani et al. 2016).
4.4.2 Dehydrogenation of Ethanol
4.4.2.1 Acetaldehyde
Acetaldehyde (CH3CHO) is the second simplest of aldehyde group and a colorless
liquid. It is miscible with water and common solvents, including ethanol, ether,
benzene, toluene, xylene, turpentine, and acetone. It is a flammable material (flash
point of −39 °C) and has a low boiling point (20.2 °C). Acetaldehyde is the main
hazard listed in a group of potential occupational carcinogens (Fleischmann et al.
2000). Acetaldehyde can be used in nonalcoholic drinks and natural fruits juices
(Fleischmann et al. 2000). Acetaldehyde has a wide application in food industries
and plastic industry as well as in the manufacturing of acetic acid and paint bind-
ers in alkyd paints (Caro et al. 2012; Fleischmann et al. 2000; Liu and Hensen
2013; Tang et al. 2016; Xu et al. 2016). Additionally, acetaldehyde is also used as
a component or in the production of materials in civil, pharmaceutical, and cos-
metic industries (Caro et al. 2012; Fleischmann et al. 2000; Liu and Hensen 2013;
Tang et al. 2016; Xu et al. 2016). In 2016, the market of acetaldehyde was US
$1.26 billion, which is expected to reach up to US $1.80 billion by 2022 and US
$1.6 million tons by 2024.
Acetaldehyde can be produced from ethanol through dehydrogenation or partial
oxidation (Autthanit et al. 2018; Campisano et al. 2018; Čičmanec et al. 2018;
Clarizia et al. 2019; Garbarino et al. 2019; Guan and Hensen 2013; Santacesaria
et al. 2003; Shan et al. 2017; Tayrabekova et al. 2018; Tu and Chen 2001; Weinstein
et al. 2011). A number of studies have focused on the catalytic reaction (Autthanit
et al. 2018; Campisano et al. 2018; Čičmanec et al. 2018; Clarizia et al. 2019;
Garbarino et al. 2019; Guan and Hensen 2013; Santacesaria et al. 2003; Shan et al.
2017; Tayrabekova et al. 2018; Tu and Chen 2001; Weinstein et al. 2011) and kinetic
and surface study (Cassinelli et al. 2015; Gazsi et al. 2011; Guan and Hensen 2009;
Shan et al. 2018). Ethanol dehydrogenation has been studied on mainly copper-
based catalysts (Table 4.2). Ethanol conversion increases with an increase of reac-
tion temperature, but acetaldehyde selectivity can decrease meanwhile (Table 4.2).
In other words, acetaldehyde selectivity can drop at higher ethanol conversion. It
can reach 100% selectivity at ethanol conversion lower than 15% at 250 °C over
Ni-Cu alloys, while it is constant at near 90% selectivity with near-complete ethanol
conversion on the 19.3 wt% Cu/ZnAl2O4 at 400 oC (Table 4.2). Additionally,
Cassinelli et al. (2015) reported that the addition of Cu+ enhanced the ethanol dehy-
drogenation than that of using only Cu0.
Platinum- and gold-based catalysts are also good candidates for ethanol dehy-
drogenation (Table 4.2). They showed the same characteristics with Cu-based cata-
lysts in the acetaldehyde selectivity with respect to ethanol conversion and reaction
temperature. Gold is the best catalyst with high acetaldehyde selectivity (>90%) at
low temperature, i.e., 180 °C (Table 4.2), and at high temperature, i.e., 400 °C
Table 4.2 Summary of ethanol dehydrogenation to acetaldehyde

Ethanol
Temperature conversion Acetaldehyde
Catalyst Support (°C) (%) selectivity (%) References
NiCu – 250–350 <15 100 Shan et al.
alloys (2017)
VOx ZrO2 200 60 90 Čičmanec et al.
(2018)
V-Zr-La SBA- 400 80 48 Autthanit et al.
15-HT (2018)
5Cu ZrO2 200 27.9 21.0a Freitas et al.
(2014)
10Cu ZrO2 33.3 16.6a
20Cu ZrO2 31.9 16.8a
30Cu ZrO2 30.9 20.1a
5Cu ZrO2 250 64.3 16.8a
10Cu ZrO2 68.4 12.5a
20Cu ZrO2 69.3 12.6a
30Cu ZrO2 68.8 14.5a
Cu ZnAl2O4 400 100 90 Garbarino et al.
(2019)
CuO- Al2O3 300 55 50 Tayrabekova
Cr2O3 et al. (2018)
Au(26) SiO2 180 56 92b Guan and
Ir(74) Hensen (2013)
Pt CeO2(rod) 200 4.3 83 Ciftci et al.
(2013)
Pt CeO2(cube) 2.0 80
Au CeO2(rod) 1.3 100
Au CeO2(cube) 0.2 100
Pt CeO2(rod) 300 30 34
Pt CeO2(cube) 9.0 32
Au CeO2(rod) 4.8 97
Au CeO2(cube) 3.3 100
Pt CeO2(rod) 400 99 0.6
Pt CeO2(cube) 14 27
Au CeO2(rod) 31 66
Au CeO2(cube) 16 93
Au (5.8) SBA- 400 90 95 Guan and
16(3.1) Hensen (2009)
a
Mainly ethyl acetate (~70–80%)
b
Trace amounts of acetic acid and ethyl acetate
(Table 4.2). Au (5.8)/SBA-16 (3.1) showed the best catalytic activity with 95% acet-
aldehyde selectivity at 90% ethanol conversion. Besides, in the case of zirconia
support, the addition of gold reduced ethanol dehydration reaction by passivation of
the acid sites of the support and improved dehydrogenation reaction by introducing
new sites for this reaction (Wang et al. 2016).
4.4.2.2 Ethyl Acetate

Ethyl acetate (CH3COOC2H5) is the ester of ethanol and acetic acid and a colorless
liquid at room temperature with a pleasant “fruity” smell. It is a flammable liquid
(flash point: – 4 °C) with boiling point and melting point of 77.1 °C and − 83.6 °C,
respectively. Ethyl acetate is miscible with common organic solvents (e.g., ethanol,
acetone, diethyl ether, and benzene), but poorly soluble in water (83 g/L at 20 °C)
(Riemenschneider and Bolt 2005). Ethyl acetate is commonly used as a solvent and
has many applications in food, cosmetic, coating, electronics, and printing indus-
tries (Cheng et al. 2016; Inui et al. 2002b; Petek et al. 2018; Shen et al. 2017; Singha
and Ray 2016; Zonetti et al. 2011). As a solvent, ethyl acetate is used for cleaning,
paint removal, and coatings depending on its purity. Its high purity can be applied in
cleaning electric circuit boards as well as a nail polish remover, while its low purity
can be applied in pharmaceuticals, perfumes, printing, decaffeination of tea or cof-
fee, food, and a carrier solvent for herbicides (Riemenschneider and Bolt 2005).
Traditionally, ethyl acetate is produced from ethanol and acetic acid through
esterification reaction (Eq. 4.12). Moreover, it can be produced through the reaction
of ethylene and acetic acid (Eq. 4.13); Tishchenko reaction, i.e., the dimerization of
acetaldehyde (Eq. 4.14); or direct dehydrogenation of ethanol (Eq. 4.15). The pro-
cess illustrated in Eq. (4.15) opens a new route to produce ethyl acetate from
biomass-derived ethanol. In parallel with Eq. (4.15), the side reaction of dehydroge-
nation of ethanol to acetaldehyde can also occur.
C2 H 5 OH CH 3 COOH CH 3 COOC2 H 5 H 2 O (4.12)
C2 H 4 CH 3 COOH CH 3 COOC2 H 5 (4.13)
2CH 3 CHO → CH 3 COOC2 H 5 (4.14)
2C2 H 5 OH CH 3 COOC2 H 5 2H 2 (4.15)
Copper-based materials are the main catalysts used in ethanol dehydrogenation

into ethyl acetate (Carotenuto et al. 2013; Colley et al. 2005; Gaspar et al. 2010; Inui
et al. 2002a, b, 2004; Santacesaria et al. 2012; Tu et al. 1994a, b; Zonetti et al.
2011). Two families of copper-based catalysts used are copper/copper chromite
(Carotenuto et al. 2013; Colley et al. 2005; Santacesaria et al. 2012; Tu et al. 1994a,
b) and copper metal supported and/or promoted by different oxides (Gaspar et al.
2010; Inui et al. 2002a, b, 2004; Santacesaria et al. 2012; Zonetti et al. 2011).
Copper/copper chromite showed higher ethyl acetate selectivity (98–99%) at 65%
of ethanol conversion at 220–240 °C (Santacesaria et al. 2012). Moreover, using
K2CO3 in the treatment of Cu-Zn-Zr-Al-O catalyst also enhanced ethanol conver-
sion (66%) and ethyl acetate selectivity (85%) at 220 °C (Inui et al. 2004). This
reaction is still less studied to produce “green” ethyl acetate from renewable etha-
nol. Other catalysts such as PdO/SiO2 (Gaspar et al. 2009), Pd/ZnO, and Pd/SnO2
(Sánchez et al. 2005) are also employed for this process.
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Fig. 4.4 Biobutanol production from biomass-derived bioethanol via Guerbet reaction
4.5 Guerbet Reaction of Ethanol
n-Butanol (C4H9OH) is a primary and colorless alcohol and a refractive organic

liquid. It has low solubility in water (73 g/L at 25 °C), but it has high solubility in
acetone, ethyl ether, and ethanol. It has a high boiling point of 117.7 °C and low
melting point of −89.8 °C (Hahn et al. 2010). n-Butanol can be produced from etha-
nol by Guerbet reaction (Fig. 4.4) (Aitchison et al. 2016; Chakraborty et al. 2015;
Dowson et al. 2013; Earley et al. 2015; Ho et al. 2016; Koda et al. 2009; Kozlowski
and Davis 2013; Tsuchida et al. 2008). The reaction includes ethanol dehydrogena-
tion to acetaldehyde followed by aldol condensation of acetaldehyde to create cro-
tonaldehyde. Butanol is produced via the crotonaldehyde hydrogenation route
(Earley et al. 2015).
n-Butanol has many applications in foods and beverages as well as using it as a
fuel (Carvalho et al. 2012; Hahn et al. 2010). As a fuel, butanol has many advan-
tages in comparison to ethanol. For example, during combustion, butanol produces
higher energy than that of ethanol and it also absorbs lower water and is miscible
with gasoline better than ethanol (Carvalho et al. 2012; Dziugan et al. 2015; Earley
et al. 2015). Moreover, using n-butanol can take advantages of the available infra-
structure for the use of gasoline, e.g., pipeline for transportation and direct use in the
gasoline engine without modification (Nanda et al. 2017a).
Ethanol can be converted into butanol using both homogeneous and heteroge-
neous catalysts. There are many homogeneous catalysts including Ir- and Ru-based
catalysts (Aitchison et al. 2016; Chakraborty et al. 2015; Dowson et al. 2013; Tseng
et al. 2016; Wingad et al. 2016; Xie et al. 2016). Ruthenium pincer complexes cata-
lyst showed 68.3% of butanol selectivity at 66.9% ethanol conversion (Xie et al.
2016). However, the use of a homogeneous catalyst poses a catalyst recycle chal-
lenge. Solid-base metal oxides (Ndou 2003), acid-base bifunctional metal oxides
(Carvalho et al. 2012, 2013; Ramasamy et al. 2016), hydroxyapatite (Ogo et al.
2011, 2012; Tsuchida et al. 2006, 2008), basic zeolites (Yang and Meng 1993), and
transition metal compounds (Gines and Iglesia 1998) have been used for this
process.
For Guerbet reaction, effective catalysts are required to integrate multifunctional

active sites for hydrogenation, dehydrogenation, and aldol condensation. Alcohol
coupling systems commonly need basic materials such as alkali metal, hydroxide,
and solid base (Kozlowski and Davis 2013). Among them, alkali metals, which are
considered as highly active catalysts of alcohol coupling systems and their metal
doping, e.g., Cu or Ni, are capable of catalyzing hydrogenation and dehydrogena-
tion (Kozlowski and Davis 2013).
Hydrogenation step needs hydrogen from dehydrogenation step adsorbed on the
surface of catalysts and, likely, the hydrogen adsorbed from dehydration of ethanol
over acid sites. In addition, acid sites need to stabilize the reactive ethoxide and
enolate intermediates formed (Ho et al. 2016). Thus, the relationship between the
acidity and basicity of the catalyst is a key feature of this reaction. Currently,
K-CuMg5CeOx and Ca/P contain both acid and base properties and show high activ-
ity and butanol selectivity (>50%) in Guerbet reaction (Gines and Iglesia 1998;
Kozlowski and Davis 2013; Tsuchida et al. 2006, 2008).
4.6 Conclusions
This chapter provided an overview of all the current catalytic bioethanol conversion
processes into chemicals and fuels. Some of the processes have already been devel-
oped and commercialized such as ethylene and propylene productions from bio-
ethanol. Other potential processes are under research and development to optimize
economical and scientific catalysis. These processes provide a route in the produc-
tion of raw materials from bioethanol, a green chemical from biomass, in order to
reduce the dependency on fossil fuels. Additionally, the use of green bioethanol-
derived products in the petrochemical industries can mitigate the environmental
pollution and improve the quality of life.
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A Spotlight on Butanol and Propanol
as Next-Generation Synthetic Fuels 5
Sonil Nanda, Rachita Rana, Dai-Viet N. Vo,
Prakash K. Sarangi, Trinh Duy Nguyen, Ajay K. Dalai,
and Janusz A. Kozinski
Abstract
The exhaustive extraction and prodigious utilization of fossil fuels have led to the
large-scale increase in the emissions of greenhouse gases. In addition, the per
capita demand of petrochemical resources is escalating due to rapid industrial-
ization and the rising number of vehicles in the transportation sector. There is a
growing interest in the development of alternative fuels to reduce the carbon
footprint and air pollution caused by the fossil fuels. Biofuels produced from
plant residues are carbon neutral and can be produced through biomass-to-liquid
and biomass-to-gas conversion technologies. Bioethanol, biopropanol, and
biobutanol are some alcohol-based fuels and chemicals that have found multi-
farious industrial applications. Although bioethanol is blended with gasoline for
use as a transportation fuel, it is often criticized over food-versus-fuel debate
because of its raw materials being food crops such as corn, sugarcane, and other
grains. In addition, butanol and propanol have high potentials over ethanol in
replacing gasoline partially or completely due to their advanced fuel properties.
This chapter throws light on butanol and propanol as the next-generation syn-
thetic fuels. The aspects discussed in this chapter include their fuel chemistry as
S. Nanda (*) · R. Rana · A. K. Dalai

D.-V. N. Vo · T. D. Nguyen
Center of Excellence for Green Energy and Environmental Nanomaterials, Nguyễn Tất Thành
University, Hồ Chí Minh City, Vietnam
P. K. Sarangi
Directorate of Research, Central Agricultural University, Imphal, Manipur, India
J. A. Kozinski
Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, Canada

106 S. Nanda et al.
well as production technologies from petrochemicals and bio-based feedstocks.

The biotechnological developments in the fermentation of lignocellulosic bio-
mass to produce butanol and propanol are provided. The chapter concludes with
a note on industrial challenges and future prospects in employing butanol and
propanol as commercial biofuels and biochemicals.
Keywords
Biomass · Biofuels · Ethanol · Butanol · Propanol · Fermentation
5.1 Introduction
The worldwide consumption of petroleum and other liquid fossil fuels is expected
to escalate from 86 million BPD (barrels per day) in 2008 to 98 million BPD by
2020 and to 112 million BPD by 2035 (USEIA 2011). Figure 5.1 illustrates the
global trend for the consumption of fossil fuels in addition to the resulting CO2
emissions. The steady search for alternative fuels to replace gasoline has brought
two biofuels into the limelight, namely ethanol and butanol. The initial focus has
been on developing processes to extract the chemical energy stored in waste
plant residues and other organic wastes. Lignocellulosic feedstocks (e.g., agri-
cultural biomass and forestry refuse), dedicated energy crops, food waste, waste
cooking oil, municipal solid wastes, industrial effluents, cattle manure, and sew-
age sludge contain renewable carbon in the form of carbohydrates, fats, lipids,
Fig. 5.1 Worldwide fossil fuel consumption and CO2 emission over the years (Data Source:
USEIA 2016)
5 A Spotlight on Butanol and Propanol as Next-Generation Synthetic Fuels 107
proteins, lignin, sugars, etc., that can be converted to biofuels through thermo-
chemical and biochemical technologies (Nanda et al. 2013, 2015b, c, 2016b, c,
d, 2017b, 2018b, 2019; Gong et al. 2017a, b).
Lignocellulosic biomass can potentially lead to a scenario secured with sus-
tainable energy supply, reduced greenhouse gas emissions, and carbon-neutral
footprint (Nanda et al. 2016a, f; Okolie et al. 2019). These materials incorporate
agricultural refuse (e.g., straw, bagasse, and husk), energy crops (e.g., temperate
grasses and short rotation coppice), and forest residues (e.g., sawdust and infested
wood). These wastes are inexpensive resources found abundantly worldwide and
have the potential to supply continually alternative biofuels through a suitable
biomass-to-liquid and biomass-to-gas conversion technology. Furthermore, ligno-
cellulosic materials are nonedible and pose a negligible threat to agricultural lands
and diversion of food crops (e.g., barley, cassava, corn, potato, wheat, etc.) for
biorefining (Nanda et al. 2015a). As lignocellulosic biomass does not complete
with the food supply chain, they have broad potential in bioethanol and biobutanol
refineries. Figure 5.2 shows the recent trend for the generation of widely accepted
biofuels such as biodiesel and bioethanol.
The amount of lignocellulosic wastes generated globally every year is in the
order of billions of tons. The annual agricultural residues in the USA and Canada
are approximately 1147 and 18 million dry tons, respectively (Jones et al. 2007;
Gronowska et al. 2009; Mabee and Saddler 2010). The respective estimates for for-
est residues in the USA and Canada are more than 100 and 46 million dry tons
per annum (Gronowska et al. 2009; Mabee and Saddler 2010). The energy crop
harvests in the USA and Canada are around 3383 and 433 million dry tons,
Fig. 5.2 Worldwide biofuel production over the years (Data Source: USEIA 2016)
108 S. Nanda et al.
respectively (Jones et al. 2007; Yemshanov and McKenney 2008). From its annually
available residues from agriculture, forests, and energy crops, Canada has a poten-
tial to produce around 4.9, 13.8, and 117 billion liters of bioethanol, respectively
(Mabee and Saddler 2010). In the UK, almost 300 million tons of wastes are gener-
ated every year, which includes nearly 100 million tons of carbonaceous materials
and 14 million tons of crop and forest residues (KTN 2016). It is suggested that at
least 25 million tons of carbonaceous wastes could be extracted and converted to
five million tons of bioethanol with a value in the proximity of £2.4 billion.
Considering the fuel chemistry, aliphatic alcohols such as methanol, ethanol,
propanol, and butanol have the potential to be implemented as synthetic fuels in
the internal combustion engines (ICE). Currently, the dominant sources for bio-
ethanol are corn and sugarcane. The USA and Brazil together contribute to over
90% of the total bioethanol produced globally (Nanda et al. 2014b). Owing to the
fact that corn and sugarcane are food crops, bioethanol is often surmounted by
the food-versus-fuel debate (Graham-Rowe 2011). Although bioethanol produc-
tion is well established at metabolic and commercial scales, its increased depen-
dency on food crops and grains has raised concerns toward compromised food
security. Owing to this exploitation of food crops for fuel production, the result-
ing inflation in the food prices has been directing the global interest to utilizing
waste biomass for fuel production.
Lignocellulosic biomasses are being deployed as food crop surrogates and
second-generation feedstocks for bioethanol production. However, the development
of innovative methods for their efficient bioconversion is still a significant challenge
as lignocellulosic biomass requires size reduction, acid pretreatment, enzymatic
hydrolysis, delignification, and fermentation (Azargohar et al. 2013, 2018, 2019;
Nanda et al. 2018a). Hence, there has always been inquisitiveness to seek a superior
fuel with flexibility in raw material selection, better bioconversion, and striking fuel
features than ethanol.
Butanol seems to be a superior biofuel compared to ethanol (Dürre 2007; Nanda
et al. 2014a, 2017a). Therefore, developments in the technologies at its upstream
(bioconversion) and downstream (recovery) processing can significantly lead to its
cost-effective production from lignocellulosic biomass and other organic wastes.
The chief confinements in the butanol fermentation are low butanol titers, compro-
mised butanol tolerance by Clostridium, and expensive solvent recovery technolo-
gies. The low butanol productivity makes the solvent recovery process expensive
and energy-intensive.
Propanol can also be used as a replacement for gasoline although it is tradition-
ally used as an industrial chemical. As opposed to the other aliphatic alcohols,
namely ethanol, methanol, and butanol, propanol is not usually used as a synthetic
transportation fuels. Instead, propanol is a good source of hydrogen in direct liquid
fuel cell because it can generate a higher voltage compared to methanol (Qi et al.
2002). Propanol in its supercritical fluid state is used in the production of compos-
ites of carbon fibers, epoxy resins, and cellulose esters (Jiang et al. 2009). In the
automotive sector, 2-propanol is used as “gas dryer” to prevent the freezing of gaso-
line in the pipelines. Moreover, 2-propanol is used to deice the windshields of
vehicles in cold weather conditions. Propanol can also be produced using petro-
chemical and biological routes like ethanol and butanol. The beneficial fuel and
solventogenic properties of butanol and propanol are discussed in this chapter. In
addition, the production pathways of these advanced solvents through synthetic and
biochemical pathways are also comprehensively discussed.
5.2 ivergent Fuel Properties of Ethanol, Propanol,

D
and Butanol
Table 5.1 makes a comparison of the chemical properties and fuel attributes of etha-
nol, propanol, and butanol in contrast to gasoline. Butanol is an excellent fuel to
replace gasoline. Butanol has a greater energy content (29.2 MJ/L) than that of etha-
nol (21.2 MJ/L) and propanol (24 MJ/L). In addition, the heating value of butanol is
only 10% lower than that of gasoline (32.5 MJ/L). Ethanol has a higher oxygen
content of 35% compared to butanol, which contains 22% oxygen (Szulczyk 2010).
Moreover, the octane ratings of butanol and propanol are near to those of gasoline
indicating their suitability for engine fuel usage. A high octane number suggests
better compression of the fuel before its detonation. Motor octane number (MON)
and research octane number (RON) are measured by burning the fuel inside an ICE
at variable compression ratios as well as with 600 and 900 rpm engine speeds,
respectively (Dabelstein et al. 2007). The anti-knock index (AKI) or posted octane
Table 5.1 Comparison of the fuel properties of ethanol, butanol, and propanol with gasoline
Property Ethanol Propanol Butanol Gasoline
Chemical formula C2H5OH C3H7OH C4H9OH H, C4 to C12
Molecular weight (g/mol) 46.07 60.09 74.12 114.23
Density at 20 °C (g/m3) 0.789 0.803 0.81 0.7
Viscosity at 25 °C (mPa·s) 1.074 1.959 2.573 0.6
Flash point (°C) 17.2 22 35 −43
Autoignition temperature (°C) 365 371 343 280
Boiling point (°C) 78.4 97 117.4 125
Melting point (°C) −114 −126 −89.8 −56.6a
Specific gravity at 15.6 °C 0.79 0.82 0.81 0.72–0.78
Acidity (pKa) 15.9 16 16.1 –
Reid vapor pressure (psi) 2.3 0.29 0.3 8–15
Calorific value (MJ/L) 21.2 24 29.2 32.5
Lower heating value (MJ/kg) 26.7 30.6 33.1 43.45
Higher heating value (MJ/kg) 29.7 33.6 37.3 46.54
Research octane number (RON) 108.6 118 92 91–99
Motor octane number (MON) 89.7 98 71 81–89
Anti-knock index (AKI) 99.5 108 97 85–96
Air-to-fuel ratio 9 – 11.2 14.7
Solubility in water (%) at 25 °C 100 100 7.3 –
References: Nanda et al. (2017a), Sarangi and Nanda (2018), Biofuel.org.uk (2018)
110 S. Nanda et al.
number (PON) is calculated using the formula (RON + MON)/2. On the other hand,
air-to-fuel ratio, a factor to measure antipollution and fuel performance, is the mass
ratio of air and the fuel inside an ICE. The air-to-fuel ratio for fuel oil-fired furnaces
and natural gas-fired furnaces are in mass units and volume (or mole) units, respec-
tively. As opposed to ethanol, butanol has its air-to-fuel ratio of 11.2, which is much
closer to that of gasoline (14.7) (MacLean and Lave 2003).
Ethanol can potentially substitute 32% of global gasoline usage when used in
E85 (i.e., 15% gasoline and 85% ethanol) (Kim and Dale 2004). The ethanol-
gasoline blended fuel (known as gasohol) is necessary, as the current vehicular
engines are mechanical restrictions in using pure ethanol. Moreover, gasohol fuel is
mostly compactible for use in flexible-fuel vehicles or dual-fuel vehicles that have
ICE designed to operate on more than one fuel or gasoline-blended fuels. Butanol
has a tendency to be blended with gasoline at higher levels providing twice the car-
bon content in every gallon of the blended fuel. The regulations in the USA allow
butanol to be blended at 16% v/v with gasoline compared to 10% v/v blending for
ethanol (Butamax™ 2018). Furthermore, butanol can be mixed with gasoline in
flexible proportions allowing for implementation in current vehicular engines either
in pure or blended forms without the requirement of intensive vehicular engine
alteration (Qureshi et al. 2007).
Ethanol has a lower viscosity than butanol, which causes progressive wearing of
the ICE engine parts. It is often reported that higher alcohol additives provide
enhanced lubrication to reduce the chances of wear and tear of the mechanical com-
ponents inside the vehicular engine. The presence of greater levels of lower alcohols
(e.g., methanol and ethanol) in the blended fuel may lead to the corrosion to the ICE
engine components due to accumulated moisture content in the fuel and the organic
acids generated as the oxygenated compounds (Surisetty et al. 2011). Although
methanol and ethanol are soluble in water, they exhibit poor miscibility in gasoline.
Hence, phase separation problems are evitable when these alcohols are blended
with gasoline at higher concentrations. On the contrary, blending higher alcohols
such as propanol, butanol, and decanol with gasoline do not pose any phase separa-
tion problems due to their hygroscopic nature. As the length of the hydrocarbon
chain in higher alcohols increases, the solubility in water decreases. The decrease in
solubility becomes evident with four or higher carbons in the hydrocarbon chain.
The reason for lower solubility in the case of longer hydrocarbon chain is more
energy requirement to overcome the tightly packed hydrogen bonds between alco-
hol molecules as their size and mass increase. It is noteworthy to mention that the
hydrocarbon chain length also has biological effects.
Butanol has many attributes that are divergent than ethanol, a few of which
includes reduced solubility in water, less volatility, low flammability, low toxic-
ity, and less corrosiveness (Nanda et al. 2017a). Moreover, butanol is considered
as an excellent fuel extender because it contains only 22% oxygen compared to
ethanol’s oxygen content of 35%. In contrast to methanol, both propanol and
butanol are less toxic with low volatility. Another disadvantage of ethanol and
propanol is vapor lock of the engine due to their vapor pressures and low boiling
points compared to butanol and gasoline. The fuel chemistry of butanol is
comparable with gasoline, which has led to an increased global interest in its
fermentative production from renewable feedstocks and eventual end use as a
gasoline-blended fuel or substitute.
5.3 Petrochemical Routes for Butanol Production
The petrochemical production of butanol involves (Fig. 5.3) (a) oxo synthesis start-
ing from propylene, (b) Reppe synthesis, (c) aldol process or crotonaldehyde hydro-
genation, and (d) Guerbet reaction. Straight chain alcohols and branched alcohols
such as ethanol, propanol, and butanol can also be synthesized from syngas (i.e., H2
and CO) as the precursor through Fischer-Tropsch catalysis using nickel and iron-
based catalysts (Zhao et al. 2002). Oxo process (or hydroformylation) is an indus-
trial process where CO and H2 are supplemented to a C=C compound with
catalyst-substituted hydrocarbonyls (e.g., cobalt, rhodium, and ruthenium) (Lee
et al. 2008). Because of hydroformylation of propene, aldehydes (e.g., n-butanol
and isobutyraldehyde) are formed which then undergo catalytic hydrogenation to
produce butanol. Butanol is generated in variable isomeric ratios depending on
operating temperature, pressure, and catalyst. The oxo process operated at 1–5 MPa
with rhodium catalyst yields up to 95% n-butanol and 5% isobutanol (or 2-methyl-
1-propanol) (Uyttebroek et al. 2015). The conventional oxo process also leads to the
generation of n-butyraldehyde from propylene. n-Butyraldehyde is a precursor in
the production of 2-ethyl hexanol via aldol condensation as well as n-butanol.
Deoxygenation of butyraldehyde by ethanol results in butylenes, whereas its reduc-
tion without dehydration produces butanol. Acetone and butanol are conventional
solvents to synthesize isoprene rubber monomers, butadiene, and dimethyl butadi-
ene (Jones and Woods 1986).
Reppe synthesis deals with catalytic carbonylation of propene (or propylene)
at 100 °C under 0.5–2 MPa pressure involving the reaction between propene,
water, and CO to produce butanol (Lee et al. 2008). The catalyst used in the pro-
cess is usually a polynuclear iron carbonyl hydride or a tertiary ammonium salt.
n-Butanol and isobutanol are obtained in a ratio of 86:14 (Uyttebroek et al. 2015).
Although Reppe process results in preferable ratio of n-butanol-to-isobutanol
under mild reaction conditions, it is usually more successful than the oxo process
from the economic point of view.
Crotonaldehyde hydrogenation of acetaldehyde is another process to produce
butanol, which is comprised of several reactions such as aldol condensation,
dehydration, and hydrogenation (Lee et al. 2008). Although the process involves
alkali catalysts and petrochemical resources, it usually requires ambient tem-
perature and pressure. The dehydration step is prompted by acidification using
acetic acid or phosphoric acid followed by distillation. Copper catalysts are
required in the hydrogenation step that is executed in the gas or liquid phase.
Approximately 1350 kg of acetaldehyde can result in 1000 kg of n-butanol from
this process (Uyttebroek et al. 2015).
112 S. Nanda et al.
Fig. 5.3 Petrochemical routes for butanol production

The industrial Guerbet process involves the following main steps: (a) dehydroge-
nation of a primary alcohol, (b) base-catalyzed aldol-coupling reaction, and (c)
hydrogenation of α,β-unsaturated aldehyde (Chakraborty et al. 2015). The final step
leads to the uniting of the two primary alcohols to form a long-chain alcohol via the
“borrowed hydrogen” phenomenon that has no net loss of gaseous hydrogen.
Guerbet reaction allows facile C-C bonding with unreactive alcohols using ruthe-
nium or iridium catalysts (Aitchison et al. 2016). Guerbet process is performed
usually with long-chain primary alcohols, but utilizing ethanol as a substrate in the
reaction to produce butanol remains a challenge. These main limitations include the
dehydrogenation of ethanol, which is a thermodynamic challenge, as well as the
generation of undesired by-products resulting from the uncontrolled aldol reaction
due to the highly reactive acetaldehyde (Carlini et al. 2003).
5.4 Biological Route for Butanol Production
The microorganisms involved in ethanol or butanol production can be assessed in

terms of feedstock utilization, fermentation parameters (e.g., oxygen, pH, light,
temperature, feed concentration, residence time, etc.), nutritional requirements, and
bioreactor design. An ideal ethanol-producing microorganism should retain the fol-
lowing features (Dien et al. 2003):
1. Ethanol yields >90% of theoretical estimation

2. Ethanol productivity >1 g/L/h
3. Ethanol tolerance >40 g/L
4. Ability to grow in inexpensive and simple growth media
5. Growth requirements (e.g., pH, temperature, oxygen necessity, etc.) to retard the
occurrence of contaminants
6. Metabolic tolerance to inhibitors
7. Resistance to high temperatures and acidic pH
The preferred microorganisms for ethanol production include fungi and yeast.
Saccharomyces cerevisiae is the most popular industrial ethanol-producing fungi
because it demonstrates a high tolerance to ethanol and sustained growth in oxygen-
limiting fermentation conditions. However, S. cerevisiae lacks the natural potency
to ferment hemicellulose (pentose or C5 sugars), especially xylose (Ha et al. 2011).
Nevertheless, the enzyme xylose isomerase facilitates the conversion of xylose to
xylulose, which can be fermented to ethanol by S. cerevisiae. A few fungi having
the ability to ferment directly cellulose to ethanol include Aspergillus, Fusarium,
Monilia, Neurospora, Paecilomyces, Penicillium, Phanerochaete, Schizophyllumi,
Sclerotium, and Trichoderma (Duff and Murray 1996). A few fungi are exempted
from their inefficiency in xylose fermentation such as Aspergillus oryzae and
Trichoderma reesei. While Aspergillus oryzae degrades xylan by secreting
β-xylosidase, T. reesei degrades hemicellulose sugars by producing two endo-β-
xylanase enzymes, viz., xylanase I and xylanase II (Nanda et al. 2014a).
114 S. Nanda et al.
Some bacteria and actinomycetes investigated for the secretion of cellulase

enzymes for ethanol production include Bacillus, Bacteroides, Clostridium,
Cellulomonas, Ruminococcus, Thermomonospora, Streptomyces, Acetivibrio,
Erwinia, and Microbispora (Bisaria 1991; Prasad et al. 2007). The following fea-
tures should be present in bacteria to make them more effective compared to fungi
for ethanol production: (a) ethanol production reliably in large-scale bioreactors, (b)
less requirement of saccharifying enzymes, and (c) viability and stability of cells
during bulk fermentation. Anaerobic and thermophilic bacteria are beneficial over
the traditional ethanol-producing yeasts for their tendency to endure extreme tem-
peratures and utilize a broad spectrum of low-cost feedstocks. However, the low
ethanol resistance (<2% v/v) by most bacteria is a key constraint in the industrial
fermentation (Georgieva et al. 2007). Unlike ethanol production that is dominated
by aerobic spore-forming fungi (i.e., S. cerevisiae), butanol production is performed
almost exclusively by a consortium of bacteria that are obligate anaerobes, spore-
forming, and Gram-positive such as Clostridium spp. On the other hand, Clostridium
spp. are also robust in utilizing both hemicellulose (pentose or C5 sugars) and cel-
lulose (hexose or C6 sugars) unlike S. cerevisiae that flourishes only in utilizing
hexose sugars (Qureshi et al. 2007).
Butanol production is accomplished through acetone–butanol–ethanol (ABE)
fermentation by using a few responsible Clostridium spp., namely C. acetobutyli-
cum, C. beijerinckii, C. butylicum, C. saccharobutylicum, C. aurantibutyricum, C.
Fig. 5.4 Biological route for butanol production. (Adapted from Nanda et al. (2017a))
saccharoperbutylacetonicum, etc. Figure 5.4 represents the metabolic steps involved

in butanol fermentation involving Clostridium spp. Typically, ABE fermentation is
carried out under anaerobic conditions at 35 °C for 36–72 h to produce a total sol-
vent (acetone, butanol, and ethanol) level up to 20–25 g/L (Qureshi and Ezeji 2008).
The ABE fermentation involves acidogenic (or acid producing) and solventogenic
(or solvent producing) phases. The acidogenic phase results in the production of
acids such as acetic acid and butyric acid, whereas solventogenic phase leads to the
generation of acetone, butanol, and ethanol. The ABE fermentation progresses with
the involvement of biosynthetic enzymes, especially aldehyde/alcohol dehydroge-
nase, acetoacetyl-CoA thiolase, 3-hydroxybutyryl-CoA dehydrogenase, butyryl-
CoA dehydrogenase, crotonase, and crotonyl-CoA. The characteristic fractions of
acetone, butanol, and ethanol obtained through ABE fermentation are in the ratio of
3:6:1 (Jones and Woods 1986).
The current butanol recovery technologies include distillation, adsorption,
liquid-liquid extraction, pervaporation, perstraction, gas stripping, and supercritical
fluid extraction (Ezeji et al. 2007). While adsorption uses molecular sieves and res-
ins to separate butanol, the gas stripping recycles the fermentation gases (i.e., CO2
and H2) to create butanol vapors for subsequent purification by condensation. Gas
stripping lowers cell toxicity and results in high substrate utilization. Liquid-liquid
extraction uses an extractant to separate the products based on their variable distri-
bution coefficients. Perstraction upgrades liquid-liquid extraction by implementing
permeable membrane to separate the cell culture from the extracting solvent, thereby
preventing the issues of toxicity and emulsion formation. Pervaporation uses the
principle of membrane permeation using nonporous membrane followed by evapo-
ration to dehydrate the organic solvent and separate the products. Further improve-
ments in butanol recovery technologies could expedite its large-scale production as
a flexible fuel or drop-in fuel for use in the current vehicular engines without any
significant modification.
5.5 Petrochemical Routes for Propanol Production
Apart from being the main source of vehicular fuels, petrochemical industries are
also the source of several organic solvents. Petrochemical resources such as natural
gas and crude oil are the main source of these organic solvents. Various organic frac-
tions and aromatic compounds that are produced during the reforming or catalytic
cracking of naphtha finally result in the formation of aliphatic hydrocarbons. To
produce oxygenated solvents, certain key ingredients are required such as ethylene,
propylene, butylene, and methane (Wypych 2001). Capello et al. (2009) performed
life cycle analysis and environmental risk assessment for the technologies relating
to the production of significant organic solvents including propanol from petro-
chemical feedstocks. The synthesis of industrial solvents (including propanol) from
petrochemical resources can be represented through the following four routes as
reported in the literature (Chauvel and Lefebre 1989a, b; Wells 1999). These routes
116 S. Nanda et al.
differ based on their key process, unit operation, and precursor materials. The four
major solvent production pathways can be characterized as follows:
1. Methanol pathway: This pathway uses methanol as the precursor that is pro-
duced from natural gas through catalytic gas-to-liquid conversion technology.
Acetic acid, formaldehyde, and tetrahydrofuran are some of the chief solvents
obtained through this route.
2. Steam cracking or naphtha pathway: This pathway involves steam cracking of
naphtha obtained from crude oil to produce a broad spectrum of alkanes and
alkenes. Aliphatic alcohols including ethanol, propanol, and butanol are obtained
along with certain intermediate by-products, which can be processed to derive
acetates.
3. Benzene-toluene-xylene (BTX) pathway: In this pathway, naphtha is derived
from BTX reformates and further extracted through molecular sieves. After
extraction, the recovered naphtha and its derivatives are used to produce alkanes
including hexanes and heptanes.
4. BTX splitting pathway: This pathway involves thermochemical and catalytic
splitting of BTX reformate and pyrolyzed gasoline to produce aromatic com-
pounds and organic solvents such as benzene, xylene, and toluene. The resulting
benzene, toluene, and intermediate by-products are treated to produce aldehydes
and organic solvents such as benzaldehyde, cyclohexane, and acetone.
The naphtha or steam cracking route is the most diversified. It accommodates a

wide variety of precursors as the raw materials to generate essential chemicals and
solvents including propene and ethane. The worldwide productions of propane and
ethane are 30 × 106 tons (Eisele and Killpack 2002) and 80 × 106 tons (Zimmermann
and Walzl 2002), respectively. Certain side reactions mark a low increase in the
cumulative energy demand (CED) per kg of the product because the subordinates
with CED values are needed for these reactions. A few of such reactions are (a)
hydrogenation to propanol, (b) methanol supplement to produce methyl tertiary
butyl ether (MTBE), and (c) esterification to generate isoamyl acetate, butyl acetate,
and isobutyl acetate. The processes resulting in greater fluctuations in CED are
hydroformylations for isoamyl alcohol, isobutanol, pentanol, and dioxane. For
hydroformylation process, the challenge in CED is due to the requirement of high
energy input and large quantities of precursors and syngas (Chauvel and Lefebre
1989a, b).
5.6 Biological Routes for Propanol Production
Propanol is commercially produced from petrochemical sources. The techniques

employed in propanol production from petrochemical sources are expensive and
environmentally unfriendly. In addition, with increasing stress on the petroleum
resources, the emphasis is now on the biological production of propanol from
renewable biomass. There is lack of information on responsible microorganisms
Fig. 5.5 Biological route for propanol production. (Adapted from Ammar et al. (2013))
that can be employed in the production of propanol in significant amounts (Janssen

2004). Clostridium spp. are found to produce smaller amounts of propanol from
threonine catabolism. Jang et al. (2012) have compiled propanol production from
carboxylic acids (propionic acid), hydroxy acids (3-hydroxypropionic acid and lac-
tic acid), diols (1,2-propandiol and 1,3-propandiol). and alcohols.
Propanol can be obtained through propionic acid fermentation using two main
Propionibacterium spp. such as P. acidipropionici and P. freudenreichii ssp. sher-
manii (Himmi et al. 2000; Eden et al. 2001; Liu et al. 2011). Reports suggest that an
overexpressed bifunctional aldehyde or alcohol dehydrogenase (adhE) can respec-
tively transform butyryl-CoA and acetyl-CoA to butanol and ethanol (Nair et al.
1994; Yu et al. 2011). Ammar et al. (2013) studied the possibility for synthesizing
n-propanol using propionyl-CoA as represented in Fig. 5.5. They investigated the
pairing of CoA with propionyl to produce n-propanol. Hence, a bifunctional adhE
gene cloned from Escherichia coli was expressed in P. freudenreichii. The produc-
tion of n-propanol from both glucose and glycerol was found along with the higher
rate of consumption of propionic acid by the adhE gene-expressing mutant. This
study was the first effort in the biosynthesis of n-propanol via genetically engi-
neered Propionibacterium.
Choi et al. (2012) engineered an E. coli strain to produce n-propanol under
anaerobic conditions. l-Threonine was found to be overproduced by the mutated E.
coli. The first step was to introduce feedback-resistant ilvA gene that encoded
l-threonine dehydratase with the deletion of all other genes that could compete for
the metabolic pathways. Additionally, the overexpression of cimA gene and ackA
118 S. Nanda et al.
gene was engineered. cimA gene encodes citramalate synthase, whereas ackA gene
encodes acetate kinase A and propionate kinase II. Genetic engineering was also
performed to introduce the altered adhE gene and delete rpoS gene. adhE gene is
responsible for encoding aerobically functional AdhE, whereas rpoS gene encodes
the sigma factor found in the stationary growth phase. The mutant strain produced
through the fed-batch culture harbored pTacDA-tac-adhEmut and pBRthrABC-tac-
cimA-tac-ackA genes. This resulted in n-propanol productivity of 0.144 g/L/h and
yield of 0.107 g/g from 100 g/L of glucose. Similarly, n-propanol productivity of
0.083 g/L/h and yield of 0.259 g/g were obtained from 40 g/L of glycerol. In another
study, Zhang and Yang (2009) reported that succinate is used to produce propionic
acid during glycerol fermentation. Genetically engineered P. acidipropionici was
found to produce 106 g/L of propionic acid with a productivity of 0.035 g/L/h and
yield of 0.56 g/g from glycerol.
Higher alcohols can also be produced by using keto-acid intermediates that are
present in the naturally occurring amino acid pathways in the microorganisms. Shen
and Liao (2008) engineered an E. coli strain to produce n-butanol and n-propanol
from glucose. The mechanism included the conversion of glucose to 2-ketobutyrate.
The biosynthesis of isoleucine usually results in the formation of 2-ketobutyrate as
an intermediate product, which is further transformed to either n-butanol or n-
propanol. The reaction for propanol is catalyzed using heterologous decarboxylase
and dehydrogenase. In contrast, butanol is catalyzed to produce amino acid norva-
line. The competing pathways were eliminated, and the amino acid biosynthesis
was deregulated to improve the yields of n-butanol and n-propanol. The final strain
showed the production of 2 g/L of total solvents with a ratio of 1:1 for propanol and
butanol.
There can be several metabolic pathways for synthesizing the desired solvent
product. Both natural evolution and synthetic biology pathways exhibit distinct
properties that are specific for the wild-type and engineered microorganisms. Shen
and Liao (2013) illustrated the principle of synergy between two varying methods
of n-propanol synthesis by E. coli. The studies on the metabolic pathways by the
host gene removal showed their discrete traits with the relevance of tricarboxylic
acid cycle for threonine pathways. In contrast, citramalate pathway was found inde-
pendent of the tricarboxylic acid cycle. Both the pathways were found to be comple-
mentary in driving the energy requirements in the host microorganisms. The
experiments on solvent production strengthened the synergistic impacts predicted
by the yield model. Thus, this study successfully incorporated the synergy into
model design principles of engineered metabolic pathways of the microorganisms
to enhance the product yield.
5.7 Challenges and Future Perspectives
Butanol can be produced both through petrochemical and biological means.

Uyttebroek et al. (2015) performed a sustainability metric analysis of butanol
derived from petrochemical and biological routes. Petrochemical routes (92%) for
butanol synthesis demonstrate a higher material efficiency compared to fermenta-

tive route (27–42%). The material efficiency in this study was calculated as the total
weight of valuable products divided by the total weight of valuable products and
waste residues (Sheldon and Sanders 2015). The E-factor is a critical concept in
estimating the material efficiency. About 0.6 kg of propene is consumed to produce
nearly 1.0 kg of butanol, referring to 95% butanol yield in pure form (Uyttebroek
et al. 2015). This resulted in an E-factor of 0.1 with a greater material efficiency of
92% considering the exclusion of water used in the petrochemical process. On the
contrary, an E-factor of 3.7 and a lower material efficiency of 21% were reported for
the bio-based process considering butanol as the only product of interest. However,
when butanol was the main product along with acetone and ethanol as the by-
products, the E-factor decreased to 2.7 and the material efficiency slightly increased
to 27%. The E-factor further decreased to 1.4 and the material efficiency increased
to 42% when biomass fiber and residual proteins were considered as the useful
products along with butanol, ethanol, and acetone. Petrochemical route for butanol
production typically results in more butanol yields and less by-product formation
leading to higher material efficiency. On the contrary, fermentative butanol produc-
tion results in lower butanol yields due to the by-products such as acetone, ethanol,
acetic acid, and butyric acid. Therefore, finding value for the by-products of ABE
fermentation can decrease the E-factor and increase the material efficiency in the
biological butanol production route.
Petrochemical routes (69 GJ/ton) are also less energy-intensive than fermenta-
tive route (116 GJ/ton) (Uyttebroek et al. 2015). This makes the fermentative route
(1041 €/ton) relatively expensive than petrochemical routes (915 €/ton). In contrast
to a fermentative route that has a land use requirement of 0.29 ha/ton, petrochemical
routes predominantly rely on petroleum supply. Regardless of the lower energy and
cost requirement by petrochemical routes, the interest in biological butanol produc-
tion is gaining momentum because of the volatility of gasoline and other fossil fuel
supplies, their increasing prices, and legislations restricting their future usage.
As discussed earlier, butanol production through ABE fermentation has many
limitations such as butanol toxicity, low butanol yields, and challenges in butanol
recovery and bacteriophage contamination. The challenges and potential solutions
during fermentative butanol production are summarized in Table 5.2. Butanol-
producing Clostridium spp. can barely tolerate butanol concentrations of 2% in the
fermentation medium, which results in solvent toxicity and ceasing of microbial
fermentation (Jones and Woods 1986). Although ethanol initiation begins at 24 g/L,
Saccharomyces cerevisiae can tolerate up to 90 g/L of ethanol during fermentation
(Ghosh and Tyagi 1979). According to reports, naturally occurring Clostridium spp.
can tolerate 12–13 g/L of butanol (Dürre 2008; García et al. 2011). However, geneti-
cally modified Clostridium beijerinckii BA101 has been reported to withstand
19.6 g/L of butanol (Qureshi and Blaschek 1999). Butanol inhibits the clostridial
growth in the fermentation medium by dissolving the phospholipid layers present in
the cell membrane of the bacteria. The solubility of the alcohol in the bacterial cell
membrane affects its membrane fluidity, which increases with the growing chain
length of the hydrocarbon (Jones and Woods 1986). The low butanol titer levels in
120 S. Nanda et al.
Table 5.2 Challenges and possible solution for butanol biosynthesis

Biorefining stage Challenge Solution
Feedstock High feedstock Transition toward cheaper, renewable, and
selection (starch-based) cost and abundantly available lignocellulosic feedstocks
ethical issues of food (e.g., straw, wood and grasses)
versus fuel
Biomass Culture degeneration Removal of inhibitory by-products from the
pretreatment by inhibitory hydrolysate can make the process expensive.
(upstream intermediary Detoxifying or neutralizing the process using
processing) by-products generated techniques such as over-liming can reduce the
during biomass concentration of inhibitory compounds.
pretreatment Developing engineered microorganisms that can
resist the effects of inhibitory compounds
Fermentation Low butanol yield and Developing engineered microorganisms with
incomplete sugar improved butanol production. Process designing
conversion for continuous fermentation and in situ product
removal to enhance butanol tolerance, better
sugar conversion, and volumetric productivity
Formation of numerous Modification of knockout genes to delete the trait
fermentation for by-product formation in recombinant
by-products microorganisms. Shifting the carbon flow and
energy flux exclusively toward butanol
production pathway
Bacteriophage Good factory hygiene by using nonionic
contamination detergents and antibiotics. Developing strains less
vulnerable to bacteriophage infection
Product Expensive and Retrofitting or developing new recovery
recovery energy-intensive technologies for enhanced solvent recovery and
(downstream butanol recovery purification. Lowering of recovery cost and
processing) technologies energy consumption by increasing butanol titer
References: Green (2011), Dürre (2011)
the fermentation also make the butanol recovery process challenging, expensive,
and energy-intensive.
Similar to butanol production, fermentative propanol production is also chal-
lenging and expensive, which restricts from making it a common fuel. Since the
energy gains of propanol over ethanol are minimal, its industrial production and
commercial uses are demanding. The challenge remains in improving both butanol
and propanol yields from the fermentative processes. Therefore, the genetic engi-
neering manipulations in E. coli and Saccharomyces cerevisiae have been investi-
gated to enhance bioproduction of propanol (Shen and Liao 2008; Atsumi and Liao
2008; Matsuda et al. 2011; Choi et al. 2012). Propanol yields were reported to
increase up to 4 g/L and 10 g/L from glucose and glycerol, respectively, by employ-
ing metabolically engineering E. coli (Atsumi and Liao 2008; Shen and Liao 2008;
Choi et al. 2012).
Syngas fermentation is a hybrid technology that connects both the petrochemical
and biochemical solvent production processes (Nanda et al. 2016e). In this tech-
nique, suitable microorganisms are used to convert syngas (a mixture of H2 and CO)
produced from biomass gasification to yield solvents such as ethanol, butanol, and
traces of propanol (Wilkins and Atiyeh 2011). Syngas fermentation is at the verge
of commercialization to produce fuels and chemicals from syngas (Liu et al. 2014).
It is necessary to select a low-cost fermentation medium to make the process feasi-
ble. For example, replacement of corn steep liquor with yeast extract as the fermen-
tation medium using Alkalibaculum bacchi strain CP15 decreased the cost of
fermentation by 27% and resulted in 78% more ethanol. When a 7-L fermenter was
used for continuous fermentation, the ethanol yield was 6 g/L in yeast extract and
yeast extract-free media. When yeast extract was replaced with corn steep liquor,
the maximum yields of ethanol (8 g/L), n-propanol (6 g/L), and n-butanol (1 g/L)
were noticed. A. bacchi strain CP15 was not typical for n-butanol and n-propanol
production. Another 16S rRNA gene-based study showed that a mixture of
Alkalibaculum bacchi strain CP15 (56%) and Clostridium propionicum (34%) gave
better yields of higher alcohols such as propanol and butanol from syngas (Liu et al.
2014).
Recently, DuPont Tate & Lyle BioProducts has announced the expansion of their
biopropanol facility in Tennessee, USA, by increasing the production of
1,3-propandiol up to 35 million pounds per annum (DuPont Tate & Lyle Bio
Products, 2018). DuPont and British Petroleum have also collaborated to form
Butamax™ Advanced Biofuels, which intends to make biobutanol an inexpensive,
versatile, and flexible fuel for the motor vehicles (Butamax™ 2018). Furthermore,
recombinant DNA technology and metabolic engineering of butanol-producing
Clostridium have resulted in significant developments in ABE fermentation. A few
process improvements include (a) high cell growth, stability, and viability, (b) lower
chances of endospore formation by Clostridium, (c) high butanol selectivity and
tolerance, (d) tolerance to lower levels of oxygen during anaerobic fermentation,
and (e) utilization of a wide variety of feedstocks (Papoutsakis 2008).
5.8 Conclusions
There is a mounting interest worldwide to efficiently produce butanol and propanol

from inexpensive feedstocks as newer biofuels for use in the transportation sector.
Butanol overshadows ethanol with its progressive fuel properties and chemistry,
which are comparable to gasoline. Butanol production through ABE fermentation
involves the solventogenic activity of Clostridium spp., which yields three solvents,
namely acetone, butanol, and ethanol in the characteristic ratio of 3:6:1. However,
by-products such as acetic acid and butyric acid are also obtained from acidogenic
stage of ABE fermentation. As opposed to ethanol fermentation by yeast
Saccharomyces cerevisiae which can only ferment hexose sugars, ABE fermenta-
tion by Clostridium spp. is beneficial because the latter can ferment both pentose
and hexose sugars. However, ethanol fermentation is commercially viable due to
high yields and greater resistance of yeast to acidic pH and high levels of ethanol in
the fermentation. Furthermore, ABE fermentation has many shortcomings such as
low butanol yields due to clostridial inhibition to butanol even at low titer levels,
122 S. Nanda et al.
uncontrolled bacteriophage infection, premature seizure of the fermentation, and

expensive butanol recovery techniques.
On the other hand, propanol is also emerging as a new candidate in the biofuel
spectrum. Similar to ethanol and butanol, propanol can also be produced from pet-
rochemicals and bio-based feedstocks. However, the literature on propanol fermen-
tation is nascent at the current stage. Several factors such as research, development,
and innovation in the bioconversion technologies, upstream processing of feed-
stocks, effective pretreatment technology to recover maximum sugars, as well as
metabolic engineering of fermenting microorganisms can help determine the sus-
tainable production of butanol and propanol from waste biomass. The principal
focus should be on developing efficient biochemical technologies including genetic
and metabolic engineering of fermenting microorganisms for converting nonedible
plant residues and biogenic wastes to butanol and propanol, which can potentially
outshine the quintessential fossil fuels.
References
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renewed. ACS Catal 6:7125–7132
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Technological Advancements
in the Production and Application 6
of Biomethanol
Prakash K. Sarangi, Sonil Nanda, and Dai-Viet N. Vo
Abstract
There is a worldwide concern for the emission of greenhouse gases from the
overdependence and exploitation of fossil fuels. Several technological and indus-
trial infrastructures heavily rely on fossil fuel-based energy systems. There is a
paradigm shift in replacing fossil fuels with cleaner fuels derived from renewable
biomass due to their carbon neutrality, sustainability, and global acceptance.
Therefore, renewable energy sources are considered as alternative energy pool
for sustainable purposes. In this context, biomass is seen as a promising option
with great potential for the conversion to biofuels and biochemicals. Biomethanol
is one of such biochemicals, which can be produced from biomass and biogenic
wastes through thermochemical and biological routes. In this chapter, the indus-
trial applications and production pathways of biomethanol is comprehensively
discussed. The challenges and perspectives of several technologies used in bio-
methanol production are summarized.
Keywords
Biomethanol · Biomass · Biofuels · Biochemical · Methane · Hydrogen
P. K. Sarangi (*)
S. Nanda
D.-V. N. Vo

128 P. K. Sarangi et al.
6.1 Introduction
The rapid urbanization and infrastructural developments in automobile and indus-

trial sectors are continually increasing worldwide energy demands, which mostly
rely on fossil fuels. Excessive use of fossil fuels emit toxic pollutants and green-
house gases, thus causing global warming and ecological imbalance (Nanda et al.
2016c). Several environmental concerns such as pollution, energy shortages, and
global warming have led the researchers around the world to seek alternative energy
sources that are clean and carbon-neutral (Nanda et al. 2015).
Many biomass resources such as lignocellulosic biomass, municipal solid wastes,
industrial effluents, and cattle manure are utilized for bioenergy, biofuel, biochemi-
cal, and biomaterial production to have both economic and ecological benefits
(Nanda et al. 2013, 2018). Waste biomass and biogenic wastes can be converted to
biofuels and biochemicals through thermochemical (e.g., pyrolysis, gasification,
liquefaction, and carbonization) and biological (e.g., fermentation and anaerobic
digestion) conversion technologies (Nanda et al. 2014b, 2016b, 2017d). Specific to
the conversion technologies, different fuel products can be produced from waste
biomass, which include bio-oil, biodiesel, syngas, biohydrogen, bioethanol, biobu-
tanol, biomethanol, and biopropanol (Reddy et al. 2014, 2018; Nanda et al. 2014a,
2017a; Sarangi and Nanda 2018).
Methanol is a simple alcohol otherwise called as wood spirits, wood alcohol, or
methyl alcohol. It is a promising alcohol traditionally used as a platform chemical,
solvent, and recently as an alternative fuel. Different thermochemical and biochemi-
cal processes can be exploited for its production. Having myriad applications in
day-to-day life, the value chain of methanol has gained prominent dimensions
toward production of high-value chemicals and materials. Like ethanol, methanol is
colorless, flammable, and liquid at room temperature with a distinctive odor. Some
other characteristics of methanol are polar at room temperature, miscible with
water, petroleum, and organic compounds.
Methanol is obtained as a by-product of biodiesel refineries along with free fatty
acids, crude glycerol, wastewater, and alkali catalysts (Ortiz et al. 2011). Methanol
can undergo reforming reaction in supercritical water to produce hydrogen-rich
syngas (Van Bennekom et al. 2011 Reddy et al. 2016). There is wide array of feed-
stocks for the production of methanol, which includes natural gas, coal, and waste
biomass. The production of methanol from renewable biomass is regarded as one of
the renewable methods when compared to its production from natural gas. Presently,
one of the main routes of biomethanol production is through Fischer-Tropsch catal-
ysis from synthesis gas (Venvik and Yang 2017). In this chapter, different applica-
tions of biomethanol are extensively discussed along with alternative production
technologies from biomass and methane. The potential of different biomasses for
biomethanol production is also summarized.
6 Technological Advancements in the Production and Application of Biomethanol 129
Fig. 6.1 Applications of methanol in fuel and chemical industries
6.2 Industrial Applications of Methanol
Methanol has wide range of applications as far as energy and chemical industries
are concerned (Fig. 6.1). Methanol had received a great attention for supplementing
fuel oil in motor vehicles in the USA during the global fuel crisis in the 1970s.
Methanol is widely used in chemical industries, plastics, paints, and explosives. In
winter, methanol can be used as an antifreeze agent in pipelines and windshield
washer fluids in vehicles. Thus, a wide range of applications of methanol has been
detected from simple chemical industries to novel applications like energy, trans-
portation, and fuel cells.
Methanol has several important fuel applications as mentioned below:
1. Used as transportation fuel

2. Blending with petroleum
3. Converted into dimethyl ether (DME) for use as diesel alternative
4. Fuel cell application to generate electricity
5. Used in transesterification to produces biodiesel
Table 6.1 makes a comparison of the fuel properties of methanol along with
other alcohol and hydrocarbon fuels. The major application of methanol has been
recognized in transportation sector due to its sustainability, carbon neutrality, and
cost-effectiveness compared to other fuels. The favorable combustion characteris-
tics of methanol can help in increasing the engine performance and efficiencies
when compared to gasoline (Bromberg and Cheng 2010). Another advantage of
methanol over petroleum-based fuels is its environmentally benign nature and
biodegradability (Malcolm 1999).
Table 6.1 Comparison of fuel properties of methanol with other fuels

Characteristic Methanol Gasoline Ethanol Hydrogen Methane Butanol
Formula CH3OH H, CH3CH2OH H2 CH4 C4H9OH
C4-C12
Molecular weight 32.04 100–105 46.1 2.02 16.04 74.1
(kg/kmol)
Air/fuel ratio 6.5 14.6 9.0 34.3 17.2 11.2
Autoignition 435 280 365 585 540 343
temperature (°C)
Boiling point (°C) 65 32–210 78 −253 −162 118
Flash point (°C) 11 −43 13 <−253 −188 28. 9
Energy density (MJ/ 19.6 44.5 26.9 120–142 50–55.5 33.1
kg)
Higher heating value 20 47.5 29.7 141.9 55.5 37.3
(kJ/g)
Research octane 136 91–99 129 >130 120 96
number
Viscosity at 25 °C 0.54 0.6 1.07 0.009 0.011 2.6
(mPa·s)
References: MacLean and Lave (2003), Dürre (2007), Lee et al. (2008), Szulczyk (2010), Surisetty
et al. (2011), Sarangi and Nanda (2018)
As methanol burns at a low temperature, it is superior to that of gasoline as far as

transportation sector is concerned (Adamson and Pearson 2000). There is low risk
of explosion due to low volatility nature of methanol. Furthermore, transportation of
methanol is very easy in its liquid form, which is superior to other gaseous fuels
such as natural gas and hydrogen. Its volumetric energy content is less than that of
gasoline, thereby requiring nominal changes for fuel distribution purposes. As far as
fuel parameters are concerned, it has greater octane number than gasoline (Fatih
et al. 2011). Being an attractive fuel substitute, it is used as a blending fuel with
gasoline in M85 (85% methanol and 15% unleaded gasoline), which does not need
any kind of technical modifications to the engines (Yanju et al. 2008). Thus, metha-
nol is a promising alternative for high-compression engine applications with low
cost and increased power.
Biomethanol has the potential for power generation (Suntana et al. 2009).
Methanol is regarded as a clean and efficient substitute for gas turbines and can be
used in power industries (Galindo and Badr 2007). Methanol shows a wide range
of downstream applications like fuel cell-powered vehicles due to easily degrad-
able to CO2 and H2 in the presence of steam. Methanol is also focused as a liquid
hydrogen carrier and as a hydrogen storage compound. In addition to chemicals
and automobile fuels, methanol acts as the substrate for production of biodiesel
through transesterification. A wide variety of chemicals is also produced from
methanol like acetic acid formaldehyde, methyl tertiary butyl ether (MTBE), and
dimethyl ether (DME). In addition, methanol acts as an anti-frost agent and
organic solvent (Ptasinski et al. 2002).
Fig. 6.2 Major sources of production and applications of methanol
About 0.19 tons of biomethanol was produced per ton of fossil fuel, resulting in
a reduction of 0.42 MT of CO2 emissions annually (Ptasinski et al. 2002). Although
methanol, ethanol, and dimethyl ether are alternative fuels, major advantages of
methanol have been detected in higher CO2 reduction (Leduc et al. 2010). As far as
environmental threats are concerned, CO2 recycling is necessary for its reduction in
atmospheric concentration. Hence, the production of methanol from waste CO2 is
another way of reducing greenhouse gases from the atmosphere. Methanol is pro-
duced using CO2 from flue gas and H2 through CO2 reforming or Fischer-Tropsch
synthesis (Treacy and Ross 2004; Singh et al. 2018). Therefore, methanol can be
considered as a suitable substrate for the production of fuel, chemical, and energy
for future generations. A wide array of sources from which methanol can be pro-
duced and applied in various sectors as shown in Fig. 6.2.
6.3 Thermochemical Production of Biomethanol
The production of methanol from biomass can be possible by two important meth-
ods such as thermochemical and biological process (Fig. 6.3). The thermochemical
route involves high temperatures and pressures to produce synthesis gas (syngas)
from biomass through gasification, which includes CO, CO2, H2, and CH4 (Nanda
et al. 2017b; Azargohar et al. 2019; Okolie et al. 2019). The conditioning of syngas
can help to remove many impurities like tars and methane, thereby adjusting the
ratio of H2 to CO up to a level of 2:l. Fischer-Tropsch catalysis or reforming process
involves catalytic reaction of syngas over a suitable metal catalyst at high tempera-
tures and pressure to produce methanol.
Depending on the gasifier, biomass is crushed and dried to reduce the moisture
content to less than 10 wt%. Biomass is dried using hot flue gas or steam. Biomass
Fig. 6.3 Production of methanol by thermochemical and biochemical routes
is converted to produce a gaseous mixture of CO, CO2, H2, H2O, and light hydrocar-
bons through gasification and steam reforming. Steam reforming is a process for the
production of synthesis gas from natural gas to produce CO and H2 through nickel
or other suitable metal catalysts at high temperatures (Katofsky 1993). The synthe-
sis gas containing H2, CH4, and other hydrocarbons accounts for a vital part to
determine the heating value of the gas. Autothermal reforming (ATR) facilitates
partial oxidation followed by steam reforming (Nanda et al. 2017c). The shift of
energy value of CO to H2 can be performed by water-gas shift reaction (Eq. 6.4).
CH 4 + H 2 O → CO + 3H 2 (6.1)
C2 H 4 + 2H 2 O → 2CO + 4H 2 (6.2)
C2 H 6 + 2H 2 O → 2CO + 5H 2 (6.3)
CO + H 2 O ↔ CO2 + H 2 (6.4)
The presence of considerable amount of CO2 in the synthesis gas can be removed,
which is increased after reforming method. To achieve the proper value in the ratio
(H2 + CO2)/(CO + CO2) for methanol production, some amount of CO2 can be
removed. There are various types of techniques for removal of CO2 such as physical
and chemical processes. The most common method commercially proven is the
chemical absorption using amines. Methanol synthesis takes places through the
hydrogenation of CO and CO2 over a suitable catalyst such as copper oxide, zinc
oxide, or chromium oxide.
CO + 2H 2 ↔ CH 3 OH (6.5)
CO2 + 3H 2 ↔ CH 3 OH + H 2 O (6.6)
Methane, which is a major component of natural gas, is considered as a next-

generation carbon feedstock (Hwang et al. 2014). Moreover, biomethane can be
produced through anaerobic digestion of organic wastes by using methanogenic
bacteria. Methane is produced from agricultural activities like enteric fermentation
and rice cultivation (Environmental Protection Agency 2013). Nevertheless, CH4 is
a potent greenhouse gas, which has global warming potential nearly 25 times greater
than CO2 (Nanda et al. 2016c). The anthropogenic share of CH4 emission was esti-
mated to be 481 billion m3 in 2010, which is almost equivalent to the global warm-
ing potential of 6867 Mt of CO2 (Environmental Protection Agency 2013).
There is much potential for the conversion of methane to methanol. Due to the
inert and saturated nature of methane, high temperature and high pressure are
employed for its conversion into methanol. Different products such as formalde-
hyde, formic acid, CO, and CO2 are also formed during the process of controlled
oxidative conversion of methane to methanol (Gesser et al. 1985). A single-step
process involving the oxidation of methane to methanol has shown as the direct way
of conversion. This process is an exothermic reaction, thereby avoiding the syngas
formation step (Bjorck et al. 2018).
The dissociation energy of C–H bond in methane (440 kJ/mol) is greater than
that of methanol (393 kJ/mol). There is also a two-step process in the conversion of
methane to methanol through which methane is first converted to syngas through
steam reforming and the second step involves catalytic synthesis of methanol. The
overall process for methanol production from natural gas or syngas is an endother-
mic reaction. The first step toward the conversion of CO and H2 is mostly energy-
intensive step that operates at very high temperature about 900 °C and pressures of
3 MPa (Wood et al. 2012). Naqvi et al. (2012) demonstrated methanol production
through gasification of black liquor, thereby proving CO2 as the potential substrate
for biomethanol industries by reduction process.
According to Hamelinck and Faaij (2002), the production of methanol is achieved
from biomass with a range between 54% and 58% of the net higher heating value
(HHV) energy efficiency. During their investigations, they detected the HHV energy
efficiency is about 55%. On the other hand, Williams et al. (1995) reported the range
for HHV energy efficiencies to be between 56.6% and 67.7% depending on differ-
ent gasification technologies. Isaksson et al. (2012) found the net HHV energy effi-
ciencies of 51%. The thermal efficiency is the ratio between the energy content of
the methanol on HHV basis to the sum of energy content of all primary energy input
sources including biomass, electricity, and heat.
Fig. 6.4 A simplified route for biomethanol production from biomass
6.4 Biological Production of Biomethanol
The production of biomethanol is achieved via anaerobic metabolism by using sev-

eral methanotrophic bacteria. During ethanol fermentation process, methanol is also
formed as a by-product. The lignocellulosic biomass containing cellulose, hemicel-
luloses, and lignin can be used for the conversion to a wide range of chemicals and
fuels (Nanda et al. 2016a). Lignocellulosic biomass including agricultural crop resi-
dues and forestry biomass contain hexose and pentose sugars, which can be extracted
through a suitable physical, chemical, or biological pretreatment for conversion to
alcohol-based biofuels (Sarangi and Nanda 2019). By avoiding the final step (i.e.,
distillation), crude methanol with about 80% purity is obtained. Being an intermedi-
ate grade product, the major application of such crude methanol is found as a marine
fuel (Brynolf et al. 2014; Winnes et al. 2015). A simplified thermochemical version
of biomass conversion into biomethanol is shown in Fig. 6.4.
Nakagawa et al. (2007) reported methanol yields of 55%, 36%, and 39% from
rice bran, rice straw, and rice husks, respectively. According to the experiments
conducted by Chia (2011), the productions of biomethanol from sugarcane bagasse
and corncob were 5.93% and 0.67%, respectively. Other organic residues that have
demonstrated the production of methanol are animal and livestock manure (Weimer
et al. 1996), industrial effluents and sewage sludge (Caballero et al. 1997), and
municipal solid wastes (Bhattacharyya et al. 2008). The production of methanol is
possible by the degradation of methyl esters. The conversion of pectin releases
uronic acid, which helps in the formation of methanol by the combination of
methoxyl group of uronic acid with ether (Bhattacharyya et al. 2008).
The potential of methanotrophic bacteria such as Bacillus methanicus has been
focused for the conversion of methane as a sole source of carbon and energy to
Fig. 6.5 Conversion of methane to methanol by methanotrophic bacteria
methanol by partial oxidation process with efficient and high conversion rate
(Bender and Conrad 1992; Hanson and Hanson 1996). The biocatalytic action of
methanotrophic bacteria helps in conversion of methane to methanol. These
methane-oxidizing bacteria are naturally present in soil, swamps, rivers, oceans,
ponds, and sewage sludge representing nearly about up to 8% of the total heterotro-
phic population (Higgins et al. 1981). Methylosinus trichosporium is one of the
notable microorganisms responsible for biomethanol production (Mehta et al. 1987;
Sugimori et al. 1995; Takeguchi et al. 1997; Xin et al. 2009a, b).
There are two categories of methanotrophic microorganisms, especially low
affinity and high affinity. The low-affinity methanotrophic bacteria have the poten-
tial to degrade methane at a higher concentrations level (i.e., >40 ppm). These are
generally found in soils having high methane concentrations. On the other hand, the
high-affinity methanotrophs use low concentration of methane (i.e., ~2 ppm). The
biocatalytic function of methane monooxygenase (MMO) enzymes helps in the
conversion of methane into methanol through oxidation process (Fig. 6.5). Two
forms of MMO have been detected in methanotrophs such as soluble cytoplasmic
form (sMMO) and particulate membrane-bound form (pMMO). The conversion
processes of methanol take place as follows (Hanson and Hanson 1996; Xin et al.
2009a, b):
1. Oxidation of methanol to formaldehyde by methanol dehydrogenase (MDH)

2. Conversion of formaldehyde to formic acid by formaldehyde dehydrogenase
(FADH)
3. Conversion of formic acid to CO2 by formate dehydrogenase (FDH)
6.5 Conclusions
As the energy security and environmental sustainability are concerned, waste bio-
mass is the potential alternative for biofuel and biochemical production. The pro-
duction of biomethanol from renewable waste materials has potential applications
in automobile and industrial sectors supplying fuel and energy. Depending on the
feedstock, methanol can be produced through a variety of thermochemical and bio-

logical conversion processes. In biological conversion pathway operated by metha-
notrophic bacteria, methanol is synthesized from methane. The production and
purity of syngas during biomethanol production have also effects toward the final
product recovery.
The process parameters such as mode of operation, biomass properties, and pro-
cess conditions have also great role toward the production rate of biomethanol.
Other reaction parameters like temperature, heating rate, conversion processes, par-
ticle size, and residence time can also affect the final product recovery. Overall, the
economics of biomethanol not only depends on the production parameters and con-
ditions but also on the purity grade of the final product. Significant improvements in
the conversion process can result in the large-scale production of methanol for
applications in fuel and chemical industries.
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Biorefinery Approaches
for the Production of Fuels 7
and Chemicals from Lignocellulosic
and Algal Feedstocks
Venkateswara R. Naira, R. Mahesh, Suraj K. Panda,

and Soumen K. Maiti
Abstract
The fuels and chemicals produced from the fossil-derived petroleum are on the
verge of completion. As a result, petro-refinery-based commodity prices are ris-
ing despite their increasing demand. Moreover, the greenhouse gas emissions
from petro-based fuels are devastating to the environment. Thus, the concerns
over the search for alternative, renewable and green sources of fuels and platform
chemicals have been raised. Among the explored bio-based sources, the biorefin-
ery potential of lignocellulosic and algal feedstocks has been found to be the
most promising due to their sustainability and versatility of multi-product gen-
eration. This chapter reviews the biorefinery approaches in various thermochem-
ical and biological conversion routes of lignocellulosic and algal feedstocks for
co-producing biofuels and biochemicals that can be widely applied in the indus-
trial sectors like energy, food, pharmaceuticals, cosmetics and textiles. From lig-
nocellulosic biomass, the co-production technologies of chemicals and fuels via
lignin and sugar (C5 and C6) platforms have been focused. On the other hand, the
generation of bioactive components such as lipids, carbohydrates and proteins
from algae along with co-production of biofuels and biochemicals is also dis-
cussed. The utilization of recycle streams like crude glycerol and spent biomass
residues is emphasized in the algal biorefineries. Finally, the current industrial
scenarios of both lignocellulosic and algal biorefineries are outlined.
Keywords
Biorefinery · Lignocellulosic biomass · Algae · Biofuels · Biochemicals
V. R. Naira · R. Mahesh · S. K. Panda · S. K. Maiti (*)

Department of Biosciences and Bioengineering, Indian Institute of Technology Guwahati,
Guwahati, Assam, India

142 V. R. Naira et al.
7.1 Introduction
Energy is one of the driving forces to meet the various demands of human popula-
tion and technological advancements. Among various forms of energy, fossil fuels,
especially crude petroleum and diesel, fulfil the needs of automobile industry and
transportation. The rising prices, global energy crisis, depletion of fossil fuels, air
and water pollution, greenhouse gas emissions, ozone layer depletion and global
warming are some of the environmental concerns related to the exploiting usage of
fossil fuels (Nanda et al. 2016b). In such a scenario, the energy security and collec-
tive demands for the use of renewable and alternative sources of energy such as
biofuels (bioethanol, biodiesel and bio-oil) can be met by using lignocellulosic and
algal biomasses (Nanda et al. 2015). Apart from biofuel, these renewable feedstocks
can also be utilized for the production of biochemicals in an eco-friendly way via
several biorefinery approaches.
The major obstacle in lignocellulosic and algal biomass biorefinery is the diffi-
culty in the separation of value-added products without causing damage to the for-
mation of other products simultaneously. Concomitant synthesis of different
intracellular and extracellular product fractions in microbial cell factories would be
an excellent biorefinery outlook to reduce the upstream and downstream processing
costs. The synthesis of high-value products concurrently from biomass feedstocks
reduces the overall cost of their production and yields huge profits. Lignocellulosic
biomass and algal biomass can be subjected to different thermochemical (pyrolysis,
liquefaction and gasification) and biochemical processes (saccharification, fermen-
tation and anaerobic digestion) for the production of alternative fuels and high-
value by-products (Nanda et al. 2014).
Biorefinery is the sustainable processing of biomass into a spectrum of bio-based
products (e.g. food, feed, chemicals and materials) and bioenergy (e.g. biofuels,
power and/or heat) (Jong et al. 2012). The biorefinery concept can be comparable
with traditional crude petroleum oil refinery (Perez et al. 2017), except that the bio-
refinery involves the processing of biomass for biofuels and platform chemicals
unlike the crude petroleum in fossil fuels. Firstly, biofuels from the second-
generation (agricultural and woody biomass) and third-generation feedstocks
(microalgae) have been developed for replacing the fossil fuels partially or com-
pletely. However, the final price of biofuel could not compete with the existing
prices of fossil fuels due to the expensive upstream and downstream processing
involved in biomass conversion technologies.
The current cost of biodiesel production from 60% oil containing microalgae
(third-generation feedstock) is US$3.96–10.56 per L, which is nearly tenfold expen-
sive than soybean-derived biodiesel (a first-generation feedstock) (Kapoore et al.
2018). Hence, biorefinery concept is introduced into both second- and third-
generation biofuel platforms to produce value-added chemicals along with the
respective biofuel to compensate the high costs of biomass processing. For exam-
ple, when a lignocellulosic feedstock contains two-thirds of sugars (cellulose and
hemicellulose) and one-third of lignin, 75% of total sugars for ethanol and 25% of
sugars for platform chemicals are more economically viable than using all the
7 Biorefinery Approaches for the Production of Fuels and Chemicals… 143
sugars for ethanol (Yamakawa et al. 2018). Alongside the enhancement of product
scope, researchers are also working extensively on process design and engineering
for enhancing the net energy ratios. However, this chapter elucidates the recent
trends in the production of platform chemicals and biofuels from the biorefinery of
second- and third-generation feedstocks.
In this chapter, lignocellulosic wastes (second-generation feedstocks) and algae
(third-generation feedstocks) are discussed due to their high potential and versatility
in biorefinery towards the generation of biofuels and biochemicals. The conven-
tional biofuel production from high-cost starch-based food crops such as sugarcane
molasses and corn has raised global concerns for food security and economic viabil-
ity. Hence, the search for a cheaper alternative, that is agro-based feedstocks like
rice straw, wheat straw and sugarcane bagasse, has paved the way to explore ligno-
cellulosic biomass for second-generation biofuels production. Such feedstocks are
available in ample amounts and could be the sustainable resources for biofuels and
biochemicals production. The lignocellulosic biomass also constitutes bamboo,
wood from forestry wastes, municipal wastes, etc.
On the other hand, algal biomass production has also received a great interest as
the third-generation feedstock due to its high growth rates, usability of non-arable
lands and less intensive cultivation requirements (Chisti 2007). However, the bio-
fuel production has not yet fully commercialized from this feedstock as the net
energy ratios (NER) are relatively lower (Slade and Bauen 2013). Apart from solv-
ing the aspects of biomass production technologies, simultaneous generation of bio-
fuels and value-added co-products from microalgae via biorefinery concept can
greatly increases the net energy ratios by adding value to the final product ranges
(Chia et al. 2018).
7.2 iofuels and Platform Chemicals from Lignocellulosic

B
and Algal Biomasses
Lignocellulosic biomass can be valorized into a wide range of fuels and platform
chemicals that are extracted either from cellulose, hemicellulose or lignin fraction of
biomass (Fig. 7.1). Lignin can be transformed into value-added chemicals like ligno-
sulphonates, ferulic acid and vanillin which are applied as cement water reducer, bind-
ers dye dispersants, cosmetics, flavouring agents, etc. The cellulose/hemicellulose
part can be hydrolysed into sugars such as glucose and xylose, which are biochemi-
cally converted into a broad range of liquid biofuels (e.g. bioethanol and biobutanol),
solvents (e.g. acetone), organic acids (e.g. acetic acid, butyric acid and lactic acid for
pharmaceutical and cosmetic applications) and other alcoholic compounds (e.g. iso-
propanol, isobutanol, 1,3-propane diol, xylitol for food and precursors of high-value
industrial products). The hydrolysed sugars can also be converted into furfural,
5-hydroxymethylfurfural (HMF), levulinic acid, formic acid and 2,5-dimethyl furan
(DMF) via chemical synthesis for use as precursors for pesticides, textile dyes and
resin production. The residual bacterial and fungal biomasses used for saccharifica-
tion and fermentation of lignocellulosic biomasses can also be used for producing
144
Fig. 7.1 The scope for production of biofuels and biochemicals from lignocellulosic biomass and algae
V. R. Naira et al.
biopolymers like chitin, polyhydroxyalkanoates (PHA) and polyhydroxybutyrate

(PHB), which are used for the manufacturing of bioplastics.
Microalgae mainly offer a wide range of bioproducts that are derived from their
biomass directly by various downstream processing techniques. The scope of intra-
cellular product generation includes carbohydrates, proteins, vitamins, lipids, spe-
cific polypeptides, pigments, biopolymers and high-value fatty acids. Lipids are the
precursors for biodiesel production from the algae via transesterification process.
The proteins like phycoerythrin, phycocyanin, allophycocyanin and phycobilipro-
teins have been extracted from algal sources extensively for producing fluorescent
dyes and food pigments. Most valuable algae-derived pigments are carotenoids
(β-carotene), fucoxanthin and astaxanthin, widely reported as dyes in food indus-
tries. Vitamins of classes B, C and E are also identified in algae (Kapoore et al. 2018).
Some specific strains of cyanobacteria and green algae are capable of photobio-
logical evolution of hydrogen (a clean burning fuel) via biophotolysis of water. Some
industrial algal species have been reported to produce extracellular products such as
exopolysaccharides, extracellular proteins (e.g. exoenzymes, protease inhibitors and
phycoerythrin-like proteins), organic acids, extracellular lipids, extracellular phyto-
hormones and allelopathic chemicals which have a wide range of industrial applica-
tions in food, pharmaceuticals, cosmetics, textiles and detergent sectors.
7.3 Lignocellulosic Biorefineries
Lignocellulosic biomass is comprised of cellulose (30–35%) which is shielded by a

matrix of hemicellulose (25–30%) and embedded by branched structure of lignin
(15–20%) (Nanda et al. 2013). Cellulose is composed of microfibrils, which are
homopolysaccharides made up of glucose units linked by β-1,4-glycosidic bonds.
Hemicellulose is a branched structure mainly composed of C5 (pentose) sugars such
as xylose and arabinose and C6 (hexose) sugars such as glucose, mannose, galac-
tose, fructose and rhamnose. Lignin provides stiffness and rigidity to plant cell
walls. Lignin is mainly composed of phenolic compounds.
Lignocellulosic biomass is very rigid and compact in nature due to its complex
structure of cellulosic and hemicellulosic network embedded by the recalcitrant lig-
nin. Moreover, the biomass has to be refined into small particle size for enhancing
the homogeneity of subsequent biochemical and thermochemical conversion pro-
cesses. Hence, the mechanical methods such as chipping, milling and grinding are
used for reducing the particle size, cellulose crystallinity and degree of polymeriza-
tion while increasing the flow properties, surface area and porosity of biomass. The
commonly used milling methods are ball milling, knife milling, centrifugal milling
and vibratory milling.
The conversion of pre-processed lignocellulosic biomass into fuels and value-
added products in the biorefinery needs fractionation of biomass into component
lignin, hemicellulose and cellulose. The recalcitrance of lignin and shielding effects
of hemicellulose around the cellulose hinder the hydrolytic enzymes from penetrat-
ing the plant cell wall and producing fermentable sugars. Lignin can be removed by
treating lignocellulosic biomass with alkali reagents (e.g. hydroxyl derivatives of

sodium, potassium, calcium and ammonium salts) at ambient temperatures via
hydrothermal treatment typically at 15 psi and 121 °C for 10–30 min of holding
time. This treatment effectively degrades the lignin by breaking the side chains of
the glycosides and esters of lignocellulosic biomass (Durot et al. 2003). Some other
lignin-removal methods like ozonolysis, ionic liquid treatment (e.g. cholinium ionic
liquid), and ammonia fibre explosion (at 60–90 °C and 3 MPa for 30–60 min) have
also been reported (Kumar et al. 2009).
The lignin platform offers the production of various chemicals like syringic acid,
p-coumaric acid, caffeic acid, syringaldehyde, naphthalene, 4-hydroxybenzaldehyde,
4-hydroxybenzoic acid, methylnaphthalene, ferulic acid, methanol, benzoic acid, tere-
phthalic acid, eugenol and vanillin (Isikgor and Becer 2015). These chemicals have a
range of applications in pharmaceuticals, nutraceutical and cosmetic industries. For
example, ferulic acid is used as antioxidant in pharmaceuticals and cosmetic industries
and as preservative in nutraceutical industries for the stabilization of vitamins C and
E. Vanillin is also widely used as a flavouring agent and fragrant substances.
The fuel products of fermentation like bioethanol and biobutanol can be blended
with gasoline because of their high octane number, complete combustion, less green-
house gas emission characteristics, etc. The enzymatic products, e.g. cellulase enzymes,
can be widely used in detergent industry, textile and paper industries for bleaching and
deinking, and cellulosic biofuel production (Ravindran and Jaiswal 2016).
7.3.1 Pretreatment of Lignocellulosic Biomass
The above-mentioned pretreatments of lignocellulosic biomass is effective for lig-

nin removal but not for the extraction of hemicellulose and cellulose. Hence, the
delignified biomass has to be treated by various hydrothermal processes like steam
explosion, dilute acid pretreatment (e.g. H2SO4, HCl and H3PO4) and ammonia per-
colation method. The steam explosion process is usually carried out with super-
saturated steam at temperatures of 180–240 °C and pressures of 1–3.5 MPa with a
biomass loading of 10–15%. The dilute acid pretreatment is carried out with an acid
concentration of 1–4% and a temperature of 120 °C for 10–60 min with 10–15% of
biomass loading. The ammonia percolation method is carried out with liquid ammo-
nia (5–15% v/v) at temperatures of 140–200 °C with biomass loading of 10–30%.
Most of these pretreatment methods generate certain amount of by-products due
to sugar degradation which generally inhibit the growth of fermenting microorgan-
ism or limit the production of end products. For example, the degradation of pentose
sugar such as xylose from hemicellulose fraction forms furfural. Similarly, glucose
also degrades into 5-hydroxymethylfurfural (HMF). Under severe pretreatment
conditions (e.g. long reaction time, high temperature or high acid concentrations),
HMF further degrades into levulinic and formic acid. During pretreatment, some
other microbial growth inhibitory compounds like acetic acid from hemicellulose
fraction and phenolic compounds such as ferulic acid from lignin fraction are also
released. Thus, the detoxification steps like charcoal adsorption, solvent-solvent
extraction, nanofiltration have to be applied prior to the fermentative process

(Jönsson and Martín 2016). These inhibitors after recovery from hydrolysate can be
used as value-added chemicals. Some value-added products such as sugar acid (e.g.
galacturonic acid and glucuronic acid) and oligosaccharides are also released during
pretreatment. The pretreated lignocellulosic biomass undergoes several conversion
steps for the biorefinery production of liquid fuels and platform chemicals (Fig. 7.2).
The pretreated lignocellulosic biomass can be directly utilized for enzymatic
saccharification and fermentation. This step has certain disadvantages such as the
presence of inhibitors that hinder the fermentation process and the productivity of
end products. The pretreated slurry can be separated into solid cellulose fraction
and liquid hydrolysate fraction in which the solid part is utilized for end-product
generation. This has several advantages such as the availability of high sugar con-
tent and absence of inhibitors. The fractionated hemicellulosic hydrolysate having
inhibitory compounds has a great potential of generating value-added products
via direct fermentation or chemical synthesis as it consists of soluble pentose and
hexose sugars.
7.3.2 Enzymatic Saccharification
After biomass pretreatment, the recovered pretreated biomass slurry or solid cellu-
lose fraction is allowed for enzymatic degradation as the high crystallinity of cel-
lulose resists the chemical degradation. Hence, the enzymatic hydrolysis of cellulose
into glucose monomeric units can be carried out by cellulase enzymes. Cellulase is
an enzyme complex mainly consisting of endoglucanase, exoglucanase and
β-glucosidase enzymes. They act synergistically for the degradation of cellulose.
Endoglucanases act on the random interior sections of cellulosic chain to break into
smaller fragments, while exoglucanases act at the ends of the fragments to catalyse
and produce disaccharides like cellobioses. Cellobioses are subsequently degraded
into glucose units by β-glucosidase enzyme (Zhang and Lynd 2004). In the whole
process, the effective utilization of sugar platform can be established by using suit-
able fermenting strains, low-cost cellulase enzymes and an efficient process design
for the biochemical conversion of both pentose and hexose sugar platforms into
fuels and chemicals. The different modes of fermentation process of pretreated lig-
nocellulosic biomass have been discussed below. Different feedstocks, products and
microorganisms used for the saccharification of lignocellulosic biomass are
described in Table 7.1.
The conventional processes of cellulosic fermentation have been carried out by
separate hydrolysis and fermentation (SHF) where initially the enzymatic hydroly-
sis of cellulose fraction takes place in one reactor vessel using commercial cellulose
enzyme followed by fermentation process of the resulted sugars in the second ves-
sel. However, the disadvantages of SHF are requirement of several steps and inhibi-
tion of cellulase enzymes by end products, which make the process expensive. By
using the SHF process, Clostridium sporogenes BE01 produced 5.52 g/L butanol
from 4% H2SO4 pretreated rice straw (Gottumukkala et al. 2013).
148
Fig. 7.2 Process network of lignocellulosic biorefinery for the production of biofuels and platform chemicals
V. R. Naira et al.
Table 7.1 Various saccharification and fermentation processes for lignocellulosic biomass
Type of
Pretreatment Feedstock fermentation Microorganism Product References
Pretreated solid cellulose fraction
1% (v/v) Sugarcane Solid state Trichoderma Cellulase Salomão et al.
H2SO4 bagasse koningii INCQS (8.2 IU/g (2019)
(100 °C 40331 substrate)
for 40 min)
1 mL of Sugarcane Solid state Aspergillus tamarii Xylanase Ferreira et al.
0.3 N bagasse (750 IU/g dry (1999)
NaOH/g weight);
substrate β-xylosidase
(250 IU/g dry
weight)
4% (w/w) Rice straw Separate Clostridium Butanol Gottumukkala
H2SO4, hydrolysis and sporogenes BE01 (5.52 g/L) et al. (2013)
solid fermentation
loading
15%,
121 °C and
60 min
1% NaOH, Rice Simultaneous Candida Ethanol Roychoudhury
121 °C and straw saccharification acidothermophilum (139 g/L) by et al. (1992)
60 min and ATCC 20381 vacuum
fermentation condensation
3.8 mg Corn Simultaneous Corynebacterium l-lysine Chen et al.
H2SO4/g stover saccharification glutamicu SIIM (33.8 g/L) (2019)
feed, and B253
175 °C, fermentation
5 min and
solid/liquid
ratio 2:1
(w/w)
1% NaOH, Rice straw Consolidated Mixed culture from Butyric acid Ai et al.
solid-to- bioprocessing cattle and pig (16.2 g/L, (2016)
liquid ratio manure, compost productivity
1:15 (w/v), and corn field soil 2.69 g/L/d)
50 °C and
72 h
Pretreated liquid hydrolysate
3% (w/w) Sugarcane Fermentation Moorella Acetic acid Ehsanipour
SO2 and straw thermoacetica (17 g/L, 71% et al. (2016)
steam ATCC 39073 of theoretical
explosion value)
(195 °C
and 5 min)
(continued)

Type of
Pretreatment Feedstock fermentation Microorganism Product References
12.9 g/L of Corn Fermentation Rhizopus oryzae AS Chitosan Yang et al.
H2SO4, stover 3.819 (10.96 g/L) (2017)
steam
explosion
(0.8 MPa
and 5 min)
Pretreated whole slurry mixture
Wet Corn Separate Saccharomyces Ethanol Rana et al.
explosion, stover hydrolysis and cerevisiae (26.8 g/L, (2014)
(170 °C, fermentation 65.3%
20 min and theoretical
79.8 psi yield)
O2)
Steam Wheat Separate Saccharomyces Ethanol Alfani et al.
explosion straw hydrolysis and cerevisiae (32 g/L, 98% (2000)
(217 °C fermentation theoretical
and yield)
10 min)
10% (v/v) Wheat Separate Clostridium Acetone, Qureshi et al.
H2SO4, 8% straw hydrolysis and beijerinckii P260 butanol, (2007)
solid fermentation ethanol
loading, (ABE:
121 °C and 25 g/L)
60 min
Maleic Rice straw Simultaneous Saccharomyces Ethanol Jung et al.
acid, saccharification cerevisiae (11.2 g/L, (2015)
190 °C, and 62.8%
0.2% (w/v) fermentation theoretical
and 20 min yield)
1% NaOH Sunflower Simultaneous Pichia stipites Ethanol Antonopoulou
(121 °C straw saccharification CECT 1922 (3.6 g/L, et al. (2016)
and 1 h) and 34.5%
fermentation theoretical
yield)
Dilute Wheat Consolidated Trichoderma reesei Ethanol Brethauer and
H2SO4 straw bioprocessing RUT-C30, (9.8 g/L, Studer (2014)
Saccharomyces 69%
cerevisiae and theoretical
Scheffersomyces yield)
stipitis
Steam Beech Consolidated Trichoderma reesei Lactic acid Shahab et al.
explosion wood bioprocessing RUT-C30, (20 g/L) (2018)
(230 °C Lactobacillus
and pentosus and
15 min) Lactobacillus brevis
To avoid the problems of two-step process and end-product inhibition, simulta-

neous saccharification and fermentation (SSF) has been developed in which the
glucose released through enzymatic saccharification (using commercial enzymes) is
simultaneously utilized by the fermenting microorganism in a single vessel. A max-
imum concentration of 67 g/L of lactic acid was produced from sugarcane bagasse
through SSF process by using Lactobacillus delbrueckii (Adsul et al. 2007). The
highest productivity and yield of lactic acid were 0.93 g/L/h and 0.83 g/g, respec-
tively. The concomitant production of acetone, butanol and ethanol through ABE
fermentation using Clostridium beijerinckii from sugarcane bagasse through a com-
bination of pretreatment, microwave decomposition, ammonia immersion, liquid
hot water, microbial decomposition and enzyme hydrolysis yielded 11.9 g/L of
ABE by SSF process (Su et al. 2015).
Consolidated bioprocessing (CB) is another interesting process that involves
co-culturing a microbial strain (for cellulase production via enzymatic saccharifi-
cation) and a fermenting strain (for simultaneous fermentation of released sugar)
in a single vessel. This process has several advantages over the other processes, e.g.
reduction of enzyme cost, simultaneous biochemical conversion of pentose and
hexose by using both pentose-utilizing and hexose-utilizing strains at the same
time. For example, the consolidated bioprocessing of dilute H2SO4-pretreated
wheat straw using Trichoderma reesei RUT-C30 (for cellulase production),
Saccharomyces cerevisiae (for glucose fermentation) and Scheffersomyces stipitis
(for xylose fermentation) produced 9.8 g/L of bioethanol with 69% theoretical
yield (Brethauer and Studer 2014).
In a solid-state (SS) fermentation, high solid loading of pretreated biomass is
used at low moisture content for enzymes and metabolites production. The advan-
tages are high concentration of end products, low water requirement, lower energy
requirement, lower sterility requirement and easy aeration. The amylase production
was carried out by Aspergillus niger using sugarcane bagasse in a solid-state fer-
mentation in which the maximum amylase activity obtained was 457.82 IU/gds
with yeast extract as the nitrogen source (Rosés and Guerra 2009).
7.3.3 Conversion of Lignocellulosic-Derived Sugars
The C5 (pentose) and C6 (hexose) sugars obtained after the enzymatic saccharifica-
tion of cellulose and hemicellulosic fractions can be chemically transformed into a
number of value-added products. The reduction of C6 (e.g. glucose) and C5 sugars
(e.g. xylose) into useful chemicals via different platforms is shown in Table 7.2
(Isikgor and Becer 2015). Every chemical has its own application in various indus-
trial sectors. For example, 2,5-dimethylfuran (DMF) from HMF platform has higher
calorific value than ethanol and can be blended with gasoline (Tian et al. 2011).
Similarly, high-value derivatives from levulinic acid can be utilized for agro-based
applications like potential herbicide and insecticide production. Furfural has indus-
trial applications for the extraction of aromatics, manufacturing of synthetic rubber,
phenolic resins, wax recovery from petroleum and vegetative oils, etc. Apart from
Table 7.2 Scope of chemicals produced from various platforms derived from C5 and C6 sugars
Platform Chemicals
1,4-Diacid Succinic acid; fumaric acid; 1,4-butanediol; malic acid;
1,4-butanediamine; succinic ester; γ-butyrolactone;
tetrahydrofuran; 2-pyrrolidone; n-methyl-2-pyrrolidone
3-Hydroxypicolinic acid 3-hydroxypicolinic acid; 3-hydroxypropionic esters;
1,3-propanediol; propene; acrylamide; malonic acid;
β-propiolactone; acrylic acid; acrylates; acrolein; acrylonitrile
3-Hydroxy-γ-butyrolactone 3-Hydroxy-γ-butyrolactone; epoxylactone; 2(5H)-furanone;
β-methacryloyloxy-γ-butyrolactone; acrylate lactone
5-Hydroxymethylfurfural 5-hydroxymethylfurfural; 2,5-furandicarboxylic acid;
and 2,5-furandicarboxylic 2,5-diformylfuran; 2,5-dimethylfuran; 1,6-hexanediol;
acid 1,2,6-hexanetriol; 2,5-bis(hydroxymethyl furan);
2,5-bis(aminomethyl furan); 2,5-dihydroxymethyl-
tetrahydrofuran; 1,6-hexanediamine
Acetone-butanol-ethanol Acetone; 2-propanol; propene; 1,2-dichloroethane; vinyl
chloride; ethylenediamine; glyoxal; ethanol; butadiene; acetic
acid; ethylene; ethylene oxide; ethylene glycol; glycolic acid;
butanol; butyric acid; 1-butene; isobutene; α-olefins; vinyl
acetate; methyl methacrylate; styrene
Aspartic acid Aspartic acid; fumaric acid; maleic acid; 2-amino-1,4-
butanediol; β-alanine; aspartic anhydride; 3-aminobutyrolactone
Glucaric acid Gluconic acid; glucaric acid; glucaro-1,4-lactone;
α-ketoglucarates; methylglucoside; glucuronic acid;
glucarodilactone
Glutamic acid Glutamic acid; 1,2,5-pentanetriol; glutaminol;
1,5-pentanediamine; 1,5-pentanediol; γ-aminobutyric acid;
glutaric acid; 4-amino-1-butanol
Glycerol Glycerol; diglycerol; mannitol; 1,3-propanediol; propylene
glycol; glycerol carbonate; ethylene glycol; glycidol; propanol;
dihydroxyacetone; 3-hydroxypropionaldehyde; propene;
propane; acrolein; acrylic acid; glyceraldehyde
Itaconic acid Itaconic acid; itaconic diamide; Itaconic anhydride;
3-methylpyrrolidine; 2-methyl-1,4-butanediol; 2-methyl-1,4-
butanediamine; 2- and 3-methyl-γ-butyrolactones; 3-methyl
tetrahydrofuran
Lactic acid Lactic acid; lactide; acetaldehyde; 2,3-pentanedione; pyruvic
acid; lactates; oxalic acid; propylene glycol; acrylic acid;
propylene oxide; pyruvaldehyde; propanoic acid; acrylates
Levulinic acid Levulinic acid; diphenolic acid; levulinate ketal;
5-aminolevulinic acid; angelica lactones; 2-methyl
tetrahydrofuran; 1,4-pentanediol; γ-valerolactones;
hydroxy(amino)amide; butane; adipic acid; adiponitrile;
pentanoic acid; pentanol; 5-nonanone; 5-nonanol;
ethylpentenoate; dimethyl adipate; methyl valerate; 2-butanone;
levulinic esters
(continued)

Platform Chemicals
Sorbitol Sorbitol; isosorbide; 1,4-sorbitan; sorbose; 2-ketogulonic acid;
vitamin C
Xylose-furfural-arabinitol Xylose; xylitol; xylaric acid; hydroxyfurans; furoic acid;
2-(5H)-furanone; furfural; furfuryl; furan; tetrahydrofuran,
furanacrylic acid; maleic anhydride; maleic acid;
2-methylfuran; difurfuryldiamines; furfuryl alcohol;
tetrahydrofurfuryl alcohol; 2-hydroxymethyl-5-vinyl furan
Others Citric acid; erythrose; 1,3-dihydroxyacetone dimer;
2,3-butanediol; isoprene; hydroxyalkanoic acid;
levoglucosenone; limonene; formic acid; glycolaldehyde dimer;
isobutanol; erythritol
the monomeric C5 and C6 sugar platforms, oligosaccharides released during the

degradation of cellulose and hemicellulose can be converted into polymeric com-
pounds like polyesters, polyamides, polycarbonates, polyurea, polyanhydrides and
polyurethanes which are used in plastic and packaging industries.
The hemicellulose fraction obtained after the pretreatment of lignocellulosic bio-
mass is usually a liquid hydrolysate that is rich in xylose and a small proportion of
glucose in soluble form and other by-products (treated as inhibitors) from sugar
degradation. Hence, it can be fermented after inhibitor separation to produce fuels
and chemicals. The separated inhibitors from the hydrolysate can be directly used
as value-added products or the whole fraction can be bypassed for direct fermenta-
tion. The inhibitors such as furfural, HMF, acetic acid and formic acid present in the
hydrolysate can be separated by either nanofiltration technique, solvent–solvent
extraction with ethyl acetate (Fenske et al. 1998) or trialkylamine (Zhu et al. 2011),
or liquid–solid extraction by using activated carbon (Parajo et al. 1997). The use of
nanofiltration membranes for maximizing the sugars’ yield by separating inhibitors
simultaneously from rice straw hydrolysate has been demonstrated. In the study,
xylose, glucose, arabinose and cellobiose were concentrated by 100%, 104%, 93%
and 151%, respectively, while the final concentration of inhibitors was reduced to
3% of the initial concentration in the sugar stream (Maiti et al. 2012).
By separating or not separating the inhibitors from the hemicellulosic fraction,
the liquid hydrolysate can be used for direct fermentation into bioethanol by pen-
tose (xylose)-fermenting yeast such as Pichia stipites and Fusarium oxysporum
(McMillan 1993). Candida boidinii, Candida tropicalis and Pachysolen tannophi-
lus can convert xylose into xylitol. Xylitol has a wide range of industrial applica-
tions as an alternative sweetener in foods and syrups and also used in pharmaceutical
formulations as an additive for patients with diabetes and dental caries (Mohamad
et al. 2015). Chitin production from fermented biomass of fungus grown using corn
stover hydrolysate was reported by Yang et al. (2017). Chitin has many medical
applications because of its biodegradability, biocompatibility and good adsorbing
behaviour within the cellular matrix. Hence, it is widely applied for stitching the
surgeries and wounds (Jardine and Sayed 2016). In acetone-butanol-ethanol (ABE)
fermentation, acetic acid and butyric acid production can also be achieved from
hemicellulosic sugar fermentation (Nanda et al. 2017). The fermentation of hydro-

lysate obtained from the pretreatment of wheat straw, forest residues, switchgrass
and sugarcane straw was carried out using Moorella thermoacetica in which sugar-
cane straw hydrolysate yielded 17 g/L of acetic acid with 71% theoretical conver-
sion yield (Ehsanipour et al. 2016).
The generation of multiple co-products along with the principal product via bio-
refinery approach from lignocellulosic biomass can solve the constraints for com-
mercialization of a single product. The choice of a suitable pretreatment strategy
based on the specificity of product, separation of treated biomass into multiple
streams (e.g. lignin, cellulose, hemicellulose and their hydrolysates) for the genera-
tion of value-added products at different stages is crucial for lignocellulosic biore-
fineries. For example, the fractionation of solid and liquid residues of pretreated
sugarcane bagasse (lime and alkaline H2O2 treatment) where the solid fractions are
enzymatically hydrolysed to produce bioethanol and lignin fraction can be streamed
to boilers for the generation of heat. The generated waste from liquid fraction and
leftover residues after enzymatic hydrolysis are anaerobically digested with mixed
culture of thermophilic microorganisms for methane (biogas) production (Rabelo
et al. 2011). Recent pretreatment and biorefinery approaches of various lignocellu-
losic feedstocks are summarized in Table 7.3.
7.4 Algal Biorefineries
7.4.1 Algae Cultivation
The generation of products in algae biorefinery is mainly decided by the composi-

tions of lipids, proteins and carbohydrates of algal species, which are the precursors
of biofuels and platform chemicals (Laurens et al. 2017). This composition of these
compounds is species-specific and can be easily varied by nutritional supply (e.g.
nitrogen starvation for biodiesel production) (Reitan et al. 1994). Algae can also be
used for the production of pigments, vitamins, nutraceuticals, pharmaceuticals and
antioxidants via selective extraction techniques. They can also secrete a wide range
of extracellular products (e.g. exopolysaccharides and exoenzymes). Thus, algal
biorefinery offers a broad range of co-products with desirable quantities of main
products (Fig. 7.3).
Several cultivation systems are established to achieve large-scale manufacturing
of products from algae. Algae are grown in both open (raceway ponds) and closed
systems (photobioreactors, PBRs) (Chisti 2007). Mostly practised cultivation sys-
tems are artificial open ponds due to their economic feasibility, easy installation and
maintenance. Due to their low biomass productivities and contamination issues,
PBR systems were developed to obtain high biomass productivities by allowing bet-
ter control over culture conditions. All PBRs result in higher biomass productivities,
but they have their own advantages and disadvantages. The tubular and flat panel
PBRs allow higher biomass concentrations with better control over the culture
Table 7.3 Multi-product generation from lignocellulosic feedstocks

Principal
product and
Feedstock Pretreatment Process co-product Microorganism References
Dairy 2% NaOH Anaerobic Methane, Rhizopus oryzae Liu et al.
manure treatment digestion, chitin, (2016b)
and other simultaneous reclaimed water
organic saccharification and electricity
wastes and fermentation,
and
electrocoagulation
Hemp Dilute H2SO4 Simultaneous Bioethanol and Saccharomyces Kuglarz
and alkaline- saccharification succinic acid cerevisiae and et al.
oxidative and fermentation Actinobacillus (2016)
method succinogenes
Rice husk Steam explosion Fast pyrolysis, and Bio-oil and Escherichia coli Wang et al.
and corn separate hydrolysis succinic acid MG-PYC (2013)
stover and fermentation
Rice Dilute H2SO4 Lignin Lignosulfonate, Saccharomyces Zhu et al.
straw pretreatment and fractionation, and xylose cerevisiae (2015)
sulfomethylation simultaneous recovery,
reagent saccharification bioethanol
and fermentation
Softwood – Pyrolysis and Bio-oil and Chlamydomonas Zhao et al.
algae growth using algae biomass reinhardtii (2013)
alkali treated
bio-oil fraction
Sugarcane Lime and Separate Bioethanol, Saccharomyces Rabelo
bagasse alkaline H2O2 hydrolysis and methane and cerevisiae et al.
fermentation, heat energy (2011)
anaerobic
digestion, and
combustion
Sugarcane Milling, H2SO4 Simultaneous Bioethanol, Saccharomyces Unrean and
bagasse pretreatment saccharification xylitol cerevisiae and Ketsub
and fermentation Candida (2018)
tropicalis
Wheat Steam explosion Simultaneous Bioethanol and Kluyveromyces Tomas-
straw saccharification bio-oil marxianus Pejo et al.
and fermentation, (2017)
and pyrolysis
Wheat Hydrothermal Batch fermentation Bioethanol, Saccharomyces Kaparaju
straw pretreatment and anaerobic biohydrogen cerevisiae and et al.
digestion and biogas thermophilic (2009)
(methane) mixed culture
156
Fig. 7.3 Process network of algal biorefinery for the production of biofuels and platform chemicals
V. R. Naira et al.
medium, i.e. control of CO2 supply, pH, temperature and salinity, and they are
highly suitable for the commercial-scale production of algae.
Algae can be cultivated in three modes, namely photoautotrophic, heterotrophic
and mixotrophic. Photoautotrophic growth using CO2 (from flue gases) of algae is
beneficial as CO2 is cheaper than any other sugars and organic acids, and it is mostly
obtained as a waste greenhouse gas emission from industries. Heterotrophic mode
of cultivation includes the utilization of carbon sources such as sugars and organic
acids by algae for their growth without light. In mixotrophic mode, both organic
source and CO2 are used for cultivating algae using a light source.
After cultivation, algae are subjected to harvesting processes such as centrifuga-
tion, filtration (cake and ultrafiltration), sedimentation, flotation, flocculation
(chemical, biological, magnetic, electro and auto-flocculation) to separate the algal
biomass and extracellular products. The leftover media after fractionation of the
extracellular products can be recycled to the next batch with adequate nutrient re-
supplementation. The wet/dried algal biomass after harvesting is extracted and frac-
tionated into platforms of lipids, carbohydrates and proteins via various downstream
processing techniques.
7.4.2 Downstream Processing of Algae for Fuels and Chemicals
Algal biorefining products are mainly intact within the cell membrane or reside
inside the cells. Hence, downstream processing is very critical for algal biorefinery
and its economics is mainly decided by the cell disruption techniques involved.
Depending on the cell wall rigidness of specific microalgal species and products of
interest, the cell disruption technology has to be decided (Günerken et al. 2015; Lee
et al. 2017). Broadly, the cell disruption methods are mainly divided into two types,
namely mechanical and non-mechanical.
The mechanical type of cell disruption needs the energy in the form of shear
force, wave energy, current and heat. The methods such as bead milling and high-
pressure homogenization can be categorized under shear-force-based cell disrup-
tion. Bead milling breaks the algal cells by creating compressive and shear forces
applied through fast-moving solid beads (Günerken et al. 2015). In high-pressure
homogenization, the cells are pressed through a small orifice where cell lysis is
promoted by turbulence, shear stress and cavitation mechanisms. Even though
shear-force-based cell disruption extracts all the intracellular cellular components,
especially lipids/biodiesel, their high-energy demand and heat generation make
them unsuitable for the biorefinery approaches. Moreover, the fragile compounds
like proteins lose their activity due to heat generation (Doucha and Livansky 2008).
The wave-energy-based cell disruption techniques include ultrasonication,
microwaves and pulsed electric field treatment (Günerken et al. 2015). In ultrasoni-
cation, the cells are lysed due to shock waves generated by bursting of microbubbles
caused by cavitation effect. During microwaves treatment, the algal cell walls are
disrupted due to high heating in short time which damages the pectin and cellulose
structures of algal cell wall. In the pulsed electric field treatment, the cell disrupts
due to an electric potential that generates across the cell wall. Except the microwave
treatment due to its high heat, other two techniques can be used for algal biorefiner-
ies that involve separation of fragile compounds like proteins. However, scaling up
of those techniques is still in early development stages. With regard to the heat-
based cell disruption, steam explosion and hydrothermal liquefaction were explored
recently. In steam explosion, the wet/dry biomass is subjected to temperatures in the
range of 180–240 °C and pressures of 1–3.5 MPa. A sudden depressurizing explodes
the algal cells to release lipids, soluble sugars and solid residues (Cheng et al. 2015).
The non-mechanical cell disruption methods include chemical and biological
techniques. In chemical methods, chemicals like antibiotics, ionic liquids, special
nanoparticles, chelating agents, chaotropes, detergents, solvents, hypochlorites,
acids and alkalis are used (Günerken et al. 2015; Lee et al. 2017). The most com-
monly used chemical methods are conventional lipid extraction followed by trans-
esterification. Both the methods are developed mainly for biodiesel production from
lipids, with the by-products such as crude glycerol and residual algal biomass. The
direct transesterification decreases the downstream cost and time durations com-
pared to the conventional ones. The direct transesterification process is carried out
using methanol and acid/base catalysts (e.g. H2SO4 and NaOH) (Mahesh et al. 2019;
Naira et al. 2018).
High temperature requirement makes the technique unfavourable for mild algal
biorefinery. Hence, mild biological cell disruption techniques like enzyme lysis and
algicidal treatment are developed. In enzymatic cell disruption, cellulases, lipases,
lysozymes, pectinases and proteases are used for lysing the rigid algal cell wall
containing cellulose, membrane lipids and proteins (Wu et al. 2017). The cocktail of
the enzymes is more powerful in breaking the cells than the single enzyme (Wu
et al. 2017). However, the enzymatic cell disruption is energy efficient as the cost of
enzyme, stability and reusability are the challenges that need to be resolved for
large-scale applications. In the algicidal treatment, bacteria, cyanobacteria, microal-
gae and viruses are the microorganisms that are reported to lyse the cell wall of
algae by releasing extracellular allelopathic compounds (Chen et al. 2013). Hence,
algicidal treatment can be considered for biorefinery applications that can also over-
come the challenges of enzyme cost, stability and reusability. The recent advances
in the application of available cell disruption methods for biorefinery product gen-
eration are tabulated in Table 7.4.
7.4.3 Extracellular Products from Algae and Their Applications
The production of extracellular metabolites during the algal growth or starvation

periods provides an excellent biorefinery opportunity for the generation of a wide
range of platform chemicals like exopolysaccharides (EPS), proteins, fatty acids,
organic acids, phytoharmones and allelopathic chemicals. This extracellular plat-
form is highly beneficial in the perspective of downstream processing economics as
they require less energy to recover. Exopolysaccharides are used in food (e.g. jelly,
candy, sauce and beverages), pharmaceuticals (e.g. capsule covering and antitumour
Table 7.4 Various cell disruption techniques for multi-product generation

Cell disruption
technique Methodology Algal species Products References
Algicidal Flammeovirga Chlorella Lipids Chen et al.
treatment yaeyamensis secreted vulgaris ESP-31 (2013)
amylase, cellulase and
xylanase
Enzymatic cell Cocktail of cellulase, Nannochloropsis Lipids, proteins Chen et al.
disruption lipase and protease and glucose (2016)
enzymes
Enzymatic cell Aqueous enzymatic Chlamydomonas Lipids and Sierra et al.
disruption extraction using reinhardtii proteins (2017)
autolysin
Hydrothermal Heterogeneous Nannochloropsis Biocrude oil, Duan and
liquefaction catalysts (Pd/C, Pt/C H2, CO2 and Savage
and Ru/C) under inert CH4 (2011)
(He) atmosphere and
high-pressure reducing
(H2) conditions
Steam Steam explosion Nannochloropsis Soluble Lorente
explosion followed by membrane gaditana monomeric et al. (2017)
filtration and n-hexane sugars and
extraction lipids
Ultrasonication 4 N HCL treatment Haematococcus Lipid and Dong et al.
followed by pluvialis astaxanthin (2014)
ultrasonication-
assisted acetone
extraction
Ultrasonication Ultrasonication- Nannochloropsis Phenolic Parniakov
assisted DMSO, spp. compounds and et al. (2015)
ethanol and water chlorophylls
extraction
Ultrasonication Ultrasonication- Dunaliella salina Carotenoids Macías-
assisted methanol and Sánchez
extraction chlorophylls et al. (2009)
Ultrasonication Ultrasonication- Chlorella Carotenoids, Plaza et al.
assisted acetone, vulgaris chlorophylls, (2012)
ethanol and hexane steroids,
extraction phytols and
fatty acids
drugs), textiles (e.g. printing and dyeing), cosmetics (e.g. body lotion and emulsi-
fier), detergents, adhesives, wastewater treatment, bioremediation, bioflocculants
and oil recovery (Liu et al. 2016a).
The exopolysaccharides from various algal groups like rhodophytes, cyanophytes
chlorophytes and dinoflagellates have been widely reported to exhibit antibacterial, anti-
viral, antitumour, anticoagulant and antioxidant activities (Chen et al. 2010; Freire-Nordi
et al. 2005). In a recent study, biodiesel (1.5 g/L) and exopolysaccharides (236 mg/L)
were concomitantly produced via Scenedesmus abundans (Mahesh et al. 2019). These
exopolysaccharides were shown to have monosaccharides like glucose, galactose, arabi-

nose and raminose. Exoenzymes such as alkaline phosphatases, chitinases, β-d-
glucosidases and proteases were also identified in algal species like Chlorella,
Scenedesmus and Anabaena. Extracellular phenoloxidases such as phenoloxidase lac-
case and laccase-like enzymes were found in the cultures of Chlorella, Scenedesmus and
Anabaena (Liu et al. 2016a; Zhang et al. 2008). These phenoloxidases can be used for
bioremediation of phenolic pollutants.
Extracellular phytohormones such as abscisic acid (from Chlorella vulgaris and
Stichococcus bacillaris), indole-3-acetic acid (from Chlorella pyrenoidosa and
Scenedesmus armatus) and gibberellic acid (from Scytonema hofmanni) are reported
to be used in food crops for alleviating stresses (Liu et al. 2016a; Rodriguez et al.
2006). Allelopathic compounds like unsaturated C18 fatty acids (from Chlorella),
polysaccharides (from Chlorella vulgaris and Anabaena PCC 7120) and alkaloids
(from Calothrix sp. and Anabaena flosaquae) are reported to inhibit the growth of
bacteria and other algae (Ikawa et al. 1984; Liu et al. 2016a).
During the cultivation of some cyanobacterial and green algal species, biohydrogen
can also be co-produced by converting light energy with the help of [Fe-Fe]-hydrogenase
Table 7.5 Recent advances in the utilization of recycle streams for expanded algal biorefineries
Microorganism or
Recycle stream process Products References
Recycle from transesterification or lipid extraction process
Crude glycerol Lactobacillus Hydroxypropionaldehyde; Lindlbauer and
diolivorans 3-hydroxypropanoic acid; Marx (2017)
and 1,3-propanediol
Crude glycerol Propionibacterium Propionic acid; succinic Pawlicka-
freudenreichii ssp. acid; acetic acid and Kaczorowska and
shermanii trehalose Czaczyk (2017)
Crude glycerol Schizochytrium Docosahexaenoic acid; Pyle et al. (2008)
limacinum lipids; proteins and
carbohydrates
Spent biomass of Hydrolysis ε-Polylysine Sivaramakrishnan
Chlamydomonas et al. (2019)
sp. after
transesterification
Spent biomass of Anaerobic digestion Biogas (methane) Hernandez et al.
Tetraselmis sp. (2014)
after supercritical
CO2 extraction
Recycle from hydrothermal liquefaction process
Hydrothermal Desmodesmus sp. Algal biomass Alba et al. (2013)
liquefaction
wastewater of
Desmodesmus sp.
Hydrothermal Chlorella Algal biomass Jena et al. (2011)
liquefaction minutissima
wastewater of
Spirulina
enzyme, that reduces protons to molecular hydrogen using photosynthetically reduced

ferredoxin (Fd) as a donor (Greenbaum 1988). The utilization of recycle streams from
biorefineries is an innovative step towards the development of green and sustainable
environment. Moreover, it adds value to the economy of biorefinery industries. Some
recent advances in using crude glycerol, spent biomass and organic-source-rich frac-
tion as recycle streams from various bio-based industries are tabulated in Table 7.5.
7.5 hermochemical Conversion of Lignocellulosic Biomass

T
and Algae
Conventionally, lignocellulosic biomass and algal feedstock can be converted into

fuels and chemicals via various thermochemical conversion routes such as pyroly-
sis, gasification, direct combustion and hydrothermal liquefaction. Before the ther-
mochemical treatments, the biomass is ground or milled for decreasing their particle
size and increasing the surface area.
7.5.1 Pyrolysis
Pyrolysis is the thermochemical decomposition of biomass feedstock at elevated

temperatures and non-oxidizing conditions into solid biochar, liquid bio-oil and
condensable or incondensable gaseous products. The process of pyrolysis mainly
consists of three stages. In stage I, dehydration of algae sample is performed where
water is released. In stage II, pyrolytic decomposition is conducted. In stage III,
char transformation and mineral matter decomposition are done. Owing to the recal-
citrant nature of lignocellulosic biomass, it can be subjected to three different kinds
of pyrolysis processes, namely slow pyrolysis (300–700 °C) to yield biochar as the
main product as well as fast pyrolysis (450–650 °C) and flash pyrolysis (800–
1000 °C) to yield bio-oil as the main product (Demirbas and Arin 2002).
Apart from bio-oil and biochar, the gaseous products like CO2, CO, H2, CH4,
C2H6, C2H4 and a small amount of other gases like C3H8, NH3, NOx and SOx are
evolved from the degradation of hemicellulose, cellulose and lignin. In the case of
algal biomass, the carbohydrates are decomposed into CO, H2O, CH4, CH3Cl,
CH3OH, CH3SH, C7H8, C2H5OH and CO2 at the temperature range of 125–
235 °C. Similarly, the proteins are decomposed into CH4N, C2H6, HCN, CO, CH4
and CO2 at the temperature range of 295–365 °C. On the other hand, the lipid frac-
tion is decomposed into ketones (C2H2O and C3H5O), CH4, HCN, C2H4, CH4N,
C2H6, C7H8, CO and CO2 at the temperature range of 400–600 °C. Although the
product of interest varies with the type of pyrolytic process, the final products are
biochar and a fraction of volatile compounds in which condensable and incondens-
able gases are present. The condensable stream of gases can be further converted
into bio-oil (main product of fast and ultrafast pyrolysis), which can be upgraded for
use as a transportation fuel. The non-condensable fraction comprising H2, CH4, CO
and CO2 can be used as fuel gases for energy generation.
The pyrolytic bio-oil (also known as bio-crude) can be upgraded for the produc-
tion of transportation liquid fuels via catalytic cracking. It can also be utilized as a
precursor for platform chemicals like phenols for resin manufacturing, additives for
fertilizers, pharmaceutical purposes and flavouring agents (e.g. glycolaldehyde) for
food industries (Balat 2011). Combustible syngas and hydrogen fuels can be gener-
ated via gasification and steam reforming. The leftover solid biochar has a wide
range of agricultural applications such as heavy metal adsorption, biodegradation of
pesticides and increasing water-holding capacity of soil (Nanda et al. 2016a).
7.5.2 Combustion
Combustion is a traditional way of burning a fuel to release heat and gaseous streams
in the presence of oxygen. Similar to the pyrolytic process stages, combustion can
also be of three stages. However, the temperature range of decomposition stage is
145–500 °C and the biochar transforms into ash due to the involvement of oxygen
in the process. Due to the oxidation reaction in all the stages of combustion, CO2 is
seen as the dominant gaseous product. The produced gas stream can be used to run
a steam turbine to generate electricity and the ash can be utilized as an additive in
fertilizer industries.
7.5.3 Gasification
The process of gasification involves subliming the biomass by feeding air or pure
oxygen to decompose lignocellulosic and algal biomasses thermally at higher tem-
peratures (>1000 °C), which results in a wide range of gaseous products. In gasifica-
tion, the biomass is heated in air, oxygen or steam to generate syngas, which contains
H2, CO, CO2 and CH4 (Okolie et al. 2019). The physical conditions and catalysts
play important roles in gasification for increasing the carbon yield. For example,
Spirulina (algae) biomass at temperatures ranging from 800 °C to 1000 °C in the
presence of oxygen produced syngas with traces of O2, N2 and C2H4 (Hirano et al.
1998). Upon increasing the temperature, the H2 yield and carbon conversion effi-
ciency increased. In another study, the combined gasification and methane (from
biogas synthesis) reforming of wood and black liquor (lignocellulosic biomass)
increased H2/CO ratio in the syngas (Åberg et al. 2015).
In another investigation with Chlorella vulgaris, the Ni catalyst in gasification
reaction increased the content of CH4 by decreasing H2 (Minowa and Sawayama
1999). Moreover, the nitrogen present in the feedstock was converted into NH3 due to
the Ni presence, making the product to manufacture a premium fertilizer. This syngas
can be utilized directly as a fuel or as precursor for hydrocarbon fuels via Fischer-
Tropsch synthesis, H2 fuel and electricity. For biorefinery routes, syngas has been
utilized for ammonia synthesis followed by biohydrogen and biomethanol production
along with various other fuels and platform chemicals (Table 7.6) (Quarderer 1986;
Van et al. 1995; Mokrani and Scurrell 2009; Molino et al. 2016; Arora et al. 2016).
Table 7.6 Fuels and platform chemicals from bio-based syngas

Source Transformation route Bioproduct
Bio-based syngas Fischer-Tropsch (Fe, Co and Ru) Gasoline, diesel, waxes
and olefins
Oxosynthesis (HCo(CO)4) Aldehydes and alcohols
Alkali-doped (ZnO) Mixed alcohols
Isosynthesis (ZrO2) I-C4 hydrocarbons
Water-gas shift reaction (H2O) H2
Cu/ZnO catalysis Biomethanol
Co/Rh catalysis; syngas fermentation Bioethanol
(acetogenic bacteria)
H2 (product of bio-based N2 over Fe/FeO Ammonia
syngas)
Biomethanol (product of Ag catalysis Formaldehyde
bio-based syngas) Acidic ion exchange, isobutylene Methyl tertiary butyl
ether
Carbonylation; CH3OH + CO, Co, Rh Acetic acid
and Ni
Zeolite catalysis Olefins and gasoline
Homologation (Co) Bioethanol
Al2O3 catalysis Biodimethyl ether
Direct use as fuel M100 and M85 blending
7.5.4 Hydrothermal Liquefaction
Hydrothermal liquefaction (HTL) is an energy-efficient thermochemical treatment that

converts biomass feedstock directly into bio-oil (bio-crude). In the HTL process, the
lignocellulosic and algal biomasses are exposed to high pressure (5–30 MPa) and high
temperature (200–700 °C) under inert atmosphere (e.g. N2 or He) or reducing gases
(e.g. H2 or CO) (Tian et al. 2014). The process yields bio-crude as an important product
along with some solid residues and gaseous phases. The solid phase can be converted
into biochar and gaseous phase into syngas and other gaseous fuels. The aqueous phase
is mainly composed of NH4+, PO43−, K+, N+ and Mg2+ ions. Hence, bacteria or algae can
directly use the post-HTL wastewater for fermentation or carbon utilization.
Other organic compounds from the aqueous phase can also be used as carbon
sources for fermentation of bacterial/fungal cultures and even for heterotrophic
algal culturing (Pham et al. 2013). The gaseous phase products from the HTL of
algae are comprised mostly of CO2; hence, the gaseous stream can be recycled back
for the growth of algae (Amin 2009). The remaining solid residue is composed of a
number of inorganic compounds that might be used for the cultivation of algae or
synthesis of new catalysts (Liu et al. 2012). A recent novel biorefinery study on
hydrothermal co-liquefaction of microalgae (Chlorella pyrenoidosa) and lignocel-
lulosic biomass (rice husk) with equal ratios at 300 °C for 60 min yielded highest
bio-crude having cyclic oxygenates (20.6%) and esters, ketones and alcohols con-
tent (17.2%) (Gai et al. 2015). This co-liquefaction strategy resulted in the decreased
acidity and lower nitrogen content of bio-crude oil.
7.6 I ndustrial Scenario of Lignocellulosic and Algal

Biorefineries
In the USA, the companies like Abengoa and POET-DSM have been working on
commercial lignocellulosic biorefineries. Abengoa has the capability to produce 25
million gallons of cellulosic ethanol per annum, 21 MW of green electricity, lignin
and animal feed from cellulosic biomass, crop residues and plant fibres as the feed-
stock (Chemicals Technology 2019). In India, Ethanol Blended Programme (EBP)
was implemented by the Government of India for boosting the agricultural sector
and to reduce imported energy requirements (Best Current Affairs 2019). In support
of EBP, 12 lignocellulosic biorefineries were planned by major oil companies (e.g.
Bharat Petroleum Corporation Ltd.). The company has planned to use agricultural
wastes and crop residues as the feedstock for producing second-generation bioetha-
nol and organic manure for improving soil fertility. Assam Biorefinery Pvt. Ltd. in
India was set up as a joint venture between Numaligarh Refinery Ltd. (NRL),
Chempolis, Finland, and Fortum 3 B.V., Netherlands, for producing 62 million
litres of bioethanol annually along with the co-production of furfural and acetic acid
from bamboo (0.5 million tons) as lignocellulosic feedstock by 2021 (Numaligarh
Refinery Limited 2017).
Volkswagen research group (Wolfsburg, Germany) has been working on micro-
algae that could excrete fuel compounds like 1-butanol, isobutanol, octanol or bis-
abolene (Bippes 2018). Buggypower (Portugal) is also producing high-quality
marine microalgae with high nutritional properties such as polyunsaturated fatty
acids (PUFAs), pigments, vitamins, essential amino acids and minerals (Real 2018).
A paper-based industry from Italy, Favini Srl., has been started extracting platform
chemicals like alginate, agar and carrageenan along with paper production from
seaweeds (macroalgae) (Monegato 2018).
Global companies like Microsynbiontix, Cellana, Fermentalg, Microphyt,
Algenuity, Algae for Future (a4f), Algafarm, Phytoplancton Marino and Parry
Nutraceuticals have exploited microalgal products like essential fatty acids, pig-
ments (astaxanthin and ketocarotenoid) and a wide range of platform chemicals for
applications in nutraceuticals, aquaculture and animal feed industries (Algal
Biomass Organization 2019). In India, Reliance Industries Ltd. and Algenol have
collaboratively designed an algal biorefinery project to convert 1 tonne of CO2 from
industrial processes into 144 gallons of fuels like ethanol, gasoline, diesel and jet
fuel (Green Car Congress 2015).
7.7 Conclusions
Both lignocellulosic biomass and algal feedstock have a huge potential for estab-
lishing multi-product biorefineries for co-production of fuels and value-added plat-
form chemicals. The recent co-production technologies of both the feedstocks for
multiple products have been discussed in this chapter. In lignocellulosic biorefinery,
fermentation technology can be improved to produce more diversified products as
compared to the existing products. For example, while co-culturing different micro-
bial strains for maximizing the utilization of complete lignocellulosic sugar content
via consolidated bioprocessing, the microbial strains can be chosen specifically for
co-production of different compounds in a single fermentation vessel although the
co-culture compatibility is a challenging task.
In the case of algae biorefinery, the advancements in developing an efficient and
mild cell disruption technology by the combination of existing techniques have to
be continued to reduce the cost of downstream processing as well as to extract frag-
ile molecules like proteins along with the lipids and carbohydrates. The innovation
in utilizing recycle streams of both the biorefineries for either microbial (bacterial
or fungal) fermentation or algae biomass production can be a promising opportunity
for integrating both the industries together. In the present industrial scenario, ligno-
cellulosic biorefineries have already been proving their potential across the world.
However, the existing industrial algae biorefineries are limited, though algae have
been highly exploited for single or dual products use.
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Conversion of Rice Husk and Nutshells
into Gaseous, Liquid, and Solid Biofuels 8
Anton P. Koskin, Inna V. Zibareva, and Aleksey A. Vedyagin
Abstract
Nowadays, biomass is considered as a main renewable energy source with a high
contribution value to the worldwide energetics. In general, biomass is repre-
sented by solid waste materials from plant and animal farming, horticulture, food
processing, etc. All these wastes are nonedible and cannot be used as food or
feed. Among the agricultural solid wastes, rice husk and nutshells are of a special
attention due to their high production. In this chapter, the main approaches and
concepts of the rice husk and nutshells transformation into valuable gaseous,
liquid, and solid products are overviewed. In some cases, the initial biomass
should be pretreated to enhance the efficiency of its further conversion. The
transformation processes can be classified onto direct combustion (solid fuel),
pyrolysis and hydrothermal methods (solid and liquid fuels) and gasification
(gaseous fuel). The commonly used fixed-bed and fluidized-bed reactors includ-
ing catalytic ones, auger reactor, and plasma gasifiers are widely applied.
Keywords
Agricultural solid wastes · Rice husk · Nutshells · Biofuels · Lignocellulosic
biomass · Waste-to-energy
A. P. Koskin · I. V. Zibareva
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
A. A. Vedyagin (*)
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
National Research Tomsk Polytechnic University, Tomsk, Russia

172 A. P. Koskin et al.
8.1 Introduction
The global population growth leads to a continuous increase in the total amount of the
worldwide agricultural crops. The subsequent processing of the agricultural sources
into the food products results in the accumulation of huge quantities of the solid wastes.
Most of these solid agricultural wastes originate from farmlands, orchards, vineyards,
dairies and feedlots. The total amount of the annual crop waste production exceeds one
billion tons. The high volume and low packing density of the crop wastes including rice
husk and nutshells complicate their transportation, thereby creating problems of their
proper disposal (Rice Market Monitor 2017). For example, rice husk is usually dis-
posed of in the farmlands, mulched or burnt, thus affecting the environment through
greenhouse gas emissions. Therefore, the utilization of the agricultural solid wastes is
of extreme importance.
The agricultural and wood processing wastes along with crop residues, urban
organic or animal wastes are considered as renewable biomass resources. The utiliza-
tion methods for processing of agricultural waste and other types of biomass have
been developed for a long time. In this connection, one of the most perspective direc-
tions is their usage as a renewable energy source. Solar energy is accumulated in vari-
ous biomass forms during the photosynthesis. Therefore, a variety of gaseous, liquid,
and solid fuels, or the so-called biofuels, can be derived from the biomass wastes. This
concept is known as waste-to-energy or energy-from-waste conversion.
Lignocellulosic biomass is a complex solid material constructed from oxygen-
containing organic polymers produced via natural processes. Carbohydrate poly-
mers and oligomers (65–75%) and lignin (18–35%) represent the major part of the
structural chemical high-molecular components. In the future, an important advan-
tage of using biofuels in comparison with traditional petrochemical hydrocarbons
would be the diminishing gaseous emissions, which affect the environment and
climate (Sudiro and Bertucco 2007). Additionally, it allows one to reduce the cost
Fig. 8.1 World map with highlighted countries producing rice in million metric tons per annum
(MMTPA): >150 MMTPA (red); >25 MMTPA (orange); >5 MMTPA (yellow); >1 MMTPA (light
yellow)
8 Conversion of Rice Husk and Nutshells into Gaseous, Liquid, and Solid Biofuels 173
of the catalytic posttreatment (Marquit 2009). Most agricultural wastes contain a

significantly lower amount of fixed sulfur and nitrogen when compared with the
fossil fuels (e.g., bituminous coal). Therefore, such fuels derived from biomass can
be considered as renewable with a diminished level of SOx and NOx emissions.
In this chapter, the approaches of biofuel production from rice residues (e.g., rice
husk) and dry tree nuts wastes (e.g., almond, walnut, cashew, pistachio, and hazelnut
nutshells) are reviewed. The attractiveness of rice wastes as a source of biofuels is
stipulated by a huge popularity of this crop in the world (747 million tons per year). In
terms of a worldwide tonnage, rice is inferior to the totality of the cereal crops. At the
same time, it gives the largest amount of the solid wastes (Nakhshiniev et al. 2014).
Figure 8.1 presents the rice production areas in the world map. As it can be seen that
the top ten countries producing rice are China, India, Indonesia, Vietnam, Thailand,
Bangladesh, Myanmar, the Philippines, Brazil, and Pakistan. Therefore, nearly 90% of
world’s areas of rice cultivation are in the Asian countries. The leading positions in this
list are occupied by China (market share of 28%) and India (market share of 28%).
The major rice residues are husk and straw. Both these types of wastes have a
great potential to be considered as the source for waste-to-energy concept. The
annual volume of rice husk production is estimated to be 149 million tons. On the
other hand, it should be mentioned that rice husk is characterized with high ash
content, which is equal to 20–25 wt% depending on the geographical area for culti-
vation. From this point of view, agricultural wastes of nuts cultivation (nutshells)
are much more attractive, since the content of ash component irrespective to the nut
type does not exceed 5 wt%, which is significantly lower.
The countries producing majority of tree nuts are shown in Fig. 8.2. The world lead-
ers are African countries (cashew), Turkey (hazelnut and pistachio), Iran (pistachio),
India (cashew), China (walnut), the USA (almond, walnut, and pistachio), and Vietnam
(cashew). It is worth mentioning that the efficient processing of agricultural wastes into
Fig. 8.2 World map with highlighted countries producing the five most widespread tree nuts in
million metric tons per annum (MMTPA): >1 MMTPA (green); >0.02 MMTPA (light green);
>0.005 MMTPA (blue)
biofuels is more advantageous comparing with the cultivation of biofuel-oriented crops

(Jatropha, Miscanthus, etc.) (Nigam and Singh 2011). In this case, firstly, the technol-
ogy of agricultural food production can become non- waste and environmentally
friendly, and secondly, no re-orientation of the current land tenure is required.
8.2 hysicochemical Characterization of Rice Husk

P
and Nutshells
8.2.1 Rice Husk
The technological scheme to produce alimentary rice from paddy consists of a

shelling process with the separation of rice husk, which results in the appearance of
the so-called brown rice. Subsequent milling and classification procedures allow
one to separate rice bran and broken rice. Therefore, the main solids being formed
during the rice production are rice straw, husk, ash, bran, and broken rice (Moraes
et al. 2014). The hull formed during the grain growth represents the rice husk, and
it is of 8–10 mm in length, 2–3 mm in width, and 0.2 mm in thickness (Fang et al.
2004). The density of the husk is quite low, i.e., 122 kg/m3. On an average, its vol-
ume is estimated to be about 20% of the rice weight.
Since the rice husk contains a low level of nutrients and a high amount of silica, it
cannot be considered as a component for the production of fodder (Moraes et al. 2014).
Along with a set of building and materials science applications (e.g., incineration with
subsequent usage of rice husk ash in concretes (Fapohunda et al. 2017)), other applica-
tions of rice harvest residues include the synthesis of the catalyst using rice husk ash
(Tang et al. 2018), production of highly porous sorbents (Larichev et al. 2013, 2015;
Yeletsky et al. 2009), carbon-based materials for supercapacitors (Lebedeva et al.
2018a, b, 2015), and use as solid fuel and feedstock in biofuel production.
When biomass is considered as a precursor for biofuels, the key characteristic is
its chemical composition. The main components of the rice husk are cellulose
(28.6–41.5 wt%), hemicellulose (14–28.6 wt%), lignin (20.4–33.7 wt%), and inor-
ganic residues (about 20 wt%). The variety of the composition depends on the
weather conditions, agronomical treatment, soil type, and other environmental
parameters. Rice husk contains more amounts of cellulose and hemicellulose than
lignin in contrast to the wood residue (Goenka et al. 2015). In the case of cellulose
and hemicellulose, the polymer chains are shorter when compared with lignin.
Therefore, the rice husk can be more efficiently depolymerized forming the biofuel
(Nelson et al. 2018). The inorganic residues consist of 95–98 wt% of silica in an
amorphous hydrated state (Housten 1972).
8.2.2 Nutshells
In the case of nutshells, the technological process of separation of nut kernel from
other parts of nut (soft nutshell or wet nutshell) can be varied significantly
depending on the type of nut. Besides the traditional drying, stages such as extrac-
tion of the components contained in the soft nutshell can be included. The finally
obtained dry nuts undergo further processing such as shelling and separation proce-
dures, giving at the end the nut kernels and the dry nut shell. It should be empha-
sized that compared to the solid wastes from the milled rice production, the amount
of the processing wastes from the nut kernel production is significantly higher. For
instance, in the case of cashew, the weight of waste exceeds 70% of the initial
unshelled nut by weight.
The range of the compounds present in the nutshell is noticeably wider. The
extracts derived from the soft nutshell are efficiently applied in synthetic chemistry,
perfumery, cosmetics, and other related sectors (Balachandran et al. 2013; Balgude
and Sabnis 2013). In particular, soft cashew nutshell contains about 30–35 wt% of
cashew nutshell liquid (CNSL or cashew shell oil), which is commercially available
and widely used in biomedicine, materials science, and chemical industry (Hamad
and Mubofu 2015; Lomonaco et al. 2017; Tullo 2008). The main difference between
rice husk and nutshells is lower ash content of the latter. This makes the nutshells a
more suitable type of the agricultural wastes as for direct combustion as for the
synthesis of biofuels. Table 8.1 summarizes the data on the composition of rice husk
and nutshells under consideration. It should be noted that the processes for nutshells
conversion are much less reported in the literature than those for rice husk, which is
due to the lower volumes of nuts production.
8.3 Conversion of Rice Husk and Nutshells into Biofuels
The processes of the agricultural wastes utilization with energy production can be
divided into two categories. The first category considers direct usage of biomass as
a fuel for combustion with the production of heat and electricity. The second cate-
gory is represented by the processes for preliminary transformation of raw biomass
into other forms of energetic products (e.g., depolymerization with elimination of
ash-forming components) for their further application as an energy source (Goyal
et al. 2008). This category includes biochemical (e.g., anaerobic digestion) and ther-
mochemical (e.g., pyrolysis or gasification) conversions. All these processes facili-
tate the synthesis of solid, liquid, and gaseous biofuels.
A tendency toward the complexity of the biomass conversion technological schemes
is observed (Fig. 8.3). Such schemes include the primary procedures of the thermo-
chemical and biochemical treatments of the raw feedstock, thereby transforming it into
an easily transportable precursor of biofuels (or synthetic transportation fuels).
Furthermore, the biofuel precursors are responsible for the realization of the final syn-
thesis stage of biofuel with high-energy characteristics. During the last few decades,
biofuel upgrading processes have gained wide attention. For example, hydrodeoxygen-
ation process is aimed at reducing the amount of oxygenates in the composition of
biomass-derived fuels, thereby diminishing the corrosive properties and increasing the
energy characteristics (Bykova et al. 2012; Dundich et al. 2010; Kukushkin et al. 2015).
176
Table 8.1 Composition and higher heating values of the rice husk and nutshells
Volatile Fixed Atomic ratios Higher
Biomass Moisture matter Cellulose Hemicellulose Lignin carbon Ash heating value
source (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) O/C H/C (MJ/kg) References
Rice husk 6.0 52.0 25.1 28.6 24.4 15.0 16.9 0.65 1.55 13.4 Fang et al. (2004),
Goenka et al. (2015)
Almond 8.7 79.7 38.5 28.8 29.5 19.3 2.3 0.70 1.44 18.9 Demirbaş (2010), Savova
nutshell et al. (2001)
Walnut shell 7.7 77.9 26.9 22. 5 47.7 13.5 0.94 0.61 1.52 17.2 Kar (2011)
Cashew 10.4 69.3 – – – 19.3 1.0 0.66 1.71 24.1 Das and Ganesh (2003)
nutshell
cake
Pistachio 5.8 84.9 43.0 25.3 16.4 12.9 2.2 0.66 1.7 18.0 Goldfarb et al. (2017), Li
nutshell et al. (2018)
Hazelnut 10.9 69.0 25.9 25.9 42.5 19.4 1.35 0.62 1.27 21.4 Çepelioğullar and Pütün
shell (2013), Demirbaş (1997)
A. P. Koskin et al.
8
• Drying
• Dewatering
Direct • Sizing
Preliminary
Combustion Treatment
Raw • Densification (Pelletization, Briquetting)
Biomass • Separation
Treated
Biomass • Torrefaction
• Lignin depolymerization
Bio-ROH Anaerobic
Pyrolysis HTC HTL Gasification
conversion digestion
Low grade High grade

Char HDO Low-MJ Gas Medium-MJ Gas
liquid fuel liquid fuel
Combustion
Use in internal combustion

Heat, External combustion engine Power engine
Conversion of Rice Husk and Nutshells into Gaseous, Liquid, and Solid Biofuels
Fig. 8.3 General scheme of biomass conversion (rice husk and nutshells) into solid, liquid, and gaseous biofuels
177
8.3.1 Pretreatment of Biomass
In some conversion processes, the initial raw biomass is required to be subjected to

pretreatment with the exact procedures depending on the type of the subsequent con-
version processes. Thus, high volatility and low density of the rice husk complicate its
processing and transportation. Consequently, typical approaches to the preliminary
treatment include size reduction, leaching (or washing), compaction (or agglomera-
tion), briquetting, and pelletization (Kaliyan and Morey 2009; Koppejan and Loo
2012). The first two procedures are required to be done before the thermochemical
processes since the last three procedures make the bioprecursor applicable for direct
combustion. During the compaction procedures, the density of biomass can increase
from 40–200 kg/m3 to 600–800 kg/m3 (Mani et al. 2003). Another way to make the raw
biomass more compactable is its partial pyrolysis knows as the torrefaction process
(Tumuluru et al. 2011).
Considering the chemical properties, it should be mentioned that the high alka-
linity of the biomass often leads to the formation of slag and other contaminants in
the combustion equipment. The leaching process (e.g., simple washing with water
or solvents) allows one to eliminate most of the undesired compounds from rice
husk and nutshells (Davidsson et al. 2002). In the case of biochemical transforma-
tions, the pretreatment of the lignocellulosic biomass is the defining stage aimed to
depolymerize lignin (Arora et al. 2019). In the initial biomass, fibers of cellulose
and hemicellulose are held together by lignin network consisting of the polysac-
charide layers, which complicates the enzymatic hydrolysis (Nanda et al. 2014).
Consequently, to subject cellulose and hemicellulose to the enzymatic action and
increase the efficiency of bioconversion, the lignin network should be destroyed and
eliminated during the preliminary treatment.
The most perspective methods of biomass pretreatment include treatment by
diluted acid, sulfur dioxide, ammonia vapors and lime (Sun and Cheng 2002). In
some cases, pretreatment procedures make significant contribution to the total cost
of the bioconversion process. The key parameters showing the efficiency of the
lignocellulosic biomass pretreatment are crystallinity, available surface area and
content of lignin and hemicellulose (Hendriks and Zeeman 2009). Therefore, the
aim of the pretreatment of lignocellulosic biomass is enlargement of the surface
area of biomass, decreasing of the cellulose crystallinity, elimination of hemicellu-
lose, and destruction of lignin (Karimi and Taherzadeh 2016).
The most investigated method for biochemical transformation of lignocellulosic
biomass into liquid biofuel is fermentation with the production of spirituous products
such as bioethanol and biobutanol. Other types of bioconversion (e.g., methane pro-
duction via anaerobic digestion as well as hydrogen production via fermentation) can
lead to formation of gaseous biofuels. In general, the process of bioethanol produc-
tion from lignocellulosic biomass consists of three main stages such as biomass pre-
treatment, enzymatic hydrolysis, and fermentation. The efficiency of pretreatment
methods defines the effectiveness of the biofuel synthesis process as a whole. The
main challenge is to destroy the lignin network, which forms protective covering
over cellulose and hemicellulose and making them inaccessible for hydrolysis.
Subsequent processes of enzymatic hydrolysis and fermentation include transforma-

tion of cellulose into glucose and hemicellulose into a number of pentose and hexose
sugars (Taherzadeh and Niklasson 2004) and production of bio-alcohols using spe-
cial microorganisms (Arora et al. 2019). The methods of simultaneous saccharifica-
tion and fermentation (SSF) are also under research (Karimi et al. 2006).
8.3.2 Direct Combustion of Rice Husk and Nutshells
Direct combustion of agricultural wastes is known as one of the oldest and fre-
quently applied processes for energy production (Yin et al. 2008). It is useful for
calorification, drying, and generation of steam for the processes of parboiling treat-
ment of the agricultural crops (Kwofie and Ngadi 2017). In an ideal case, all the
oxidized components of biomass can be saturated with oxygen in accordance with
the following equation:
C x O y H z N w Sv + aO2 → Energy + bCO2 + cH 2 O + eN m O p + dSOr (8.1)
Incineration of the agricultural wastes can be performed in the stoves of various
types such as stoves of opened fire, boilers, fixed-bed combustors, or fluidized-bed
combustors. It should be mentioned that in the case of the fixed-bed incineration,
only biomass with moisture less than 50% could be used. Among the disadvantages
of this technology, incomplete combustion of biomass, high atmospheric emissions,
incrustation, and corrosion in the burning chamber and ancillary equipment are
reported (Miles et al. 1996; Saidur et al. 2011).
Completeness of combustion can be achieved by using the preliminary treatment
described above (e.g., drying, milling, and leaching) or by the application of other
costly pretreatment technologies. For example, the highest efficiency of rice husk and
nutshells conversion processes including combustion, pyrolysis, and gasification can
be attained in a fluidized-bed reactor. Such reactor consists of a chamber containing a
bed of inert particles such as sand or catalytically active particles supported by a dis-
tributor plate (Natarajan et al. 1998). Extremely high heat transfer and mass transfer
characteristics of the fluidized-bed regime allow performing fast and practically com-
plete transformation of biomass into energy. The main advantage of fluidized-bed
reactors is that low-grade, less heat content, and low-density biomass sources with
irregular size of grains and high moisture content can be efficiently used.
The modern state of the technologies based on the fluidized-bed reactors guaran-
tees the high uniformity of the side combustion products. It gives an opportunity to
selectively trap particles of a defined size (e.g., silica-reached particles of rice husk
ash) for their further practical application (Fernandes et al. 2016; Pode 2016).
However, despite all the disadvantages of the direct biomass combustion in the
fixed-bed reactors, this technology is cost effective, which makes its application
more attractive in rural areas and especially in the developing countries (Moraes
et al. 2014). It should be emphasized that the rice production capacity in the world
is higher in the rural regions. Therefore, low-cost fixed-bed reactors could be a suit-
able alternative for bioenergy generation.
Another approach to enhance the efficiency of the direct combustion processes is

a briquetting technology. Rice husk and nutshells briquettes are obtained by press-
ing or compaction of biomass via compression at elevated temperatures (Ndindeng
et al. 2015). To achieve the required compaction degree, various binding compounds
can be used. The final briquettes are cylindrical in shape with a varied diameter from
3 to 20 cm and length from 15 to 50 cm. Thus, direct combustion of the briquette
made from rice husk emits noticeably lower amount of particulate matter when
compared with raw rice husk. Besides, the higher heating value and density of this
solid biofuel can be increased up to 15.5–16.3 MJ/kg and 360–600 kg/m3, corre-
spondingly (Yank et al. 2016).
Comparative analysis of the direct combustion processes with similar technologies
is reported in a number of research and review papers (Baetge and Kaltschmitt 2018;
Lim et al. 2012; Pode 2016; Quispe et al. 2017; Simonov et al. 2003). Unfortunately,
the combustion of nutshells is poorly described in the literature. da Silva et al. (2017)
studied the pistachio shell combustion. Other researchers have reported a benefit of an
alternative technology considering the usage of joint combustion (or co-firing) of rice
husk or nutshells along with other types of biomass such as sugarcane bagasse and
coal (Kuprianov et al. 2006; Sathitruangsak and Madhiyanon 2017; Wu et al. 2015).
Combining briquetting and co-firing technologies together can be promising. In this
case, rice husk or nutshells are pressed together with fossil fuel residues (e.g., lignite)
or other types of wastes (Özyuğuran et al. 2017). No additional binding compounds
are required to achieve the desired density of the briquettes.
8.4 Rice Husk and Nutshells as Sources of Biochar
During the last decades, the more advanced methods alternative to the direct com-
bustion of the agricultural wastes are under intensive development. Within the con-
cept of these methods, biomass is preliminary converted into high-calorific value
product with denser and less-ash-containing materials (Basu 2010). The energy
content is usually increased by the elimination of oxygenates from the raw biomass.
Compression of the solid fuel materials simplifies the logistics of the processes. The
main methods for the synthesis of solid fuels from biomass are predominantly slow
and intermediate pyrolysis, inert and hydrothermal carbonization, and torrefaction.
In the case of accelerated processes (e.g., fast and flash pyrolysis), liquid and gas-
eous fuels are being formed (Mohan et al. 2006).
8.4.1 Pyrolysis
Pyrolysis is a thermal process used for the decomposition of organic sources at high
temperatures in the absence of oxygen. Such kind of thermal treatment results in
irreversible changes in both the chemical composition and physical properties of
biomass (Mohan et al. 2006). The pyrolysis processes can be easily used in rural
regions dealing with a huge variety of biomass and agricultural byproducts, which
could make these processes the most advantageous. Characteristics of the main
pyrolysis processes are summarized in Table 8.2. As seen, in the most cases, a com-
position of liquids (bio-oil), gases (producer gas) and solids (biochar) results from
the process. Carbonization process leads to the formation of biochar. The phase
composition and energy characteristics of the pyrolysis products depend signifi-
cantly on the process conditions (Neves et al. 2011). Thus, depending on process
conditions such as heating rate, residence time, reaction temperature, and feed rate,
the pyrolysis processes can be divided into carbonization and slow, fast and flash
pyrolysis (Basu 2010; Mohan et al. 2006; Nanda et al. 2016).
In some investigations, intermediate and ultra-fast pyrolysis are also mentioned.
In general, the conditions of the process are selected to maximize the yield of the
desired product. Byproducts are often used for the generation of energy, which is
required for drying of raw biomass (pretreatment) or considered as a part of energy
consumed during the pyrolysis (Dufour et al. 2009). Non-condensable gases (e.g.,
H2, CO, CO2, CH4, and CxHy) formed as pyrolysis byproducts can be reused as gas-
eous fuel in boilers or as a source for hydrocarbon production using catalytic
Fischer-Tropsch process.
In general, the yield of the solid fuel (biochar) can be increased by using the
smaller fraction of biomass, lower heating rates, longer duration of the process, and
lower maximum temperature (Neves et al. 2011). Carbonization method is optimal
in terms of the highest biochar yield. However, in this case, the expenditure of
energy is not comparable with energy profit. The efficiency of this process can be
improved by performing it in the presence of water steam under high pressure (i.e.,
hydrothermal carbonization) or methane (i.e., methanopyrolysis) instead of inert
atmosphere. The method of methanopyrolysis is quite unique since it allows to
obtain the semi-products for synthetic chemistry (Mohan et al. 2006).
Both slow and intermediate pyrolysis processes are carried out at temperatures
below 500 °C in a regime of slow heating rate and longer residence time (Park et al.
2014). Another process of biomass conversion into solid biofuel is torrefaction. In
this process, raw biomass is partly pyrolyzed within a temperature range of 200–
300 °C, which leads to diminishing the moisture content in biomass and depolymer-
ization of hemicellulose (Medic et al. 2012). Therefore, this process allows
producing energy dense and easily transportable precursors of solid fuels.
Different generic types of biomass gasifiers and pyrolyzers have been developed
and commercialized for the conversion of biomass of different nature. The construc-
tion of these reactors can be categorized using the following criteria:
1. Type of the mutual displacement of the layers of biomass and decomposition

medium inside the reactor.
2. Type of the process defined by the heating rate and temperature, decomposition
medium, and biomass feeding rate (residence time).
According to the abovementioned criteria, the reactors can be divided into batch
reactors, moving-bed reactors, reactors with mechanical movement, and fluidized-
bed reactors (Basu 2010). In the case of batch reactors, no solid movement through
182
Table 8.2 Main types of the pyrolysis processes

Reaction conditions Biofuel yield (wt%)
Process Temperature (°C) Residence time Heating rate Medium Char Liquid Gas
Carbonization 400 Days Slow Inert <40 – –
Slow pyrolysis 400–600 5–30 min Slow Inert 25–35 20–50 20–50
Fast pyrolysis 450–600 1–2 s Fast Inert 10–25 50–70 10–20
Flash pyrolysis <650 <1 s Fast Inert – 70–80 20–30
Vacuum pyrolysis 350–550 2–30 s Medium Vacuum – 60–70 –
Hydrothermal carbonization 180–250 1–2 h Fast Water vapors 50–90 – –
Reference: Mohan et al. (2006), Basu (2010), Nelson et al. (2018)
A. P. Koskin et al.
the reactor takes place during the pyrolysis process. The moving-bed regime is real-
ized in the shaft furnaces. Mechanical forces (e.g., rotary kiln, rotating screw, or
auger reactor) result in the movement and mixing of biomass particles. In the case
of fluidized-bed reactors, movement of biomass is caused by a fluid flow (e.g.,
fluidized-bed, spouted-bed, and entrained-bed). The majority of the reactors men-
tioned above are applied for conversion of rice husk and nutshells into solid biofuels
(Chakma et al. 2015; Demirbas 2006; Jeong et al. 2016; Lim et al. 2012; Moreira
et al. 2016; Quispe et al. 2017; Taghizadeh-Alisaraei et al. 2017; Unrean et al.
2018). Some of the technologies of rice husk processing into biochar by the pyroly-
sis methods are realized on a pilot-scale or large-tonnage scale in China, the USA,
India, and Brazil (Lim et al. 2012).
8.4.2 Hydrothermal Carbonization
Hydrothermal processes for biomass transformation are of great interest. Similarly

to the traditional pyrolysis, hydrothermal carbonization is realized at anaerobic con-
ditions, but water steam at elevated pressure is used instead of the inert medium
(Wang et al. 2018). Initial raw biomass can be used without preliminary drying, and
this is the advantage of the present approach. Dissolution and crystallization of
biomass occur under pre-critical and supercritical conditions. It allows avoiding
problems such as agglomeration that occur in the case of traditional pyrolysis. As
described above for pyrolysis, the conditions of the hydrothermal process determine
the phase composition of the resulting biofuel (Wang et al. 2018).
Hydrothermal biomass conversion processes include hydrothermal carbonization
(HTC), hydrothermal liquefaction (HTL), and hydrothermal gasification (HTG). The
choice of the exact process depends on the target products. In general, the hydrothermal
processes are performed at relatively low temperatures (180–250 °C) and under autog-
enous pressure (Funke and Ziegler 2010). As a result, the oxygen and hydrogen contents
become significantly lower due to dehydration and decarboxylation reactions.
On the other hand, it is worth to note that additional stage of filtration is required
to obtain the char in a purified state. Moreover, the necessity of the usage of high
pressures and catalysts reduces the attractiveness of this process. Despite the great
fundamental interest to the conversion of rice husk and nutshells using this approach
(Kalderis et al. 2014; Yang et al. 2015), the continuous process of the hydrothermal
carbonization is not yet realized on the industrial scale as most of the achievements
are obtained on the laboratory scale (Elliott et al. 2015).
8.5 ice Husk and Nutshells as Sources of Bio-oil: Pyrolysis

R
and Hydrothermal Liquefaction
In the case of slow pyrolysis, the liquid phase (bio-oil) is considered as an undesired
byproduct since it contains a large amount of oxygenates (Mohan et al. 2006;
Mohanty et al. 2013). The fast pyrolysis methods give higher portion of liquid
biofuels, which are characterized by better energy parameters (Goyal et al. 2008).
Typically, fast pyrolysis is carried out at a temperature range of 500–700 °C with
fast heating and low contact times (Balat and Balat 2009). For vacuum pyrolysis,
the heating rates are noticeably lower when compared to fast pyrolysis. Moreover,
an increase in the bio-oil yield in the case of vacuum pyrolysis is achieved due to
lower residence time of the pyrolysis vapors and limited secondary gas-phase reac-
tions (Nachenius et al. 2013).
The production of bio-oil via the conversion of rice husk and nutshells of pista-
chio, cashew, hazelnut, and walnut have been described in detail elsewhere (Chakma
et al. 2015; Das and Ganesh 2003; Goldfarb et al. 2017; Lim et al. 2012; Miranda
et al. 2012; Patel et al. 2011; Pütün et al. 1999; Taghizadeh-Alisaraei et al. 2017;
Unrean et al. 2018; Zhang et al. 2017). The conceptual scheme of the pyrolysis
process is shown in Fig. 8.4. According to the literature, rice husk is preferable than
any other crop residues to obtain bio-oil. First of all, it is connected with the lower
amount of oxygenates formed as a result of rice husk conversion (Lim et al. 2012).
Secondly, pyrolysis or hydrothermal conversion of biomass with high content of
lignin including rice husk and nutshells gives a large portion of bio-oil. Due to this
feature of rice husk and nutshells, they were efficiently applied in various methods
of joint pyrolysis (co-pyrolysis) or hydrothermal co-carbonization along with other
types of biomass and solid wastes (Çepelioğullar and Pütün 2013; Hu et al. 2018;
Kar 2011; Onay 2014). For example, during the co-pyrolysis and co-hydrothermal
liquefaction of rice husk with wet algae, a synergetic effect attributed to the improve-
ment in the bio-oil quality was observed (Hu et al. 2018).
The quality of the produced bio-oil can be improved by using catalysts during
pyrolysis (Kwofie and Ngadi 2017; Yin et al. 2008). Various zeolite-based catalysts
and rice husk ash can be used in the catalytic pyrolysis processes of rice husk and
nutshells. Another alternative method is based on the intensified mass transfer
between pseudo-fluidized medium containing gaseous nitrogen and gases formed
during the pyrolysis process. It allows to increase the bio-oil yield up to 60 wt% at
a higher heating value (HHV) of 24.8 MJ/kg (Park et al. 2010).
The selection of hydrothermal conversion conditions gives a possibility to con-
sider the present method as an approach for the production of liquid biofuels (hydro-
thermal liquefaction). During the process of thermal depolymerization, raw biomass
is being converted into bio-crude oil under moderate temperatures and high
Non-
condensable
gases
Rice husk
Drying Pyrolysis Cyclone Cooler Bio-Oil
Nut shells
Hot
gases Char
Char
combustor
Fig. 8.4 Conceptual scheme of pyrolysis process for rice husk and nutshells
pressures (Shi et al. 2013). Carbon and hydrogen contents in the biomass undergo
transformation into hydrophobic compounds with low viscosity and high solubility.
Depending on the treatment conditions, the biofuel can be used either directly or
with upgrading in the heavy engines including ships and railway transport vehicles.
Bio-crude oil can also be upgraded to motor fuels as diesel fuel, gasoline, or jet
engine fuel (Quispe et al. 2017). However, it should be noted that hydrothermal
liquefaction and hydrothermal carbonization usually require the use of homoge-
neous or heterogeneous catalyst to improve the yield and quality of bio-oils.
Moreover, these processes are also considered to be operated under high pressures.
Along with it, aperiodicity of the technological regime worsens their practical value
(Elliott et al. 2015).
8.6 Rice Husk and Nutshells as Sources of Gaseous Fuels
8.6.1 Gasification
Gasification of biomass is a process of thermochemical conversion when biomass is

being transformed into synthesis gas consisting of CO and H2 gas mixture with
traces of CO2 and CH4 (Nelson et al. 2018). A schematic diagram of the gasification
process is presented in Fig. 8.5. The process is performed in gasifiers with con-
trolled feeding of the gasification agents such as steam, oxygen, and/or air and CO2.
The gasification process includes several oxidation reactions with the participation
of oxygen and steam as mentioned below.
C + H 2 O → CO + H 2 (8.2)
C + CO2 → 2CO (8.3)
The composition of synthesis gas depends on the gasification conditions and the
type of the gasifier. Another factor affecting the composition is the type of the bio-
mass source. Thus, the gas produced from rice husk typically contains CO2 (12.6%),
CO (17.9%), N2 (57.0%), H2 (8.8%), CH4 (1.9%), and others gases (1.8%) (Pode 2016).
Rice husk
Nut shells Syngas
Oxygen/Air/
Gasification Scrubbing Condensation Filtration
/Steam/CO2
Rice husk ash

Tar
Fig. 8.5 Conceptual scheme of gasification process for rice husk and nutshells
All the characteristics of biomass (i.e., particle size, moisture content, and density)
are also of equal importance. Ash formed during the gasification can be eliminated
in a dry state or in the form of slag. The slag-forming gasifiers are characterized by
the low gasification agent/carbon ratio. Along with it, the temperature of the process
is higher than the ash fusion temperature.
All the gasification processes have one general disadvantage, i.e., formation of
high-molecular gases, which undergo condensation and form tar (Reddy et al.
2014). It decreases the portion of biomass converted into target gaseous biofuel. The
HHV of synthesis gas produced is also reduced with tar formation. There are a few
alternative approaches to prevent the tar formation (Nelson et al. 2018). For exam-
ple, the amount of formed tar can be decreased by thermal cracking in the gasifying
reactor working at high temperature (>1000 °C) or by catalytic cracking at rela-
tively lower temperatures (≤750 °C) (Moghtaderi 2007). The produced synthesis
gas can be further used for the production of heat, electricity, or other types of fuel.
In average, the gasification of biomass allows to achieve an increase in HHV from
12 to 28 MJ/m3 (Sikarwar et al. 2016).
The gasification of rice husk and nutshells in different reactors is described else-
where (Farzad et al. 2016; Natarajan et al. 1998; Nelson et al. 2018). In the case of
the fixed-bed reactors, the gasification agent (steam, oxygen or air) is purged
through the biomass bed in counter-current or co-current flow configuration. In the
entrained flow regime, the gasification process (interaction with the gasification
agent) takes place in a dense cloud of dry pulverized biomass fine particles in co-
current flow. In the case of the moving-bed reactors, the biomass bed is purged with
the gasification agent at continuous stirring. Auger technology is based on the tubu-
lar reactor of continuous action with biomass feeding by rotating screw, and the heat
is transferred along the reactor wall. Another process, which should be mentioned,
is the gasification under autothermal conditions. In this case, the heat required for
the gasification of biomass is produced directly from the combustion of a part of raw
biomass (Milhé et al. 2013). Plasma gasifiers are also widely investigated (Rutberg
et al. 2011). Unfortunately, plasma-based processes are still unprofitable.
All the technologies mentioned above were applied for the gasification of rice
husk and nutshells (Chakma et al. 2015; Chen and Zhang 2015; Dogru et al. 2002;
Jain 2000; Makwana et al. 2019; Nadaleti 2019; Pode 2016; Shen et al. 2015; Sun
et al. 2009; Unrean et al. 2018; Wu et al. 2009; Yin et al. 2002). Similarly to the
methods of direct combustion and pyrolysis, the use of the fluidized-bed concept
gives significant preferences over other technologies (Natarajan et al. 1998). Along
with the complete oxidation of biomass, the temperature control is another impor-
tant characteristic feature. When biomass source is introduced into the fluidized-
bed, the high heat transfer and mass transfer parameters of the bed permit
the rapid energy conversion at practically isothermal condition. The reactors used
can be constructed in a traditional bubbling regime when biomass is fluidized by the
flow of gasification agent or in a circulating regime when additional stirring of the
fluidized bed is performed to provide a better gas–solid contact.
Since the potential of the biomass gasification is very high, the possibility of the
local electricity production using the biomass gasifying reactor system was recently
estimated (Abe et al. 2007; Mehrpooya et al. 2018; Pode 2016). It was shown that
despite the high-energy potential of rice husk, in the long term, additional bio-
mass resources would be required. The reasonability of such large-scale projects
mainly depends on the location of the processing plant, which affects the resource
availability and logistics costs of raw biomass supply. Therefore, it can be con-
cluded that to be prospective, the approach for the processing of rice husk and nut-
shells into gaseous fuels should consider performing the transformation of biomass
into easily transportable precursors and their further conversion (e.g., drying, pyrol-
ysis, volatiles oxidation/cracking, and gasification) at pilot-scale plants.
8.6.2 naerobic Digestion and Hydrogen Production

A
Via Fermentation
In the process of anaerobic digestion, microorganisms convert biomass in the

absence of oxygen into biogas, which is a mixture of CH4 and CO2. The gaseous
products can be subsequently used as a fuel to produce heat and electricity. This
process is well known and was reviewed several times (Angelidaki and Batstone
2010; Saxena et al. 2009). The anaerobic digestion of rice residues and nutshells is
widely reported in the literature, but most of these reports indicate the higher pros-
pect of rice straw and soft nutshells compared to rice husk and dry nutshells
(Gnansounou and Dauriat 2010; Khoo 2015). In the case of residue with increased
lignin content and low moisture content, higher economic resources are required in
the biomass pretreatment stage to facilitate the depolymerization of lignin.
Contrary to anaerobic digestion, the process of hydrogen production via fermen-
tation of agricultural wastes is relatively new. During the fermentation, anaerobic
bacteria transform carbohydrates into volatile fatty acids, H2, and CO2. The fermen-
tation process can be divided into photo fermentation and dark fermentation, when
different types of bacteria functionalize at different working conditions (Hallenbeck
2002). The key parameter defining the applicability of biomass in the bioconversion
processes is the ratio of the holocellulose (cellulose and hemicellulose together) and
lignin (Baetge and Kaltschmitt 2018).
The theoretical (maximum possible) yield of biogas in the case of rice husk was
calculated to be 542 m3/tODM. At the same time, experimentally this value was
found to be only 212 m3/tODM. The observed difference is attributed to the fact
mentioned above that lignin forms stable network which blocks the accessibility of
cellulose and hemicellulose. Thus, effective conversion of biomass with high lignin
content requires additional pretreatment procedures that can also increase the cost
of the entire process. Among the considered agricultural wastes, pistachio nutshells
only contain relatively lower amount of lignin. However, their usage is also limited
due to low moisture content. In this term, bioconversion of pistachio soft nutshells
is more economically preferable (Taghizadeh-Alisaraei et al. 2017). The same con-
clusions can be made for other types of nutshells when comparing them in the soft
and dry states.
8.7 Calorific Values of Rice Husk and Nutshells as Biofuels
The most important parameters of the raw biomass including agricultural wastes
and the derived biofuels are volatile matter, moisture, ash, and fixed carbon con-
tents. The contents of volatile matters in the solid fuel can be measured experimen-
tally as a part exuded in the gaseous form including water at a temperature range of
25–850 °C in an inert atmosphere. The ash content can be also determined experi-
mentally. The fixed carbon value can be calculated as the difference excluding ash
content. The volatile matters and fixed carbon parameters define the value of the
chemical energy accumulated in the solid fuel. Therefore, the HHV depends on the
biomass composition and is estimated as the amount of energy which can be poten-
tially obtained from the biomass or biofuel.
To compare the biomass sources or the derived biofuels, the elemental composi-
tion is proposed as an essential parameter. The significance of O/C and H/C atomic
ratios of the biomass or biofuels on their calorific value is illustrated in Fig. 8.6
using the Van Krevelen diagram (Van Krevelen 1950). The values of H/C and O/C
atomic ratios depend on the biomass source, operating conditions, moisture content,
and the treatment procedures. Figure 8.6 demonstrates these ratios for various bio-
masses and products.
CH4
Hydrogenaon
Tends to higher
HHV
Reducon Oxidaon
EtOH
anaer. dig.
BuOH Dehydrogenaon
Gasoline to H2
Diesel
Bio-oil
C
Biodiesel HT-oil Raw biomass

Crude oil
HT-char HC to CO2
L
to syngas mixture
Lignite Torriefied biomass
Coals
Bio-char
Anthracite CO
Fig. 8.6 Van Krevelen diagram comparing the heating value of different biomass and fuel prod-
ucts derived via biomass conversion processes
8.8 Conclusions
The growing demands for crops have resulted in an increasing amount of accumu-
lated agricultural solid wastes annually. On the other hand, these wastes can be
considered as the bioresources to produce biofuels. In this chapter, the conversion
of rice husk and nutshells into solid, liquid, and gaseous biofuels was reviewed. The
areas of application and efficiency of the conversion technologies strongly depend
on the chemical composition and physical properties of the processed biomass.
Thus, direct combustion of rice husk and dry nutshells is the simplest and cheapest
method of their usage as a solid fuel, but it is not the highly efficient one. On the
contrary, a variety of the solid and liquid biofuels can be achieved by tuning the
technological conditions of the pyrolysis processes. Gasification, anaerobic diges-
tion, and fermentation processes allow the production of energy-rich gases (e.g.,
synthesis gas, methane, and hydrogen), which can be easily used in the existing
industrial infrastructures. The final choice of the appropriate process should be done
considering the necessity of the additional preliminary treatment procedures, which
can make significant contribution to the overall cost of the process.
Acknowledgments The financial support by the Ministry of Science and High Education of
Russian Federation (project AAAA-A17-117041710086-6) is acknowledged with gratitude.
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A Review of Thermochemical
and Biochemical Conversion 9
of Miscanthus to Biofuels
Arshdeep Singh, Sonil Nanda, and Franco Berruti
Abstract
Miscanthus is recently being considered as an energy crop for biofuel production
because of certain features, such as adaptability to lower temperature, efficient
use of water and nutrients, low or no need of nitrogen fertilisers, high biomass
yield, fast-growing cycle and less-intensive agricultural cultivation practices
than other energy crops. This review is focused on the value-added applications
and conversion of Miscanthus for bioenergy and biomaterial applications. The
thermochemical conversion technologies reviewed in this chapter include pyrol-
ysis, liquefaction, torrefaction and gasification, whereas biochemical conversion
technologies include enzymatic saccharification and fermentation. The value-
added applications of Miscanthus discussed in this chapter include pulp and
papermaking, biocomposites and biochemical production. The physicochemical
properties of bio-oil and biochar generated from Miscanthus have been thor-
oughly described for fuel and material applications.
Keywords
Miscanthus · Energy crop · Bio-oil · Biochar · Pyrolysis · Liquefaction
A. Singh · F. Berruti
Department of Chemical and Biochemical Engineering, University of Western Ontario,
London, Ontario, Canada
S. Nanda (*)

196 A. Singh et al.
9.1 Introduction
Waste plant biomass has been used as the traditional source for heating and cooking
by the rural population worldwide. Owing to their renewable nature, low-cost avail-
ability and abundancy, waste plant biomass and organic residues are considered for
the production of biofuels that are carbon neutral and generate low net greenhouse
gas emissions (Nanda et al. 2016d, 2017d). However, for the sustainable production
of bioenergy, it is important that the biomass is non-edible to prevent any food ver-
sus fuel controversy with no competition to food supply and arable lands (Nanda
et al. 2015a). Lignocellulosic biomass is a collective group of non-edible plant resi-
dues containing cellulose, hemicellulose and lignin, examples of which include
agricultural biomass, forestry residues, energy crops and invasive plants (Nanda
et al. 2013). Lignocellulosic biomass is also known as second-generation feedstock
because it is non-edible and includes residues such as wheat straw, corncobs, rice
husk, hybrid poplar, switchgrass, Miscanthus, etc.
Coal has been traditionally one of the most widely used fossil fuel resources
because it has carbon content of 75% to 90% (Jenkins et al. 1998). On the other hand,
biomass consists of 50% carbon, along with considerable amounts of oxygen, gener-
ating lower heating value than other fossil fuels. The combustion of biomass is also
hindered by the presence of alkali and alkaline earth metals, which form ash, resulting
in corrosion, plugging, agglomeration, silicate melt-induced slagging and ash fusion
in biomass-based power plants (Niu et al. 2016). Hence, suitable thermochemical and
biochemical conversion technologies should be implemented to efficiently convert
waste biomass to liquid and gaseous fuels (Fig. 9.1). Moreover, lignocellulosic bio-
mass is more suitable for thermochemical conversion to produce alternate fuels than
petrochemical resources, such as coal, because of its high volatile components.
Fig. 9.1 Conversion of biomass to biofuels through thermochemical, hydrothermal and biochemi-
cal technologies
9 A Review of Thermochemical and Biochemical Conversion of Miscanthus… 197
Miscanthus is one of the invasive plants, a genus of almost 20 perennial grass

species, predominantly found in Asia and the pacific islands but invasive in most
other geographical regions. Most of the native species of Miscanthus are found in
China, Korea, Japan, Taiwan and the Philippines (Clark et al. 2014). Miscanthus has
been recently targeted as a potential energy crop for biofuel production. As an
energy crop, Miscanthus has many salient features, such as adaptability to lower
temperature, low requirement of nutrient, efficient use of water and nutrients, low or
no need of nitrogen fertilisers, high biomass yield, fast-growing cycle and less-
intensive agricultural cultivation practices (Nanda et al. 2016b). Some of the com-
monly found species of Miscanthus are M. giganteus, M. sinensis, M. sacchatiflorus,
M. floridulus, M. fuscus, M. junceus and M. changii.
Miscanthus exhibits better properties than switchgrass, another energy crop, in
terms of tolerance to low temperatures, higher biomass yield, higher heating value
and lower moisture content (Robbins et al. 2012). For instance, the typical biomass
yield from M. floridulus (27.8–38 tons/ha/year) is much higher than that from
switchgrass, Panicum virgatum L. (15 tons/ha/year) (Lee and Kuan 2015). In con-
trast, another invasive crop, giant reed (Arundo donax), has an even higher biomass
yield and enhanced tolerance to drought than Miscanthus (Ge et al. 2016). However,
Miscanthus has high tolerance to the flooding pattern than giant reed. When com-
pared with maize, Miscanthus can perform photosynthesis and grow at much lower
temperatures (Dohleman and Long 2009).
Energy crops, such as switchgrass (Yu et al. 2016), timothy grass (Nanda et al.
2016b), elephant grass (Fontoura et al. 2015), hybrid poplar (Shooshtarian et al.
2018), giant reed (Low et al. 2011) and microalgae (Su et al. 2017), have been inves-
tigated for second-generation biofuel production through thermochemical and bio-
logical conversion processes. However, there is limited literature available on the
biorefining of Miscanthus for biofuel, biochemical and biomaterial production. This
chapter aims at reviewing the current knowledge on the potential of Miscanthus as
an energy crop for biorefining. This chapter summarises the thermochemical con-
version technologies (e.g. pyrolysis, gasification, liquefaction and torrefaction) and
biological conversion technologies (enzymatic hydrolysis and fermentation) of
Miscanthus to produce value-added products, such as biofuels, biochar, as well as
combined heat and power (Fig. 9.1).
9.2 Cultivation of Miscanthus
The annual biomass yields from M. giganteus, M. floridulus and M. lutarioriparius

is found to be 14.8–33.5, 27.8–38 and 32 tons/ha, respectively (Lee and Kuan 2015).
M. giganteus is a sterile hybrid between M. sinensis and M. sacchatiflorus, which is
beneficial in generating high biomass yields. Typically, mature M. giganteus can
grow up to 3–4 m in height. Moreover, it is also resistant to pests and diseases and
has extraordinary tolerance to draught and cold temperatures, thus making it a desir-
able energy crop (Lewandowski et al. 2003, Yu et al. 2013). However, the disadvan-
tage of culturing M. giganteus is that it does not produce any seed. Therefore, it can
198 A. Singh et al.
only be propagated through rhizome cutting (Bousiosa and Worrell 2017). Typically,
C4 plants can convert solar energy into carbohydrates in their biomass through pho-
tosynthesis 40% higher than C3 plants.
The plants can be classified based on the process of photosynthesis, i.e. light reac-
tion and dark reaction. In light reaction, chlorophyll in plants in the presence of sun-
light (solar energy) synthesise energy-rich compounds such as adenosine triphosphate
(ATP) and some co-enzymes, whereas in dark reactions, ATP and co-enzymes are con-
verted into carbohydrates and CO2. The dark reaction follows C3 and C4 cycles. C3
plants use Calvin cycle (or C3 cycle), while C4 plants use Hatch-Slack pathway (or C4
cycle) for photosynthesis. The names C3 and C4 appears in these photosynthetic path-
ways because of the first stable carbon products, such as phosphoglyceric acid (a three-
carbon compound) and oxaloacetic acid (a four-carbon compound), respectively.
Product quality and quantity mainly depend on the composition of the raw mate-
rial. The composition of Miscanthus genotype varies according to the harvesting
season. The contents of hemicellulose and cellulose in Miscanthus in the summer
harvest are higher than in the winter harvest. For instance, the yield of cultivation of
M. giganteus in Austria in autumn harvest was 17–30 tDW/ha compared to the win-
ter harvest of 22 tDW/ha (Nsanganwimana et al. 2014). Similarly, biomass yield
from M. giganteus in Germany during the autumn season (17–30 tDW/ha) was
higher than in the winter season (10–20 tDW/ha). Likewise, the autumn harvest
from M. giganteus cultivated in Portugal was also higher (39 tDW/ha) than in the
winter (26–30 tDW/ha) (Nsanganwimana et al. 2014).
In a study, M. sinensis genotype showed a significant difference in the production of
biogas because of two different harvests, i.e. summer cut versus winter cut (van der
Weijde et al. 2016). The biogas yield from Miscanthus from its summer harvest (539–
591 mL/g dry matter) was found to be greater than its winter harvest (441–520 mL/g dry
matter). Fermentation and the ability to release sugar was also higher in the summer
harvest than in the winter harvest. An important parameter for combustion quality, i.e.
ash content, was higher in the summer harvest (3.3 wt%) than in the winter harvest
(1.5 wt%). Therefore, a delay in the spring harvest benefits the combustion of Miscanthus
quality due to the relatively lower K, Cl and N contents (Brosse et al. 2012).
Miscanthus can be cultivated for up to 25 years. It has two growth phases, namely
building phase and adult phase. The biomass yield in the first year of cultivation is
around 5.9 ton/ha, whereas in the second and third year of the growth, the biomass
yield can be between 8 and 13 ton/ha (Arnoult and Hulmel 2015). The canopy height
and stem mass also increase rapidly within three years. The genotype variability is
more evident in the initial two to three years. Weather conditions and atmospheric
temperature affect the biomass production in the first year of crop establishment.
Low atmospheric temperatures after the first winter of crop establishment decreases
biomass yield. For instance, M. giganteus and M. sacchariflorus died after the first
winter when cultivated in Sweden and Denmark, whereas M. sinensis clones sur-
vived. The drop in the temperature explained the cause of the death during the first
year of plantation (Arnoult and Hulmel 2015).
Nitrogen application via fertiliser also affects the biomass quality of M. giganteus.
When the content of nitrogen was increased, the levels of cellulose, hemicellulose and
lignin in the above-ground biomass decreased while ash concentration increased. The
heating value of biomass is dependent upon the elemental composition (carbon,
hydrogen and oxygen) and the variation in the content of cell wall composition and
ash (Nanda et al. 2014a). Typically, on a dry basis, Miscanthus contains 47.1–49.7 wt%
carbon, 5.38–5.92 wt% hydrogen and 41.4–44.6 wt% oxygen. The reported higher
heating value of M. giganteus ranges between 17 and 20 MJ/kg (Brosse et al. 2012).
Miscanthus is a candidate energy crop within the lignocellulosic biomass family.
As the name suggests, lignocellulosic biomass comprises of cellulose (35–55 wt%),
hemicellulose (20–40 wt%) and lignin (10–25 wt%) (Nanda et al. 2017c). Cellulose
is a repeating polysaccharide of β-d-glucopyranose units, whereas hemicellulose is
a matrix polysaccharide containing pentose sugars, hexose sugars and sugar acids.
Lignin is a three-dimensional phenylpropane polymer, which binds cellulose and
hemicellulose together to provide structural rigidity and integrity to the biomass
(Fougere et al. 2016). The relative concentration of lignin acts as the determinant
factor during the thermochemical and biochemical conversion of lignocellulosic
biomass to biofuels. Since lignin is insoluble in acids and enzymes, except for
alkali, its presence creates hurdles for the biological conversion of lignocellulosic
biomass to alcohol-based biofuels. However, for thermochemical conversion, such
as pyrolysis and hydrothermal liquefaction, the high-content lignin results in bio-oil
with satisfactory fuel properties (Hodgson et al. 2011).
The composition of Miscanthus depends upon different genotypes, harvesting
time, growth seasons, geographical locations and type of fertilisers applied.
Miscanthus also contains fatty acids, sterols and other aromatic compounds as the
extractives (Brosse et al. 2012). These extractives are of high value in terms of pre-
cursors for industrial chemicals and materials. The polysaccharides in Miscanthus
include α-cellulose (50.9 wt%), β-cellulose (11.9 wt%) and γ-cellulose (10.6 wt%),
whereas monosaccharides include xylose (14.9 wt%), arabinose (1.1 wt%) and
galactose (0.3 wt%) (Villaverde et al. 2010). The compositions of cellulose in M.
giganteus, M. floridulus and M. lutarioriparius are, respectively, 33.9, 43.1 and
43.9 wt% (Lee and Kuan 2015). Similarly, lignin contents in M. giganteus, M.
floridulus and M. lutarioriparius were found to be 26.9 wt%, 22.3 wt% and
23.2 wt%, respectively. The composition of acid insoluble and acid soluble lignin in
Miscanthus is 20.8 wt% and 0.9 wt%, respectively (Villaverde et al. 2010). The
effect of biomass composition upon the higher heating value (HHV) also depends
on the presence of lignin because lignin has nearly 30% higher calorific value than
cellulose and hemicellulose together, along with lower oxygen content (Nanda et al.
2015b).
9.3 Value-Added Industrial Applications of Miscanthus
Some developing applications of Miscanthus in the chemical, pulp and papermak-

ing and biocomposite industries have been reported (Fig. 9.2). The cellulose present
in Miscanthus is being considered as a promising substrate for ethylene glycol pro-
duction (Pang et al. 2014). Ethylene glycol is one of the bulk chemicals used
200
Fig. 9.2 Uses of Miscanthus for biofuel and biomaterial production

A. Singh et al.
worldwide with its consumption increasing over the years. Ethylene glycol is mostly
used to produce polyester and polyester resins and as a component for anti-freeze
solvent and reductive agent. It is traditionally produced from ethylene oxide, which
is a petroleum-base material. Another factor that makes Miscanthus more attractive
for ethylene glycol production is its lower lignin content, compared to other ligno-
cellulosic feedstocks. Moreover, lignin in herbaceous biomass is more easily
decomposed than woody biomass-based lignin. The water-soluble components in
Miscanthus (5.3 wt%) are much lower than those of corn stalk (33.1 wt%) and lig-
neous woody biomass (15–25 wt%), which makes it a suitable raw material to pro-
duce ethylene glycol.
To produce paper and board from lignocellulosic biomass, many methods have
been used to reduce pretreatment and logistics cost. Pulp and paper industries at a
global scale are now seeking for alternative feedstocks (i.e. agricultural biomass and
invasive plants) to reduce the dependency on woody biomass. Invasive plants like
Miscanthus have shown some promising attributes for use in pulp and paper indus-
tries. In China, M. sacchariflorus is being used for papermaking because of its fast-
growth cycle, high biomass yield and easy pulping (Cappelletto et al. 2000). When
compared with oat hull, pulp obtained from Miscanthus with sodium hydroxide
treatment gave better yield, which could be used as a main component of low-grade
paper and cardboard owing to satisfactory structural-dimensional characteristics
(Budaeva et al. 2015). On the experiment basis, Miscanthus pulp also showed prom-
ising results concerning yield and strength than hybrid poplar pulp (Bousiosa and
Worrell 2017). Refined Miscanthus soda pulp has abilities for use in packaging
paper, which also reduces the amount of starch added to the paper for strength
enhancement. In the Netherlands, it is already used to produce writing paper
(Bousiosa and Worrell 2017).
Nowadays, biopolymers are attracting global attention because of their biode-
gradable properties, which are retained from their sustainable biomass precursors.
However, due to lack of efficient technologies, the large-scale production of bio-
polymers is costlier than that of polymers derived from petroleum resources. To
reduce the cost of biopolymers, filler or binder materials from lignocellulosic bio-
mass are often used. Lignocellulosic polymers seem very effective because they can
be added up to 49% as binders without affecting the quality of the biocomposite
material. Adding fibres from Miscanthus into biopolymeric materials can improve
their performance and decreases their cost of biopolymer (Johnson et al. 2005).
However, it requires more research to be applied at an industrial level.
Two of the major components present in lignocellulosic biomass, i.e. cellulose
and hemicellulose, are used to generate natural fibres and biopolymers for biocom-
posite applications. On the other hand, polymeric and aromatic lignin has many
applications to be used to produce biofuels and platform chemicals. Many heteroge-
neous metal catalysts can be used to convert lignin into chemicals. Nickel is one of
such heterogeneous metal catalysts that can cleave the C–O and C–C bonds of lig-
nin. Different noble metals can also be used to depolymerise lignin, but their high
cost restricts large-scale applications (Finch et al. 2012).
202 A. Singh et al.
In catalytic depolymerisation of lignin, Miscanthus was milled to pass through a

40-mesh screen and reacted with Ni/C catalyst in methanol solvent at 225 °C under
H2 pressure (Luo et al. 2016). The liquid phase of lignin (279 mg/g) conversion con-
tained aromatic products rich in phenolics, whereas the solid phase (612 mg/g) was
composed of carbohydrates (e.g. glucan, xylan and arabinan). These depolymerised
products can be further converted into high-value chemicals. Despite the relatively
lower content of lignin in Miscanthus (13 wt%) than in hardwood (20–25 wt%), its
higher conversion in Miscanthus was observed, which makes it a potential feedstock
to produce phenolic compounds. Lewis acid catalysts were also used to convert the
solid carbohydrate residues to furfurals and levulinic acid (Luo et al. 2016).
Regardless, the major application of Miscanthus is realised in biofuel production.
Table 9.1 summarises the thermochemical and biochemical conversion processes
involved in the conversion of Miscanthus to solid, liquid and gaseous biofuels.
9.4 Pretreatment and Bioconversion of Miscanthus
9.4.1 Pretreatment Technologies
Lignocellulosic biomass requires pretreatment technologies involving chemical,

physical and biological agents to depolymerise the cellulose–hemicellulose–lignin
matrix and release the fermentable sugars for fermentation to alcoholic biofuels and
chemicals (Nanda et al. 2014c). There are many pretreatment methods available, but
some of the promising ones include mechanical methods (grinding, milling and
crushing of biomass), acid and alkali treatment, liquid hot water, organosolv, wet
oxidation, ozonolysis, CO2 explosion, steam explosion, ammonia fibre explosion
(AFEX) and ionic liquids (Menon and Rao 2012).
Liquid hot water has certain advantages over other widely used pretreatment
technologies (e.g. acid/alkaline pretreatment, ozonolysis, ammonia fibre explosion,
microwave etc.) concerning no chemical involvement, non-corrosiveness and lower
production of intermediate components, such as furfural and 5-hydroxymethylfurfural
(HMF). Liquid hot water is an environmental-friendly method and an attractive pro-
cess for the biomass pretreatment. A study by Li et al. (2013) indicated that water
washing of Miscanthus resulted in approximately 75 w/w% of suspended solids, 18
w/w% of precipitated solids, as well as 6 w/w% sand and salt.
Both furfural and HMF are sugar dehydration products obtained as intermediates
of biomass pretreatment. Owing to their wide applications, these are considered
among the top ten chemicals derived from bio-based materials (Yi et al. 2015).
However, the presence of furfural and HMF in the biomass hydrolysate is inhibitory
for the microorganisms to ferment monomeric sugars to alcohol-based biofuels, i.e.
bioethanol or biobutanol (Nanda et al. 2014b, 2017a, b; Sarangi and Nanda 2018).
Therefore, their recovery and separation from the biomass hydrolysate is highly
essential for the bioconversion of biomass to bioethanol and biobutanol. Moreover,
Table 9.1 Comparative yields of solid, liquid and gaseous biofuels from Miscanthus
Process Process conditions Product yield References
Slow pyrolysis Temperature: 500 °C Bio-oil: 45–51 wt% Oginni et al.
Reaction time: 30 min Biochar: 30 wt% (2017)
Feed amount: 400 g Gas: 20–25 wt%
Heating rate: 7 °C/min
N2 flow rate: 2 L/min
Reactor type: fixed bed batch
reactor
Fast pyrolysis Temperature: 350–550 °C Bio-oil: 25–69.2 wt% Heo et al.
Feeding rate: 2.5 g/min Biochar: 15–30 wt% (2010)
N2 flow rate: 3.0 and 4.0 L/ Gas: 5–55 wt%
min
Reactor type: fluidised-bed
reactor
Fast pyrolysis Temperature: 350–500 °C Bio-oil: 47.7–57.2 wt% Kim et al.
Feeding rate: 150 g/h Biochar: 17.1–22.0 wt% (2014)
Residence time: 1.29 s, Gas: 20.9–35.5 wt%
1.93 s and 3.87 s
Run time: 1 h
N2 flow rate: 3.0 and 4.0 L/
min
Reactor type: fluidised-bed
reactor
Gasification Temperature: 639–726 °C For lowest ER (0.234) at Xue et al.
Biomass flow rate: 639 °C: (2014a)
3.51–3.15 kg/h CO: 23.4 vol%
Air flow rate: 52.5–53 Ndm3/ H2: 16.9 vol%
min CO2: 42.5 vol%
Bed material loaded: 6.6 kg For highest ER (0.262) at
Equivalence ratio (ER): 639 °C:
0.234–0.264 CO: 39.5 vol%
N2: 5.5 kg/h CO2: 33.3 vol%
Reactor type: air-blown H2: 17 vol%
bubbling
Fluidised-bed gasifier
Liquefaction Temperature: 220–280 °C 50% bio-oil yield at 280 °C Hafez and
Feed: 10 g and 50% water/ethanol Hassan
Heating rate: 15 °C/min ratio; 280 °C was (2015)
Liquefying agent: water/ considered as the optimal
ethanol temperature
Catalysts: formic acid, zinc
chloride,
trifluoroacetic acid and
sodium carbonate
Biomass/solvent ratio (w/w):
1:6, 1:8 and 1:10
Water/ethanol ratio (v/v):
100:0, 90:10, 80:20, 70:30,
60:40 and 50:50
Reactor type: high-pressure
Parr reactor with stirrer
(continued)
204 A. Singh et al.

Process Process conditions Product yield References
Torrefaction Temperature: 250 °C Mass yield: 73 wt% Wafiq et al.
Run time: 30 min Energy yield: 80% (2016)
Feed: 130 g
N2 flow rate: 40 L/h
Reactor type: electrically
heated retort furnace
Torrefaction Temperature: 230–290 °C Mass yield: 65.3–92.3 wt% Xue et al.
Run time: 10–30 min Energy yield: 76.7–96% (2014b)
Feed: 130 g
N2 flow rate: 100 mL/min
Reactor type: horizontal
furnace and tubular quartz
reactor
Fermentation Pretreatment method: dilute Ethanol: 64–66% Guo et al.
acid (2008)
Temperature: 24 °C
Fermentation microorganism:
Candida shehatae
Fermentation Pretreatment method: Ethanol: 27–54% Guo et al.
0.73 wt% H2SO4 blended (2012)
with trifluoroacetic acid and
maleic acid
Temperature: 30 °C
Fermenting microorganism:
Saccharomyces cerevisiae
Fermentation Pretreatment method: NaOH Ethanol: 84.7% Han et al.
Fermenting microorganism: (2011)
Saccharomyces cerevisiae
Temperature: 32 °C
Time: 48 h
dilute sulfuric acid or alkaline pretreatment methods require solvent recovery and
wastewater disposal, which are often difficult, expensive and energy intensive.
Aqueous ammonia is also a good candidate for pretreatment because it shows
higher lignin removal with a 5% mixture of hydrogen peroxide. Ammonia is a suit-
able pretreatment agent because it is volatile, easily regenerated and weakly reactive
with carbohydrates (Yu et al. 2013). As Miscanthus has higher cellulose content
than other invasive crops, extracting it in liquid solution is beneficial for bioconver-
sion. When untreated Miscanthus was hydrolysed, it gave less than 5–10% glucan
and xylan conversion (Murnen et al. 2008). On the other hand, ammonia fibre explo-
sion (AFEX) pretreatment significantly increases the enzymatic hydrolysis of
Miscanthus and enhances the conversion between 30% and 90%, depending on the
pretreatment parameters used.
9.4.2 Bioconversion to Bioethanol
The biological production of bioethanol from lignocellulosic biomass is a multistep

process, which consists of physicochemical pretreatment, enzymatic saccharifica-
tion and microbial fermentation. In the first step, depolymerisation of lignin is
essential to break the cellulose-hemicellulose-lignin complex in the biomass. In the
second step, degradation of structural polysaccharides into fermentable sugars is
done via physicochemical and enzymatic pretreatments. In the second step, mono-
meric sugars are fermented to bioethanol using suitable bacterial or fungal species.
As mentioned earlier, the pretreatment of lignocellulosic biomass followed by enzy-
matic saccharification can degrade the complex polysaccharides, such as cellulose and
hemicellulose, into simple sugars, such as glucose and xylose, which can be converted
into bioethanol through fermentation. As mentioned earlier, the pretreatment of holo-
cellulose (cellulose and hemicellulose) and lignin sometimes releases certain interme-
diate degradation compounds, such as furfural, HMF and phenolics, at moderate to
high levels, which inhibit fermenting microorganisms (Hodgson et al. 2010). The neu-
tralisation of inhibitors in the fermentation medium (containing biomass hydrolysate
and monomeric sugars) or the separation of inhibitory compounds through adsorption
is essential for microbial fermentation (Nanda et al. 2017b, Sarangi and Nanda 2019).
Xylose-containing liquor can be fermented using the yeast Candida shehatae
because the common baker’s yeast, i.e. Saccharomyces cerevisiae, lacks the natural
ability to ferment C5 sugars. Nevertheless, glucose, a widespread C6 sugar present
in Miscanthus, can efficiently be fermented to bioethanol using S. cerevisiae. By
using C. shehatae, a 64–66% yield of ethanol was obtained from the dilute acid-
pretreated Miscanthus (Guo et al. 2008). However, the lower yield was due to the
presence of inhibitors in the liquor. Similar yield was reported when the fermenta-
tion was carried out by S. cerevisiae when sulfuric acid and trifluoroacetic acid were
used for the pretreatment of biomass (Lee and Kuan 2015). On a theoretical basis,
70% yield can be obtained within 48 h of fermentation (Brosse et al. 2009).
On an economical basis, the operating cost of ethanol fermentation from ligno-
cellulosic biomass (second-generation feedstocks) is still higher than that of starch
or sugar-based feedstocks (first-generation feedstocks) (Nanda et al. 2015a). The
main bottleneck is to have an efficient technology for biomass pretreatment to maxi-
mise fermentable sugar yields, as well as simultaneous fermentation of xylose and
glucose by a suitable yeast species (Lee and Kuan 2015). Although the development
of genetically engineered fungi is found to resolve the simultaneous fermentation of
glucose and xylose at the laboratory scale, their stability, vitality and efficiency are
still questionable when applied at the industrial level (Chandel and Singh 2011).
9.5 Thermochemical Conversion of Miscanthus
9.5.1 Pyrolysis of Miscanthus
Pyrolysis is a process involving thermal decomposition of biomass and organic wastes

in the absence of oxygen to produce condensable vapors (bio-oil), biochar and
206 A. Singh et al.
Fig. 9.3 Distribution of components in the pyrolysis of biomass
non-condensable gases, as shown in Fig. 9.3 (Bridgwater 2012). The condensable

vapors released from biomass pyrolysis can be quenched at different temperatures
into several bio-oil fractions, whereas the solid residues are carbonised to form char
(Azargohar et al. 2013). The gas products mostly arise from the carboxylic groups in
the unbranched structure of saccharides in biomass. Usually the thermal cracking of
hemicellulose releases CO2 and water vapor. On the other hand, during pyrolysis, cel-
lulose depolymerises, resulting in the cleavage of O–H and C–O groups, thus releas-
ing CO and water vapors (Azargohar et al. 2014).
The gaseous products from lignin include CH4 and H2, which mostly arise from
the branched polymer of aromatic rings and methoxy groups (–O–CH3) (Osman
et al. 2017). During pyrolysis, cellulose decomposes in the temperature range of
300–350 °C, while hemicellulose degrades at 250–280 °C and lignin cracks at 200–
500 °C (Jeguirim and Trouve 2009, Correa et al. 2010). Therefore, at relatively low
pyrolysis temperatures, a significant amount of lignin remains non-carbonised,
which results in less biochar yield (Oginni et al. 2017).
Depending on the heating rate and vapor residence time, pyrolysis can be classi-
fied into slow, intermediate or fast pyrolysis. Moreover, the pyrolysis process can be
operated in batch or continuous modes. In the continuous process, the feeding of
biomass and the removal of biochar work continuously compared to the batch pro-
cess. Batch process is mainly considered optimal for biochar production, requires
less nitrogen and has abilities to accommodate longer residence times. In contrast,
continuous processes require more nitrogen to flush the vapors to the condensers by
rapid quenching, resulting in bio-oil as the main product. Moreover, compared to
batch pyrolysis processes, which are relatively easier to operate, continuous
processes require maintenance as they are prone to plugging by tar in the case of
improper insulation of the reactor and tubings.
Depending on the heating rate and vapor residence time, pyrolysis can be classi-
fied into slow, fast and intermediate pyrolysis. Fast pyrolysis of Miscanthus was
carried out at 350–500 °C with different residence times of 1.29–3.87 s (Kim et al.
2014). With the increase in pyrolysis temperature, it was noted that the yield of bio-
oil decreased (from 57.2 to 47.7 wt%), whereas this yield of gases increased (from
20.9 to 35.5 wt%). The energy conversion efficiency is also found to be lower in the
case of Miscanthus-derived bio-oil compared to softwood-derived bio-oil due to the
presence of more inorganic components in Miscanthus (Kim et al. 2014).
Greenhalf et al. (2013) performed a pyrolysis of M. giganteus at 490 °C and
obtained the yield of bio-oil and gases in the range of 41–51% and 22–35%, respec-
tively. An increase in vapor residence time showed a decrease in bio-oil yield and an
increase in gas yield. Oginni et al. (2017) compared the product yields from the
pyrolysis of Miscanthus and switchgrass grown on reclaimed mine lands at 500 °C
in a fixed bed batch reactor with a heating rate 70 °C/min for 30 min. Miscanthus
resulted in greater bio-oil yields of 51 wt% compared to switchgrass.
Pham et al. (2018) conducted an oxidative pyrolysis of Miscanthus pellets in a
fixed bed reactor at 650 °C. In this type of pyrolysis, partial oxidation of biomass
occurs auto-thermally and with the aid of low air mass flux. The biochar produced
contained 91.2 wt% carbon and 6.6 wt% oxygen. This also attributed to the catalytic
effect of ash with the formation of secondary biochar with the condensation and
polymerisation of primary tar and contact between volatile matter and biochar par-
ticles. Du et al. (2014) performed the pyrolysis of Miscanthus in a spouted bed
reactor at variable temperatures of 400–600 °C for a reaction time of 10 min. It was
reported that as the temperature increased from 400 to 600 °C, the gas yield signifi-
cantly amplified from 16 to 25 wt%, while the biochar and bio-oil yields decreased
from 43 to 35 wt% and from 43 to 33 wt%, respectively.
9.5.1.1 Bio-oil
Bio-oil, a major product of biomass pyrolysis, is a mixture of oxygenated and aro-
matic compounds. When compared to petroleum-derived oil, bio-oil contains oxy-
genated compounds as opposed to hydrocarbons. Pyrolysis liquid is composed of
both organic and aqueous fractions. These fractions are present due to the condensa-
tion process during biomass pyrolysis. While the aqueous fraction contains an
acidic phase, the organic fraction consists of an oily phase (Nanda et al. 2016c).
Bio-oil cannot be mixed with hydrocarbon liquids because it is composed of oxy-
genated compounds, which offer potential challenges for direct application.
Water content of bio-oil usually depends on the moisture content of the biomass
feedstock. The acidic pH of bio-oil, along with its higher water content and oxygen-
ation, causes many issues relating to storage, polymerisation and low calorific value.
The acidic pH also raises concerns for reactor or storage container corrosion. The
high concentrations of oxygen, and possible presence of nitrogen and sulphur of
certain bio-oils, require upgrading, such as hydrodeoxygenation, hydrodenitrogena-
tion and hydrosulphurisation, to enhance fuel properties and direct use (Zacher et al.
208 A. Singh et al.
2014). Bio-oil consists of more than 300 different compounds grouped under the
classes of aldehydes, ketones, esters, ethers, alcohols, carboxylic acid, nitriles, car-
bohydrates and hydrocarbons (Czernik and Bridgwater 2004). It should be noted
that the bio-oils obtained at longer residence times and higher temperature have
higher pH because of lower organic acids. The thermal cracking of organic acids at
higher temperatures and longer residence times could further decompose into non-
condensable gases (Nanda et al. 2014d).
Pyrolysis temperature is one of the most important variables to determine the
yield of bio-oil, biochar and gases. In an experiment on the pyrolysis of Miscanthus,
it was observed that by increasing the temperature from 350 °C to 550 °C, the bio-
char yield decreased from 32.4 to 12.1 wt% (Heo et al. 2010). However, maximum
bio-oil yield of 69.2 wt% was observed at a temperature of 450 °C, while the yield
decreased to 25 wt% at 550 °C. This is because of the increased degree of primary
tar produced in the pyrolysis vapors that crack to gases. A rapid increase in aromatic
components in the bio-oil occurred at 550 °C (Heo et al. 2010). In contrast, maxi-
mum yield of bio-oil of 53.9% in the case of hardwood was recorded at 500 °C,
which can be due to the higher content of lignin compared to Miscanthus (Mohan
et al. 2006). Higher temperatures lead to the breakdown of lignin, which slowly
decomposes and results in biochar as the main product.
Bio-oil derived from the pyrolysis of Miscanthus at 1.9 s of residence time at
500 °C (31.5 wt%) was higher than the bio-oil derived at 350 °C (25.3 wt%) (Kim
et al. 2014). The water content in bio-oils influences its viscosity and flowability
(Oginni et al. 2017). The viscosity of Miscanthus-derived bio-oil produced at
350 °C (16.5 cSt) was relatively greater than 500 °C (13.9 cSt) (Kim et al. 2014).
The HHV of bio-oil generated from Miscanthus at 500 °C (17.7 MJ/kg) was greater
than that at 350 °C (16.6 MJ/kg). Vapor residence time also has a significant impact
on the quality of bio-oil. The water content of bio-oil produced from the pyrolysis
of Miscanthus at 400 °C at 3.8 s (56.9 wt%) was much higher than that produced at
1.2 s (21.1 wt%) (Kim et al. 2014). However, the viscosity of bio-oil produced at
3.8 s (12.1 cSt) was lower than the bio-oil derived at 1.2 s (16.1 cSt).
Catalytic pyrolysis of M. giganteus with two different heating of 10 °C/min
and 50 °C/min was studied at 550 °C (Yorgun and Şimşek 2008). In the first case
(i.e. 10 °C/min), pyrolysis conversion increased from 59.7 to 79.9 wt%, but the
solid yield decreased from 40.2 to 23 wt% with the catalyst loading (activated
alumina) increasing from 10 to 100 wt% of the feedstock. In the second case (i.e.
50 °C/min), as the catalyst loading increased in the same range, the pyrolysis
conversion and solid, gaseous and liquid product yields were in the range of 65.2–
79.4 wt%, 34.8–20.6 wt%, 16–31.7 wt% and 47.2–51 wt%, respectively. As the
catalyst loading increased, the increase in the active sites also occurred, which
enhanced the rate of depolymerisation and decarbonylation. This is the reason for
an increase in gaseous products, a decrease in solid product, and an increase in
pyrolysis conversion. The maximum bio-oil yield was observed at 51 wt% with
the heating rate of 50 °C/min at 60 wt% catalyst loading (Yorgun and Şimşek
2008). In addition, the bio-oil produced in the presence of catalysts had higher
degree of aromaticity than those produced during non-catalytic pyrolysis. Bio-oil
produced through non-catalytic pyrolysis contained 63.2 wt% carbon, 8.1 wt%
hydrogen and 27.1 wt% oxygen. In contrast, bio-oil produced through catalytic
pyrolysis contained lower carbon (51.1 wt%) and hydrogen (6.4 wt%) but higher
oxygen (48.4 wt%) levels.
In an experiment on the pressurised pyrolysis of Miscanthus using a fixed bed
reactor at 550 °C for 25 min with the heating rate of 13 °C/min with 50 cm3/min
flow of N2, the yield of the bio-oil remained constant at approximately 35 wt% but
increased in the case of the pressure above 16 bars. High yield of tar was observed
in the pyrolysis experiments performed at atmospheric pressures. With the increase
in the pressure during the reaction, an elevation in the carbon content was noted,
which also increased the HHV of the liquid product. This can be due to the second-
ary decomposition reactions during which large amount of oxygen and hydrogen
also are removed from the feedstock, thus retaining carbon in the tar or char. This
confirms that pressure has an influence on the quality rather than the quantity of the
product (Melligan et al. 2011).
9.5.1.2 Biochar
Biochar is the solid carbonaceous product of the pyrolysis, gasification and carbon-
ization of biomass, which attracts widespread attention for its potential environmen-
tal and industrial applications (Mohanty et al. 2013, Kang et al. 2019). Biochar is a
carbon-rich product obtained from the thermal decomposition of biomass in
oxygen-deprived conditions. Biochar can sequester carbon in soil and helps to
decrease the amount of net CO2 emissions into the atmosphere. It can be used for
agricultural applications, water purification, catalyst support, electronics and bio-
medicine (Budaia et al. 2017, Nanda et al. 2016a).
There are some evidence that indicates that biochar not only increases the stabil-
ity of carbon stocks in the soil but also enhances the nutrient availability more than
inorganic fertilisers do. Biochar can enhance soil quality than any other organic soil
amendment. Biochar acts as a soil conditioner and organic fertiliser by providing
soil organic carbon and improving microbial carbon metabolism and population
dynamics (Kwapinski et al. 2010). The microbial response after the addition of
biochar to the soil is mainly due to the available carbon and inorganic elements
present in the biochar, which alter the soil pH in the relatively long term.
It is also concluded that the content of Gram-positive bacteria, Gram-negative
bacteria, actinobacteria and fungi biomarkers has been increased in the biochar-
modified soil (Lehmann et al. 2011). The large ratio of fungi/bacteria in the soil
amended with biochar concluded that fungi colonisation is very important to break
the structure of polyaromatics in the contaminated soils so that they will be avail-
able for other microbial groups for decomposition (Nanda et al. 2018). Moreover, it
has been noted that regardless of the temperature of the biochar production, biochar
application to highly acidic soils caused an increase in all phospholipid fatty acids
by microorganisms. Biochar produced at lower temperature are more utilizable by
microorganisms (Kwapinski et al. 2010).
The type of feedstock influences the composition and surface area of the biochar.
Biochar from crop residues and woody biochar has larger surface area when
210 A. Singh et al.
compared to the ones produced from other sources. Biochar generates oxygen-
containing compounds when it undergoes oxidation in the soil, a few examples of
which include carboxylic and lactonic acids and phenolic groups. The oxidation in
biochar-amended soils occurs through microbial action, organic matter and solutes
(Kim et al. 2018). The content of carbon availability instead of pH change is the
main point to consider for determining the microbial utilisation of biochar in acidic
soils (Luo et al. 2017). In addition to sequestering soil carbon, biochar also provides
several other advantages, such as increasing soil fertility and crop productivity. The
contribution of biochar in improving crop productivity is achieved through the
retention of plant-available nutrients in the rhizosphere, which results to increase in
soil pH, cation exchange capacity, water-holding capacity, decrease in greenhouse
gas emissions and immobilisation of toxic compounds including heavy metals
(Gronwald et al. 2016).
Greater yields of biochar are produced from pyrolysis at moderate temperatures
and longer vapor residence time, especially the conditions optimal for slow pyroly-
sis. Temperature and heating rate are the most considerable factors in pyrolysis,
gasification and carbonization, which can alter the yield and properties of the result-
ing biochar (Azargohar et al. 2019). Biochar from Miscanthus is found to have rela-
tively large surface areas (50.9–51.1 m2/g) when produced at higher temperatures
(e.g. 600 °C) and longer residence times (e.g. 60 min) (Kwapinski et al. 2010).
These properties are relevant for using biochar as the soil conditioner. The aromatic-
ity of the biochar also determines its thermal stability in the soil at extreme environ-
ments (Budaia et al. 2017). The composition of feedstocks (i.e. contents of cellulose,
hemicellulose, lignin, minerals and ash) also determines the chemical composition
of the resulting biochar. The organic and inorganic components in the original pre-
cursor (biomass) act as catalysts during the pyrolysis and carbonization processes to
improve the quality of the biochar (Hodgson et al. 2016).
Dependent on pyrolysis temperature, the properties and yield of the biochar
from Miscanthus varied largely. The yield of biochar from Miscanthus reduced
from 25.9–26.2 wt% at 500 °C (for 10 min of reaction time) to 19.8–20.2 wt% at
600 °C (at 60 min of reaction time) (Kwapinski et al. 2010). The surface area of
Miscanthus-derived biochars also showed a rising trend with the increase in the
temperature from 500 °C (1.65–1.95 m2/g) to 600 °C (50.9–51.1 m2/g). The HHV
data showed little difference at variable temperatures of 400 °C (29.4–30.3 MJ/kg),
500 °C (29.9–30.7 MJ/kg) and 600 °C (31.5–32.5 MJ/kg). As temperature plays a
significant role for the biochar production and its properties, biochar produced at
high temperature has high pH and more compact structure of polyaromatic com-
pounds than biochar produced at lower temperature. It is suggested that the large
surface area of biochar is usable for the adsorption of pollutants from wastewater
and retaining soluble carbon and nutrients, which is beneficial for soil applications
(Luo et al. 2017).
In an assessment, Miscanthus cultivated on the contaminated land was found to
accumulate more metals in the roots and rhizomes and less in shoots and stems
compared to Miscanthus cultivated from uncontaminated land (Janus et al. 2017).
Biochar produced from Miscanthus cultivated on the contaminated land were
efficient for the removal of Cd, Pb and Zn from the aqueous solution. Moreover,
higher efficiency in the removal of impurities was found in case of biochar produced
at higher pyrolysis temperatures. Greater desorption and lower sorption abilities of
biochar is suitable for the treatment of wastewater (Janus et al. 2017).
In a study by Yang et al. (2017), biochar was produced from different feed-
stock (e.g. Masson pine wood, Chinese fir wood, Chinese fir bark, bamboo
leaves, bamboo sawdust, Miscanthus, pecan shells and rice straw) through slow
pyrolysis at 350 °C and 500 °C. Slow pyrolysis at 350 °C showed the biochar
yield trend as bamboo sawdust > pecan shells > Miscanthus > Masson pine wood
> Chinese fir bark > rice straw > Chinese fir wood > bamboo leaves. However, at
500 °C, the yields of all biochars decreased. The yields of biochar from the slow
pyrolysis of all these feedstocks differed because of the variable composition of
cellulose, hemicellulose and lignin, which have different thermal degradation
kinetics. It has been proven in this study that the yield and thermal properties of
biochar were vastly affected by the composition of different feedstocks. The
HHV of biochars also showed an increasing trend at 350 °C but decreased at
500 °C (Yang et al. 2017).
As opposed to the benefits of biochars, there is a negative influence due to the
presence of polycyclic aromatic hydrocarbons (PAH), naturally generated during
the pyrolysis process. A few studies have shown that the total bioavailability of the
PAHs is low in the biochar. Hence, biochar can play the role of a carbon sink rather
than of an organic pollutant (Hale et al. 2012, Mayer et al. 2016). The factors that
affect the concentration of PAHs in biochar are temperature, feedstock composition
and carrier gas. The levels of PAHs in the biochar usually increase with the rise in
pyrolysis temperature. Aromatic hydrocarbons in the feedstocks depend on the pro-
cess parameters, which determine their fate in the biochar, bio-oil or gases. High
carrier gas flows result in decreasing the PAH concentration (Madej et al. 2016).
A comparison between pyrochar and hydrochar obtained from slow pyrolysis
and hydrothermal carbonization was made. For pyrochar from M. giganteus, a
Pyreg reactor was used at 750 °C for 0.75 h, and for the hydrochar mixture, 1 kg of
dry Miscanthus with 10 kg of water in tubular reactor was used at 200 °C and
2 MPa for 11 h (Gronwald et al. 2016). Hydrochar is produced from hydrothermal
carbonization, which is usually performed at low temperature (180–300 °C) in the
presence of water under high pressure (2–2.5 MPa) for several hours. The hydro-
char was found to have low surface area, low degree of carbonization and less
aromatic carbon compared with pyrochar. Moreover, hydrochar had a high ratio of
H/C (1.01) than O/C (0.31) from pyrochar (Gronwald et al. 2016). Compared to
hydrochar, the application of pyrochar in the soil can retain the carbon for a longer
period. On the other hand, hydrochar applied directly to the soil showed a slow
release of fertiliser.
Like nitrogen and potassium, phosphorus is one of the essential elements for crop
growth and yield. The impact of phosphorous can be seen in more tropical weathered
soils where bioavailability of soil happens under natural conditions. The weathering
of rocks releases essential elements for the growth of the crop at a slower rate (Trazzi
et al. 2016). The surface area of biochar, volatile matter content and surface organic
212 A. Singh et al.
functional groups influence the phosphorus bioavailability in soils amended with

biochar. It has been reported that biochar produced from wheat straw can affect phos-
phorous concentration, depending on its quantity of amendment in the soil. It was
noted that fast pyrolysis biochar decreased phosphorous fixation capacity in the soil
(Trazzi et al. 2016). Increased temperature and residence time also increased the
fixed carbon and surface area of Miscanthus biochar, which resulted in higher phos-
phorus adsorption capacity compared to sugarcane bagasse biochar.
9.5.2 Torrefaction of Miscanthus
Torrefaction was the most promising pretreatment process for biomass before pyrol-
ysis. The physicochemical properties of torrefied biomass are like those of coal.
Torrefaction is a process of moisture removal at low temperature, and hemicellulose
decomposition is another key aspect of this process. By losing CO2, moisture and
other oxygen-containing compounds, the torrefied product demonstrates high
energy density than the raw material. Furthermore, torrefaction helps to improve the
grinding property of biomass, which helps to reduce electric power consumption.
Torrefaction decreases the content of oxygen and increases carbon content due to
loss of moisture, CO2 and CO (Wafiq et al. 2016).
The impact of pressure on the yield of char from the torrefaction of Miscanthus
was studied at 250 °C with a heating rate of 10 °C/min and N2 flow rate of
40 L/h for 30 min of reaction time. The results indicated that at 1 bar, the char
yield increased from 22 to 29 wt% until 10 bar, beyond which no further increase
was observed with rising pressure. The biochar with torrefied Miscanthus
showed a similar trend of yield increase from 32 to 42 wt% at 1–10 bar and no
further increase at higher pressures (Wafiq et al. 2016). On the other hand, liquid
products from pyrolysis decreased as the pressure increased for torrefied
Miscanthus due to secondary pyrolysis reactions. In terms of the porosity of
biochar, the porosity of raw Miscanthus decreased until 15 bars and increased at
30 bars. However, in the case of torrefied Miscanthus, the porosity decreased as
the pressure increased.
Raw Miscanthus also has some disadvantages, such as low bulk density, low
energy density and non-uniform physical and chemical properties, which could lead
to storage problem, lower thermal conversion and utilisation. Torrefied Miscanthus
also has high energy density and bulk density, making it easier for transportation
and storage. Miscanthus torrefied at 270 °C for a residence time of 30 min achieved
good properties like low moisture and hemicellulose contents, lower O/C ratio, as
well as porous structure, larger surface area and high alkali metal content in the
solid products, which are optimal for pyrolysis or gasification (Xue et al. 2014b).
Furthermore, raw and torrefied Miscanthus were gasified at 850 °C under N2 and
CO2 atmosphere. During the torrefaction, the overall O/C ratio decreased while the
pore volume and surface area increased, which improved the gasification properties
of torrefied Miscanthus compared to the raw Miscanthus. The penetration of CO2
inside the porous particles improved, which positively affected gasification
reactivity. Regardless, the composition of gas obtained from gasification depends

upon the nature and composition of the feedstock.
9.5.3 Liquefaction of Miscanthus
The thermochemical technologies for biomass conversion into liquid fuels also
include direct liquefaction and hydrothermal liquefaction. In hydrothermal lique-
faction and hydrous pyrolysis, the use of water and catalyst is required for the con-
version of biomass. According to Balat (2008), there are some reactions that occur
during this process, such as the following:
1. Decomposition and reduction of cellulose, hemicellulose, lignin and lipids

2. Hydrolysis of cellulose and hemicellulose to the simple sugars
3. Hydrogenolysis in the presence of hydrogen
4. Reduction of amino acids
5. Reformation reactions
6. Degradation of C–O and C–C bonds
7. Hydrogenation of functional groups
Most typical temperature for liquefaction is between 300 °C and 500 °C. Over the
years, many improvements have been made to overcome certain technical problems
associated with liquefaction. Another iteration of liquefaction, i.e. hydrothermal liq-
uefaction, involves alcohol and water as the reaction medium. The advantage of such
system is that the solvents can be evaporated, recycled and reused (Cheng et al.
2010). It is found that replacing 50% of water with alcohol during liquefaction
increased bio-oil yield, whereas replacing water more than 50% can adversely affect
the bio-oil yields (Cheng et al. 2010). The drying of biomass is necessary for pyroly-
sis but not for hydrothermal liquefaction because of water as the aqueous medium.
Catalyst requirement is a very essential part of liquefaction. Alkali catalysts, such as
Na2CO3 and K2CO3, aid liquefaction reactions (Nanda et al. 2014c, 2016c).
Hydrothermal liquefaction involves the application of subcritical or supercritical
water as the reaction medium (Kamio et al. 2006). The critical temperature (Tc) and
critical pressure (Pc) of water determines the subcritical phase (Tc < 375 °C and
Pc < 22.1 MPa) and supercritical phase (Tc > 375 °C and Pc > 22.1 MPa) of water
(Nanda et al. 2019, Rana et al. 2019). Subcritical water acts as a green solvent that
dissolves highly complex organic residues to simple hydrocarbons and permanent
gases through ionic and free radical mechanisms (Reddy et al. 2014, 2016).
Supercritical water has found applications in hydrothermal gasification, liquefac-
tion and oxidation of biomass and organic refuse (Reddy et al. 2015, 2017).
During the liquefaction of Miscanthus, it has been noted that by increasing the
temperature from 220 to 280 °C, the quantity of residues decreased while the liquid
yields increased. According to the value of oil yield, residue content and heating
value, 15 min liquefaction time was efficient for Miscanthus liquefaction without
any catalyst. Reaction temperature (280 °C) and water/ethanol ratio (50%) were the
214 A. Singh et al.
most effective parameters for this process. The optimal results obtained in the case
of Miscanthus liquefaction was 52% yield of bio-oil having a heating value of
25 MJ/kg when the biomass-to-solvent ratio used was 1:8 with ZnCl2 as the catalyst
(Hafez and Hassan 2015).
9.5.4 Gasification of Miscanthus
Gasification operates in the presence of a limited supply of oxygen to produce syn-

gas, which mainly contains H2 and CO, along with other products, such as CO2, CH4
and C2+ (Okolie et al. 2019a, b). During gasification, carbon conversion is a key
feature that is used to determine gasification efficiency (Rana et al. 2018). Biomass
gasification is emerging as one of the cleanest technologies to produce biofuels and
decrease the dependence on fossil fuels. Because of the high reactivity of biomass
char, gasification is gaining widespread interest for energy production. The reactiv-
ity of biochar depends upon three basic properties such as chemical structure,
porosity and inorganic constituents. Miscanthus has been proved as an appropriate
biomass for thermochemical conversion because of its higher volatility and low ash
content (Karampinis et al. 2012).
The gasification of Miscanthus char was investigated above 800 °C specifically
in the presence of steam, and the complete burnout of Miscanthus was detected at
1000 °C in the blended (air/oxygen) ambience, as well as 1050 °C for the steam
medium (Jayaraman and Gökalp 2015). This shows that the amount of oxygen
affects reaction rate and temperature. About H2 gas evolution during the whole pro-
cess from pyrolysis to gasification of Miscanthus, it was observed that it started at
350 °C with the highest concentration at 950 °C and then decreased similar to CO
content. It was also observed that the H2 yield decreased when the gasification
medium changed from pure steam to steam enriched with oxygen and air (Jayaraman
and Gökalp 2015).
The bubbling fluidised bed is the simplest and most cost-effective method for bio-
mass gasification. Such reactors are flexible to gasify a wide variety of biomass
because of high heat transfer and uniform temperature distribution. However, the dis-
advantage of such reactors is the risk of bed agglomeration because of the presence of
sintering ash and high alkali metals in the biomass, which might also affect the reactor
material (corrosion) at high temperatures and catalyse or retard the reaction. During
Miscanthus gasification, agglomeration was observed at low temperature due to the
presence of high silica, potassium and sodium content (Xue et al. 2014a). It was
reported that in the case of gasification of M. giganteus, the quality of product gas
deteriorated with the rise in temperature from 645 °C to 726 °C using optimal equiva-
lence ratio of 0.26 and air flow rate of 53 Ndm3/min. Among all the gases, CO yield
decreased from 39.5 to 33.4 vol%, but the concentration of CO2 increased from 33.3
to 36.8 vol%. The yields of H2 and hydrocarbons did not show any deviation at higher
temperature (700–726 °C) in comparison with 645 °C (Xue et al. 2014a).
9.6 Conclusions
Miscanthus is a lignocellulosic energy crop that can be used to produce biofuels

through thermochemical and biochemical conversion technologies. Biochemical
conversion technologies have shown promising results in producing ethanol from
Miscanthus through fermentation. The bioconversion of lignocellulosic biomass to
ethanol operates in three steps, which involves pretreatment, enzymatic saccharifi-
cation and fermentation. On the other hand, thermochemical conversion technolo-
gies, such as pyrolysis and liquefaction of Miscanthus, are useful for producing
energy dense bio-oil, whereas gasification of Miscanthus can produce syngas. The
syngas can be either used directly for combustion or catalytically converted to
hydrocarbon fuels and chemicals through the Fischer-Tropsch process. Miscanthus-
derived bio-oil produced from pyrolysis and liquefaction can be upgraded to syn-
thetic transportation fuels.
Biochar is a solid residue of pyrolysis, gasification and torrefaction. Biochar
generated from Miscanthus has been found to have promising properties for appli-
cation in the environment and industry. The physical and chemical properties of
biochar are greatly dependent upon a variety of process parameters, such as tem-
perature, heating rate, residence time, pressure, biomass composition and biomass
particle size. Temperature has a direct impact on the surface properties of biochar,
like surface area, pH and cation exchange capacity. Miscanthus has shown promis-
ing results among other energy crops for thermochemical and biochemical conver-
sion, as well as for the generation of value-added products. There is also an
opportunity to design technologies, which will be efficient at a commercial level for
getting value out of this energy crop.
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Process Improvements and Techno-
Economic Feasibility of Hydrothermal 10
Liquefaction and Pyrolysis of Biomass
for Biocrude Oil Production
Pravin G. Suryawanshi, Sutapa Das, Venu Babu Borugadda,

Vaibhav V. Goud, and Ajay K. Dalai
Abstract
Biocrude oil production from biomass has gained huge attention globally to
complement the conventional fuels and reduce the environmental impact caused
by fossil fuels. To produce renewable energy from biomass, several technologies
have emerged, such as physical (e.g., drying, pressing, crushing, and pelletiza-
tion), biochemical (e.g., fermentation and anaerobic digestion), and thermo-
chemical (e.g., pyrolysis, gasification, liquefaction, and combustion) pathways.
Among all, thermochemical technologies have gained much attention due to
their high-energy content products and process efficiency. The biocrude oil pro-
duced from pyrolysis and hydrothermal liquefaction has similar chemical prop-
erties to conventional liquid fuels. Therefore, this chapter discusses the current
status, challenges, opportunities, recent process developments, and techno-
economic feasibility of hydrothermal liquefaction and pyrolysis of biomass for
biocrude oil production.
Keywords
Biocrude · Hydrothermal liquefaction · Pyrolysis · Lignocellulosic biomass ·
Techno-economic assessment
P. G. Suryawanshi · S. Das · V. V. Goud

Department of Chemical Engineering, Indian Institute of Technology Guwahati,
V. B. Borugadda (*) · A. K. Dalai

222 P. G. Suryawanshi et al.
10.1 Introduction
Urbanization, population growth, and technology development are causing ever-

increasing energy demands. However, conventional fuels are finite, requiring poten-
tial replacement in the future (Chen et al. 2015). Thus, researchers all around the
world are working toward developing sustainable technologies to derive energy
from renewable sources, to minimize energy dependence on depleting fuels.
Currently, 10% of the global energy supply comes from biomass-derived energy
sources, and biomass has much higher potential to complement fossil fuels if com-
pletely utilized (Khan et al. 2009). According to the Union for the Promotion of Oil
and Protein Plants (UFOP) global supply report, if all the available biomass can be
completely converted to energy, it would yield as high as 1,081,011 tons of oil
equivalent (toe). This figure is huge and is nearly ten times the world’s present
energy needs (Hussain et al. 2017). The main driving force behind the utilization of
biomass is its abundant reserves, renewability, and most importantly CO2 neutrality
(Kumar et al. 2010; Nanda et al. 2015a).
Until date, the U.S. and Brazil have commercialized biocrude oil and its deriva-
tives. Canada has also about 190 establishments that are solely involved in produc-
ing bio-oil and other value-added products obtained from biomass. Recently,
Germany has also invested in this area with an emphasis on biodiesel and biogas. In
2016, globally, 34 million tons of biodiesel was produced, of which 37% (12,610
million tons) was solely produced by EU-28 member countries (Babu and
Subramanian 2013). Apart from the U.S. and the European Union, many other
countries have begun to contribute toward producing biocrude oil and its derivatives
Fig. 10.1 Pathways for the conversion of biomass into bioenergy. (Reproduced with permission
from Sharma et al. 2015)
10 Process Improvements and Techno-Economic Feasibility of Hydrothermal… 223
from biomass (Brownsort 2009). The main advantage of using a green raw material
is that it has less environmental impact as it produces much less CO2, SOx, and NOx
emissions as compared to petroleum oil or coal when gasified, pyrolyzed, or hydro-
thermally liquefied (Nanda et al. 2016a).
A variety of biomass available for energy purposes includes oil seeds, starch-
based feedstocks, lignocellulosic biomass (agricultural crop residues and woody
biomass), aquatic biomass, municipal solid waste, and industrial wastes (Nanda
et al. 2018a). Lignocellulosic biomass (including herbaceous energy crops, agricul-
tural crop residues, forestry residues, and wood-processing wastes) is one of the
most abundant feedstock on earth, which is highly promoted for the sustainable
production of fuels and chemicals. At present, there are several biochemical and
thermochemical technologies (Fig. 10.1), which can be used to produce biofuels
from biomass, such as fermentation, anaerobic digestion, gasification, pyrolysis,
and hydrothermal liquefaction. Among these techniques, pyrolysis and hydrother-
mal liquefaction are found to be the most promising for biocrude oil production and
upgradation into liquid transportation fuels (biogasoline, biodiesel, and biojet fuel).
Biocrude oil or biodiesel can also be blended with conventional diesel for use in
standard diesel engines. The major advantage is that biodiesel has a relatively lower
environmental impact compared to petroleum diesel and it is biodegradable without
compromising its combustion properties (Babu and Subramanian 2013). It can also
be used as a low-carbon alternative to heating oil.
The scope of the chapter is to demonstrate the current state-of-the-art research
undertaken in pyrolysis and hydrothermal liquefaction of biomass for the produc-
tion of liquid transportation fuels and value-added chemicals. Furthermore, the cur-
rent technical challenges in this field are reviewed for process development. New
strategies and their techno-economic feasibility toward commercialization of bio-
fuel products are discussed based on the recent developments in the field.
10.2 Biomass Pyrolysis
Pyrolysis is a thermal decomposition process of dry biomass at elevated tempera-

tures under inert atmosphere. Based on operating process conditions, the pyrolysis
process can divided into fast, slow, flash, and hydropyrolysis techniques. Table 10.1
Table 10.1 Process parameters of different pyrolysis processes and their major products
Temperature Heating rate Residence
Pyrolysis (°C) (°C/s) time Major products
Slow pyrolysis 400–600 0.1–0.3 30–60 min Biochar, biocrude oil,
and gas
Fast pyrolysis 700–1200 10–100 <10 s Biocrude oil
Flash pyrolysis 800–1150 >1000 1s Biocrude oil
Hydropyrolysis 400–700 0.2–10 15–30 min Biocrude oil
References: Manyà (2012), Brownsort (2009)
shows the detailed process conditions and main products in each pyrolysis process.
During pyrolysis, the yield of the products depends not only on the type of pyroly-
sis but also on the nature of biomass feedstock and operating conditions, i.e., tem-
perature, heating rate, pressure, and vapor residence time (Azargohar et al. 2013;
Nanda et al. 2014a).
Lignocellulosic biomass is a promising feedstock for biorefineries, where the
spectrum of products include biofuels, polysaccharides, fatty acids, proteins, pig-
ments, aromatics, biopolymers, and biomaterials (Fig. 10.2). Lignocellulosic bio-
mass typically consists of cellulose (25–50 wt%), hemicellulose (15–40 wt%),
lignin (10–40 wt%), and extractives (up to 15 wt%) with trace amounts of inorganic
and mineral matter (Guo et al. 2010). Table 10.2 shows the distribution of cellulose,
hemicellulose, and lignin of some chief biomass.
Cellulose is a linear polymer composed of glucose monomers connected by ether
bonds, hydrogen bonds, glycosidic linkages, and van der Waals forces (Nanda et al.
2015b). Hemicellulose is a heteropolymer formed from predominantly xylose and
mannose monomers. On the other hand, lignin has a complex structure of aromatic
polymer formed from phenyl propanol monomers (Fougere et al. 2016; Cao et al.
2018). Cellulose and hemicellulose are utilized effectively for the production of
fuels, sugars, and paper. Efficient utilization of lignin is challenging due to its high
molecular weight, complex three-dimensional polymeric structure formed from
condensation and ether linkages, and heterogeneous nature (Mahmood et al. 2016).
Therefore, lignin remains as an underutilized biopolymer (estimated 1.5–1.8 billion
tons per year) obtained from many industrial activities (Cao et al. 2017, 2018).
Many platform chemicals, such as furfural, guaiacol, and catechol, have been iden-
tified from lignocellulosic materials, opening many opportunities to explore these
key substances (Kruse et al. 2013; Schuler et al. 2019). Despite extensive research,
Fig. 10.2 Spectrum of valuable products from the thermochemical processing of biomass
Table 10.2 Distribution of the components of biomass (Reproduced with permission from Wang
et al. 2017)
Cellulose Hemicellulose Lignin Extractives Biochar (wt
Biomass (wt%) (wt%) (wt%) (wt%) %)
Rice 37 16 13 13 20
straw
Corn 42 23 17 10 7
straw
Wheat 37 18 20 4 4
straw
Pine 49 20 25 5 0.3
Bamboo 40 20 20 7 1
the depolymerization of lignin and effective recovery of aromatic monomers from

lignin still have not been possible to reach a pilot scale.
Biocrude oil is mainly obtained by thermal degradation of cellulose and hemi-
cellulose, while lignin contributes to biochar production. The extractives present
are mainly waxes, fatty acids, and sterols, which can be extracted using various
solvents like methanol, ethanol, hexane, water, and supercritical fluids (Nanda
et al. 2013). The mass ratio of the organic to inorganic content varies with the
biomass, and it greatly affects the pyrolysis process conditions. The pyrolysis of
each component has its respective pathway, which affects its product distribution
(Fahmi et al. 2007).
Vast research has been carried out on slow, fast, and flash pyrolysis of different
biomass. Currently, there is another budding type of pyrolysis, called hydropyroly-
sis, in which nitrogen is replaced by hydrogen during pyrolysis. In this case, the
reaction takes place under hydrogen pressure, which hinders the formation of free
radicals; i.e., the formation of unsaturated hydrocarbons is reduced, thereby upgrad-
ing the biocrude oil. A study reported by Balagurumurthy et al. (2015) with rice
straw as the biomass under both nitrogen and hydrogen environment revealed that
biocrude oil obtained under hydrogen pressure was more selective toward the phe-
nolic compounds, but the higher biocrude oil yield is obtained under the conven-
tional nitrogen environment. A study on the pyrolysis of wheat straw and corn stalk
suggested that extractives increase the yield of biocrude oil and in turn suppress the
yield of biochar and gas (Wang et al. 2017). Another study on pyrolysis of Mongolian
pine, confirmed that the lowering of activation energy could increase the acidic
products in biocrude oil (Guo et al. 2010). The trace amounts of minerals also affect
the pyrolysis process as they act as catalysts to enhance the process.
10.2.1 Biocrude Oil Production Through Pyrolysis
Biocrude oil is produced by fast pyrolysis technique, which involves the rapid
breakdown and fragmentation of biomass composed of cellulose, hemicellulose,
and lignin. Sharma et al. (2015) reported the detailed mechanism of cellulose,
Fig. 10.3 Schematic representation of the physicochemical processes in lignocellulosic biomass

during pyrolysis. (Reproduced with permission from Sharma et al. 2015)
hemicellulose, and lignin decomposition during pyrolysis. Figure 10.3 shows the
physicochemical changes in biomass during pyrolysis. The obtained products from
pyrolysis can be subsequently separated from a gas stream (by-product) by conden-
sation and immediate cooling (Czernik and Bridgwater 2004; Mohan et al. 2006).
Since the feedstock composition plays a major role in determining the quality of
biocrude oil, the properties are much closely associated with its source. The pres-
ence of oxygen and water in biocrude oil is one of the major disadvantages for its
immediate application.
Oxygen combines with different carbon components to form a variety of functional
groups such as ketones, aldehydes, phenols, sugars, and other aromatic compounds in
bio-oil (Bridgwater 2012). Severe drawbacks arise with the high oxygen content in
biocrude oil, which not only causes compatibility issues with the fossil fuels but also
leads to a massive reduction in energy density (almost to an extent of 50 wt%). To
prevent the formation of higher amounts of oxygen content, process parameters such as
heating rate and vapor residence time can be altered (Wang et al. 2017). Biocrude oil
can be considered as a potential source to complement conventional liquid transporta-
tion fuels, which have the capability to match the economical aspect of petroleum
derivatives (Bridgwater et al. 1999; Isahak et al. 2012). Table 10.3 represents the com-
parative differences between biocrude oil and conventional crude oil.
10.2.2 Biochar Production Through Pyrolysis
Biochar is a carbonaceous residue of the biomass decomposition process whose

constituents vary considerably depending on the feedstock composition and
process parameters employed during pyrolysis, gasification, and carbonization

(Mohanty et al. 2013; Azargohar et al. 2014; Nanda et al. 2016a). For instance, the
high heating value (HHV) can vary from 20 to 36 MJ/kg, while the carbon content
can vary from 53 to 96 wt% (Brownsort 2009). The process conditions primarily
determine the different physical, chemical, and mechanical attributes of biochar.
Slow pyrolysis not only changes the chemical composition of biochar by varying
the C/H and O/H ratios but also significantly contribute toward its physical charac-
teristics by making it highly porous (Azargohar et al. 2019). Volatile removal at
these high temperatures equip them with honeycomb-like structures with a high
surface area (100–500 m2/g), which is ideal for pollutant adsorption and filtration
applications (Ahmad et al. 2014).
Biochar produced from conventional carbonization or slow pyrolysis techniques
has high carbon content (low bio-oil content), which can be utilized mainly for soil
supplements in enhancing soil fertility and carbon sequestration (Lee et al. 2013).
Another facet of biochar is its high HHV, which endows it with the potential of
being a high-energy supplement and possibly replacing coal in certain applications
(Worasuwannarak et al. 2007). The biochar yield greatly depends on the pyrolysis
temperature and the nature of the biomass, which is shown in Table 10.4.
Table 10.3 Comparison of Biocrude

chemical composition and Properties oil Crude oil
properties of biocrude oil and Water content (wt%) 15–30 0.1
conventional crude oil
pH 2–3 Neutral
(Reproduced with permission
from Mohan et al. 2006) Carbon (wt%) 54–58 85
Hydrogen (wt%) 5.5–7 11
Oxygen (wt%) 35–40 1
Nitrogen (wt%) 0–0.2 0.3
Sulfur (wt%) Traces 0.5–3
Ash (wt%) 0–0.2 0.1
Higher heating value (MJ/ 16–19 40
kg)
Specific gravity 1.2 0.94
Viscosity at 50 °C (cP) 40–100 180
Pour point (°C) −33 −18
Table 10.4 Effects of temperature on the biochar yield

Biomass Temperature (°C) Biochar yield (wt%) References
Rice husk 400–600 25.5–33 Williams and Nugranad (2000)
Corncob 450–1250 5.7–30.6 Demirbas (2004)
Olive husk 450–1250 19.4–44.5 Demirbas (2004)
Pine cone 300–450 26–58 Shabangu et al. (2014)
Sewage 350–950 39–52 Sánchez et al. (2009)
sludge
10.2.3 Gaseous Products from Biomass Pyrolysis
The pyrolysis of biomass also results in the formation of certain gaseous products,
such as hydrogen (H2), ammonia (NH3), methane (CH4), propane (C3H7), ethylene
(C2H2), carbon monoxide (CO), and carbon dioxide (CO2). Hydrogen is generally
released upon the decomposition and reforming of the aliphatic and aromatic
groups. Higher moisture content in the biomass can contribute toward higher H2
content compared to dried feedstocks (Guoxin et al. 2009; Uddin et al. 2014; Nanda
et al. 2017a). CH4 and CO2 generally originate after the breakage of methylene and
methoxy, bonds while CO and CO2 are produced from the decomposition of car-
boxyl and carbonyl groups (Strezov et al. 2008).
A variation in process parameters such as initial moisture content, feedstock par-
ticle size, and reaction temperature can significantly affect the gas composition. High
moisture-containing feedstocks generally release higher H2 content in gases. In addi-
tion, such feedstocks usually result in a higher extraction of water-soluble compo-
nents in gases, thereby resulting in reduced gas yields (Dasappa et al. 2004).
Furthermore, higher reaction temperatures lead to higher rates of thermal degradation,
causing increased volatile products. The gaseous products undergo various reactions
such as decarbonylation and dehydrogenation at these conditions (He et al. 2010).
Feedstock size also plays a vital role in determining the overall gas composition
as smaller size particles favor the cracking of hydrocarbons, thereby producing
more H2 due to enhanced heating rates. Larger size particles led to lower heating
rates, which result in increased biochar yield and decreased gas production because
of the low residence time of volatiles in the reactor (Hu and Gholizadeh 2019).
Gaseous products from pyrolysis find applications in combustion engines for trans-
portation purposes and in the production of liquid biofuel production through the
Fischer-Tropsch (FT) process (Kan et al. 2016).
10.2.4 Challenges in Biomass Pyrolysis
Though pyrolysis processes can be applied to a range of feedstocks, the products

obtained are dependent on the composition of the feedstock and are inconsistent in
nature. The quality of the feedstock can also be varied by the harvesting culture,
collection techniques, and type of pretreatment (mechanical, chemical, or biologi-
cal). Therefore, the establishment of some standard protocol in this direction can
help eradicate the issue of inconsistency. The scale-up to pilot plants from labora-
tory scale research becomes difficult. Another aspect of biomass, which demands
intensive research, is ash content characterization. Elements such as Ca and K, pres-
ent in ashes, have been reported to facilitate biomass decomposition while assisting
in char formation.
Gu et al. (2013) reported that elements Na, K, and Va present in the ash were
found to be responsible for the high-temperature corrosion of the reactor. On the
other hand, Ca is responsible for hard deposit formation. Such studies pointed
toward the harmful effects of ash content, especially when its content is more than
0.1 wt% in biocrude oil. Particular attention has to be diverted toward the ash con-
tent in the entrained char as it has been known to catalyze the polymerization reac-
tions in biocrude oil, thereby enhancing its viscosity. In practical applications,
negative effects of ash content in the biocrude oil can be directly related to the
occurrence of erosion, corrosion, and knocking problems in engines and valves.
The heterogeneous nature of the decomposed biomass products makes the pyrol-
ysis process harder to control and the different constituents of biomass breakdown
under reaction conditions. These distinct reaction rates further complicate the pyrol-
ysis process and the selection of reactor design, which determines their thermal
processing conditions. Unwanted moisture in the biocrude oil is usually very detri-
mental to biocrude oil properties as it lowers the heating value and flame tempera-
ture. This generally leads to delayed ignition times and subsequently affects the
combustion rates in a negative way. Moisture content not only creates filtration
problems but also causes heterogeneity in biocrude oil, which can lead to layering
or partial separation of different phases. Due to the presence of reactive oxygenated
functional groups in biocrude oil, its thermal stability is adversely affected, and this
creates problems in its storage.
Another factor, which contributes to slow combustion rates and the sudden
appearance of “sparklers,” is the existence of suspended char. The abovementioned
problems mostly lead to large potential deposits or high levels of CO emissions. Char
is also well known for its high catalytic activity and usually assists in the potential
cracking of bio-oil components while reducing the condensables’ yield up to 20%.
10.2.5 Recent Technological Developments in Biomass Pyrolysis
Although the pyrolysis technique has been extensively studied, it is still behind
large-scale commercialization owing to several bottlenecks. Techniques for pyroly-
sis still demands strict control over the process parameters for the production of
conventional products (biochar and biocrude oil). Moreover, the actual relationship
between biomass products and pyrolysis conditions remains to be unraveled for
achieving a better understanding of the process.
The lack of comprehensive molecular simulations creates difficulty in under-
standing the products’ distribution and the effect of the process parameters on the
kinetic measurements (Editors et al. 2016). These are some of the different prob-
lems that not only plague the actual scaling up of the process but also harms the
overall outlook of this technology. In order to address and tackle these issues, a
comprehensive understanding of pyrolysis at different lengths and time scales is
required. On a macro-scale, implementing the correct conditions for maximal pro-
duction demands a better suited reactor design. Moreover, to make the technology
commercially competitive, enhancement in the pyrolytic products is required. The
by-products themselves need to be upgraded to not only enhance the overall value
of the system but also devise ways to construct a circular economy (Jiang et al.
2017). A few of the measures intended to alleviate the problems associated have
been discussed in the following section.
10.2.5.1 Reactor Design

To make the pyrolysis process more efficient, heat transfer characteristics of the
biomass have to be improved as it possesses poor thermal conductivity. Initial size
reduction or comminution of the biomass can alleviate this shortcoming. A few
reactors, which have been employed for carrying out the pyrolysis of biomass,
include tube furnace and fluidized bed reactor. Although these are the conventional
methods utilized, they too suffer from many drawbacks, such as long operational
hours, resulting in low-quality products due to the appearance of secondary
reactions.
In addition, a large amount of heat is required in pyrolysis to carry out the reac-
tions (Palgan and McCormick 2016). Microwave heating is an attractive alternative
to reducing heat losses. Microwave heating delivers enhanced, faster, and uniform
heating rates. This technique also improves the quality of the downstream products
by keeping the secondary reactions under control (Tsagkari et al. 2016).
10.2.5.2 Biocrude Oil Upgrading Techniques

The techno-economical facet of the pyrolysis process provides the main impetus
behind the continual search for an improved process. Over the years, many alternate
techniques for upgrading the characteristics of biocrude oil have been proposed,
such as catalytic cracking, catalytic pyrolysis, molecular distillation, and esterifica-
tion, to name a few. In particular, biocrude oil upgradation by employing catalytic
cracking involves several steps such as cracking, decarboxylation, hydrodeoxygen-
ation, etc. One of the favored techniques utilized is esterification, which consists of
the addition of certain polar solvents (ethanol and furfural) into biocrude oil to
homogenize the mixture. This eventually decreases the biocrude oil’s density, vis-
cosity, and corrosiveness, thus improving its stability characteristics. Moreover, the
addition of solvents increased the organic content of the upgraded bio-oil (Peng
et al. 2009). Simpler alternatives for improving biocrude oil properties include the
addition of diesel fuels and forming an emulsion. This emulsification process not
only is cost-effective but also provides for a short-term route to the deployment of
biocrude oil in the diesel engines. Additionally, this process results in the improve-
ment of its properties such as water content, flow properties, and viscosity (Cao
et al. 2018).
The drive for discovering better alternatives in bio-oil upgradation has led
researchers to employ supercritical fluids (Reddy et al. 2018). Supercritical fluid is a
state of fluid that exists beyond its critical temperature and pressure. At this condi-
tion, the fluid behaves in an interesting way, wherein it can easily pass through sur-
rounding materials and even diffuse through solids. In particular, the fluids possess
the ability to dissolve and liquefy the materials which are not soluble either in a solid
or liquid state, thereby enhancing their liquefaction reactions (Zhang et al. 2016).
The process involving the utilization of supercritical fluids demands lower operating
temperatures and is relatively ecofriendly, but it is more expensive than conventional
processes (Nanda et al. 2018b). In order to overcome this shortcoming and make this
process economically viable on a large scale, the utilization of certain low-cost
chemicals such as methanol and glycerol has gained popularity (Sandun et al. 2006;
Reddy et al. 2016).
10.2.5.3 Extraction of Value-Added Chemicals

There are various upgradation techniques available for biocrude oil to enhance its
calorific value. However, these processes have become difficult to use due to the
high tendencies of biocrude oil to get polymerized to form coke at elevated tempera-
tures. Therefore, a new gateway to extract other value-added products from bio-
crude oil have come into existence. Sugar or its derivatives present in biocrude oil
can be separated from aromatics, as they have distinct polarities, by using water/
chloroform extraction. It is a simple extraction procedure where the biocrude oil is
mixed with water to form two separate phases. The sugar derivatives are present in
the lighter phase, and the aromatics and other compounds go into the heavier phase.
Furthermore, by performing acid catalysis of the lighter phase, various chemicals
like levulinic acid, furfural, acetic acid, 5-hydroxyfurfural, etc. can be obtained. The
heavier phase is further hydrotreated to obtain transportation fuels (Hu et al. 2012).
In a study on the pyrolysis of olive mill wastes, the biocrude oil produced have
two distinct phases, i.e., an aqueous phase and an organic phase or the tarry phase.
The aqueous phase consisted of monosaccharides, phenolic derivatives, and acetic
acid, while the tarry phase consisted of methyl esters. Two liquid–liquid extraction
techniques were used mainly, first one at original pH and other with acid-base
extraction at pH 12. At the original pH, the nonaqueous phase was dissolved in
methanol first before extraction. The results showed that the best method for extrac-
tion was the acid-base procedure. Phenolic derivatives were found to be present in
both the aqueous phase (hexane) and nonaqueous phase (ethyl acetate phase). The
nonaqueous phase (hexane phase) consisted of methyl esters, which could be fur-
ther used for the production of biodiesel (del Pozo et al. 2018).
10.2.5.4 Techno-Economic Feasibility of Biomass Pyrolysis

To demand widespread usage and compete with the existing conventional technolo-
gies, biomass degradation via pyrolysis needs to be revamped in different sectors.
The need for developing a deeper understanding of the process can not only help
improve the overall processing but also play a vital role in enhancing the economic
outlook in terms of the development of different pyrolytic products. The commer-
cial aspect of the pyrolysis process can be quantified when it is employed at an
industrial-scale production capacity. To effectively measure its economic potential,
the total annual biomass production capacity has to be taken into account.
Furthermore, the energy density of conventional fossil fuels is considerably higher
than that of biomass. For biofuels to achieve grid parity with fossil fuels, the costs
associated with feedstock supply, processing, and postprocessing becomes signifi-
cant. Its direct implication can be observed on the scale of operations where bio-
mass is being utilized. The average production in a typical oil refinery in the U.S. is
18,000 metric tons per day (MTPD), which is considerably more than the average
biomass production plant (1800 dry metric tons per day, DMT) (Hu et al. 2012;
Zhang et al. 2016; del Pozo et al. 2018).
There are many factors that can contribute toward the determination of the eco-
nomic feasibility of pyrolysis, such as reactor configuration, catalyst selection,
applied process parameters, rate of pyrolysis, feedstock source, and its associated
logistics. Despite several challenges, pyrolysis retains the position of the most
promising candidate for an economical thermochemical route of biomass conver-
sion. With certain measures like effective upgradation of product yields, the integra-
tion of value-added by-products (biochemicals) could increase the overall economic
potential of the refinery. Moreover, utilization of the existing infrastructure of pet-
rochemical refineries for biorefining with minimal reconstruction could result in a
positive ecological footprint. Thus, the implementation of the techno-economic
analysis method for detailed cost analysis over the operational lifetime can go a
long way in successfully implementing the pyrolysis technology.
10.3 Hydrothermal Liquefaction
Hydrothermal liquefaction (HTL) is an efficient thermochemical process in which

hydrolysis and pyrolysis are carried out simultaneously (also termed as hydrous
pyrolysis). Under these conditions, macromolecules from biomass are converted to
produce low molecular weight hydrocarbons. HTL is a versatile process in terms of
feedstock quality, which converts high moisture containing (wet biomass) feedstock
into biocrude oil, biochar, gases, and aqueous products. This process is advanta-
geous for the utilization of environmentally benign solvents with easily adjustable
properties and also contributes to decreasing the greenhouse gas emissions (Arturi
et al. 2019).
Thermochemical processes such as pyrolysis, gasification, and combustion use
dry feedstock, requiring time, labor, and energy for drying the feedstocks for the
removal of moisture and volatile components. However, HTL can process the wet
feedstocks where water serves as a reaction medium and catalyst. Therefore, HTL
is considered as an eco-friendly, economical, and promising process compared to
other thermochemical processes. This chapter emphasizes the improvement of bio-
crude oil yield and quality by reducing carbon distribution in the aqueous, gaseous,
and solid residue phases.
The yield of different products varies substantially with feedstock type, reaction
conditions, and reactor configurations (Dimitriadis and Bezergianni 2017). The
most sensitive operating parameters to be maintained carefully during hydrothermal
liquefaction of biomass are the type of biomass, reaction time (5–120 min), biomass
loading (2–30 wt%), reaction temperature (250–370 °C), pressure (5–25 MPa),
heating rate, cosolvents, and catalysts (Xue et al. 2016). The effects of these param-
eters on product formation have been discussed in the literature (Xue et al. 2016;
Sandquist et al. 2019). The hydrothermal processing of biomass feedstock for the
bulk production of biocrude has been demonstrated in the small batch reactor, as
well as in the continuous-flow process, whereas continuous-flow reactors are advan-
tageous for upscaling.
In HTL, the depolymerization of biomass feedstocks occurs in fuels and valuable
chemicals in the near-critical or supercritical water (374 °C and 22.1 MPa) medium.
Under high pressure and temperature near subcritical conditions, water dissociates
to form ionic products, which may catalyze hydrolysis or depolymerization
reactions, whereas at supercritical conditions, the free-radical reactions promote

degradation (Nanda et al. 2015c, 2016b, 2017b; Song et al. 2017; Cao et al. 2017).
By increasing the temperature and pressure of water from normal temperature and
pressure conditions to supercritical conditions, the hydrogen bonding is weakened.
Therefore, the dielectric constant (relative permittivity) of water decreases from
80.4 F/m to 14.07 F/m. This results in the decreased polarity of water whose value
is comparable to organic solvents such as alcohols (Kumar et al. 2010; Pearce et al.
2018; Okolie et al. 2019b). Thus, the hydrophobic organic molecules (called bio-
crude oil) are solubilized in supercritical water. Subcritical water and supercritical
water have been employed for a variety of hydrothermal reactions, such as gasifica-
tion (Reddy et al. 2016; Rana et al. 2018, 2019; Okolie et al. 2019a), liquefaction
(Alper et al. 2019), oxidation (Reddy et al. 2017, 2019), incineration (Reddy et al.
2015), and carbonization (Kang et al. 2019).
In HTL process, the major constituents of lignocellulosic biomass, i.e., cellulose,
hemicellulose, and lignin, are converted into liquid biocrude oil, along with aqueous,
gaseous, and solid products through a series of mechanisms including hydrolysis,
C–C bond cleavage, alkylation, isomerization, deoxygenation, reforming, depolymer-
ization, and repolymerization reactions (Dimitriadis and Bezergianni 2017; Miliotti
et al. 2019). The main oily product of this process termed as biocrude oil is mainly
composed of catechol, phenols, and methoxyphenols, which can be further upgraded
for the production of synthetic transportation fuels and valuable chemicals (Miliotti
et al. 2019). Lignin is the most stable compound in lignocellulosic biomass and is dif-
ficult to liquefy through HTL, whereas cellulose and hemicellulose have a simpler
structure and are less branched than lignin with high reactivity during HTL. HTL is
used as an intermediate reaction to produce bio-oil, phenolic compounds, organic
acids, furfurals, and cyclopentenes from these biomass constituents.
10.3.1 B
iocrude Oil Production Through Hydrothermal
Liquefaction
The biocrude oil obtained from HTL is a dark brown and viscous liquid constituting
18–67% of the total weight of the feedstock. The quality and yield of biocrude oil
vary with the type of biomass, operating conditions, and type of catalyst or cosol-
vent used. The HTL biocrude oil contains a large fraction of phenolic compounds
where the fraction of polar compounds such as acids and sugars are less. Typically,
the energy content is about 30–36 MJ/kg, and the elemental composition is as fol-
lows: 64–73 wt% carbon, 8–10 wt% hydrogen, 10–25 wt% oxygen, and 3–5 wt%
nitrogen (Jiang et al. 2018). Biocrude oil can be further upgraded to produce com-
mercial grade liquid transportation fuels using catalytic processes such as catalytic
cracking, hydrodeoxygenation, desulfurization, and denitrogenation.
After the liquefaction process, product separation is a crucial stage for the recovery
of biocrude oil from the aqueous by-products and solid residues, which can be accom-
plished by using any of the existing technologies such as solvent extraction, centrifu-
gation, filtration, sedimentation, etc. (Funkenbusch et al. 2019; Miliotti et al. 2019).
Where gravimetric separation of biocrude is not possible, a solvent extraction process

is efficiently used. Furthermore, biocrude oil upgradation is required to improve the
quality and flow properties similar to the properties of commercially used petroleum
hydrocarbon fuels.
Hydrotreating (HDT) is a process for the upgradation of biocrude oil by hydro-
deoxygenation, which is carried out by treating biocrude oil with hydrogen gas at a
temperature range of 330–390 °C and 1.5–3 MPa pressure (Patil and Vaidya 2017,
2018). The dewatering process is necessary prior to the hydrotreating for better
purity and less hydrogen consumption (Elliott et al. 2015; Funkenbusch et al. 2019).
Aqueous phase by-products can be recycled or mixed with other solvents to extract
the value-added chemicals or used effectively for the cultivation of biomass. The
aqueous phase obtained from HTL is considered as a useful by-product, which con-
stitutes 20–50% of the total weight of feedstock, depending on the operating condi-
tions and type of biomass. Major chemicals extracted in the aqueous phase contain
organic acids, alcohols, ketones, and phenolic compounds.
10.3.2 Gaseous Products from Hydrothermal Liquefaction
The gaseous by-products constitute 5–10% of the total weight of feedstock. CO2 is
the main gaseous product of HTL, followed by H2, CO, and CH4 in small fractions
(Magdeldin et al. 2018). Similar to hydrothermal liquefaction, hydrothermal gasifi-
cation is another hydrothermal process, which is aimed to produce gases by treating
biomass in subcritical or supercritical water medium under high pressure and high
temperature (Gong et al. 2017a, b; Nanda et al. 2018c). Hydrothermal gasification
has been proven advantageous for achieving higher thermal efficiency from wet
biomass, producing hydrogen-rich gas with low CO, and reducing char formation
and negligible levels of heteroatoms like sulfur, nitrogen, and halogens, which are
solubilized in aqueous by-products (Reddy et al. 2014).
10.3.3 Solid Residue from Hydrothermal Liquefaction
Biochar is a solid residue from the hydrothermal and thermochemical processing of

biomass, which contains high fractions of aromatic carbon (Nanda et al. 2014b).
Generally, char from hydrothermal liquefaction is used as a potential source of
nutrient for soil amendment. Similar to hydrothermal liquefaction, hydrothermal
torrefaction, carbonization, and gasification are other processes in which solid prod-
uct is targeted for value-added applications. The hydrochar produced from hydro-
thermal processing has different physicochemical properties than pyrolysis-derived
biochar (Azargohar et al. 2019). Furthermore, both hydrochar and biochar have
been used for soil amendment, soil fertility, water retention, capacitor application,
low-cost adsorbent, heavy metal removal, phosphate removal, and medical applica-
tions (Ruan et al. 2014; Nanda et al. 2016c; Fang et al. 2018).
10.3.4 Catalytic Hydrothermal Liquefaction
Catalytic HTL encounters one of the major challenges related to the deactivation
and stability of heterogeneous catalysts under high temperature and pressure condi-
tions. Most oxide catalyst support materials undergo a phase transformation and
dissolution in the presence of water mainly due to the hydrolysis of metal oxides
with adjacent hydrophilic sites, e.g., Si–O–Si and Al–O–Al bonds, thus leading to
the loss of pores and surface area (Murphy and Xu 2018). In a study by Sudarsanam
et al. (2019), HTL at 200 °C for 10 h using a mesoporous silica catalyst resulted in
about 90% loss in the surface area due to the hydrolysis of the silica. The factors
affecting catalyst support stability under hydrothermal conditions are the severity of
hydrothermal process conditions, pH of the solution, and hydroxyl ions (Xiong
et al. 2014; Rinaldi et al. 2016).
The recovery of homogeneous catalysts from the aqueous phase and the degrada-
tion of active sites of heterogeneous catalysts raise concerns of high cost and envi-
ronmental problems. The choice between homogeneous and heterogeneous catalysts
is crucial because both types of catalysts have certain advantages and disadvan-
tages. Heterogeneous catalysts (like Fe, Co, and Ni) increase biocrude oil yield and
decrease its O, N, and S contents. On the other hand, active sites of homogeneous
catalysts are uniformly distributed and remain available until the completion of the
process (Chen et al. 2019).
Understanding of the chemical interactions between water, cosolvents, and cata-
lysts is challenging to improve product yields, the stability of catalysts, the effi-
ciency of separation, and the possibility of process integration. The development of
a homogeneous catalyst for denitrogenation of biocrude oil is still a research gap
(Chen et al. 2019). There is an opportunity for developing multifunctional catalysts
targeting green engineering principles to have higher efficiency, long shelf life,
reduced reaction time, as well as lower temperature and pressure requirements,
which could overall reduce energy and time consumption. More research is expected
to be undertaken to investigate the activity and selectivity of the catalyst to mitigate
the challenges due to several technical and economic barriers in the commercial
production of biofuels and biochemicals (Murphy and Xu 2018).
10.3.5 C
hallenges and Opportunities of Hydrothermal
Liquefaction
Various methodologies have been developed for the conversion of biomass to biofu-
els and value-added chemicals, but the cost of drying, biomass pretreatment, bio-oil
extraction, and upgradation is still high. Therefore, some thermochemical methods
aim for the direct conversion of wet biomass to biocrude oil, along with in situ
upgrading to biofuels and biochemicals. HTL is considered as a promising technol-
ogy to advance the applications of biofuels and value-added chemical intermedi-
ates. Besides many possibilities, there are some challenges that need to be addressed
for the commercial uses of HTL.
10.3.5.1 Biocrude Oil Production

In the last decade, more research has been undertaken to increase biocrude oil yield
by reducing the organic content dissolved in the aqueous phase (Chen et al. 2019).
Higher yields of biocrude oil can be achieved with HTL when compared to other
thermochemical processes, but it cannot be used directly as a transportation fuel. In
order to replace the petroleum fuels, advanced biofuels are expected to have supe-
rior fuel properties facilitating effective storage, distribution, and combustion
(Román-Leshkov et al. 2007). Further improvements are required in the properties
of biofuels, such as purity, heating value, and flow properties. Biocrude oil has high
nitrogen and oxygen heteroatom contents. Furthermore, the investigation is expected
to understand denitrogenation and deoxygenation mechanisms for designing an effi-
cient catalytic process. Therefore, to improve the quality of biocrude oil, further
refining and upgrading need to be investigated (Cao et al. 2017). In addition, break-
through researches are required to develop new methods and technologies to under-
stand the mechanism among the heterogeneous chemical compounds present in the
biocrude oil refining and upgrading (Castello et al. 2019).
10.3.5.2 Value-Added Chemicals Production

Maximum utilization of extracted products by comprehensively targeting each func-
tional group to produce value-added products can improve their economic benefits.
As shown in Fig. 10.2, the broad spectrum of chemical products possibly produced
from lignocellulosic biomass include phenolic compounds, antioxidants, pigments,
aromatics, fatty acids, etc. Many reactions (e.g., hydrolysis, alkylation, degradation,
and repolymerization) take place during the HTL of biomass through ionic and free
radical intermediates, depending on the operating conditions. Although the desired
product can be formed in the HTL process, it is difficult to control its further loss due
to cleavage or repolymerization reactions (Schuler et al. 2019).
On the other hand, the difficulty to break C–C type bonds in lignin is a chal-
lenge to recover valuable functional compounds from lignin, which leads to the
formation of oligomers and tar-like molecules (Kruse et al. 2013; Yong and
Yukihiko 2013; Schuler et al. 2019). To address these challenges, a systematic
optimization of operating conditions for a higher yield of the selective products is
desired. Limited research in identifying more numbers of key substances and
investigating the reaction pathways to understand their formation gives an oppor-
tunity to address these questions.
10.3.6 R
ecent Technological Advancements in Hydrothermal
Liquefaction
10.3.6.1 atalytic and Cosolvent-Assisted Hydrothermal

C
Liquefaction
Various homogeneous and heterogeneous catalysts have been studied for the HTL
of biomass in the last few decades. Homogeneous catalysts are known to increase
biocrude oil yield, suppress char formation, and promote water-gas shift reaction
(Toor et al. 2011). Heterogeneous catalysts are used to improve the quality of bio-
crude oil by deoxygenation, decarboxylation, denitrogenation, and desulfurization
mechanisms. Several types of catalysts have been studied to improve the productiv-
ity and quality of biocrude oil. Homogeneous catalysts are water soluble at room
temperature and include alkali salts (Na2CO3 and KOH) and organic acids
(CH3COOH and HCOOH). Heterogeneous catalysts are water insoluble at room
temperature and include metal catalysts (Pd, Pt, Ni, Ru, etc. supported on activated
carbon, Al2O3, and zeolite), transition metal oxides (NiO), insoluble salts or earth
metals (Ca3(PO4)2), and molecular sieves (zeolite and HZSM-5).
Yue et al. (2018) investigated the two-stage HTL of sweet sorghum bagasse to
produce biocrude oil followed by its upgradation via catalytic hydrodeoxygenation.
First-stage HTL was carried out at 200 °C, and the lignin-rich solid fraction from
the first stage was applied to second-stage HTL at 350 °C in the presence of a
K2CO3 catalyst to obtain biocrude oil. Biocrude oil from the second-stage HTL
process was upgraded using 5% Ru/C catalyzed hydrodeoxygenation at 350 °C to
form upgraded drop-in biofuel with qualities comparative to the petroleum diesel.
Table 10.5 presents the comparative properties of fuels from different stages and
sources. The different properties of biocrude oil are taken as average from a variety
of biomass feedstocks.
The yield of HTL biocrude oil is higher when compared to the organic solvolytic
liquefaction process because water allows high reaction temperature for the lique-
faction of biomass (Sandquist et al. 2019). However, cosolvents such as tetralin,
acetone, ethanol, and methanol are used to improve HTL biocrude oil properties by
the solubilization and stabilization of products formed during HTL and by scaveng-
ing the reactive intermediates. Cosolvents used to alter the physical properties of a
reaction medium (such as viscosity, ion solvation, and compound solubilization)
and the thermodynamic properties (such as activation energy). Proton donor sol-
vents can promote the reduction of reactive intermediates (Arturi et al. 2019).
Table 10.5 Properties of fuels obtained from the HTL of biomass and petroleum source
Bio-oil (from Biodiesel (from second-stage Heavy fuel
Properties HTL) HTL-HDO) oil Diesel
Yield (%) 18–67 41–43 – –
Carbon (wt%) 63.55–73 85.9–90.5 85 86
Hydrogen (wt%) 7.66–9.76 8.91–9.31 11 13
Oxygen (wt%) 10.5–25.1 0.24–3.88 0–1 0
Nitrogen (wt%) 3.71–4.47 0.58–0.64 0.3 –
Water content 1.0–8.7 – 0.1 0.1
(wt%)
Ash (wt%) 0.2–0.8 – 0.1 –
HHV (MJ/kg) 21.15–36.1 42.2–43.3 40 43
Viscosity at 843 23.7–2.5 180 2.5
50 °C (cP)
Note: HTL hydrothermal liquefaction, HDO hydrodeoxygenation, HHV high heating value.
Reference: Cao et al. (2017), Shakya et al. (2018), Yue et al. (2018)
10.3.6.2 evelopment of Hybrid Catalysts for Better Selectivity

D
and Stability
The stability of heterogeneous catalysts is one of the major issues for the HTL conver-
sion of biomass to biofuels and biochemicals. Recently, new strategies are being
developed to improve the stability of catalyst supports under hydrothermal conditions.
In the last few decades, significant research and development have been done in the
field of catalytic thermochemical upgradation of biomass to improve the yield and
selectivity of desired products. However, there is scope for experimental investiga-
tions and computational modeling of liquid phase intermolecular forces and catalyst-
solvent interactions to accurately predict the overall operating conditions in HTL.
Hybrid catalysts are hybrid materials, composites, or organocatalysts generally
synthesized by the immobilization of catalytically active phases (homogeneous or
heterogeneous) on mesoporous and microporous supports to enhance selectivity
and stability with an ease of separation from the product stream. Catalytic synthesis
techniques such as coating, overlayer deposition, and impregnation of heteroatoms
have been found effective to mitigate the hydrothermal instability, leaching, and
sintering of metal oxide supports or catalytically active sites. Introducing heteroat-
oms such as La3+, Ga3+, Sm, Ce, and Ti4+ has significantly improved the hydrother-
mal stability of oxide supports (Xiong et al. 2014).
10.3.6.3 Value-Added Chemical Production

The utilization of lignin for value-added chemical production and sustainable
resource management becomes possible through technological advancement.
Table 10.6 summarizes a few studies that have shown the production of biochemi-
cals through the HTL of biomass. Cardoso et al. (2018) explored the catalytic HTL
for the upgradation of Kraft lignin to monoaromatic compounds, particularly guaia-
col and creosol. Ni-CeO2 catalyst supported on carbon nanofiber (Ni-CeO2/CNF)
showed improved yield over 55% and better stability at 400 °C, 23 MPa, and 15 min.
The presence of carbon nanofiber (CNF) improved the selectivity of methoxyphe-
nols, whereas CeO2 improved the selectivity of guaiacol. Creosol was the main
product from HTL with a Ni/CNF catalyst.
Trajano et al. (2013) carried out the HTL of Populus trichocarpa × P. deltoides
wood samples to study the depolymerization of wood lignin. About 75% lignin was
recovered in the form of phenolic monomers at 180 °C and 1.1 MPa in 192 min with
a 5% biomass loading. Under these HTL conditions, it was observed that the prod-
uct molecules were extracted by depolymerization and redeposited by the conden-
sation mechanism. Among the identified 18 different phenolic monomers,
p-hydroxybenzoic acid yield was 83% of the total phenolic compounds.
Bbosa et al. (2018) demonstrated the production of acetic acid, catechol, cresols,
and phenol in an integrated biorefinery. Román-Leshkov et al. (2007) used a
microwave-assisted catalytic HTL to improve the yield and total phenolic content in
biocrude oil products from pine-spruce biomass. Kim et al. (2014) studied the anti-
oxidant activity of hydrothermal extracts of watermelon (flesh, white rind, and
green rind). Total phenolic content of 7626.5 μg GAE/g, lycopene content of
60 μg/g, and β-carotene content of 4.8 μg/g were extracted under hydrothermal
Table 10.6 Value-added chemicals produced from the hydrothermal liquefaction of biomass
Experimental
Biochemicals Feedstock conditions Product yield References
Acetic acid, Corn stover 350 °C, 20 MPa 39% (acetic Bbosa et al.
catechol, cresols, lignin acid), 28% (2018)
and phenol (catechol)
12% (cresols)
and 8%
(phenol)
Antioxidants (total Watermelon 300 °C, 30 min, 7626.5 μg Kim et al.
phenol content) 5 g/5 mL GAE/g (2014)
β-carotene Watermelon 300 °C, 30 min, 4.8 μg/g Kim et al.
5 g/5 mL (2014)
Catechol Beech wood bark 300 °C, 1 wt% 30 mg/g Schuler
lignin KOH, 180 min et al.
(2019)
Creosol Kraft lignin 400 °C, 23 MPa, 30–40% Cardoso
water, Ni/CNF et al.
catalyst, 15 min (2018)
Cyclopentenes, Lactose, maltose 350 °C, 2 MPa, 6–10% Fan et al.
furfurals, levulinic 10 wt% biomass, (2018)
acid 20 min
Fluorescent Cocoon silk 200 °C, 72 h, 5% – Ruan et al.
quantum dots Na2CO3, 1 g/10 mL (2014)
Guaiacol Beech wood bark 300 °C, 1 wt% 28 mg/g Schuler
(2019)
Guaiacol Kraft lignin 400 °C, 23 MPa, 55% Cardoso
water, Ni-CeO2/ et al.
CNF catalyst, (2018)
15 min
Lycopene Watermelon 300 °C, 30 min, 60 μg/g Kim et al.
5 g/5 mL (2014)
Phenolic monomers Populus 180 °C, 1.1 MPa, 75% Trajano
trichocarpa × P. 192 min, 5% mass et al.
deltoides wood loading, 8 mL (2013)
p-hydroxybenzoic Populus 180 °C, 1.1 MPa, 62% Trajano
acid trichocarpa × P. 192 min, 5% mass et al.
deltoides wood loading, 8 mL (2013)
Piperidines and Lysine 350 °C, 2 MPa, 5–17% Fan et al.
quinolines 10 wt% biomass, (2018)
20 min
Pyrazine and its Lactose+lysine/ 350 °C, 2 MPa, 10–39% Fan et al.
derivatives maltose+lysine 10 wt% biomass, (2018)
20 min
(continued)

Experimental
Biochemicals Feedstock conditions Product yield References
Syringol Beech wood bark 300 °C, 1 wt% 3.27 mg/g Schuler
(2019)
Total phenol Pine and spruce 250 °C, 8 MPa, 14% Remón
content pallets 10 g/500 mL et al.
biomass, 115 min, (2019)
Ni-Co/Al-Mg
catalyst, 2.45 GHz
microwave
Note: CNF carbon nanofiber, GAE gallic acid equivalents
conditions of 300 °C, 30 min, and 5 g/5 mL biomass loading. In addition, phenolic
compounds such as catechol and its derivatives were identified in the HTL extract
of watermelon. These findings reveal the possible applications of HTL for nutraceu-
tical compound extraction.
10.3.6.4 echno-Economic Feasibility for Hydrothermal

T
Liquefaction
The techno-economic analysis study by Nie and Bi (2018) shows the minimum sell-
ing price of HTL biofuel to be about 60–80% higher than that of petroleum fuel. A
paradigm shift is needed in the research and development of alternative fuels. A
reduction in the overall operating cost for the conversion of biomass to commercial
grade biofuel is a key for the sustainability of any biorefinery process. Utmost care
is required during the process and equipment design to minimize production cost.
The water-insoluble tar-like solid residues formed during the reaction creates the
obstruction and risk for the functionality of the equipment. The deposits formed as
undesired by-products not only create concern for cleaning but also become the
bottleneck for product recovery.
Accurate analysis of the effects of temperature and time is difficult due to the
thermal transience during the heating and cooling cycles of the HTL reactor. The
equipment design needs highly advanced instrumentation and safety measures to
handle high temperature, high pressure, increased corrosion possibilities, and foul-
ing resistance to avoid unexpected accidental scenarios. The selection of operating
parameters for process optimization is based on technical perception and knowl-
edge, which may involve a certain degree of biases, thus creating hurdles in the
optimum reaction conditions. The requirement of reducing gas utility can increase
the operating cost, thus investigating efficient and cost-effective hydrogen donors to
mitigate the operating cost (Cao et al. 2017).
The kinetics and mechanistic investigations of complex reactions to develop accu-
rate mathematical models for process optimization can promote the industrial appli-
cations of HTL technology. Trained labor versus automation choices can improve
production economics. In addition, it is worth mentioning that the hidden cost of the
adverse impact on the environment due to fossil fuels is much higher. Thus,
government policies (such as carbon tax and biofuel subsidies) for damage control
due to climate change can improve the profitability of biofuel production process.
However, the opportunity of HTL as a cleaner processing, sustainable development,
and feedstock flexibility keeps the gateways open for its large-scale applications.
10.3.6.5 I ntegrated Biorefinery Approaches for Sustainable

Development
The production of any single product from biomass is neither economically feasible
nor environmentally viable. Therefore, integrated production of biofuels, biochemi-
cals, and biomaterials for the maximal utilization of biomass is an excellent way to
achieve the sustainability and commerciality of the biorefining process (Yadav et al.
2019; Sarangi and Nanda 2019). Bbosa et al. (2018) investigated the integration of
HTL in the ethanol production plant. Lignin waste from the ethanol process effi-
ciently produced biochemicals within the ethanol biorefinery using HTL. Ong et al.
(2018) evaluated the integration of the pine biomass HTL process to utilize black
liquor from Kraft pulp mill to coproduce biocrude oil and biopower. Black liquor
from Kraft pulp mill utilized for the co-HTL of pine biomass and part of the heavy
biocrude oil from HTL was utilized as feed to the boiler of Kraft pulp mill.
Heat integration reduced the steam demand for the boiler by 3%. Valuable prod-
ucts like BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) can be
coproduced using HTL in an integrated Kraft pulp mill (Funkenbusch et al. 2019).
Yu et al. (2011) introduced an environment-enhancing-energy treatment process
that integrates HTL gaseous by-products (as a CO2 source) and HTL aqueous by-
products (as a nutrient source) for the cultivation of algae for sustainable wastewater
treatment and the sequestration of CO2. Novel approaches can be developed based
on interdisciplinary knowledge and applications. HTL process allows the integra-
tion of fresh feedstocks, by-products, and residues from other processes for maxi-
mum biomass conversion to biofuels and biochemicals. This approach can turn into
a sustainable, techno-economically feasible, and cleaner technology in the future.
10.3.6.6 rocess and Equipment Design for Hydrothermal

P
Liquefaction
New innovative approaches can significantly improve the profitability and sustain-
ability of the HTL process. Remón et al. (2019) introduced an advanced process
intensification approach of microwave-assisted catalytic HTL for the liquefaction of
pine-spruce biomass to improve the yield and quality of biocrude oil. Quantitative
mathematical models can be developed to optimize HTL process variables from the
knowledge of feedstock composition. Yang et al. (2019) developed a quantitative
model to predict HTL product yields by understanding the chemical interactions
between biomolecules in the biomass. Development of batch to a continuous pro-
cess for the HTL of biomass has been studied in the recent years, which is found to
be advantageous for eliminating the limitations of thermal transience, reactant con-
tact patterns, production capacity, and capital investment cost (Elliott et al. 2015;
Castello et al. 2018).
The National Advanced Biofuels Consortium (NABC) in the U.S. developed a

continuous flow process for biocrude oil production from loblolly pine and corn
stover (Elliott et al. 2015). Comparing the performance of 1 L continuous stirred
tank reactor and plug flow reactor, it was recommended to use scalable plug flow
reactor for high biocrude oil yield, high carbon efficiency (>50%), and low capital
cost. More research is anticipated in the continuous HTL process to optimize phase
separation, product yield, space velocity, solid content of slurry, heat recovery, and
operating cost. The sensitivity analysis of techno-economic assessment specifies
that current technological advancement is the most important factor to make the
HTL process competitive and profitable. Therefore, current strategies to increase
the productivity of biocrude oil and biofuels to improve the quality of value-added
products and the integrated production of valuable products and biofuels are inevi-
table for technology advancement.
10.4 Conclusions
A wide variety of biomass feedstocks have been processed through pyrolysis and
hydrothermal liquefaction over the last few decades. Several experimental and sta-
tistical studies have been performed to optimize the effect of operating variables,
catalysts, and cosolvents to improve biocrude oil yield and quality. The challenges
and opportunities in the pyrolysis and hydrothermal liquefaction of biomass have
been addressed. The challenges vary depending on the biomass composition and
targeted products in HTL and the pyrolysis process. In the progress to make biofuels
produced from HTL and pyrolysis competitive with fossil fuels, the aspect of tech-
nological advancement is most sensitive.
Current technological advancements are reviewed, and new strategies are discussed
to overcome the existing challenges. From the review of literature, it is evident to sug-
gest that HTL technique can be utilized to improve the yield of biocrude oil from high-
moisture containing biomass. Further investigations on the selection of a suitable
catalyst and cosolvent are required to ascertain the increase in biocrude oil yield and
quality and to reduce the overall cost of biocrude oil production. The developments in
hybrid catalytic systems and recent progress are certainly leading to overcoming some
universal challenges, which can result in HTL and pyrolysis as commercial biorefining
processes. Innovative approaches such as process intensification, mathematical model-
ing for process simulation, and equipment design for energy efficiency can signifi-
cantly improve the profitability and sustainability of HTL and the pyrolysis process. An
integrated biorefinery approach based on the coproduction of biofuel and valuable plat-
form chemicals from biomass has promising potential to access affordable energy sup-
ply with positive effects on the environment and economy.
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Biocrude Oil Production via
Hydrothermal Liquefaction of Algae 11
and Upgradation Techniques to Liquid
Transportation Fuels
Shima Masoumi, Venu Babu Borugadda, and Ajay K. Dalai
Abstract
Hydrothermal liquefaction of algae is regarded as a favorable thermochemical
process to produce biocrude oil from biomass with potential to complement con-
ventional crude oil. This chapter discusses the production of biocrude oil via
hydrothermal liquefaction of microalgae. Due to the presence of high protein
content in algal species, the catalytic removal of heteroatoms is required to make
liquid transportation fuels (biodiesel and biogasoline) from algal biocrude oil.
Therefore, different upgradation techniques are explored to remove the heteroat-
oms using various heterogeneous acid catalysts. Special focus is given to the
effects of process parameters on hydrothermal liquefaction and upgradation
techniques to escalate biocrude oil yield and liquid transportation fuels.
Keywords
Algae · Hydrothermal liquefaction · Liquid transportation fuels · Process param-
eters · Fuel upgrading
11.1 Introduction
For the last few decades, due to incremental human population, industrialization, and
energy consumption, there is a rapid increase in CO2 emission into the environment
(Nanda et al. 2016f). Furthermore, a drastic increase in energy consumption and the
lack of sustainable resources have concerned scientists for alternative sources of energy.
S. Masoumi · V. B. Borugadda · A. K. Dalai (*)


250 S. Masoumi et al.
Therefore, many researchers have focused on finding an alternative fuel source for
commercialization. Waste organic biomass is regarded as an inexhaustible and sustain-
able future energy source. This includes biomass sources such as forestry wastes, agri-
cultural crop residues, energy crops, microalgae, and animal manure (Nanda et al.
2014b, 2016b, c). Of the candidate biomass feedstocks for biofuel production, much
attention is given to microalgae due to faster growth, higher yield, and higher ability to
CO2 sequestration as compared to other biomasses (Duan and Savage 2011).
Algal biofuels, considered as third-generation biofuels, can be obtained through
thermochemical conversion processes. Hydrothermal liquefaction (HTL) of algae is
considered as a well-known technique to transform algae feedstocks into biocrude
oil in water or solvent medium under high pressures and moderate temperatures.
Although high biocrude oil yield can be obtained through this process, large amounts
of nitrogen, sulfur, and oxygen can still be present in biocrude oil (Guo et al. 2015).
This leads to the instability of biocrude oil, which creates many difficulties for its
applications. Therefore, subsequent upgrading of biocrude oil and improving its
stability will make it more suitable for producing liquid transportation fuels.
Environmentally friendly transportation fuels such as biodiesel obtained from the
transesterification of algal biocrude oil is a promising alternative due to its advantages,
such as higher flash point and low sulfur content, and it also can be considered as a
better lubricant (Toor et al. 2013). Esterification is an important upgrading process for
biocrude oil to convert carboxylic acids into desirable esters. Esterification under a
supercritical fluid environment with higher temperatures and mass transfer rates to
remove organic acids in biocrude oil has attracted much attention. Additionally, the use
of catalysts increases the efficiency of the esterification and transesterification of bio-
crude oil.
Significant research has focused on heterogeneous catalysts due to their separa-
tion and reusability over homogeneous catalysts. An option that has great feasibility
but has not been fully explored is the preparation of catalysts from sustainable
renewable sources (Nanda et al. 2016e). Nanda et al. (2016e) have demonstrated
synthesizing nanocatalytic nickel particles in the cell wall of agricultural (wheat
straw) and forestry (pinewood) biomass in subcritical and supercritical water for
hydrothermal gasification. Moreover, functionalized biochar-based catalysts are
considered desirable because of their favorable properties, such as low material
cost, high surface area, and thermal stability (Manayil et al. 2016, Nanda et al.
2016a). Thus, the production of biocrude oil from algae via liquefaction and upgra-
dation routes is discussed with a focus on the effect of process parameters on bio-
crude oil yield and liquid transpiration fuel production technologies.
11.2 First-Generation and Second-Generation Biofuel Refining
Based on the nature of the feedstock used to produce biofuels, they are divided into
three generations. First-generation biofuels are obtained from food crops like corn,
wheat, and soybean, which can also be consumed as human food. Their use in biore-
fineries for biofuel production has led to an increase in food prices and created many
11 Biocrude Oil Production via Hydrothermal Liquefaction of Algae… 251
social, economic, and environmental challenges (Azad et al. 2015, Nanda et al. 2015).
In terms of first-generation biofuels, biodiesel and bioethanol are produced from veg-
etable oils and sugar/starch-based crops (corn, wheat, and potato). Non-edible ligno-
cellulosic biomass, which consists of nonfood crops such as grasses, wood, and
agricultural wastes, is considered as second-generation feedstock. Second-generation
biofuels are known as advanced biofuels because they are carbon neutral and do not
compete with food supply and arable lands. The need for a large area of land with
moist soil is one of the disadvantages of first-generation biofuels (Azad et al. 2015).
Biofuels derived from marine biomass are considered as third-generation biofuels,
and they provide more advantages compared to biofuels generated from previous gen-
erations. Microalgae are photosynthetic microorganisms that can also grow in saline
environments and transform sunlight and CO2 to renewable algal biomass and lipids.
The second- and third-generation feedstocks can be converted into biofuels
through three main processes: thermochemical process, biological process, and
direct combustion (Tsukahara and Sawayama 2005, Nanda et al. 2013, Azargohar
et al. 2013). Thermochemical conversion leads to biomethanol, biodiesel, biocrude
oil, biosyngas, and biohydrogen production. Gasification, pyrolysis, and liquefac-
tion are the three main routes for biomass thermochemical conversion. Biochemical
conversion technologies result in the production of bioethanol, biobutanol, biohy-
drogen, and biomethane through respective technologies such as ethanol/butanol
fermentation, dark/photofermentation, and anaerobic digestion (Nanda et al. 2014a,
2017a, c). In comparison to biochemical technologies, thermochemical processes
are preferred due to their ability to convert biomass into transportation fuels with
higher heating value (Akia et al. 2014).
Out of all the processes, gasification and pyrolysis require higher temperature
and dried biomass as feedstock. During gasification, biomass produces synthesis
gas (a mixture of H2 and CO), which can be converted to liquid fuel over a suitable
catalyst via the Fischer-Tropsch synthesis process. Pyrolysis is used to produce bio-
oil from dried biomass, whereas hydrothermal liquefaction and gasification can use
high-moisture-containing biomass because the medium of reaction is water or sol-
vents in the presence of suitable catalysts. Liquefaction technique is a low-
temperature and high-pressure process that can convert the components of biomass
into hydrocarbons in water or solvent medium (Dimitriadis and Bezergianni 2017).
Table 11.1 shows the oil content of algal biomass when compared to nonedible
feedstocks. Algae can be categorized into microalgae and macroalgae. Compared to
microalgae, macroalgae produce superior biomass densities. However, their lipid
content is less compared to their high carbohydrate and protein contents. Therefore,
it is believed that macroalgae cannot be an economically feasible source of bio-
diesel production (Van et al. 2014). Biofuel production from algae is promising
because of the following advantages:
1. Algae have fast growth rate. It is assessed that compared to crops such as canola
(200–450 L/ha), algae could yield 61,000 L/ha.
2. Able to sustain themselves under harsh condition due to their unicellular
growth.
3. Have a simple multicellular structure.

4. Short harvesting cycle.
5. Able to capture CO2.
6. Can be cultivated in nonarable lands.
7. Do not compete for food resources.
8. Can produce a remarkable variety of biofuels such as biodiesel, biogasoline,
bioethanol, and biojet fuel.
9. Capable of higher biocrude oil yield.
10. Relatively higher photosynthesis rate compared to terrestrial plants.
11. Algal biofuels are nontoxic and biodegradable, as well as contain less sulfur.
Although the potential for the production of algal biofuels is high, the capital and
operating costs are relatively high. It requires further research and innovation to
develop sustainable and viable methods of biofuel production on a commercial
scale. Currently, a number of companies worldwide are working on the commercial
development of algal biofuels, a few of which include ALG Western Oil (South
Africa), Algae Link (Netherlands), Affinity Eenergy and Health (Australia),
AlgaFuel (Portugal), Algenol (USA), Aurora Algae Inc. (USA), British Petroleum
(England), BRTeam (Iran), DENSO Corporation (Japan), Eni (Italy), Greon
(Bulgaria), Neste Oil (Finland), OilFox (Argentina), Pond Biofuels (Canada), Total
(France), and Varican Aqua Solutions (UK) (Saber et al. 2016).
Typically, algal biomass contains three major compounds in varying proportions:
lipids, proteins, and carbohydrates. During photosynthesis, microalgae capture
CO2, resulting in the synthesis of carbohydrates. At this stage, lipid content can be
varied based on some stress factors such as nitrogen starvation, which causes the
photosynthetic mechanism to switch to accumulating lipids. The lipid content as a
precursor for fatty acid depends on the algal strain (Demirbas and Demirbas 2011).
The typical oil contents of most widely used microalgae are given in Table 11.2. The
Table 11.1 Oil content of different feedstocks for the production of first-, second-, and third-
generation biofuels (Baskar and Aiswarya 2016)
Type of oil Feedstock Oil content (wt%)
Edible Soybean 15–20
Rapeseed 38–46
Sunflower 25–35
Peanut 45–55
Coconut 63–65
Palm 30–60
Nonedible Jatropha seed 35–40
Pongamia pinnata 27–39
Neem 20–30
Castor 53
Other sources Rubber seed 40–50
Sea mango 54
Cottonseed 18–25
Microalgae 30–70
Table 11.2 Oil contents of Microalgae Oil content (wt% on dry basis)
microalgae species (Shuba Botryococcus braunii 25–75
and Kifle 2018)
Chlorella sp. 28–32
Crypthecodinium cohnii 20
Cylindrotheca sp. 16–37
Dunaliella primolecta 23
Isochrysis sp. 25–33
Monallanthus salina >20
Nannochloris sp. 20–35
Nannochloropsis sp. 31–68
Neochloris oleoabundans 35–54
Nitzschia sp. 45–47
Phaeodactylum 20–30
tricornutum
Schizochytrium sp. 50–77
Tetraselmis suecica 15–23
productivity of algae-derived biofuels is approximately in two orders of magnitude

more than that from terrestrial oilseed crops. Algal biodiesel has lower melting
point and better cold flow properties owing to the presence of polyunsaturated fatty
acids (Demirbaş 2008).
11.3 Hydrothermal Liquefaction of Algae
Although lipid conversion technology via HTL is relatively recognized, it requires

algae with a high lipid content to be economically feasible. Thus, rapid reaction and
use of feedstocks (considering the high moisture content in algae) with no limitation
in terms of lipid content make the HTL process an appropriate method for produc-
ing biocrude oil. One of the problems related to the liquefaction of algae is the dif-
ficulty to convert high-quality hydrocarbons than lipids in biocrude oil because it
contains high concentrations of nitrogen, and consequently the biocrude oil is richer
in heteroatoms.
The typical reaction network of algae HTL is presented in Fig. 11.1, which
includes the hydrolysis of major components such as lipid, protein, and carbohy-
drate. The biocrude oil extracted from liquefaction has higher yield and quality,
moderate oxygen concentration, and higher heating value (HHV) in the range of
25–35 MJ/kg as compared to those of the traditional pyrolysis biocrude oils (14–20
MJ/kg) (Yang et al. 2016). Furthermore, the advantage of HTL is the formation of
distinct oil and water phases, whereas pyrolysis oil contains a substantial quantity
of water and oxygenated compounds.
Hydrothermal liquefaction process includes three main stages: depolymeriza-
tion, decomposition, and recombination. During the depolymerization of biomass,
long-chain macromolecules consisting of hydrogen, carbon, and oxygen are
254
S. Masoumi et al.
Fig. 11.1 Typical reaction network of algae HTL (Xu et al. 2018)
converted into short-chain molecules under high temperature and pressure condi-
tions. Decomposition of biomass involves dehydration (loss of water molecules),
deamination (loss of amino acid content), and decarboxylation (loss of CO2). The
recombination of the fragments forming compounds with high molecular weight
occurs when a large number of free radicals are present during the process
(Gollakota et al. 2018).
As can be seen in Fig. 11.2, four phases were generated after the HTL process:
light gases (principally CO2), a solid residue (biochar), biocrude oil, and an aqueous
phase having a high organic carbon content. The relative reaction rates are strongly
dependent on the nature of the feedstocks and processing conditions such as reac-
tion temperature, residence time, and biomass loading affecting the ultimate prod-
uct distribution and composition (Nanda et al. 2016d). Biochar is a carbon-rich solid
product of thermochemical biomass conversion technologies having potential appli-
cations in environmental (adsorption of pollutants from wastewater and air, as well
as carbon sequestration), agricultural (soil fertility and crop productivity), and
material engineering (activated carbon, carbon nanotubes, electrode materials, fuel
cells, etc.) (Mohanty et al. 2013, Azargohar et al. 2014, Nanda et al. 2016a).
Fig. 11.2 Process flow diagram for the extraction of hydrothermal liquefaction products
11.4 ffects of Hydrothermal Liquefaction Process

E
Parameters on Biocrude Oil Yield
The yield and physicochemical properties of the biocrude oil obtained from the
liquefaction of algae are impacted by operating factors such as reaction time, pro-
cess temperature, solvent type and solvent-to-biomass ratio, algae composition,
catalyst type, and loading. This section elaborates the effects of all these process
parameters on biocrude oil yield.
11.4.1 Effects of Reaction Temperature
Temperature is considered as an important factor in the safety and economics of

industrial operation, suitable range of operating temperature relied on the nature of
biomass feedstock, solvent polarity, catalyst loading, and other process factors.
The ionic characteristic of water, which changes with temperature, causes different
reactions to dominate. At low-temperatures, hydrolysis dominates, thereby bio-
crude oil yield is reduced. However, biocrude oil yield increases with increasing
reaction temperature and then decreases at a certain temperature (Dimitriadis and
Bezergianni 2017). The highest biocrude oil yields can be obtained at the tempera-
ture range of 250–370 °C. Furthermore, as temperature increases, biocrude with
higher quality (higher HHV) is produced, while the carbon and hydrogen contents
present in the aqueous phase are reduced. Simultaneously, the nitrogen content in
the biocrude oil starts to increase significantly, suggesting higher incorporation of
protein-derived molecules (Garcia Alba et al. 2011). It is clear that maximum bio-
crude yield does not correspond to the best biocrude oil quality, and these two
factors must be carefully balanced.
11.4.2 Effects of Reaction Time
Reaction time is a critical factor to be considered during the HTL of algae. To evalu-
ate the process economically, sufficient reaction time is necessary to have maximum
biocrude oil through the conversion of algal biomass components. A longer reaction
time results in lower biocrude oil yields because of the higher production of gases
and aqueous products (Zhou et al. 2010). On the other hand, reduced reaction time
leads to lower equipment and operational costs.
Anastasakis and Ross (2011) investigated the optimum reaction time to have
higher biocrude oil yield. Their results showed that 15 min at a temperature of
350 °C could be considered as an appropriate condition for the HTL conversion of
algae. However, these values are generally reported at the reaction temperature and
do not include heating times. Furthermore, the increase in reaction times resulted in
increased N/C ratios, whereas the O and H concentrations in the oil dropped. This
shows that similar to the reaction temperatures, the holding times need to be care-
fully adjusted to obtain an optimal balance between biocrude yields and quality.
11.4.3 Effects of Solvent
As can be seen in Fig. 11.3, the efficiency of HTL depends on the critical point of
water or other solvents used during the reaction. At near-critical conditions, water,
which is a polar solvent, converts into nonpolar solvent due to weak hydrogen bond-
ing (Rana et al. 2018). In this situation, water as a nonpolar solvent is able to dis-
solve and extract the organic components from the biomass (Peterson et al. 2008,
Reddy et al. 2016, 2017, 2019). Furthermore, near critical point, the water dissocia-
tion constant (Kw) is higher in several orders of magnitude than at ambient condi-
tions, significantly increasing the ionic products of water, i.e., H+ and OH− ions,
which help to promote base- and acid-catalyzed reactions, as well as ring-opening
reactions (Toor et al. 2013, Gong et al. 2017a, b).
Singh et al. (2015) studied the effects of various solvents such as water and
alcohol, including methanol and ethanol, on the product distribution of the HTL
process. The results showed that supercritical alcohols used for HTL process are
effective to produce liquid hydrocarbons. Furthermore, Biswas et al. (2017) con-
firmed that biocrude oil yield increases with the use of alcoholic solvents. Zhang
et al. (2014) studied liquefaction of algae in ethanol-water and cosolvent system
to produce biocrude oil. Their results showed that compared to monosolvent, the
mixtures of solvents with different polarities yield higher biocrude oil and less
solid residue.
Fig. 11.3 Phase diagram of hydrothermal liquefaction reaction (Tran et al. 2017)
11.4.4 Effects of Algal Composition and Feedstock Loading
Microalgae are predominantly composed of three main biochemical compounds,

namely proteins, lipids, and carbohydrates. Their contributions are dependent on the
algal species and their growth conditions. Lipid-rich algae are found to have much
higher oil yield than protein-rich algae. Some studies have confirmed that lipids are
more readily converted into biocrude oil than proteins or carbohydrates (Gollakota
et al. 2018). Research on the HTL of algae has been conducted over a wide range of
biomass loadings (1–50 wt%) (Li et al. 2010). Peterson et al. (2008) proposed that
biomass concentrations should be in the range of 15–20 wt% for higher biocrude oil
yield, whereas Barreiro et al. (2013) suggested slightly lower loadings ranging from
5 to 15 wt%, and these studies were mainly focused on Chlorella, Nannochloropsis,
Dunaliella, Spirulina, and Phaeodactylum.
Biller and Ross (2011) converted a number of model compounds, which showed
that the highest oil yields were obtained from lipids (55–80%), followed by proteins
(11–18%) and carbohydrates (6–15%). They obtained similar biocrude oil quanti-
ties from two microalgae, Chlorella and Nannochloropsis, whereas the obtained
yields were different for Porphyridium and Spirulina. Toor et al. (2013) found that
Nannochloropsis salina as feedstock seems to be more appropriate than Spirulina
for biocrude oil production based on the H/C ratio in the biocrude oils.
11.4.5 Effects of Catalysts
Catalysts are considered as one of the most important factors for biocrude oil pro-
duction, which affect the reaction rate, product composition, and quality of biocrude
oil. Typically, the catalysts used in the HTL of algal biomass are divided into homo-
geneous and heterogeneous catalysts. Compared to heterogeneous catalysts, homo-
geneous catalysts are economical and produce less coke. The homogeneous catalysts
applied for HTL are acids such as sulfuric acid, metal ions, and alkalis (i.e., CaCO3
and Ca(OH)2) (Tian et al. 2014). Acids and alkalis are often used to weaken bonds,
including C–C bond, which could improve the hydrolysis of biomass during HTL,
while metal ions can affect hydration.
Jena et al. (2012) reported that HTL using catalysts increased the yield of
biocrude oil up to 50% in comparison to the noncatalytic HTL process. Besides,
catalysts play a crucial role in enhancing the hydrocarbon ratio and removal of
oxygen to increase biocrude oil quality. It is reported that liquefaction with base
catalyst (KOH) gave the highest biocrude oil yield than without catalyst (Yang
et al. 2016, 2017). Likewise, sulfuric acid and acetic acid favor oxygen removal
during biocrude oil upgradation. Furthermore, the lighter component proportion
in catalytically upgraded biocrude oils is higher than biocrude oil produced with-
out a catalyst.
11.5 Algal Biocrude Oil Upgradation Techniques
Algal biocrude oil produced by HTL process has similar properties to that of crude
oil derived from fossils. On the other hand, biocrude oil contains higher oxygen
(10–20 wt%) and nitrogen (1–8 wt%). The presence of these heteroatoms causes
several undesired properties, as mentioned below, which limit its direct application
in compression-ignition (CI) engines (Roussis et al. 2012):
1. High viscosity
2. High corrosiveness because of high amount of fatty acids
3. Thermal and chemical instability
4. Low heating value owing to higher oxygenated compounds
Therefore, the quality of biocrude oil needs to be improved to be used as a syn-

thetic liquid transportation fuel. Due to the identical physicochemical properties of
vegetable oils, the technologies used for biodiesel production from plant and vege-
table seed oils can be applied to algal biocrude oils. There are varieties of techniques
for biocrude oil upgradation, such as solvent addition, emulsification, esterification,
transesterification, hydrotreating, hydrodeoxygenation, and catalytic
hydrotreating.
11.5.1 Solvent Addition
Solvent addition enhances the quality of the biocrude oil in terms of homogeneity,
stability, acidity, and viscosity to be used as liquid transportation fuels (Oasmaa
et al. 2004). Further, the addition of polar solvents enhances the heating value of
biocrude oils. On the other hand, the addition of polar solvents promotes aging
reactions such as polymerization and condensation due to large polar differences
among the biocrude oil components and solvents, which results in phase separa-
tion and increase in viscosity (Pidtasang et al. 2013). Therefore, to increase stabil-
ity and decrease viscosity, aging could be slowed through the irreversible reaction
of oligomers with low molecular weight reactants or the reversible reaction of
acidic oligomers with alcohol, e.g., methanol (Liu et al. 2014). Diebold and
Czernik (1997) studied the development of adding solvent to enhance the stability
of biocrude oil viscosity during storage. Their results showed that using methanol
as the best additive enhances the stability of biocrude oil viscosity during the stor-
age time of 96 h.
Boucher et al. (2000) modified the biocrude oil via solvent addition and found that
it meets the ASTM No. 4 specifications of diesel fuel in terms of viscosity. Oasmaa
et al. (2004) investigated the upgrading of the biocrude oil quality by methanol addition
and found significant reduction in viscosity during the aging of softwood pyrolysis
liquids. In addition, the stability of the biocrude oil was enhanced by the addition of
more than 10% alcohol; thereby aging reaction was suppressed for an year. Liu et al.
(2014) investigated the effects of adding acetone as a solvent on the properties of
biocrude oils. The results indicated that with an increase in acetone concentration, the
final viscosities decreased. In addition, gas chromatography-mass spectrometry (GC-
MS) data indicated that acetone probably suppressed aging reactions of biocrude oil.
Therefore, the addition of acetone as solvent revealed significant effects on the proper-
ties of biocrude oil.
11.5.2 Emulsification
Emulsification is a feasible method used to promote the application of biocrude oil

by blending with other fuels using suitable surfactants (Zhang et al. 2013). It does
not require chemical reaction for the application of biocrude oils in CI engines. For
having a stable emulsion, the following basic conditions must be provided (Leng
et al. 2018):
1. The two liquids must be immiscible.

2. Adequate agitation must be applied to dissolve the liquids.
3. An emulsifying agent may be required.
Although emulsification can increase the ignition characteristics of biocrude oil,

it is still difficult to develop other fuel characteristics, such as heating value, to meet
desirable requirements. Moreover, it requires a large amount of energy to form an
emulsion. Stirring intensity and temperature are found to be the most significant
parameters affecting the emulsification process. During emulsification, interfacial
tension increases along with rotational speed, which causes to have a better emul-
sion and adsorption of the emulsifier. It was also reported that mixing multiple sur-
factants is often more efficient than using a single surfactant due to their mutual
interaction, which reduces interfacial tension (Liu et al. 2014).
Al-Sabagh et al. (2011) concluded that compared to individual surfactants (Span
80 or EMAROL 85), blends of the surfactants possess superior thermodynamic
properties with less interfacial tension. Jiang and Ellis (2009) found the optimum
conditions for a stable emulsion with octanol as an emulsifier was found to be at the
surfactant dosage of 4 vol%, 1200 rpm stirring intensity at the emulsifying tempera-
ture 30 °C with mixing time of 15 min. Furthermore, the storage and thermal stabil-
ity of the mixture of biocrude oil and biodiesel were measured up to 180 h. During
the storage, water content of the mixtures slightly increased with time, while acid
number and viscosity showed an overall decreasing trend.
Wang et al. (2012) studied mechanical and ultrasound emulsification methods to
blend biocrude oil and diesel. The emulsions prepared via the ultrasound technique
were more stable with lower surface tension and smaller droplet size than mechani-
cal emulsions. Xu et al. (2010) investigated the lubricity of biocrude oil and diesel
fuel blend and found that blend showed higher lubricity than conventional diesel
fuel. However, compared to conventional diesel fuel, anticorrosion properties of the
blend were not acceptable.
11.5.3 Hydrodeoxygenation, Hydrogenation, and Hydrocracking
As discussed earlier, biocrude oil has high oxygen content, which leads to undesir-
able properties such as chemical instability and low heating value. Hydrotreating is
a process used to improve heating value by increasing hydrogen content and reduc-
ing O, N, and S through catalytic reaction conditions of pressure up to 20 MPa and
temperatures in the range of 300–450 °C. The simplest hydrotreating reaction for
biocrude oil is mentioned below:
Biocrude oil + H 2 → Upgraded biocrude oil + H 2 O (11.1)
The acceptable amount of oxygen present in hydrocarbon liquid fuels should
be less than 1 wt%, but the oxygen content of algal biomass is around 40–60 wt%.
Therefore, the main reaction involved in hydrotreating is hydrodeoxygenation
due to a significant amount of oxygenated compounds present in biocrude oil.
Oxygen can be removed as water, CO2, and/or CO through a combination of
decarbonylation, decarboxylation, and hydrodeoxygenation reactions, shown in
Scheme 11.1.
Oxygen removal through CO2 and CO formation leads to lower carbon yield, so
removing oxygen, as water is the preferred route. Hydrogenation can also be used
to improve biocrude oil quality. It is believed that as the content of H/C present in
liquid fuel increases, the quality of the liquid hydrocarbons also increases. The par-
tial cracking of heavy components is also expected during this process. Therefore,
hydrocracking and hydrogenation also occur during hydrotreating (Scheme 11.2).
Due to H2 consumption during hydrocracking and hydrogenation, unsaturated com-
pounds become saturated compounds (Scheme 11.2).
Hydrogenation is carried out at moderate conditions, followed by operation at
moderate temperature (300–450 °C) and relatively high pressure (75–300 bar)
(Saber et al. 2016). High pressure increases the reaction rate, as well as the solubil-
ity of hydrogen in the biocrude oil. It also decreases coking in the reactor. Owing to
moderate operating conditions, hydrotreating favors lower coking. Cracking can be
Scheme 11.1 Deoxygenation reactions during hydrotreating technologies, i.e., hydrodeoxygen-

ation, carbonylation, and decarboxylation
Scheme 11.2 Reactions during hydrogenation, i.e., hydrogenation and hydrocracking
carried out using H-ZSM-5 as catalysts for upgrading biocrude oil. However,
hydrotreating and hydrodeoxygenation using zeolite catalysts result in low-grade
hydrocarbon fuels; i.e., HHV of these fuels are 25% less than that of biocrude oils
produced via catalytic HTL (Mortensen et al. 2011).
11.5.4 Catalytic Hydrotreating
Biocrude oil upgrading through catalytic hydrotreatment promises to produce

hydrocarbon-rich fuel. Notable research has focused on the development of cata-
lysts with higher activity and stability for hydrodeoxygenation of biocrude oil,
especially at milder reaction conditions (Ramirez et al. 2015). Heterogeneous cata-
lysts have several advantages over traditional homogeneous catalysts such that
they can be easily recovered and reused. Different heterogeneous catalysts have
been used in biocrude oil upgrading reactions, such as zeolites, noble metals, tran-
sition metals, and carbides mostly supported on alumina or activated carbon.
CoMo- and NiMo-based catalysts are commercially used for industrial hydrotreat-
ing to remove O, N, and S. Due to their instability during the hydrotreating pro-
cess, some research has focused on noble metal (Pt, Pd, and Ru) catalysts for the
hydrotreating of biocrude oil. This helps to convert aromatic compounds into
hydrocarbons suitable for diesel fuel applications (Galadima and Muraza 2018).
However, due to the higher cost of noble metals, their application is limited to cata-
lytic hydrotreating.
Duan et al. (2016) evaluated the effect of zeolite catalysts on algal biocrude oil at
reaction conditions of 400 °C, 6 MPa for 240 min in supercritical water. Nine dif-
ferent zeolites were selected in order to investigate their effects on product yields
and the properties of the upgraded biocrude oil. Due to the acidic characteristics of
zeolites, all of them improved the denitrogenation, deoxygenation, and desulfuriza-
tion in comparison with noncatalytic upgrading reactions.
Barreiro et al. (2016) studied the effect of commercial catalysts (Pt/Al2O3 and
HZSM-5) for biocrude oil upgradation via the liquefaction of Scenedesmus almer-
iensis (freshwater) and Nannochloropsis gaditana (marine) algae species. The non-
catalyzed reaction of S. almeriensis revealed that the highest biocrude oil yield was
Scheme 11.3 Esterification or transesterification of fatty acid with alcohol
obtained at 4–8 MPa of H2 pressure, 400 °C of reaction temperature for 4 h in 10 mL

micro autoclaves. At these process conditions, catalysts did not show significant
activity, and the process was promoted by the temperature rather than the catalysts.
The main products obtained during upgradation was found to be 50–70% alkanes,
gaseous cracking species, unsaturated fatty acids, and phenols.
Elliott et al. (2013) investigated the catalytic hydroprocessing for algal bio-
crude oil in a continuous-flow reactor using sulfided CoMo/γ-Al2O3 and found
that hydrotreating is efficient in removing S and N to undetectable levels. Konwar
et al. (2014) studied the hydroprocessing of rapeseed biocrude oil produced via
pyrolysis using NiMo/γ-Al2O3 catalyst. Their results showed that S, O, and N
was reduced to 33.3, 70.8, and 21.1 wt%, respectively. Furthermore, the effi-
ciency of hydroprocessing is enhanced by the removal of lighter hydrocarbons
from biocrude oil through fractionation and reducing the biocrude oil LHSV to
0.5 h−1.
Wildschut et al. (2009) achieved 90% hydrodeoxygenation of biocrude oil using
Ru supported on carbon, which has a higher conversion in comparison to commercial
catalysts (sulfided NiMo/γ-Al2O3 and CoMo/γ-Al2O3). Tian et al. (2014) examined
the catalytic efficiency of Ru, Pd, and Pt on carbon support; Pt/Al2O3; Pt/C-sulfide;
Rh/Al2O3; activated carbon; moly sulfide; moly carbide; Co-Mo/Al2O3; and zeolite
on the hydrodeoxygenation of biocrude oil. Among all the catalysts studied, Pt sup-
ported on carbon catalyst promoted hydrodeoxygenation of biocrude oil.
11.5.5 Esterification and Transesterification
Esterification or transesterification is considered as one of the best routes for

increasing the quality of biocrude oil suitable for CI engines. Esterification or trans-
esterification enriches the flow properties (viscosity) and heating value of the bio-
crude oil by removing glycerol and other carboxylic acid groups. During
esterification, fatty acids react with methanol or ethanol in the presence of an acid
catalyst to form corresponding methyl or ethyl esters (biodiesel). A wide variety of
feedstocks can be used as a source of fatty acids or triglycerides, which include
biocrude oil, edible and nonedible oils, animal fats, and lipids from algae. During
the transesterification and esterification (Scheme 11.3), different alcohols (metha-
nol, ethanol, propanol, and butanol) were used by varying carbon number to decrease
the viscosity and acidity as well as increase the heating value. Methanol is the
typical alcohol used during transesterification and esterification due to its low cost.
The overall transesterification reaction is shown in Eq. (11.2):
Catalyst
Tryglycerides + 3 Methanol ↔ Glycerol + 3 Methyl esters ( Biodiesel ) (11.2)
During transesterification, excess alcohol has been used to promote alkyl ester
production (Eq. 11.2), and the unreacted alcohol can be recovered by Rotavapor and
reused. The yield and quality of biodiesel depend on process parameters such as
reaction time, temperature, catalyst loading, the type of alcohol, and the nature of
feedstocks (Tran et al. 2017). Transesterification process is a catalytic process con-
sisting of the separation of by-products from biodiesel, recovery of glycerol, cata-
lysts, and purification of biodiesel. Conventional transesterification demands higher
energy, as well as excessive stirring speed, to mix the feedstocks and alcohols due
to their immiscibility. Supercritical fluids promote the reaction due to the unique
transportation properties such as gas-like diffusivity and liquid-like density results
in dissolving complex feedstocks (Reddy et al. 2014a, b, 2015; Verma et al. 2016;
Nanda et al. 2017b; Okolie et al. 2019a, b).
Transesterification can also be performed in supercritical condition to utilize
organic acids present in biocrude oil with catalytic and noncatalytic reactions owing
to their distinctive properties of dissolving power, faster heat, and mass transfer
rates (Demirbaş 2008). The solubility of triglycerides or fatty acids exceptionally
increases under supercritical conditions to accelerate the process to a more homoge-
neous phase (Tran et al. 2017, Nanda et al. 2019). Furthermore, this process requires
low energy due to simplified separation and purification steps. It has demonstrated
great potential for producing biodiesel with high calorific values and lower viscos-
ity. The conversion of fatty acids and triglycerides into biodiesel is subjected to
supercritical process conditions such as reaction temperature and pressure, the
nature of alcohol and supercritical solvent, the purity of reactants, the molar ratio of
alcohol to oil, and the nature of the feedstocks (Reddy et al. 2018).
The utilization of homogeneous catalysts requires catalyst removal by water
washing of biodiesel, which generates a large quantity of wastewater. Therefore, the
cost of the production process can be minimized by the utilization of heterogeneous
catalysts because they can be easily separated, regenerated, and recycled. Thus,
most of the studies concentrated on the improvement of the heterogeneous acidic
Scheme 11.4 Hydrolysis and saponification reactions of fatty acid alkyl esters
catalysts for biocrude oil esterification (Hu et al. 2012). Although alkali-catalyzed
transesterification of triglyceride is fast, free fatty acids may react with the base
catalyst to form soap and water, which leads to the loss of catalysts during the reac-
tion, as shown in Scheme 11.4 (Fukuda et al. 2001). Figure 11.4 shows the sche-
matic representation of biodiesel production via transesterification using
heterogeneous catalysts.
Many heterogeneous acidic catalysts such as carbon-based acids and bases, CaO,
TiO2/ZrO2, MgO, and Amberlyst-15 have been used for biodiesel production with
acidic sites on the catalyst surface to adsorb oxygenated compounds. The study by
Guo et al. (2015) revealed that 1.56 wt% of catalyst loading, 3.2:10 alcohol-to-
biocrude oil molar ratio, 125 min of reaction time at 50 °C of reaction temperature
yielded 88.9% of biodiesel. The pros and cons of the transesterification catalysts are
tabulated in Table 11.3.
Methanol + Activated catalyst + Algal oil
Transesterification
Catalyst + Crude biodiesel +

(Glycerol and alcohol phase)
Catalyst
recycling
Settling
(Crude biodiesel, top layer) + (Catalyst + Glycerin and

alcohol phase, bottom layer)
Filtration
Crude biodiesel + (Glycerin + alcohol)

Methanol
Separation recovery
Crude Biodiesel Glycerol and Alcohol mixture
Pure Biodiesel
Pure Glycerin
Unreacted oil
Fig. 11.4 Schematic representation of biodiesel production via the transesterification process
using heterogeneous catalysts
Table 11.3 Overview of biodiesel production by transesterification using different catalysts

Type of catalyst Advantage Disadvantage
Homogeneous alkali • Reacts fast • Difficult to reuse
(NaOH and KOH) • Inexpensive • Sensitive to free fatty
acids (causes soap
formation)
Traditional mineral • Insensitive to free fatty acids • Has slow reaction rate
acids (H2SO4 and HCl) • Corrosive
• Difficult to reuse and
recover
Heterogeneous alkali • Has faster reaction rate compared • With expensive
catalysts to acid-catalyzed transesterification synthesis route
• Sensitive to water and
free fatty acids
• Can cause soap
formation
Heterogeneous acid • Insensitive to free fatty acids • With expensive
catalysts • Simultaneously catalyzes both synthesis route
esterification and transesterification • Has slow reaction rate
Carbon-based catalysts • Reusable • Has slow reaction rate
• Has simple synthesis route • Leaches away
• Inexpensive
• With high thermal stability
• Capable of uniform distribution of
active sites
Reference: Konwar et al. (2014)
11.6 Conclusions
In recent times, there is a growing interest in the valorization of algal biomass

(third-generation biofuels) into liquid transportation fuels owing to higher calorific
value and the fact that hydrocarbons are suitable to complement gasoline, diesel,
and jet fuels. This chapter established that algal biomass is a potential feedstock for
the production of biocrude oil via hydrothermal liquefaction. However, biocrude oil
yield and quality depend on the nature of the biomass feedstocks, the nature of the
liquefaction catalysts, and process conditions of liquefaction. On the other hand,
biocrude oil can be upgraded through catalytic hydrotreating after the liquefaction
process via heterogeneous catalysts.
This chapter discussed the various heterogeneous acidic catalysts used for the
removal of heteroatoms (N, S, and O) to enhance the quality of biocrude oil. Among
the heterogeneous catalysts, it was reported that the maximum biocrude oil yield
was in the range of 20–60 wt%. Furthermore, the upgrading of biocrude oil with
zeolites proves to be a great means for producing synthetic liquid transportation
fuels. Moreover, efficient catalysts and process design need to be developed to
enhance biocrude oil yield and the respective hydrocarbon yield for industrial appli-
cations. The detailed mechanism that catalyzes hydrocarbon formation in liquefac-
tion and upgradation process, effects of zeolites textural properties for producing
specific group of hydrocarbons and their stability in hydrothermal conditions is yet

to be understood. Therefore, catalysts, including zeolites, require substantial
research and development work for the industrialization and commercialization of
liquid transportation fuels derived from algal biomass.
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Co-pyrolysis of Lignocellulosic Biomass
and Polymeric Wastes for Liquid Oil 12
Production
Wan Adibah Wan Mahari, Shin Ying Foong,

and Su Shiung Lam
Abstract
Co-pyrolysis has been researched as a promising technique for thermochemical
conversion of biomass with plastics and other organic wastes into potentially use-
ful products due to the ability to recover energy from these materials. This chapter
presents a review of the development and application of co-pyrolysis as a next-
generation thermochemical conversion technique for energy recovery from bio-
mass waste materials (e.g., food waste, waste cooking oil etc.). This includes a
discussion on the characteristics of co-pyrolysis, the key process parameters, the
issues, and challenges arising from the application of co-pyrolysis, and the fea-
tures and combustion performance of the liquid oil product. Co-pyrolysis using
microwave technique shows ability to rectify certain limitations shown by con-
ventional pyrolysis with a potential as a viable means to produce next-generation
fuels from biomass wastes. This co-pyrolysis approach is capable of increasing
the yield and enhancing the quality of the bio-oil product. Thus, it can be a poten-
tially sustainable and feasible approach for energy recovery from biomass and
wastes polymers.
Keywords
Pyrolysis · Co-pyrolysis · Microwave · Biomass · Plastics · Bio-oil
W. A. W. Mahari · S. Y. Foong · S. S. Lam (*)

Pyrolysis Technology Research Group, Institute of Tropical Aquaculture and Fisheries,
Universiti Malaysia Terengganu, Kuala Terengganu, Terengganu, Malaysia

272 W. A. W. Mahari et al.
12.1 Introduction
The global production of biomass waste such as waste cooking oil and household
organic waste is estimated around 29 million tons each year (Maddikeri et al. 2012).
Waste cooking oil is commonly discharged into plumbing system, but this practice
has led to the accumulation of fatberg that can cause sewer blockage. Owing to
these problems, valorization of biomass waste materials is proposed to transform
these waste materials into second-generation fuel. Valorization of waste materials
can be defined as an increase in the value of worthless waste materials by producing
value-added products that can be used in many applications (e.g., energy source). In
addition, second-generation biofuel is referred to the fuels produced from non-food
materials such as lignocellulosic biomass or other organic residues including waste
cooking oil by several valorization techniques.
Recently, pyrolysis technique has received more attention in transforming biomass
wastes into an energy source with improved fuel properties (Lam et al. 2019, 2016;
Lam and Chase 2012). Pyrolysis is a thermochemical conversion method performed
in an inert atmosphere (e.g., vacuum atmosphere or nitrogen atmosphere) at high pro-
cess temperatures (400–900 °C) to generate three types of fuels (e.g., liquid fuel,
gaseous fuel, and solid fuel) (Lam et al. 2016; Nam et al. 2017). The distinct advan-
tages shown by pyrolysis may lead to the potential for a greater production of desir-
able pyrolysis products that can be used in many applications such as diesel engines,
boilers, and turbines for the generation of power and electricity, while at the same time
serving the purpose of recovery and treatment of these wastes. Currently, there are a
few pyrolysis technologies developed to treat and recover the energy content from
biomass wastes such as waste cooking oil and food waste.
12.2 Co-pyrolysis of Waste Biomass and Polymeric Wastes
In recent years, co-pyrolysis of waste materials with other lignocellulose or triglyc-

eride materials has attracted attention. Table 12.1 shows numerous studies on co-
pyrolysis of biomass, plastic wastes, and other waste materials to produce pyrolysis
products that can be used as chemical additives or fuels. Several studies have revealed
that co-pyrolysis of biomass wastes is capable of enhancing the yield and properties
of liquid oil, which are nearly comparable to commercial transportation-grade fuel.
Co-pyrolysis is an effective upgrading technique that not only increases the yield
of liquid oil, but also improves the properties of liquid oil by reducing the concen-
trations of oxygenated compounds and increasing the levels of aliphatic hydrocar-
bon components and the overall calorific value of the oil. Co-pyrolysis of biomass
and waste materials has been demonstrated to be a reliable technique in improving
the stability of liquid oil through the interactions of hydrocarbon radicals that reduce
the oxygen content in liquid oil, thereby improving its stability as a high-grade fuel.
Many studies have revealed that the key factor that contributes to the accomplish-
ment of this technique is the synergistic effect and the interactive reaction mecha-
nisms during co-pyrolysis of biomass and waste materials.
12
Table 12.1 Summary of studies on co-pyrolysis of biomass, plastic, and other types of waste materials
Feedstocks Product yield (wt%) Elemental composition (wt%) Calorific
Process value
Biomass Plastic Other wastes configuration Oil Gas Char Carbon Hydrogen Nitrogen Sulfur Oxygen (MJ/kg) References
– High-density Waste Quartz 81.0 18.0 1.0 85.0 14.0 1.0 0.0 0.0 46.0 Mahari
polyethylene cooking oil reactor et al.
(heated by (2018a)
microwave)
Potato High-density – Stainless 50.9 9.16 21.0 80.5 12.5 0.3 – 6.7 44.0 Önal et al.
skin polyethylene steel reactor (2012)
(heated by
furnace)
Wood Polystyrene – Fixed bed 58.2 21.5 20.2 – – – – – – Ephraim
reactor et al.
(heated by (2018)
furnace)
Wood Polyvinyl – Fixed bed 78.6 8.30 13.1 46.6 5.9 0.7 0.0 29.4 – Ephraim
chloride reactor et al.
(heated by (2018)
furnace)
Sugarcane Low-density – Stainless 52.8 39.0 8.2 75.4 9.3 0.2 0.0 15.1 40.0 Dewangan
bagasse polyethylene steel et al.
semi-batch (2016)
reactor
Rice bran Polypropylene – Semi-batch 80.5 – – 83.5 16.1 0.0 0.3 0.0 43.76 Kumari and
reactor Singh
(heated by (2019)
furnace)
Co-pyrolysis of Lignocellulosic Biomass and Polymeric Wastes for Liquid Oil…
(continued)
273
274
Feedstocks Product yield (wt%) Elemental composition (wt%) Calorific

Process value
Biomass Plastic Other wastes configuration Oil Gas Char Carbon Hydrogen Nitrogen Sulfur Oxygen (MJ/kg) References
Biomass Low-density – Dropdown 64.1 7.98 9.32 – – – – – – Yang et al.
polyethylene tube (2016)
pyrolyzer
Bamboo – Waste tire Quartz 30.2 33.0 37.0 – – – – – – Wang et al.
sawdust reactor (2017b)
(heated by
microwave)
Grape – Waste tire Fixed bed 40.3 23.5 32.4 65.1 10.3 2.9 0.1 21.5 32.6 Sanahuja-
seed reactor Parejo et al.
(heated by (2018)
furnace)
Kitchen – Microalgae Fixed bed 57.0 – – – – – – – 33.9 Chen et al.
waste reactor (2018)
(heated by
furnace)
– High-density Newspaper Quartz tube 68.4 25.0 6.6 84.4 12.9 0.3 – 7.7 34.79 Chen et al.
polyethylene waste reactor (2016)
(heated by
furnace)
W. A. W. Mahari et al.
12 Co-pyrolysis of Lignocellulosic Biomass and Polymeric Wastes for Liquid Oil… 275
It is worth mentioning that there are several factors influencing the synergistic
effects during the co-pyrolysis process such as the type of feedstock, feedstock mix-
ture ratio, reactor temperature, heating rates, reactor pressure, and reaction time. In
addition, co-pyrolysis of biomass and waste materials has shown an effective alter-
native for waste management problems in reducing the massive volumes of waste
materials. The use of biomass waste and household waste materials for co-pyrolysis
can reduce the cost for waste disposal and lessen the amount of space or land needed
for landfilling of the wastes. Therefore, co-pyrolysis of biomass and waste materials
could offer the advantages in waste management and recovering energy from bio-
mass and waste materials. Nevertheless, it is crucial to understand the reaction
mechanism and interactions during the co-pyrolysis process to improve the overall
planning, operations, process design, and development of the process.
Chen et al. (2014) investigated co-pyrolysis of corncob and waste cooking oil in
a fixed-bed reactor. The influence of different temperatures (500–600 °C) and corn
cob/waste cooking oil mass ratios (1:0, 1:01, 1:0.5, 1:1 and 0:1) were investigated.
A stainless-steel tube was used as the reactor and temperature controller was used
to control the furnace temperature. The findings showed that the temperature of
550 °C with corn cob-to-waste cooking oil mass ratio of 1:1 produced the highest
bio-oil yield (68.9 wt%). The bio-oil comprised of fatty acids, aldehydes, alcohols,
phenols, ketones, and furans with a high calorific value of 32.8 MJ/kg.
Tang et al. (2018) studied the co-pyrolysis of food waste (soybean protein) and
plastic wastes (Polyvinyl chloride, PVC) in a fixed bed reactor. Nitrogen was purged
at a flow rate of 100 mL/min to maintain an inert environment during co-pyrolysis.
Different ratios of food waste and plastic waste (4:1, 1:1 and 1:4) as well as process
temperatures (400–600 °C) were investigated in this study. It was revealed that the
addition of the high proportion of PVC in the food waste (1:4 of food waste-to-PVC
ratio) had accelerated the occurrence and intensity of co-pyrolysis reactions that led
to the reduction of tar and char yields (Tang et al. 2018). Aromatic compounds such
as benzenes and polycyclic aromatic hydrocarbons (PAHs) dominated the tar prod-
uct. This may be attributed to the release of HCl from PVC during co-pyrolysis
reactions that promoted the conversion of light tar compounds into heavy com-
pounds (e.g., benzenes and PAH). The addition of PVC into food waste also contrib-
uted to the reduction of nitrogen-containing compounds (amine-N, pyridine-N,
pyrrole-N, indol-N, and nitrile-N) in the tar product (from 66% to 15%). This was
due to the formation of HCl form PVC that acted like an acid catalyst to suppress
the formation of nitrogen-containing compounds during co-pyrolysis. Nevertheless,
no chlorinated compounds in the tar product were detected. It should be noted that
PVC contains halogen (Cl−). Thus, dehydrochlorination may occur at high process
temperatures (Sharuddin et al. 2016). Therefore, gases product may be released and
lead to low tar or liquid yields. The gases product may comprise of chlorine that
could lead to the corrosiveness of the pyrolysis system and product storage. Kim
(2001) who studied pyrolysis of PVC waste also supported this view.
Mahari et al. (2018a) studied the co-pyrolysis of waste cooking oil and plastic
waste (high-density polyethylene, HDPE) in a microwave pyrolysis system. Different
ratios of waste cooking oil and plastic waste (1:2, 1:1.5, 1:1, 1.5:1, and 2:1) were
investigated in this study. It was revealed that a high yield of liquid oil (up to 81 wt%)
with desirable fuel properties was obtained. It should be noted that plastic waste has
higher carbon (85 wt%) and hydrogen content (15 wt%), but possess lower oxygen
content (<1 wt%) compared to waste cooking oil (carbon: 72 wt%, hydrogen:
13 wt%, and oxygen: 15 wt%). Hence, plastic waste could provide more hydrogen to
the waste cooking oil to improve the hydrocarbon content (hydrogen and carbon) in
the liquid oil.
Plastic waste has nearly no oxygen compared to waste cooking oil, thereby lead-
ing to a positive synergistic effect to reduce the oxygenated compounds and improve
the fuel properties of co-pyrolysis liquid oil. In particular, this can contribute to the
high calorific value of liquid oil (46 MJ/kg) obtained from co-pyrolysis process
compared to that obtained from microwave pyrolysis of waste cooking oil alone
(40–43 MJ/kg) (Lam et al. 2017) and microwave pyrolysis of plastic waste alone
(41 MJ/kg) (Undri et al. 2014). Wang et al. (2017a) studied on the co-pyrolysis of
waste vegetable oil and HDPE to produce hydrocarbon fuels. It was reported that
the co-pyrolysis process produced 60 wt% of liquid oil at the process temperature
of 430 °C (Wang et al. 2017a). The liquid oil consisted of high composition of ali-
phatic hydrocarbons (e.g., alkanes, cycloalkanes and olefins) and low oxygenated
compounds (<5%). The low oxygenated compounds in the liquid oil resulted in the
low viscosity of liquid oil (3.31 mm2/s), which is nearly comparable to the viscosity
of diesel (3–8 mm2/s). The low oxygenated compounds also led to the high calorific
value of liquid oil (46.2 MJ/kg), which is higher than biodiesel (38 MJ/kg) and die-
sel (45 MJ/kg) (Wang et al. 2017a).
Önal et al. (2012) studied the co-pyrolysis of potato skin and HDPE waste in an
electric furnace. The potato skin and HDPE were mixed with different ratios (1:2,
1:1 and 2:1). It was reported that higher yield of liquid oil (50.9 wt%) was obtained
from the co-pyrolysis of potato skin and HDPE compared to that obtained from the
pyrolysis of potato skin alone (~24 wt%). This was attributed to the high hydrogen
content of HDPE that enhanced the hydrogenation reaction during the co-pyrolysis
process, thereby increasing the yield of liquid oil (Önal et al. 2012).
Yang et al. (2016) investigated the co-pyrolysis of lignocellulosic biomass (e.g.,
cedar wood and sunflower stalk) and low-density polyethylene (LDPE) for liquid
oil production. The pyrolysis of cedar wood and sunflower stalk alone produced
38.8 wt% and 29.9 wt% of liquid oil, respectively, whereas the pyrolysis of LDPE
alone produced 83.3 wt% of liquid oil. It was revealed that co-pyrolysis of cedar
wood with LDPE and co-pyrolysis of sunflower stalk with LDPE improved the
production of co-pyrolysis liquid oil up to 64.1 wt% and 30.4 wt%, respectively.
The studies by Önal et al. (2012) and Yang et al. (2016) clearly showed the positive
synergistic effects of the co-pyrolysis of biomass materials (potato skin, cedar
wood, and sunflower stalk) with plastic material (HDPE and LDPE), which
enhanced the yield of co-pyrolysis liquid oil.
Chen et al. (2016) studied the co-pyrolysis of newspaper waste and HDPE for
liquid oil production. The newspaper waste-to-HDPE ratios investigated were 1:0,
2:1, 1:1, 1:2, and 0:1. The results showed that the synergistic effect occurring at 1:2
newspaper waste-to-HDPE ratio produced the highest yield of liquid oil (68.4 wt%)
with lower yield of gases (~25 wt%) and solid char (~6.6 wt%). This was attributed
to the transfer of hydrogen atoms and generation of free radicals that led to the cross-
reactions between newspaper waste and HDPE. These reactions interfered with the
degradation of functional groups bound to the cellulose structure of newspaper waste
and inhibited the release of gaseous products while favoring the formation of organic
compounds in the liquid oil. In addition, the liquid oil obtained from the co-pyrolysis
of newspaper waste and HDPE (68.4 wt%) was higher than that obtained from the
pyrolysis of newspaper waste alone (40.5 wt%) and HDPE alone (52.8 wt%). The
positive synergistic effects of newspaper waste and HDPE were also observed in the
fuel properties of co-pyrolysis liquid oil. The viscosity (5.8–14.5 mm2/s) and total
acid number (8.4–15.2 mg KOH/g) of the co-pyrolysis liquid oil were significantly
lower than that obtained from the pyrolysis of newspaper waste alone (viscosity:
68.4 mm2/s and total acid number: 82.3 mg KOH/g). The co-pyrolysis liquid oil also
consisted of higher carbon (up to 84.4 wt%) and hydrogen (up to 12.9 wt%) contents,
but lower oxygen content (up to 7.69 wt%) compared to that obtained from the pyrol-
ysis of newspaper waste alone (carbon: 37.4 wt%, hydrogen: 7.59 wt%, oxygen:
54.6 wt%). As a result, the co-pyrolysis liquid oil possessed higher calorific value (up
to 34.79 MJ/kg) compared to the pyrolysis oil obtained from the pyrolysis of news-
paper waste alone (16.98 MJ/kg) (Chen et al. 2016).
Wang et al. (2017b) investigated the co-pyrolysis of bamboo sawdust and waste
tires in microwave pyrolysis system for liquid oil production. The pyrolysis of bam-
boo sawdust alone produced approximately 29 wt% of liquid oil, 42 wt% of gas, and
26 wt% of char. On the other hand, the pyrolysis of waste tire alone produced nearly
36 wt% of liquid oil, 24 wt% of gas, and 43 wt% of char. It was revealed that the
addition of waste tire to bamboo sawdust during the microwave co-pyrolysis pro-
cess increased the yield of co-pyrolysis liquid oil up to 30.2 wt%. This was attrib-
uted to the transfer of hydrogen atoms that promoted radical reactions and enhanced
the formation of volatiles during the co-pyrolysis reaction, which later condensed
into liquid oil product. The composition of the co-pyrolysis oil can be classified into
several groups such as aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated
compounds, PAHs, and nitrogen-containing compounds. Nevertheless, the compo-
sition of oxygenated compounds (>10 wt%) and PAHs (3–58 wt%) in the co-
pyrolysis liquid oil was high. Thus, the upgrading of co-pyrolysis liquid oil is
required to improve its properties and composition.
Sanahuja-Parejo et al. (2018) reported on the co-pyrolysis of grape seeds and
waste tires in a fixed-bed reactor to produce drop-in biofuels. The pyrolysis of grape
seeds alone produced 38.8 wt% of liquid oil, whilst the pyrolysis of waste tires pro-
duced 43.7 wt% of liquid oil. Interestingly, the addition of waste tires to the grape
seeds during co-pyrolysis had improved the yield of co-pyrolysis liquid oil up to
40.3 wt%. Nevertheless, the addition of waste tires to the grape seeds during co-
pyrolysis had decreased the hydrocarbon composition (hydrogen and carbon con-
tent) and increased the oxygen content in co-pyrolysis liquid oil. As a result, the
co-pyrolysis liquid oil possessed lower calorific value (32.6 MJ/kg) compared to the
original grape seeds (36.8 MJ/kg) and waste tires (43.3 MJ/kg) (Sanahuja-Parejo
et al. 2018). This result indicated that the combination of biomass materials and
other hydrogen-rich materials could also lead to some negative synergistic effects
during the co-pyrolysis.
12.3 Physicochemical Properties of Co-pyrolysis Bio-oil
The liquid oil obtained from co-pyrolysis of biomass and organic wastes is yellow-
ish to brownish colored oil produced after co-pyrolysis of biomass and waste mate-
rials. The physical and chemical properties of liquid oil are dependent on the
characteristics of the feedstock used. Table 12.2 summarizes the physical properties
of liquid oil obtained from the co-pyrolysis of biomass and waste materials.
The calorific value is determined by the combustion of liquid oil with oxygen
that releases a certain amount of energy. The calorific value of the liquid oil can be
an indicator of the energy output for combustion in the fuel engine. It was found that
the liquid oil obtained from the co-pyrolysis of corn cob (biomass) and waste cook-
ing oil (biomass) possessed lower calorific value (32.8 MJ/kg) (Chen et al. 2014)
compared to other liquid products obtained from the co-pyrolysis of biomass and
plastic wastes. This was attributed to the high content of acidic compounds (e.g.,
fatty acids) in the liquid oil, which dominated the composition of liquid oil (57 wt%),
thereby deteriorating its fuel properties.
Liquid oil obtained from the co-pyrolysis of biomass (e.g., waste cooking oil and
sugarcane bagasse) and polyethylene (e.g., HDPE and LDPE) possessed high calo-
rific values (40–46 MJ/kg). This is attributed to the high content of aliphatic hydro-
carbons (39.5–64 wt%), low content of aromatic hydrocarbons (up to 12 wt%), and
low content of acidic compounds (<3 wt%) in the liquid products. Co-pyrolysis of
biomass (e.g., rice husk and rice bran wax) and polypropylene (PP) also produced a
liquid oil with high calorific value (42–43.8 MJ/kg). This was due to the high con-
tent of aliphatic hydrocarbons (33–39 wt%), low content of aromatic hydrocarbons
(<4 wt%), and low content of acidic compounds (<2 wt%). Co-pyrolysis of biomass
(grape seeds) and waste tire also produced liquid oil with high calorific value
(40.4 MJ/kg). This was attributed to the high content of aliphatic hydrocarbons
(64 wt%), low content of acidic compounds (<3 wt%), and low content of oxygen-
ated compounds (<3.5 wt%).
Viscosity is defined as the liquid’s resistance to flow, which is determined by
measuring the time taken by a liquid to flow via an injector nozzle of an engine
(Mahari et al. 2018a). Table 12.2 reveals that the liquid oils produced from the co-
pyrolysis of biomass and waste materials possess low viscosities (3–5 mm2/s),
which are comparable to diesel, biodiesel, and gasoline (2–6 mm2/s). The total acid
number (TAN) is determined to measure the acidity value of pyrolysis oil. The liq-
uid products obtained from the co-pyrolysis of corn cob with waste cooking oil,
newspaper waste with HDPE, and grape seed with waste tire showed high TAN,
which was more than 24 mg KOH/g (Table 12.2). These results suggest that the co-
pyrolysis liquids produced from these feedstocks need to be upgraded to reduce the
acid number.
12
Table 12.2 Comparison of the physicochemical properties of liquid oil obtained from co-pyrolysis process
Corn cob
and Sugarcane Newspaper Waste cooking Grape seeds PP waste
waste bagasse and waste and oil and Ground-nut and waste and rice
cooking low-density high-density high-density Rice husk and shell and tire bran wax Diesel
oil (Chen polyethylene polyethylene polyethylene polypropylene polystyrene (Sanahuja- (Alagu and (Mahari
et al. (Dewangan (Uzoejinwa (Mahari et al. (Suriapparao (Suriapparao Parejo et al. Sundaram et al.
Properties 2014) et al. 2016) et al. 2018) 2018b) et al. 2018) et al. 2018) 2018) 2018) 2018b)
Calorific 32.8 40.0 28.2–34.4 46.1 42.0 39.6 40.4 43.8 45.0
value (MJ/kg)
Dynamic 3.1 4.09 10.3–18.8 – – – – 5.03 2.0–4.0
viscosity
(mm2/s)
Density (g/ 1.03 – 1.14–1.2 0.760 0.963 1.161 – 0.80 0.82–
cm3) 0.86
Total acid 25 – 17.8–24.5 – 1.63 0.63 14.2 – –
number (mg
KOH/g)
Aliphatic 21.2 39.5 58 64 33.2 1.0 64.6 38.9 –
hydrocarbons
(wt%)
Aromatics 3.98 12.0 – – 4.3 48.9 14.3 – –
hydrocarbons
(wt%)
Acids (wt%) 57.1 0.87 2 3 – – 3.0 1.91 –
Amines – – – – – – – 19.8 –
(wt%)
Co-pyrolysis of Lignocellulosic Biomass and Polymeric Wastes for Liquid Oil…
Furans (wt%) – – 2 – 0 0.2 – – –

Oxygenates 4.71 6.44 3 5 2.7 0.9 3.5 12.2 –
(wt%)
(continued)
279
280
Corn cob
and Sugarcane Newspaper Waste cooking Grape seeds PP waste
waste bagasse and waste and oil and Ground-nut and waste and rice
cooking low-density high-density high-density Rice husk and shell and tire bran wax Diesel
oil (Chen polyethylene polyethylene polyethylene polypropylene polystyrene (Sanahuja- (Alagu and (Mahari
et al. (Dewangan (Uzoejinwa (Mahari et al. (Suriapparao (Suriapparao Parejo et al. Sundaram et al.
Properties 2014) et al. 2016) et al. 2018) 2018b) et al. 2018) et al. 2018) 2018) 2018) 2018b)
Esters (wt%) 3.51 – – – – – 5.3 1.84 –
Alcohols 2.68 5.87 – – – – – 15.8 –
(wt%)
Phenols 3.60 24.9 1 – 0 0.4 6.2 – –
(wt%)
Others (wt%) 3.22 10.4 21 28 60 51.4 3.1 9.55 –
W. A. W. Mahari et al.
Table 12.2 also shows that the chemical composition of co-pyrolysis oil that can
be classified into several components such as aliphatic hydrocarbons, aromatic
hydrocarbons, acids, amines, furans, oxygenates, esters, alcohol, phenols, and other
minor and unidentified compounds. The aliphatic hydrocarbons can be derived from
alkanes, alkenes, alkynes, and cycloalkanes. The carbon component of aliphatic
hydrocarbons in liquid oil can range from C5 to C30 hydrocarbons, depending up on
the thermal cracking of the waste materials. The hydrocarbon compositions of the
liquid oil can be classified into three petrochemical fractions according to the carbon
fragments. The carbon component ranging from C4 to C12 is referred as gasoline,
C11–C15 is referred as kerosene, and C15–C24 is referred as diesel (Lam et al. 2012a).
The liquid oil is also composed of aromatic hydrocarbons, which can be derived
from benzenes and its derivatives (e.g., toluene, xylene, and phenol). Amines can be
derived from nitrogen-containing compounds such as amine-N, pyridine-N, pyr-
role-N, indol-N, and nitrile-N. The oxygenates can be derived from oxygen-
containing compounds such as ketones and aldehydes. The acid compounds in
liquid oil can be derived from fatty acid obtained from triglycerides (e.g., waste
cooking oil) (Nanda et al. 2019). The presence of both the acids and oxygenate
compounds is not desirable in the pyrolysis liquid. The high composition of acids
and oxygenate compounds indicates the high content of oxygen in the liquid oil,
which makes the liquid oil reactive and not stable, thus may undergo several unfa-
vorable changes in their characteristics during storage and combustion. In addition,
the acids and oxygenate compounds can cause corrosion and oxidation during the
oil storage, which may lead to the deterioration of fuel quality.
12.4 Engine Performance and Emission Characteristics
Kalargaris et al. (2017) investigated the performance, combustion, and emission

characteristics of a diesel engine fueled by pyrolysis oils obtained from pyrolysis of
LDPE and ethylene-vinyl acetate plastics. The pyrolysis oil blended with diesel
(termed as PPO 25, PPO 50, PPO 75, PPO 90, and PPO 100) was tested on an
AKSA four-cylinder diesel engine with a bore of 110 mm and stroke of 120 mm,
rated power of 68 kW, rated speed of 1500 rpm, and injection pressure of 240 bar.
There were three types of pyrolysis oil tested in this study, namely LDPE700,
EVA900, and EVA900 75. The pyrolysis oil obtained from pyrolysis of LDPE at
700 °C is termed as LDPE700, pyrolysis oil obtained from pyrolysis of ethylene-
vinyl acetate plastics at 900 °C is termed as EVA900, while 75% of pyrolysis oil
obtained from pyrolysis of ethylene-vinyl acetate plastics at 900 °C blended with
25% of diesel fuel is termed as EVA900 75. LDPE700 demonstrated an excellent
combustion characteristic, short ignition delay, and the brake thermal efficiency was
almost like diesel fuel operation. LDPE700 also released lower amounts of NOx,
CO, and CO2, but higher amounts of unburnt hydrocarbons compared to diesel. In
contrast, EVA900 and EVA900 75 showed longer ignition delay, lower brake ther-
mal efficiency (1.5–2%), higher emission of NOx and unburnt hydrocarbons com-
pared to diesel fuel. Nevertheless, EVA900 has reduced the emission of CO and
CO2. The addition of 25% of diesel fuel to EVA900 (EVA900 75) showed no
improvement in the engine performance.
In other work, Alagu and Sundaram (2018) investigated the combustion, perfor-
mance, and emission characteristics of a compression ignition (CI) engine using
pyrolysis oil derived from neem seed. The pyrolysis oil was blended with diesel
fuel at proportions of 5% (termed as NB5) and 10% (termed as NB10). Kirloskar
four-cylinder diesel engine with a bore of 87.5 mm and stroke of 100 mm, rated
power of 4.4 kW, rated speed of 1500 rpm, and injection pressure of 200 bar were
used in this study. The brake thermal efficiency for NB5 and NB10 (up to 3.7%) at
full engine load was higher than diesel fuel. In addition, the use of NB5 and
NB10 in the engine has reduced the emissions of hydrocarbons (46.9%), CO
(42.2%), CO2 (29.8%), and NOx (20.7%) at full engine load condition. This study
demonstrated that pyrolysis oil obtained from pyrolysis of neem seed in fixed bed
reactor showed a promising potential to be used in fuel engine as a renewable and
sustainable green fuel.
In summary, most of the studies showed that the engine performance of pyrolysis
oil was less efficient compared to diesel fuel due to low brake thermal efficiency,
low cetane number, and high viscosity of pyrolysis oil, and high emissions of HC,
CO, CO2, and NOx. Nevertheless, a few studies have also revealed the excellent
performance of pyrolysis oil in diesel engine. The pyrolysis oil was reported to
increase the brake thermal efficiency and reduce the emission of undesirable gases.
Therefore, the use of pyrolysis oil as fuel is believed as a promising and sustainable
technique to recover the energy from waste materials, while simultaneously reduc-
ing the volume of waste disposed of in landfill, which could release more harmful
gases (CO2, CH4, SOx, and NOx) over the long term.
12.5 Conclusions
It is revealed that co-pyrolysis demonstrates a promising fuel processing technology

for the recovery of sustainable energy from lignocellulosic biomass and polymeric
wastes. Despite the numerous advantages reported by current pyrolysis technolo-
gies, the existence of high oxygen content, high water content, high PAH concentra-
tion in liquid oil, and poor physical properties (e.g., high viscosity and high acid
value) could lead to many undesirable effects on the fuel engine (e.g., instability,
corrosiveness, oxidation and poor atomization). Therefore, it would be worth to
investigate co-pyrolysis techniques, which is a promising upgrading technique to
improve the yield and properties of liquid oil, and discover the feasibility of this
approach in the treatment and recovery of biomass materials. Nonetheless, there are
several issues such as maintaining the co-pyrolysis condition, the influence of oper-
ating parameters on product distribution and production, which necessitate to be
addressed to improve this co-pyrolysis approach.
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Conversion of Waste Biomass to Bio-oils
and Upgradation by Hydrothermal 13
Liquefaction, Gasification,
and Hydrodeoxygenation
Vikranth Volli, Anjani Ravi Kiran Gollakota,

Mihir Kumar Purkait, and Chi-Min Shu
Abstract
Biofuels produced from biomass are clean, renewable, and eco-friendly alterna-
tives to the conventional fossil fuels in the transportation sector. However, the
presence of high-water content, low pH, high viscosity, and oxygenates limits the
direct use of biofuel in vehicular engines. The in situ and ex situ catalytic as well
as noncatalytic hydrothermal upgradation of bio-oil (converting into hydrocar-
bons or less oxygenated compounds) are very promising. The recent advances in
thermochemical conversion processes, improved strategies in feedstock pretreat-
ment, and optimized use of both homogeneous and heterogeneous catalysts have
enhanced the fuel properties of biofuels. The available literature was reviewed
extensively to perceive the pros and cons in the selection of the suitable upgrad-
ing process to produce the bio-oil based on the end use. In this chapter, the tech-
nical developments toward improving the bio-oil properties, both in quality and
quantity, the influence of process parameters, reactor configurations, and their
primal source were discussed in detail. By comparing the various conversion and
upgrading technologies, hydrodeoxygenation is considered as the prominent
alternative and the latest technology in contrast to gasification and liquefaction.
However, the complexities of the hydrodeoxygenation mechanism, optimal pro-
cessing conditions, and the choice of the catalysts are yet to be understood.
Furthermore, the chapter points out the main barriers for the commercialization
of bio-oil upgrading technologies for the future.
V. Volli (*) · A. R. K. Gollakota · C.-M. Shu (*)

Department of Safety, Health and Environmental Engineering, National Yunlin University of
Science and Technology, Douliou, Taiwan, China
e-mail: [email protected]; [email protected]
M. K. Purkait
Department of Chemical Engineering, Indian Institute of Technology Guwahati,

286 V. Volli et al.
Keywords
Biomass · Bio-oil · Thermochemical conversion · Pyrolysis · Gasification ·
Hydrodeoxygenation
13.1 Introduction
The need for alternative energy sources, exhausting conventional fossil fuels, and the
colossal increase in population growth over the decades have impelled the focus on
developing efficient processes, innovative technologies, and sustainable growth in
energy production. The rate of energy consumption substantially increased up to 5755,
1768, 382, 87, 2121, and 463 Mtoe for Asia, Europe, Africa, Australia, North America,
and South America, respectively, during the period of 2000–2017. The distribution of
total energy supply increased from 97, 152, 86.7, 28.3, and 55 Mtoe in 2000 to 164,
179, 121, 27.7, and 80.8 Mtoe in 2014 with a growth rate of 3.8, 1.1, 2.4, 0.2, and
14.4% for coal, oil, natural gas, nuclear, and renewable energy, respectively
(International Energy Outlook 2017). The continental distribution of total energy con-
sumption for the year 2016 with the contribution of renewables is presented in Fig. 13.1.
The increased consumption of fossil fuels with the growing energy needs along
with the consequential greenhouse gas emissions (CO, CO2, NOx, and SO2) from
industries and automotives has significantly influenced the growth in pollution and
global warming. This complex situation has resulted in exploring the renewable
200
Biomass
Hydro
Geothermal
Solar PV
Solar thermal
Wind 17%
Total energy consumpon (Mtoe)
150 4%
73%
1%
2%
3%
100
Renewables
Nuclear
50 Natural gas
Oil
Coal
0
Asia Americas Europe Africa Australia
Fig. 13.1 Total energy consumption in different continents and the distribution of renewable
energy in 2016
13 Conversion of Waste Biomass to Bio-oils and Upgradation by Hydrothermal… 287
energy sources from biomass, hydro-, geothermal, solar, and wind energy. Among
these various alternatives, bioenergy from biomass would replace nearly 27% of the
world’s transportation fuel and cater 10% of the global energy requirements in the
near future (He et al. 2018). Waste organic biomass is a renewable energy source,
widely available in nature, and is considered carbon neutral. Biomass is defined as
the organic or biodegradable fraction derived from living organisms, residues of
biological origin from agricultural, forestry, industrial, and related municipal
wastes. Suitable pretreatment of biomass would result in products including trans-
portation fuels, chemicals, biomaterials, and thermal energy.
13.2 Classification of Waste Organic Biomass
The different sources of biomass include wood, agricultural crop residues, food
processing wastes, aquatic plants, animal wastes, algae, and their waste by-products.
Biomass resources vary with geographical location and are categorized based on
their origin, chemical composition, and end use. Biomass can be broadly classified
into primary, secondary, and tertiary wastes. The primary wastes are produced
directly by the process of photosynthesis (woody, herbaceous, forestry, and agricul-
tural crop residues). The secondary wastes are processed from primary biomass
(e.g., sawdust, black liquor, and animal waste). On the other hand, tertiary wastes
include by-products and residue streams (e.g., vegetable oils, legumes, and packag-
ing wastes). However, industrial-based classification of raw biomass is as follows
(Sánchez et al. 2019):
1. Wood or forest products are one of the largest contributors to lignocellulosic

biomass. The wood processing wastes are available in four major forms includ-
ing firewood, wood logs, wood chips, and pellet.
2. Energy crops are nonfood crops, such as short rotation woody crops, mostly
classified into second-generation feedstocks (switchgrass, Miscanthus, elephant
grass, and hybrid poplar).
3. Agricultural residues are produced after harvesting of agricultural products
including sugarcane, cotton, maize, cereals, wheat, palm, peanut, and jute
(Ashter 2018).
4. Food and industrial wastes are the by-products generated from municipal waste
streams and processing industries (restaurants, paper, pulp, tea and coffee pro-
cessing, meat production, domestic and household wastes) (Wang et al. 2017).
Except for the first-generation feedstocks (corn, oil palm, soybean, and rapeseed),
the individual contribution of aforementioned biomass to bioenergy on a global
scale has now been well assessed. The effective conversion of biomass to bioenergy
depends on the physicochemical composition of feedstocks, which varies with geo-
graphical location and origin. However, the exploration for new and efficient tech-
nologies to process biomass for the production of liquid biofuels is still limited and
may become economically viable in the near future.
288 V. Volli et al.
13.3 Characterization of Biomass
13.3.1 Proximate Analysis
The physical characteristics of biomass include moisture content (external and

inherent), volatile matter (condensable vapors and gases), ash (inorganic residues),
and fixed carbon (nonvolatile fractions). Higher the volatility, greater the bio-crude
generation from biomass. American Society for Testing and Materials (ASTM)
E1358-97, E872-82, and E1755-01 standards are used to measure the moisture
(105 ± 3 °C for 16 h), volatile matter (950 ± 25 °C for 7 min), and ash content
(575 ± 25 °C for 3 h) in the biomass while fixed carbon is calculated by the differ-
ence on dry weight basis (Cai et al. 2017). The range of moisture, volatile matter,
ash, and fixed carbon for woody biomass is typically 1.5–9.5, 65–79, 0.5–1.7, and
13–26 wt%, respectively. Energy crops typically contain 2.5–10 wt% moisture,
70–85 wt% volatile matter, 0.5–1.7 wt% ash, and 12–18 wt% fixed carbon. On the
other hand, agricultural residues usually contain 6–10 wt% moisture, 28–85 wt%
volatile matter, 2–10 wt% ash, and 4.9–28 wt% fixed carbon. Last but not the least,
industrial wastes comprise of 1.5–11 wt% moisture, 29–78 wt% volatile matter,
4.5–39 wt% ash, and 3.5–16 wt% fixed carbon (Cai et al. 2017; Dhyani and Bhaskar
2018).
13.3.2 Ultimate Analysis and Heating Value
The elemental composition of biomass is the measure of carbon (C), hydrogen (H),
nitrogen (N), sulfur (S), and oxygen (O) on dry mass basis. Typically, lignocellu-
losic biomass consists of 40–55 wt% C, 35–40 wt% O, 3–7 wt% H, 0.5–1.5 wt% N,
and 0.1–2% S. For example, wood bark contains 53.1 wt% C, 6.1 wt% H, 0.2 wt% N,
and 40.6 wt% O; flax straw contains 43.1 wt% C, 6.2 wt% H, 0.7 wt% N, and
49.9 wt% O; rice husk contains 36.9 wt% C, 5 wt% H, 0.4 wt% N, and 37.9 wt% O;
switchgrass contains 48.6 wt% C, 5.5 wt% H, 0.5 wt% N, and 39.5 wt% O; and
swine manure contains 30.7 wt% C, 4.4 wt% H, 2.5 wt% N, and 61.7 wt% O (Ashter
2018). However, the sulfur content in biomass is lower in beechwood, almond shell,
flax straw, bamboo, and orchard grass as 0.7, 0.3, 0.09, 0.26, and 0.03 wt%, respec-
tively. Ash vitrification of inorganic compounds (Na and K) improves the environ-
mental performance.
Apart from the presence of macronutrients (P, K, Ca, and Mg), the trace elements
(Na, Cl, Fe, Mn, Cu, Zn, and Si) are also present in lignocellulosic biomass. The
presence of respective inorganic content in Albizia, Iroko, and Spruce biomass was
Na (22.9, 32.1, and 25.9 ppm), Zn (5.7, 8.3, and 11.4 ppm), Cu (5.1, 0.5, and
0.1 ppm), Fe (331.2, 379.6, and 9 ppm), Al (188.4, 209.1, and 4.6 ppm), and Mg
(171.5, 790.5, and 101.3 ppm) (Cai et al. 2017).
Leguminous-based biomass is rich in amine- and carboxyl functional groups that
contribute to the enzymatic activity and protein content with a relatively high nitro-
gen composition (16 wt%) and are responsible for the increase in higher heating
value (HHV) when compared to cellulose. Higher heating value is the measure of
the energy content of biomass and the total amount of heat energy available includ-
ing the latent heat of vaporization in the fuel and reaction product. The empirical
equations are developed based on the elemental composition of biomass to deter-
mine the HHV (Dhyani and Bhaskar 2018). The HHV for biomass is in the range of
12.5–24 MJ/kg. Woody biomass, agricultural residues, energy crops, and industrial
wastes have an average HHV of 14.2–17.8, 15.6–21.7, 17.5–24.9, and 6.5–17.1 MJ/
kg, respectively (García et al. 2017).
HHV ( MJ / kg ) = 0.3491 ( C wt% ) + 1.1783 ( H wt% ) − 0.1 ( S wt% )

−0.013 ( O wt% ) − 0.0151 ( N wt% ) − 0.0211 ( Ash wt% ) (13.1)
13.3.3 Chemical Composition
It is known that biomass can be characterized based on the presence of extractives,

hemicellulose, cellulose, and lignin contents. The major chemical components of
biomass feedstock include lignocellulose, starch, sugars, carbohydrates, lipids, pro-
teins, fatty acids, ash as well as organic and inorganic compounds. Biomass grouped
on the basis of the aforementioned are classified as lignocellulose-based (straw,
wood, herbaceous, and energy grasses); sugar-based (mono-/disaccharides from
beet and sugarcane); starch-based (polysaccharides from wheat, corn, potato, and
artichoke); oil-based (rapeseed, sunflower, and microalgae and macroalgae); and
protein-based (soybean, legumes, animal and aquatic waste) biomass (Tekin et al.
2014).
Cellulose exists in both crystalline and amorphous forms as linear chain mono-
molecular polysaccharide glucose units (natural and most abundant) and has a high
degree of polymerization (ca. 15,000) (Nanda et al. 2015). Cellulose consists of two
anhydroglucose units (rotation of anhydroglucose by 180° to the left and right)
linked to a helical axis. Biomass consists of 40–60 dry wt% of high-molecular
weight (≥106) of β-glycosidic-linked cellulose chains (Wang et al. 2017). For one
single glucosyl unit in cellulose, two intra- and one intermolecular hydrogen bonds
with van der Waals forces contribute to the significant thermal stability (crystallinity
index of 80%) than the amorphous region (packed cellulose structure).
Hemicellulose is an amorphous short-chain heteropolysaccharide (branched
structure) with the degree of polymerization in the range of 50–200. It acts as a con-
nective linkage between cellulose and lignin. The typical composition of hemicel-
lulose is the monosaccharide unit comprising pentose and hexose sugars (l-arabinose
and d-xylose, d-galactose, d-glucose, and d-mannose). Hemicellulose in biomass
can range up to 20–40 wt% and can be extracted by using hot alkali, ozonolysis,
enzymatic hydrolysis, and pressurized hot water. However, complete extraction or
separation of hemicellulose cannot be achieved because of its accessible inclination
to decomposition (Dhyani and Bhaskar 2018).
290 V. Volli et al.
Lignin is an amorphous three-dimensional aromatic polymer matrix of

p-hydroxyphenyl, guaiacyl, and syringyl units as its main composition with values
of degree of polymerization between 6 and 41. Ether and ester bonds as well as
other C–C bonds are the major linkages in lignin, apart from methoxy, hydroxyl,
carboxyl, and carbonyl oxygenated functional groups attached to the propyl side
chain resulting in high structural rigidity (Tekin et al. 2014). Softwood and hard-
wood consist of guaiacyl and syringyl units and are present. The fraction of lignin
can be in the range of 10–25 wt% in dry biomass. Kalson method, Kraft process,
Bjorkman, organosolv, and sulfate pulping processes are used to separate lignin.
Lignin is a biopolymer and highly branched polyphenolic constituent of biomass
and is more difficult to be dehydrated than cellulose and hemicelluloses.
Extractives are the nonstructural components of biomass consisting of lipids,
waxes, fats, and pigments. They are mainly classified into aliphatic, phenolic, ter-
penes, and terpenoid compounds. The typical composition of the extractives
includes triglycerides, hydroxy fatty acids, resins, and sterols that are responsible
for high viscosity in bio-oil, which contribute to a maximum of 2–10 wt% in bio-
mass (Arregi et al. 2018). The presence of extractives promotes the decomposition
of cellulose and hemicellulose.
Physically, biomass has an extremely complex structure with an uneven distribu-
tion of cellulose, hemicellulose, and lignin. Cellulose microfibrils form the cell wall
framework coated with hemicellulose (hydrogen bonds) and the empty spaces filled
with lignin linker materials (both covalent and hydrogen bonds). Based on the type
of biomass, the contents of extractives, hemicellulose, cellulose, and lignin vary
from 2 to 10 wt%, 15 to 30 wt%, 40 to 60 wt%, and 10 to 25 wt%, respectively, on
dry weight basis. The presence of small fractions of nonstructural components, car-
bohydrates, inorganics, trace elements, proteins, and HHV makes them an inexpen-
sive renewable energy resource. The effective utilization of biomass as a feedstock
for energy production (bio-oil, fuel gases, and char) could be a value-added alterna-
tive. The presence of excess moisture, varying nature of feedstocks, oxygenates, and
acidic compounds in bio-oil pose a major challenge in the effective utilization of
biomass. Currently, the growing concern on the economical uses of biomass, its
seasonal availability, and environmental impacts have attracted tremendous atten-
tion in the scientific community.
13.4 Biomass Conversion Processes
Energy from biomass can be derived in various forms. The form of energy deter-
mines the conversion process and depends on the availability, type, and quantity of
the feedstock. It depends on the desired energy form, end use, project factors, envi-
ronmental, and economic conditions (Adams et al. 2017). The biomass conversion
processes can be broadly classified into three types such as physicochemical, bio-
chemical, and thermochemical processes (Fig. 13.2).
Fig. 13.2 Different biomass conversion processes to value-added products
13.4.1 Physicochemical Process
Physicochemical conversion of biomass includes the extraction of oils from oil-

based feedstocks, such as sunflower, palm, hemp, flax, canola, rice bran, soybean,
mustard, rapeseed, and waste vegetable oils. The extracted vegetable oils are highly
viscous and the presence of free fatty acid content makes them unfit for direct use in
diesel engines. Converting these feedstocks to biodiesel using catalyzed reaction
(e.g., esterification or transesterification) to corresponding methyl ester has proven
to be advantageous because of its reduction in pollution levels. The process of trans-
esterification involves the mixing of alcohol, catalyst, and purification of methyl
ester (alcohol removal, glycerine neutralization, and water washing) (Gebremariam
and Marchetti 2018).
Transesterification is mostly influenced by the alcohol-to-oil molar ratio, catalyst
concentration, time, and temperature of reaction. In stoichiometric conditions, to
produce 3 mol of fatty acid esters, 1 mol of triglyceride requires 3 mol of alcohol
and depends on the type of catalyst used. The optimal alcohol-to-triglycerides ratio
for the formation of biodiesel is 6:1. Moreover, the conversion of triglyceride
increases with catalyst concentration. For conventional homogeneous (NaOH,
KOH, HCl, and H2SO4) and heterogeneous (CaO, Ca/TiO3, Ca/ZrO3, and CaO/
CeO2) acid/base catalysts, maximum conversion can be achieved at 1.5 and 10 wt%,
respectively (Volli et al. 2019). Higher temperatures also reduce the viscosity of the
oil affecting the reaction time. The range of optimal temperatures to achieve maxi-
mum conversion is the temperature close to the boiling point of the type of alcohol
used (50–60 °C). Furthermore, for a conventional homogeneous catalytic
292 V. Volli et al.
transesterification, biodiesel conversion is slow during the initial stages of the reac-
tion, owing to low dispersion of catalyst and alcohol in oil. The reaction time less
than 90 min and a longer reaction time of 6–8 h are required to achieve maximal
conversion for homogeneous and heterogeneous catalysts (Bhandari et al. 2015).
Other processes involving noncatalytic, microwave irradiation, ultrasonication,
and enzymatic reactions for biodiesel production are widely studied. The reaction
conditions and lower conversion rates significantly influence the economic aspects.
Edible and nonedible oils are the potential feedstocks for biodiesel production. With
the increasing demand for these oils, large-scale production of biodiesel may cause
negative impacts on the environment and economic disproportion.
13.4.2 Biochemical Processes
The process to produce bioethanol or biomethane and their use as an alternative to

conventional fuels have been a viable alternatives, owing to the cumbersome pre-
treatment processes of lignocellulosic biomass. Biochemical conversion of biomass
is a combination of different processes including the separation of cellulose and
hemicellulose, enzymatic hydrolysis, and fermentation of hexose and pentose
(Ghosh et al. 2017). However, biochemical processes are classified into two main
technologies, namely anaerobic digestion and alcoholic fermentation.
13.4.2.1 Anaerobic Digestion

Anaerobic digestion is considered as the natural process that utilizes bacteria and
other microorganisms to convert organic matter to gaseous products (biogas) and
nitrogen-rich liquid digestate in the absence of oxygen. It is the most prevalent sta-
bilization procedure to produce biogas, in which the dissolved organic compound at
high temperatures generates biogas with increased carbon-to-nitrogen (C/N) ratio.
The feedstock for anaerobic digestion includes animal manure, harvest remains,
sewer sludge, slaughterhouse wastes, food wastes, pulp and paper wastes, and dairy
industrial wastes (Shin et al. 2017).
Digesters with pretreated (mechanical preheating and thermal treatment) bio-
mass are usually used to produce biogas. The degradation pathway is classified into
hydrolysis, acidogenesis, aceteogenesis, and methanogenesis, which depends on the
type of bacteria used. The feedstock usually consists of 60–80 wt% moisture with
the heating value of biogas as 20–40 wt% of the feedstock (Chen and Wang 2017).
The biogas thus generated can be directly used for cooking, household heating, and
as gas fuel in engines or can be further upgraded to natural gas.
13.4.2.2 Alcoholic Fermentation

The process to produce bioethanol from feedstock with sugars and starch including
sugarcane, corn, sweet potatoes, wheat, barley, oat, and rice is alcoholic fermenta-
tion. It is a two-step process that involves enzymatic hydrolysis followed by fermen-
tation. The optimum temperatures for fermentation and hydrolysis are 30 and 50 °C,
respectively, at pH 4.5–6.0. The most commonly used microorganisms for
enzymatic saccharification are Saccharomyces cerevisiae, Trichoderma reesei,

Candida brassica, and Clostridium (Chen and Wang 2017). Industrial by-products
specifically molasses can be converted to bioethanol.
The factors effecting the conversion of bioethanol are biomass pretreatment,
temperature, pH, enzymes (hydrolytic, cellulolytic, and ligninolytic), and substrate
concentrations. Stoichiometrically, 1 mol of glucose gives 1 mol of adenosine tri-
phosphate (ADP), 2 mol of CO2, and 1 mol of ethanol. Reactor configurations,
namely fluidized-bed bioreactors, immobilized cell and tower reactors, are excep-
tionally promising for better conversion of bioethanol. The presence of lignin
restricts the decomposition of hemicellulose and cellulose to fermentable sugars.
Enzymatic hydrolysis at lower temperatures reduces the bioethanol formation, as it
is the rate-limiting step during hydrolysis. The selection of appropriate thermal tol-
erant enzyme for hydrolysis, detailed studies of the optimal composition of feed-
stock based on geographical location, and their pretreatment could be contributing
factors for the improved formation of bioethanol (Shin et al. 2017).
13.4.3 Thermochemical Process
Thermochemical process involves thermal energy to convert biomass chemically

into energy and chemical products. They are classified into three major categories
combustion, pyrolysis, and hydrothermal process. Biomass also includes feedstocks
with high moisture content (anaerobic digestate, manure, food waste, aquatic bio-
mass, and sewage sludge). The conversion of such feedstocks and organic wastes at
high temperatures (180–360 °C) and pressures (4–22 MPa) to biofuels is also
achieved through hydrothermal technologies (Tekin et al. 2014). Hydrothermal
treatment of biomass is classified into three categories, namely carbonization, gas-
ification, and liquefaction.
13.4.3.1 Combustion
The traditional process of burning biomass (exothermic reaction) in the presence of
excess oxygen (5–50%) to generate energy in the form of heat is called combustion.
The common feedstocks used for combustion are woody biomass and agricultural
crop residues. Direct heating of biomass results in evaporative, decomposition, sur-
face, and smoldering combustion. Strong turbulence of air as mixture and longer
residence times provide enough oxygen to improve combustion (Ashter 2018).
Biomass combustion process generates gaseous products at 800–1000 °C that can
directly be used to produce electricity.
Combustion is classified into four stages, such as drying, pyrolysis, volatiles’
release, and char combustion, which are influenced by temperature, biomass parti-
cle size, feedstock composition, and combustion atmosphere. Suspension and
fluidized-bed furnaces are widely used for bulk biomass feedstock and require pre-
heating for efficient energy production. However, high particulates, ash handling,
and emissions of CO, CO2, and NOx make the combustion process challenging and
non-environmental friendly. Selective non-catalytic reduction technique that
294 V. Volli et al.
reduces NOx to N2 in the presence of amine-based reagent (urea and ammonia) is

used. The flue gas recirculation has been found to be promising (Tekin et al. 2014).
13.4.3.2 Pyrolysis
Pyrolysis is a widely accepted process preceded by combustion and gasification due
to its versatility and flexibility in the choice of feedstock (Onay and Kockar 2003).
The word “pyro” and “lysis” mean “fire” and “decomposition,” respectively, in the
absence of oxygen to produce liquid (bio-oil), solid (char), and gaseous (H2, CO2,
CO, CH4, and NH3) products (Dhyani and Bhaskar 2018). The reaction temperature,
heating rate, vapor residence time, particle size, biomass composition, and feed rate
influence pyrolysis. Lower process temperatures (<300 °C) and longer residence
time (10–60 min) favor char production (80 wt%), whereas higher reaction tem-
peratures (750–900 °C) and longer residence time favor the formation of gaseous
products (96 wt%). On the other hand, moderate temperatures (400–550 °C) and
short residence time favor liquid product (bio-oil) yields.
Pyrolysis is classified into slow or conventional pyrolysis (heating rate: 3–5 °C/
min and temperature: 300–400 °C), fast pyrolysis (heating rate: 50–90 °C/min and
temperature: 450–600 °C), and flash pyrolysis (heating rate ≥ 100 °C/min and tem-
perature ≥ 750 °C). Alternate to conventional heating systems, the microwave-
based technology has already been successfully utilized in biomass pyrolysis for the
production of biochar and bio-oil (Volli and Singh 2012). Different reactor configu-
rations including fluidized-bed, auger, ablative (vortex/cone), bubbling, rotating
cone, and circulating-bed reactors are used for pyrolysis.
The fraction of cellulose, hemicellulose, and lignin as well as their interactions
are responsible for the pyrolytic behavior and provides the flexibility of using dry
and wet biomass. Hemicellulose (d-xylose) upon pyrolysis forms a reaction inter-
mediate xylulose, which undergoes hydrogenation, cyclization, and dehydration to
generate furfurals with apparent activation energy of 259.8 kJ/mol. Homolysis and
concerted mechanisms are widely studied for the pyrolysis of lignin (Wang et al.
2017). The interactions of hemicellulose, cellulose, lignin and the presence of oxy-
genated compounds braced the use of catalyst to understand and improve the distri-
bution of pyrolysis products. The major catalytic reaction pathways for biomass
include deoxygenation, cracking, aromatization, ketonization, aldol condensation,
hydrotreating, and steam reforming.
The use of inorganic salts (K, Ca, Na, and Mg), metal oxides (SiO2, Al2O3, NiO,
CuO, MoO3, CeO2, ZrO2, and TiO2), zeolites (Ni/Co/Fe/Zr/HZSM-5), the in situ
catalytic pyrolysis (catalyst mixed with feedstock), and ex situ catalytic pyrolysis
(pyrolysis of feedstock and catalytic conversion performed in separate reactors)
have been extensively studied (Guedes et al. 2018). A considerable reduction in the
formation of coke, phenols, and increase in aromatic hydrocarbons with change in
chemical pathway were observed in catalytic pyrolysis. Copyrolysis was also sug-
gested as an alternative to pyrolysis. Copyrolysis of biomass, polymers (polysty-
rene, high-density polyethylene, and low-density polyethylene), waste plastics, and
coal has been found to significantly improve the polyaromatic content in the bio-oil
(Abnisa and Wan Daud 2014).
13.4.3.3 Hydrothermal Carbonization

It is an inexpensive technique where biomass is treated in the presence of water at
temperatures of 180–300 °C with residence time of 5–240 min to produce hydro-
char (up to 90%). Both wet biomass (animal manure, human waste, sewage sludge,
municipal solid waste, and algal residues) and dry biomass (agricultural and forest
wastes) can be used for carbonization. Carbonization involves three important steps,
such as dehydration, polymerization, and carbonization of organic matter, to form
spherical (micron-sized with multiple polar functional groups) particles with heat-
ing value of 20–29 MJ/kg (He et al. 2018). Moisture content, biomass particle size,
heating rate, operating temperature, precursor concentration, and reaction time
greatly influence carbonization process. Hydrochars with lower hydrogen/carbon
(H/C) and oxygen/carbon (O/C) molar ratios (equivalent to coal and lignite) are
obtained with high temperature carbonization (Kang et al. 2019). Hydrothermal
carbonization has an ability to produce high-energy content hydrochars at relatively
lower residence times.
13.4.3.4 Gasification
Gasification is the most common thermochemical biomass conversion process that
generates energy in the form of combustible gases (syngas or producer gas) com-
prising of CO (25–40 vol%), H2 (30–50 vol%), CH4 (6–15 vol%), and CO2
(8–20 vol%) with heating values and conversion efficiencies of 0.4–10 MJ/m3 and
50–70%, respectively (Juárez et al. 2012). Gasification involves vaporization,
devolatilization, pyrolysis, cracking of tars, reduction, and reaction step at 700–
1200 °C using air, oxygen, steam, and other gasifying agents. The factors affecting
gasification process are the type of biomass feedstock, moisture content, particle
size, temperature, and steam-to-biomass ratio. Different reactor configurations,
such as fixed-bed (updraft and downdraft), fluidized-bed, entrained flow, spouted-
bed, rotary kiln, plasma, and dual fluidized-bed (bubbling and fluidized-bed) reac-
tors, are widely used.
Attempts have been made to co-gasify coal with cellulosic materials such as rice
straw, corn straw, sawdust, pine sawdust, bean stack, peanut stalk, spent mushroom
compost, and Cryptomeria wood (Widjaya et al. 2018). Natural minerals (dolomite
and olivine) and nickel-based catalysts are widely used for their superior activity in
tar cracking and reforming. Few studies have reported the use of secondary catalysts
(Mg, Ca, K, and La supported on Al2O3) and supercritical water gasification (tem-
perature >374 °C; pressure >22.1 MPa) as an alternative to conventional steam gas-
ification (Reddy et al. 2014; Nanda et al. 2017a).
13.4.3.5 Hydrothermal Liquefaction

Hydrothermal liquefaction is the process of converting biomass into liquid oils in
pressurized water environment (5–20 MPa) at 300–400 °C for longer residence time
(0.2–1 h) with biomass-to-water ratio from 3:1 to 10:1 (Beckman and Elliott 1985).
For woody and lignocellulosic biomass, feedstock pretreatment (particle size, con-
taminant removal, and alkaline treatment) is generally preferred. Biomass decom-
poses into monomeric units and undergoes dehydration, dehydrogenation,
296 V. Volli et al.
deoxygenation, decarboxylation, and deamination to produce liquid products (35–

60 wt%) with heating value in the range of 20–35 MJ/kg. The use of methanol, etha-
nol, glycerol, acetone, phenol, ethylene glycol, and water at subcritical and
supercritical water conditions is also evaluated.
Furthermore, to increase the bio-oil production, homogeneous (NaOH, KOH,
KHCO3, K2CO3, and Na2CO3) and heterogeneous (Ni and Zn/HZSM-5, Mo, Co, Ru,
and Fe) solid acid catalysts were also applied (Tekin et al. 2014). However, the
complex composition of feedstock, undesirable reaction intermediates, and excess
oxygenates restricts the clear understanding of the reaction mechanism of hydro-
thermal liquefaction. Bio-oils obtained from hydrothermal processing of biomass
can be improved and used as a replacement to conventional fuels through certain
upgrading technologies.
13.5 Bio-oil Upgrading Processes
The transformation of biomass feedstock to achieve maximum bio-crude conver-

sions and their extensive utilization can be accomplished by the aforementioned
technologies. However, the following limitation restricts the direct use of bio-crude.
The physical appearance of the bio-oil varies from dark brown through black
depending on the presence of micro-carbon with a smoky odor. The chemical com-
position of bio-oil is intricate due to the presence of more than 400 different oxy-
genated hydrocarbons (Lopes et al. 2012) such as R–COOH (carboxylic acid),
–CHO (aldehydes), CnH2n+1 OH (alcohols), CH3–C(=O)–CH3 (ketones), RCOOR′
(esters), C4H10O (ethers), C12H22O11 (sugars), C6H5OH (phenols), C4H4O (furans),
CH2O (carbohydrates), multifunctional compounds, and large oligomers.
Moisture content, acids, aldehydes, and large molecular oligomers are pivotal
factors for the deprived fuel properties of bio-oils. The presence of these undesired
properties tends to impart low heating value (<50% compared to conventional
fuels), immiscibility with hydrocarbons, thermal and chemical instabilities, higher
density (1200 kg/m3), oxygenates, higher acidic nature (pH: 2–3.7), viscosity (25–
1000 cP), and corrosive nature to the bio-crudes (Chaiwat et al. 2013).
Various physical and chemical approaches toward the bio-crude upgrading ought
to use as a commercial green fuel replacing the fossil feedstocks. This is achieved
via various physical, chemical, and catalytic upgrading processes (Si et al. 2017).
Physical upgrading includes filtration, solvent addition, and emulsion, whereas
chemical upgrading involves esterification, mild cracking, gasification, catalytic
upgrading or hydrodeoxygenation (HDO), zeolite cracking, and steam reforming.
Among all, the most effective, advanced, and novel processes include hydrodeoxy-
genation, hydrothermal liquefaction, and gasification.
13.5.1 Hydrodeoxygenation (HDO)
As per the standards of the American Petroleum Institute (API), the normal oxygen
content of bio-oil should not be more than 1.2%. However, bio-crude exceeds these
limits, consequently tethering the possibilities of their replacement to fossil fuels.
Further, the incessant growth of hydrogen technology, advanced catalysis, and HDO
technology has become the trending and top among the others in producing second-
generation fuels. Hence, the HDO technology has engrossed the attention of
researchers due to its tactical importance. By nature, HDO is an exothermic reaction
that involves high temperature and pressure causing carbon deposition on the cata-
lyst surface and affecting the catalytic activity.
Furimsky (1983) presented a comprehensive framework, such as mechanism,
catalyst, and the respective kinetics of the HDO process. Later, the research on the
HDO received very little attention due to the complexities involved in the mecha-
nism untill the revisiting studies of Furimsky (2000), which redefined the simplifi-
cation of the process mechanism. Since then, considerable attempts have been made
toward the objective of optimizing the process parameters such as temperature,
catalysts, pressures, types of reactors, etc. An interesting outcome of these research
studies over the decades revealed that the HDO process might not be directly appli-
cable to all the organic and inorganic species (more than 300) which is tedious, so
the redefined research was targeted on the specific compounds that hamper the com-
merciality of bio-crudes, especially the phenolic compounds. Table 13.1 presents
the summary of some important findings related to HDO.
Hydrodeoxygenation, as the name indicates, is a combination of hydrogenation
and deoxygenation. The combination of these processes tends to cleave the H2 and
O2 atoms, to stabilize the unsaturated bonds, and reduce the oxygenates of bio-
crude. HDO chemical reaction in the presence of H2 occurs in congestion with
hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) during the catalytic
hydrotreatment of the liquid fuels. For better understanding, the process of HDO
revolves around the critical factors and the optimal conditions that help in the com-
plete elimination of oxygenates in the form of water. Additionally, HDO is similar
to the HDS reaction, which involves sulfide catalyst that has good stability and high
conversion tendency of bio-crude (Si et al. 2017). The methodology of HDO is
extremely productive due to the higher conversion rates of carbon to useful hydro-
carbons. The detailed chemistry of HDO is illustrated in Fig. 13.3.
Catalytic upgrading of bio-crude is a complex phenomenon due to the composi-
tion and the typical operating process parameters including higher temperatures
(300–600 °C) and pressure (10–25 MPa) under the influence of H2 gas in the pres-
ence of catalyst to eliminate the O2 molecules (Gollakota et al. 2016). The overall
reaction of HDO is presented in the following Eq. (13.2):
Catalyst
CH 2 O ( carbohydrate ) + H 2 → CH 2 + H 2 O (13.2)
298 V. Volli et al.
Table 13.1 Comparison of representative biomass, observations, and optimum parameters for
hydrodeoxygenation
Temperature Pressure
Feedstock (°C) (MPa) Catalyst Observation References
Rice stalk 370 – NiS/MoS The effect of zerovalent Yang et al.
Al on in situ HDO of (2019)
bio-oil revealed that this
reaction could yield a
significant amount of
98% H2 regeneration
that could serve the
cumulative HDO batch
Pine 100 3 MoNi/γ-- The effect of the Xu et al.
sawdust Al2O3 catalytic promoter (Mo) (2010)
on the HDO of bio-oil
was examined by
considering acetic acid
as a model compound
and converting to methyl
acetate
Switchgrass 320 14 HZSM-5 The suitability of the Elkasabi
feedstock, catalyst, and et al.
H2 consumption rate for (2014)
the HDO process were
critically emphasized.
The results indicated
that the upgrading is
independent of the
feedstock and catalyst
types
Pyrolysis 300–350 – Ru/C A unique approach of Ahmadi
oil using HDO oil as a et al.
solvent to treat the (2017)
pyrolytic oil showed a
substantial improvement
in the heating values
compared to the
conventional solvents
Bio-oil 300 3 Noble metal Interesting facts were Oh et al.
revealed using noble (2016)
metals as catalyst for the
HDO process that
unaltered the
physicochemical
composition of the
upgraded bio-oil upon
extended periods of
storage
(continued)

Temperature Pressure
Feedstock (°C) (MPa) Catalyst Observation References
Pinyon- 450 6.2 Ni/RM The addition of red mud Jahromi
juniper to the catalyst during the and
HDO process Agblevor
significantly increased (2018)
the heating value and
drastically reduced the
water content for
commercial scaling
Wheat 400–450 0.101 MoO3 A comparative study on Zhou et al.
straw the HDO of the model (2016)
compounds and the
pyrolysis vapors was
performed under the
influence of MoO3
catalyst. The results
revealed that higher
degree of upgrading is
possible for the liquid
masses rather than
vapors
Anaerobic 229–369 14 Ni-Mo/ The study elucidates Neumann
digestate Al2O3 that the upgrading of et al.
bio-oil obtained via (2016)
thermal catalytic
reforming yields better
HHV when compared to
the raw crude from
pyrolysis process
Woody 450 0.101 Ni-ZSM-5 A high Si/Al ratio Veses et al.
biomass zeolite catalyst was used (2015)
to upgrade the pyrolysis
bio-oil drastically
reducing the acidic and
furan compounds,
thereby increasing the
hydrocarbon fractions
Cornstalk 280–370 4 Bimetallic The effect of Yang et al.
ammonium temperatures on the (2016)
nickel upgrading of bio-oil was
molybdate evaluated with a
decrease in the yield and
contrasting increase in
the heating value as a
function of the
temperature
300 V. Volli et al.
OH
Hy
sis dro
oly gen
rogen ati
d on
Hy
OH
sis
oly
Hy
gen
dr
dro
o
Hy
ge
na
tio
Hydrogenation
Hydrogenation
O
De
hy
dr
at
io
n
OH
H2, CH4, C2H6,

H2 C3H8, CO2
Feedstock Liquid Products

Low temperature Aqueous phase Separa on C4 – C6 Alkanes
Carbohydrates
hydrogena on hydrodeoxygenaon system C1 – C6 Alcohols
Bio-oils
Hydrolysis C2 – C4 Polyols
Products Tetrahydrofurans
Tetrahydropyrans
Waste water (Ketones)
treatment facility
Fig. 13.3 Reaction mechanism of hydrodeoxygenation
Unlike other processes, HDO involves simultaneous secondary reactions target-

ing to avoid the deleterious contents of the bio-crude (Choudhary and Phillips
2011).
1. Removal/separation of water.
2. Dehydration is a conversion mechanism that involves the loss of water molecule
from reacting molecule or ion.
3. Decarboxylation is the process of eliminating carboxyl group that liberates CO2
from the bio-crude.
4. Hydrogenation is a chemical reaction to treat the unsaturated compounds with
H2.
5. Hydrogenolysis is the process of splitting C–O bonds and releasing O2 in the
form of H2O.
6. Hydrocracking is a phenomenon of splitting macromolecules into smaller
fragments.
The critical parameters that influence the HDO process are the operating tempera-
ture, H2 flow rate, catalysts’ active sites, residence time, pressure, and catalyst sta-
bility. Among all these factors, catalyst loading plays a crucial role. Lower ratio of
catalyst loading favors the dispersion of active components, thereby restricting the
formation of active sites. The higher catalytic loading also reduces the dispersion
rate, subsequently increasing the crystal size (Gollakota et al. 2016). The second
aspect is the choice of the catalyst, i.e., the sensitivity of the catalyst to the operating
parameters, which plays a significant role in the catalyst deactivation.
Higher temperatures, pressures, and short residence times favor superior cata-
lytic activity. However, prolonged reaction time results in catalytic poising and
deactivation. The widely used catalysts for HDO process are Pt, Ni, and Co with
supports of Al2O3 due to higher catalytic active and thermal stability. However, in
the recent times, the trend of using noble metal catalysts is increasing due to the
inert nature of the catalyst, i.e., the regeneration of the catalyst with the same activ-
ity near to the original characteristics. On the other hand, the complexity of the
secondary reactions and undesired product phase is also a problem.
13.5.2 Hydrothermal Liquefaction
The pioneering research on hydrothermal liquefaction (HTL) dates back to the early
nineteenth century. However, the Pittsburgh Research Institute initiated the com-
mercial utilization of HTL process in 1970. Since then, many revolutionary attempts
were made to optimize the physicochemical properties of feedstocks, products,
treatment procedures, catalysts, and operating parameters (Schaleger et al. 1982;
Thigpen 1982; Beckman and Elliott 1985). The main drawback of this mechanism
is lenience toward the wet feedstock compared to the dry biomass. Table 13.2
explains the several other research findings related to hydrothermal liquefaction.
Hydrothermal liquefaction is the conversion technique of both wet and dry bio-
mass feedstock to liquid product along with the traces of the gaseous stream. It is
known that the composition of wet biomass are lipids, fats, proteins, and amino
acids which are nonpolar, resembling aliphatic compounds otherwise known as tri-
glycerides. The typical HTL process operates at the temperatures ranging between
250 and 350 °C (Shakya et al. 2015) and the higher pressures of 10–25 MPa
(Chiaramonti et al. 2016) to separate maximum moisture content and reduce the
oxygenates. At normal temperature and pressure conditions, fats and strong peptide
chains of amino acids are highly insoluble in solvents, thus demanding for higher
temperature and pressure scenarios.
At higher temperatures, the lipid content gradually turns into bio-crude. However,
there is no change in the glycerol content, except being a water-soluble compound.
Furthermore, the peptide chains of protein fraction undergo decarboxylation and
deamination reactions forming CnH2n+2 (hydrocarbons), amines, C2H4O (aldehyde),
and acids. The characteristic features of the HTL process are the higher energy con-
tents for the product phase and possessing enhanced heat recovery options. The
detailed mechanism of the HTL process comprising three major steps, namely
302 V. Volli et al.
Table 13.2 Comparison of process parameters, feedstock, and observations for hydrothermal
liquefaction
Temperature Pressure Time
Feedstock (°C) (MPa) (min) Observation References
Seaweed meal 350 16.5 15 A comparative study on Bach et al.
heating rates of bio-oil (2014)
with and without
catalysts was performed.
Higher heating rates
were achieved without
catalyst support
Anaerobic sludge 350 5–8 60 The effect of the Shakya
Swine manure temperature on the et al.
bio-oil yield was (2015)
critically analyzed and it
was concluded that the
increase in temperature
resulted in higher yield
of bio-oil and the
composition resembled
the petroleum crude,
except for a slight
deviation with the N2
content
Chaetomorpha, 350 14–17 15 The influence of Neveux
Cladophora, biomass composition on et al.
Oedogonium, the bio-crude yield for (2014)
Derbesia, and different algal
Ulva feedstocks was
evaluated. The main
research observation is
that the biomass with
lower N2 content tends
to yield higher energy
Scenedesmus 350 2 15 The research elucidates López
almeriensis and the effect of separation et al.
Nannochloropsis methods on bio-oil (2015)
gaditana yields. Two techniques,
namely gravity
separation and organic
solvent separation, were
tested. It was observed
that the addition of
solvents reduced the
industrial scalability
depolymerization, decomposition, and recombination, followed by hydrotreating is

illustrated in Fig. 13.4.
Depolymerization involves the sequential dissolving of macromolecules to over-
come the difficulties to obstinate the physicochemical properties of the biomass.
The detailed chemistry of depolymerization involves the splitting of the ether link-
ages of lignin in the biomass into methoxyl groups. The second step is the splitting
Hydrolysis Decomposition
Wet
Biomass Chemical Hydrothermal

Recombination Hydrotreating
pretreatment liquefaction
Dry Acid/alkaline
Depolymerization
medium
Fig. 13.4 Reaction stages involved in hydrothermal liquefaction
of the side chains into various free radicals and hydrogenated compounds into phe-
nolic and alcohol derivatives. Finally, the ether bonds of the methoxyl groups con-
vert into monophenols (Akash 2015).
Decomposition is the process of breaking large compounds into smaller compo-
nents via three major steps, namely dehydration, decarboxylation, and deamination.
During dehydration and decarboxylation, the oxygenated compounds are separated
from biomass in the form of water and CO2 while the macromolecules are hydro-
lyzed into polar oligomers and monomers. The moisture content of biomass breaks
the hydrogen bonds easily at the prevailing temperatures of HTL process and forms
the glucose monomers. The majorly degraded or decomposed products of the bio-
mass are polar organic molecules, furfural, glycoaldehydes, phenols, and organic
acids (Gollakota et al. 2018).
Recombination is the third step of the HTL process, which includes polymeriza-
tion and rearrangement of the monomers into new molecules. The structural
arrangement of the free radicals in the biomass organic matrix is solely dependent
on the presence or the absence of the H2 compound. The presence of the H2 results
in the stable structural matrix of constant molecular weight and the unavailability of
H2 leads to an increase in the concentration by the fragments’ recombination,
thereby forming higher molecular weight species otherwise known as char
(Gollakota et al. 2018).
The pivotal factors influencing the HTL process are temperature and residence
time, whereas quantity of biomass and solvent have a diminutive contribution. Low
reaction temperature causes the incomplete conversion of the biomass macromole-
cules with lower yields, despite longer residence time. Contrary to this, higher tem-
peratures and reaction times promote effective deoxygenation, thereby increasing
heating value and energy recovery of the end product. Nonetheless, higher tempera-
tures and residence time yield significant quantity of the water-soluble fractions,
increasing the nitrogen content, which is undesirable. On the other hand, the addition
of cosolvents proved to render enhanced yields. Furthermore, the addition of cosol-
vents drastically lessens the char formation because the solvent does not participate
in the chemical reaction but facilitates the extraction of the organic molecules.
304 V. Volli et al.
13.5.3 Gasification
Among the various thermochemical conversion pathways, gasification is an auto-

thermic procedure in terms of energy balance. The energy recovery and heat capac-
ity of the gaseous products from gasification are greater compared to the other
processes due to the optimal utilization of carbon and hydrogen, which contribute to
the higher calorific values compared to the other processes. The gasification product
(syngas) can be effectively converted to synthetic natural gas through catalytic
methanation of CO and CO2, which is quite complex compared to the other tech-
niques. Furthermore, gasification is the most effective process for producing hydro-
gen from biomass, which is a key intermediate in the chemical industry. The process
of gasification originated before World War II, i.e., 1798, but the actual implementa-
tion was around the 1860s, and gradually evolved as the key resource of H2 and CO
(Basu 2010). During the early twentieth century, many rural and urban areas in the
USA implemented an integrated gas supply for cooking and lighting. Later, during
the second phase of the twentieth century, i.e., in 1973, the severe crisis of oil short-
age gave the real start to this gasification technology as an alternate to the conven-
tional fossil fuel resources. At present, the technology is completely matured for
generating high-quality syngas from biomass. A detailed summary of literature per-
taining to the gasification of various biomass feedstocks is presented in Table 13.3.
Gasification process uses a wide range of feedstocks, namely natural gas, coal,
petroleum, pet coke, biomass, and industrial wastes. The process of gasification
takes place at higher temperatures (600–1000 °C) under the influence of an oxidiz-
ing agent or gasification agent. The typical oxidizing agents for the gasification
process are air, steam, N2, CO2, O2, or a combination of all of the above (Juárez et al.
2012). The presence of oxidizing agent, high temperature conditions decompose the
heavier polymeric fractions of biomass into lighter hydrocarbons, gases (a mixture
of CO, H2, CH4, CO2, and C2+), and solid residues (char, ash, and tar). The overall
gasification process is illustrated in Fig. 13.5 and the reaction scheme is shown in
the following Eq. (13.3):
Catalyst
CH x O y ( biomass ) + O2 + H 2 O → CH 4 + CO + CO2 + H 2 + H 2 O + C + tar (13.3)
Gasification involves four inherent procedures, such as drying, pyrolysis, com-

bustion, and reduction as presented in Fig. 13.5 (Kumar et al. 2009). Drying process
of biomass reduces the moisture content to the range less than 5% at the tempera-
tures of 100–200 °C. During devolatilization or pyrolysis stage, the volatile matter
of the biomass is reduced by the thermal decomposition in the absence of oxygen
and air. Subsequently, the biomass is turned into solid charcoal, thereby releasing
the hydrocarbon gaseous vapors, and upon condensation at low temperatures, it
generates liquid tars. Contrary to the previous stage, oxidation is a complex chemi-
cal reaction of solid biomass in the presence of oxygen converting carbon into CO2
and CO while exerting large amount of thermal energy, as shown in the following
equations. Several reactions, such as partial oxidation, complete oxidation, steam
Table 13.3 Summary of some notable studies on the gasification of biomass

Temperature Pressure Gasifying
Feedstock (°C) (MPa) agent Observation References
Rice straw 1000–1200 0.1 Oxygen The influence of the Gu et al.
gasification agent and (2019)
temperature was evaluated
Fruit waste – – A comparative study on Langè and
the process solutions for Pellegrini
producing H2 was assessed (2013)
from biomass to achieve
the target of 10 MW H2
energy
Palm shell 750–900 0.1 Steam The newly developed Li et al.
trimetallic catalyst (2009)
(nano-NiLaFe/γ-Al2O3)
was used for upgrading of
the biomass steam
gasification. A significant
removal of over 99% tar
was reported with an
increase in H2 volume up
to 17%
Wheat 700–750 0.1 Water The exergy analysis was Li et al.
straw performed for different (2019)
gasification configurations
projecting the optimized
processing conditions for
the efficient tar removal
and higher gas phase
generation
Kenaf and 700–900 0.1 Steam The research is a Seçer et al.
Sorghum sensitivity analysis of (2018)
lignocellulosic biomass,
biomass hydolysate, and
coal. The results indicated
that hydrolysates were
more sensitive to
degradation, yield higher
fractions of H2 and gas
phase
Sawdust 660 – Air The effect of gasification Huang et al.
temperature altered the (2012)
composition of the gases.
H2 promotion ratio was a
strong function of
condensable product phase
(continued)
306 V. Volli et al.

Temperature Pressure Gasifying
Feedstock (°C) (MPa) agent Observation References
Municipal – 0.1 Air A mathematical and Thakare
solid numerical approach to and Nandi
wastes study the feasibility and (2015)
potential of municipal
solid waste gasification for
energy generation was
performed
Pinewood 800–950 0.1 Oxygen The effect of potassium Jia et al.
char salts’ impregnation on the (2017)
catalyst substantially
improved the syngas
composition. The influence
of various parameters,
such as particle size,
temperature, and gasifying
agents, was also explained
Karanja 400–1000 0.1 Oxygen The research was focused Shah et al.
press seed and steam toward the sensitivity (2018)
cake analysis of the critical
parameters on the
gasification process. A
numerical approach of
gasification process was
introduced for future
research prospects
Sugarcane 1000 0–1.5 Oxygen The potential of sugarcane Motta et al.
bagasse bagasse gasification for (2019)
higher heating value
material was explored. The
choice of the gasifier was
also detailed along with
the optimal operating
conditions
reforming, Boudouard reaction, water–gas shift reaction, hydrogenation, and

methanation, are involved in gasification process. Reduction is the process of strip-
ping oxygen atoms off the combustion products of hydrocarbons to return the mol-
ecules to form the gaseous stream. During the reduction reaction, the char and tar
produced from the oxidation release gases at 600–950 °C. The typical reactions
including the heterogeneous water–gas shift reaction take place to produce CO and
H2.
Partial oxidation:
2C + O2 → 2CO (13.4)
Complete oxidation:
C + O2 → CO2 (13.5)
High temperature catalyc process

(1200 – 1400 oC)
Low temperature
(800 – 1000 oC) Producer gas Syngas
Biomass Gasificaon CO, H2, CH4,
CO, H2
C xH y Thermal cracking
or reforming
Drying Pyrolysis Combuson Reducon
Charcoal
H 2O H2O and CO2 H2 and CO
and tar
Tar gas and Hot

Biomass Biomass charcoal charcoal
Heang Heat no air O2/air H2O and

CO2
Fig. 13.5 Feedstock, process parameters, and products of biomass gasification process
Steam reforming reaction:
CH 4 + H 2 O → CO + 3H 2 (13.6)
Boudouard reaction:
C + CO2 → 2CO (13.7)

Water–gas reaction:
C + H 2 O → CO + H 2 (13.8)
Water–gas shift reaction:
CO + H 2 O → CO2 + H 2 (13.9)
Critical factors that influence the gasification process include the design of the
gasifier, gasification temperature, feed rate of biomass, oxidizing agents, type, and
load of the catalyst as well as biomass type and properties (Nanda et al. 2017b).
Biomass feed rate is a vital parameter and overloading/overfeeding results in chock-
ing of the reactor, thereby reducing the conversion efficiency, and the yields. The
choice of biomass is another aspect that needs careful attention due to its complex-
ity in composition.
Various studies have revealed that cellulosic biomass tends to have a higher car-
bon conversion to CO and CH4 as well as lower CO2 and H2, in comparison to xylan
and lignin fractions (Couhert et al. 2009). The equivalence ratio (ER) and the super-
ficial velocity (SV) are also important factors during the combustion reaction
308 V. Volli et al.
influencing the gasification products’ composition. Higher flow rate of air probes
higher temperatures and shortens the residence time, higher conversion, and quality
of fuel. Furthermore, the gasification agent increases the partial pressure of water to
favor several reactions (e.g., water–gas shift and methane reforming reactions) to
improve the H2 production (Kumar et al. 2009). A higher ratio of gasifying agent-
to-biomass attributes to steam reforming of tar at high partial pressure, thereby
reducing the tar content in the product stream. Gasification temperature is the most
crucial parameter that dictates the entire gasification reaction and product
composition.
Higher temperatures yield higher conversion efficiencies, with increasing yield
of H2 attributing the endothermic reactions (pyrolysis and steam reforming) and
decreasing CH4 content (Hanaoka et al. 2005). It is reported that the temperatures
ranging between 750 and 800 °C dominate the H2 rather than CH4 yields. On the
other hand, temperatures between 850 °C and 900 °C result in the higher fractions
of CO due to the higher decomposition of biomass and the reforming of tar.
Therefore, the optimal temperatures of the higher efficacy of the syngas production
via gasification are reported to be between 800 and 1000 °C (Sikarwar et al. 2017).
13.6 Future Prospects and Recommendations
In summary, there exist substantial merits and demerits for all the aforementioned
methodologies holding back the real-time applicability of biofuels. Biomass gasifi-
cation process still suffers from the maintenance, operating costs, and lack of
generic gasifiers for efficient biomass conversion. To surpass these limitations, inte-
grated gasification combined cycle (IGCC) technology, a post treatment of syngas,
is used to ensure the versatility of the process for efficient conversion and niche
applications. On the other hand, hydrothermal liquefaction holds the key problem of
excess usage of solvents and the batch system of processing. To date, a majority of
the hydrothermal liquefaction research is carried out on algal biomass in small-scale
batch autoclaves. Moreover, it is suggested that product separation followed by the
thermochemical conversion can significantly improve the yield of the products,
thereby improving the overall economic balance of the process.
Finally, upgrading biofuels via hydrodeoxygenation requires relatively higher
hydrogen at higher pressure to convert the oxygenated compounds of bio-oils to oxy-
gen-free products. In the interim, the higher hydrogen pressure leads to the complete
hydrogenation of unsaturated hydrocarbon products. Furthermore, at elevated tempera-
tures, and due to the thermodynamic limitations, phenol is the main compound of bio-
crude, which is a complex compound from which the separation of oxygen is difficult.
Despite these limitations, hydrodeoxygenation holds the key and futuristic approach,
as most of the biomass is from dried sources. However, in the case of the wet feed-
stocks, hydrothermal liquefaction holds the key that can produce green fuels with bet-
ter properties. Tables 13.4, 13.5, and 13.6 summarize the proximate and ultimate
analyses of the various feedstocks and the conversion and upgrading products because
of gasification, hydrothermal liquefaction, and hydrodeoxygenation, respectively.
Table 13.4 Comparison of improved physicochemical properties of feedstocks and respective products from gasification
Feedstock properties Product properties
Feedstock C H N S O A M HHV H2 CO CH4 CO2 References
Rice straw 47.5 5.7 0.2 0.73 40.1 5.6 9.3 19.1 30.1 37.4 7.6 23.4 Gu et al. (2019)
Fruit waste 45.1 6.4 0.2 1.1 47.3 7.5 60.1 – 71.8 1.4 1.5 25.1 Langè and Pellegrini (2013)
Palm shell 53.7 7.2 – 0.5 36.3 2.2 5.7 – 36.5 25.8 10.2 24.5 Li et al. (2009)
Wheat straw 36.5 4.9 0.5 – 40.5 7.7 9.6 – 0.04 8.7 2.8 19.1 Li et al. (2019)
Kenaf 48.6 5.7 0.1 – 42.5 3.1 10.4 – 79.4 1.7 12.1 6.8 Seçer et al. (2018)
Sorghum 39.8 5.2 0.8 – 45.8 8.4 8.1 – 28.3 43.2 9.1 14.5
Sawdust 47.9 5.9 0.4 – 45.8 0.6 6.3 – 24.2 39.5 6.2 30.1 Huang et al. (2012)
Municipal solid waste 30.3 3.4 1.4 – 35.8 29.1 – – 7.5 20.2 1.5 7.9 Thakare and Nandi (2015)
Pinewood char 87.2 2.4 1.1 – 10.3 2.2 – 31.2 62.7 14.9 1.2 21.2 Jia et al. (2017)
Karanja press seed cake 47.2 6.5 4.3 – 42.1 4.1 7.2 18.3 37.2 48.7 2.3 4.2 Shah et al. (2018)
Sugarcane bagasse 46.9 5.7 0.2 0.02 44.1 2.9 50.1 18.5 35.9 12.7 5.5 42.6 Motta et al. (2019)
Notes: Carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O), ash (A), moisture (M), and higher heating value (HHV)
13 Conversion of Waste Biomass to Bio-oils and Upgradation by Hydrothermal…
309
310
Table 13.5 Comparison of improved physicochemical properties of algal feedstocks and respective products from hydrothermal liquefaction
Feedstock C H N S O A M HHV C H N S O A M HHV References
Seaweed meal 39.4 5.1 2.9 0.6 52.1 16.5 – 14.4 75.5 9.1 3.65 0.6 11.6 – – 35.97 Bach et al. (2014)
Nannochloropsis 56.8 9.3 10.1 0.3 19.9 3.42 68.8 24.1 79.3 11.9 5.2 0.2 3.1 0.2 7.1 34.8 Shakya et al. (2015)
Pavlova 54.3 8.6 8.67 0.8 24.1 3.4 17.7 22.6 78.3 10.1 4.7 0.2 6.3 0.4 5.6 32.2
Chaetomorpha 26.5 4.1 3.4 2.1 31.1 36.6 5.1 10.3 70.9 7.7 6.8 0.1 11.4 – – 32.5 Neveux et al. (2014)
Cladophora 30.9 5.1 5.2 2.3 34.9 25.5 6.7 12.7 71.6 8.1 7.1 0.9 10.6 – – 33.3
Oedogonium 36.6 5.7 4.8 0.4 30.9 20.6 6.5 15.8 72.1 8.1 6.3 0.8 10.4 – – 33.7
Derbesia 29.2 4.8 4.5 2.8 27.4 34.7 6.4 12.4 73.1 7.5 6.5 0.7 10.6 – – 33.2
Ulva 27.7 5.5 3.5 5.1 41.1 30.7 7.2 11.7 72.6 8.2 5.8 0.4 11.1 – – 33.8
Scenedesmus 38.1 5.6 5.5 0.5 30.4 20.1 – 16.8 74.9 9.1 5.9 0.7 9.6 – – 36.2 López et al. (2015)
Nannochloropsis 47.6 7.5 6.9 0.5 25.1 12.4 – 23.1 76.1 10.3 4.5 0.4 8.8 – – 38.1
gaditana
V. Volli et al.
Table 13.6 Comparison of improved physicochemical properties of feedstocks and respective products from hydrodeoxygenation
Feedstock C H N S O A M HHV C H N S O A M HHV References
Rice stalk 39.4 5.5 1.2 0.1 53.6 15.8 5.9 14.5 80.4 8.7 2.1 1.6 7.1 – – 35.8 Yang et al. (2019)
Pine sawdust 53.6 6.2 0.02 – 40.1 – 35.5 13.9 53.8 6.9 0.01 – 39.2 – 41.5 14.1 Xu et al. (2010)
Switchgrass 53.8 5.3 0.5 – 33.2 – 7.9 – 72.1 7.8 0.8 – 19.2 – 2.3 – Elkasabi et al. (2014)
Pyrolysis oil 38.2 7.6 – – 54.1 – 27.9 – 71.1 8.3 – – 20.4 – 4.1 – Ahmadi et al. (2017)
Bio-oil 40.2 7.5 0.2 – 52.2 – 17.7 18.2 55.1 9.1 0.4 – 35.6 2.3 23.4 Oh et al. (2016)
Pinyon- 54.4 6.2 0.1 – 38.6 0.5 6.6 19.3 83.1 16.5 0.3 – – – – 45.8 Jahromi and Agblevor
juniper (2018)
Wheat straw 51.3 5.7 0.2 0.03 40.5 2.7 7.1 – 67.8 7.9 2.3 – 22.1 29.3 18.2 – Zhou et al. (2016)
Anaerobic 34.8 4.3 1.9 0.4 26.9 16.7 15. – 86.2 13.1 0.1 – 0.80 – – Neumann et al. (2016)
digestate
Woody 60.1 7.4 0.3 0.04 32.1 – 11.1 25.1 70.1 7.9 0.20 0.03 22.1 – – – Veses et al. (2015)
biomass
Cornstalk 41.2 5.4 0.8 0.2 52.4 – – 14.5 72.1 7.7 0.02 0.01 20.2 – 25.6 32.1 Yang et al. (2016)
13 Conversion of Waste Biomass to Bio-oils and Upgradation by Hydrothermal…
311
312 V. Volli et al.
13.7 Conclusions
Anticipated depletion of the fossil fuels and growing energy demand, especially
from transportation sectors, have generated consideration for alternate fuels from
biomass as a definitive answer to the declining oil production. Additionally, biofuels
are the imperative choices to seek the complete decarbonization of the transporta-
tion sector. With the devoted interest in this area, various biomass to bio-crude tech-
nologies are discussed in this chapter. This led to the development of several
upgrading technologies but the targeted perspective of clean energy and substantial
replacement to the conventional fossil resources is not yet commercially feasible.
While some intriguing data have been made available by previous biomass
upgrading strategies, several gaps still exist in this area. These gaps are divided into
two groups (optimization and technology gaps), both contingent upon the feedstock
utilized for producing renewable fuels. The optimization gaps of the biomass
upgrading technologies can be addressed by means of additional research and
through understanding of the inhibition effects, while the technological gap of bio-
crude upgrading is exceedingly challenging. From the technical standpoint, there
exists a substantial gap in the choice of the catalyst, optimal reactors, and varied
operating parameters, which restrict the biofuels to reach the energy nexus. On the
other hand, the nontechnical perspectives are to be considered in competencies to
reach the desired objective of commercializing the biofuels. Despite uncertainties
allied with renewable energy, the certainty factor of the research on renewable fuels
will be vibrant and evergreen, as there is a scope to find the better way of coupling
the economic and environmental factors and the associated challenges.
Acknowledgements The authors greatly appreciate the PS&DPL group, National Yunlin
University of Science and Technology, Taiwan, for their cooperation and support.
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Upgrading of Bio-oil from Biomass
Pyrolysis: Current Status and Future 14
Development
Quang Thang Trinh, Arghya Banerjee, Khursheed B. Ansari,

Duy Quang Dao, Asmaa Drif, Nguyen Thanh Binh,
Dang Thanh Tung, Phan Minh Quoc Binh,
Prince Nana Amaniampong, Pham Thanh Huyen,
and Minh Thang Le
Q. T. Trinh
Cambridge Centre for Advanced Research and Education in Singapore (CARES), Campus for
Research Excellence and Technological Enterprise (CREATE), Singapore, Singapore
A. Banerjee
Department of Chemical Engineering, Birla Institute of Technology and Science (BITS)
Pilani, Pilani, Rajasthan, India
K. B. Ansari
Department of Chemical Engineering, Aligarh Muslim University,
Aligarh, Uttar Pradesh, India
D. Q. Dao
Institute of Research and Development, Duy Tân University, Thanh Khê, Đà Nẵng, Vietnam
A. Drif
INCREASE, Université de Poitiers, Poitiers, France
N. T. Binh
Faculty of Chemistry, Vietnam National University, Hà Nội, Vietnam
D. T. Tung · P. M. Q. Binh
Vietnam Petroleum Institute, Vietnam National Oil & Gas Group, Hà Nội, Vietnam
P. N. Amaniampong
Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers,
Poitiers, France
P. T. Huyen · M. T. Le (*)
School of Chemical Engineering, Hanoi University of Science and Technology,
Hà Nội, Vietnam

318 Q. T. Trinh et al.
Abstract
For the sustainable production of fuel, biomass pyrolysis processes have appeared
as a promising alternative for the efficient utilization of biomass. The liquid
product obtained from biomass pyrolysis, i.e., bio-oil has a very complex com-
position including large proportion of organic oxygenated hydrocarbon com-
pounds and appreciable amount of water. The high oxygen content of the bio-oil
creates many major drawbacks that hinder its vast application. The quality of
bio-oil is not applicable for direct transportation purposes, and its upgrading is
mandatory before it can be used practically in power engines. The abovemen-
tioned drawbacks can be overcome by the catalytic hydrodeoxygenation of bio-
oil, in which the functional groups containing oxygen are removed and replaced
by hydrogen atoms. For this purpose of selectively activating and breaking the
C–O bonds while trying to maintain the C–C bonds intact, processing knowledge
base of petroleum industry may not be utilized for hydrodeoxygenation of bio-
oil. Therefore, novel catalysts, solvents, and processes need to be developed.
This chapter reviews the state-of-the-art results obtained from the research and
development of these technologies. The pros and cons, potential of future appli-
cations, challenges related to these technologies, and opportunities to maximize
economic and environmental benefits while minimizing pollution are high-
lighted. Besides, the application of molecular modeling in the integration with
experiment is highlighted in this chapter as a new paradigm for mechanistic stud-
ies, which could open new avenues to design and develop catalysts for a plethora
of bio-oil upgrading processes that require high activity and selectivity. Finally,
the breakthrough applications of novel sonochemical technique in biomass treat-
ment and conversion are introduced in this chapter.
Keywords
Pyrolysis · Bio-oil upgrading · Hydrodeoxygenation · Density functional theory
(DFT) · Molecular modeling · Sonochemical technique · Catalyst design
14.1 Introduction
Although conventional fossil fuels currently contribute to 80% of the world’s energy
consumption, their resources are diminishing. Therefore, there are strong incentives
in finding alternative resources to reduce our reliance on fossil fuels (Amaniampong
et al. 2015, 2017, 2018b, c; Trinh et al. 2015, 2016). Besides, fossil fuels also create
several environmental problems such as increasing greenhouse gas emissions, accu-
mulating CO2, and pollution (release of fine particulate matter, NOx and SOx) of air
and water systems. Among possible solutions, biofuel from renewable biomass is
one of the potential alternatives to replace the fossil fuel.
Biomass is defined as materials produced by the growth of microorganisms,
plants, or animals. It includes all the biological organic materials from living organ-
isms produced by photosynthesis either indirectly or directly (Nachenius et al. 2013).
14 Upgrading of Bio-oil from Biomass Pyrolysis: Current Status and Future… 319
Biomass comprises animal-derived and mostly plant-derived materials such as crops,

forestry and agricultural residues, wood, and industrial and municipal solid wastes.
The estimation of biomass availability is reported as more than ten times higher than
the energy demand of the world, which could be a promising resource for cleaner and
sustainable energy production (Adams et al. 2018). A report from the International
Energy Agency (IEA) shows that by 2035, approximately 15% of the global energy
supply could be contributed from biomass and bioenergy, and by 2050, a large por-
tion of world transportation fuel (~30%) could be replaced by biofuel (Nachenius
et al. 2013; Trinh et al. 2016).
The first-generation biofuel raw materials are mostly food crop sources, such as
sugar, starch, vegetable oil, and animal fats. These raw materials can generate a
wide range of products, including biodiesel (via the transesterification), biogas, syn-
gas, and bio-alcohols (via fermentation). However, the utilization of such feedstocks
to produce biofuels is difficult and unsustainable globally due to the stress they put
on the nutritional needs of the population. An alternative way to convert biomass to
energy is the development of second-generation biofuels, which are produced from
nonfood lignocellulosic biomass with many environmental and social benefits
(Mushrif et al. 2015; Nanda et al. 2015). A major portion of biomass produced on
earth is not utilized in the food and nonfood sectors such as animal feeds and paper-
making, which could be utilized to produce next-generation biofuels. Among these
nonfood biomasses, the renewable lignocellulosic biomass is the biggest carbon-
containing source. It mainly consists of three basic components, i.e., cellulose (40–
50 wt%), lignin (10–40 wt%), and hemicellulose (20–40 wt%), with the
corresponding content amount of the individual components varying with the bio-
mass type (Adams et al. 2018, Nachenius et al. 2013; Nanda et al. 2013).
To transform biomass into chemicals and fuels, three main technologies are
available, such as thermal, physical/mechanical, and biochemical processes (Adams
et al. 2018, Bridgwater 2012; Kabir and Hameed 2017; Nachenius et al. 2013;
Nanda et al. 2014). Biochemical methods can only process the feedstock containing
sugars and carbohydrates available in a relatively high purity. Additionally, they can
barely breakdown some of the main biomass components like lignin. Hence, the
thermochemical pyrolysis of biomass is the most promising method to convert cel-
lulosic waste biomass into biofuel due to its convenience in scale-up and flexibility
in controlling operation conditions to give a wide range of desired products and cost
effectiveness. Primary processes in the thermal treatment of biomass include gasifi-
cation (conversion of biomass to syngas and subsequently to liquid fuels via
Fischer–Tropsch synthesis), combustion/incineration at high temperature (to
recover heat, which is then used to produce electricity), and pyrolysis process (con-
version of biomass to liquid fuels, gases, and solid char). Figure 14.1 summarizes
various thermal processes along with the relevant primary products and their cor-
responding markets. Gasification and combustion processes are highly energy
intensive. Therefore, pyrolysis is considered as the most promising method to make
liquid fuels from the lignocellulosic biomass.
Technically, pyrolysis involves the decomposition of biomass in the absence of
oxygen under high temperatures to produce solid char, liquid bio-oil, and
Fig. 14.1 Products from thermochemical biomass conversion (Bridgwater 2012)
noncondensable gases. There are three main types of pyrolysis processing, namely
slow pyrolysis, fast pyrolysis, and flash pyrolysis, which are categorized based on the
operation conditions (Adams et al. 2018; Bridgwater 2012; Bridgwater and Peacocke
2000; Mushrif et al. 2015; Nachenius et al. 2013). In slow pyrolysis process, biomass
is heated for long residence times at low temperatures of 300–700 °C and slow heat-
ing rates to maximize the solid char product. In fast pyrolysis, a higher temperature
range of 400–800 °C, coupled with short residence times and much faster heating
rates (10–200 °C/s), promotes liquid product (bio-oil) formation. Very high tempera-
tures in the range of 800–1000 °C along with extremely high heating rates (>1000 °C/s)
and short residence times (<0.5 s) are characteristic of flash pyrolysis process with a
high yield of bio-oil (up to 75 wt%). However, severe operating conditions along with
the technical challenges related to its scalability make it difficult to commercialize the
process. Fast pyrolysis is, therefore, still the most preferred method to convert bio-
mass to liquid product.
14.2 Fast Pyrolysis Technology: Technoeconomic Assessment
As mentioned in the previous section, one of the most convenient technologies to

convert biomass to fuels is the fast pyrolysis process. However, transportation of
biomass appeared to be the major logistic issue for the conversion of cellulosic bio-
mass to biofuel. It has been shown that the profitability of a power plant operated on
biofuels could be affected to an extent of 30% due to transportation costs alone
(Mushrif et al. 2015). Hence, to facilitate the commercialization of biomass to bio-
fuel technology, the crucial step is to compromise between the transportation, han-
dling, and processing of biomass, which is not the case for petroleum fuels. Fast
pyrolysis process, on that front, is the only biomass processing technology, which
offers the unique advantage of setting up processing plants at multiple geographic
locations to convert biomass to bio-oil, which later can be stored/transported for the
end use or for the upgradation in a much more economical fashion. In addition, an
economical evaluation on a case study of a biomass processing plant with daily
capacity of 2000 tons showed that fast pyrolysis process has the lowest capital and
operating cost among other biomass platforms such as gasification and biochemical
conversion (Anex et al. 2010; Swanson et al. 2010; Wright et al. 2010). The esti-
mates of the product (gasoline equivalent) value for a pioneer plant and for the nth
plant have also shown that the cost of pyrolysis fuel is almost half of that produced
using biochemical methods.
Fast pyrolysis of biomass may appear to be an energy intensive process. However,
analysis of the electricity consumption of a fast pyrolysis plant of the capacity of 20
tons of dry biomass per day has shown that if the product bio-oil is used to satisfy
the plant’s electricity requirement (with 40% efficiency), 18% of the total bio-oil
produced would be used to run the plant. The key advantages that pyrolysis offers
over the conventional incineration/combustion and gasification systems with respect
to the generation of electricity from bio-oil are as follows:
1. The conversion of biomass to bio-oil can be decoupled from the electricity gen-
eration system, since bio-oil can be stored and transported. This not only pro-
vides flexibility in terms of electricity generation and distribution but also allows
further production of high-grade fuels and chemicals from biomass. This decou-
pling becomes even more critical for geographically large countries.
2. The production cost of the pyrolysis-based electricity generation would be sig-
nificantly lower than that of incinerators due to the decoupling.
3. The net system efficiency, in terms of energy in the electricity per unit heating
value of the feedstock of the pyrolysis-generated electricity, is 25–50% more
than that of incinerators, even with the existing pyrolysis technology. Further
improvement can be achieved with improved bio-oil quality and yield.
4. The emission of furans and dioxins into the atmosphere and the generation of
toxic fly ash and bottom ash in incinerators are hugely reduced.
5. Two side products generated by pyrolysis are char and gases. The gases formed
can be utilized to heat the pyrolysis reactor, thus contributing to the economy
of the process, and the char formed can be used as activated carbon for soil
amendment.
6. The anthropogenic CO2 emissions are significantly lower in the case of pyroly-
sis than that of conventional incineration/combustion.
The literature on the economic analysis of biomass pyrolysis to bio-oil for elec-
tricity and fuels/chemicals production suggests that the cost of the electricity gener-
ated from bio-oil and the cost of high-grade fuel produced from it are most sensitive
to the yield and quality of bio-oil. To take a significant step forward to advance this
technology, it is extremely crucial to be able to improve the pyrolysis process, to get
higher bio-oil yields with better fuel quality.
14.3 io-oil Quality from Fast Pyrolysis and the Need

B
for Upgrading
In fast pyrolysis, biomass is heated rapidly without the presence of oxygen at 400–
1000 °C, leading to the formation of a short-lived condensed phase in which a variety
of reactions occur to form volatile products and solid char. Most of the volatile prod-
ucts (except some light gases like CO, H2, and light hydrocarbons) are later con-
densed to form a viscous fluid called as bio-oil. The quantity and quality of bio-oil
depend strongly on the biomass feedstock, but other factors involving operating con-
ditions and reactor design are also very important in varying the bio-oil properties.
The operating temperature including heating and cooling rates, grinding particle size
of the material, and pyrolysis residence times could significantly impact the distribu-
tion of the bio-oil liquid products and can even change the balance of bio-oil-to-char
ratio (Adams et al. 2018; Bridgwater 2012; Kan et al. 2016; Nachenius et al. 2013).
Bio-oil obtained from fast pyrolysis process of biomass is a dark brown liquid
with a characteristic acrid smoky smell due to high content of light aldehydes and
acids. Its composition is very complex, including large proportion of organic com-
pounds (oxygenated hydrocarbons like hydroxyaldehydes, hydroxyketones,
hydroxyacetic acids, etc.) and appreciable amount of water. Bio-oil could be used as
fuel for heating and electricity generation in diesel engines, combustors, furnaces,
boilers, and gas turbines. Since there are many value-added chemical compounds in
bio-oil, they can be extracted and used as the feedstocks for pharmaceutical, food,
and fertilizer industries.
Some major drawbacks hinder the wider application of bio-oils. First, the bio-oil
is highly acidic (pH ~2.5) due to its high content of organic acids, making it highly
corrosive than fossil fuels. The corrosiveness of bio-oil is even much more severe at
higher temperature and, therefore, limits the choice of material for bio-oil usage.
Second, the presence of appreciable amount of water in the bio-oil (15–35 wt%)
increases the ignition delay and reduces the heating value and the combustion rate
of the bio-oil fuel. The high oxygen content of bio-oil resulting from the biomass is
the main reason contributing to its low quality due to high polarity, low energy den-
sity, and low miscibility with other hydrocarbons components of the bio-oil.
Besides, the oxygenated compounds (aldehyde and acids) are highly reactive and
cause the bio-oil to become unstable due to the favorable condensation reactions
occurring between these compounds at higher temperatures.
The drawbacks of bio-oil properties and their impact are summarized in
Table 14.1. Therefore, it is generally accepted that the quality of bio-oil is not appli-
cable for direct transportation purposes and significant upgrading of the bio-oils is
required before it can be used practically as a transportation fuel (Elliott 2016). The
upgrading of bio-oil can be done physically (e.g., extraction, filtration, and emul-
sion) or chemically with the help of a catalyst. The catalytic upgrading is the most
widely applied technique, which involves different reaction pathways such as decar-
bonylation, decarboxylation, hydrodeoxygenation, and esterification for reduction
of the oxygen content of the pyrolysis-derived bio-oil. The catalytic upgrading of
bio-oil can be done in situ (co-introduction of the catalyst with biomass during the
Table 14.1 Drawback of bio-oils (Bridgwater 2012)

Characteristic Cause Effects
Acidity or low pH • Organic acids from biopolymer • Corrosion of vessels and
degradation pipelines
Aging • Continuation of secondary • Slow increase in viscosity
reactions including polymerization from secondary reactions such
as condensation
• Potential phase separation
Alkali metals • Nearly all alkali metals retain in • Catalyst poisoning
the char • Deposition of solids in
• High ash feed combustion
• Incomplete solid separation • Erosion and corrosion
• Slag formation
• Damage to turbines
Char • Incomplete char separation • Aging of oil
• Sedimentation
• Filter blockage
• Catalyst blockage
• Engine injector blockage
• Alkali metal poisoning
Chlorine • Contaminants in biomass feed • Catalyst poisoning in
upgrading
Color • Cracking of biopolymers and char • Discoloration of some
products such as resins
Contamination of • Poor harvesting practice • Contaminants notably soil
feed act as catalysts and can increase
particulate carry over
High oxygen • Biomass composition • Poor stability
content • Nonmiscibility with
hydrocarbons
High viscosity • Organic and aqueous phase • Gives high-pressure drop
composition increasing equipment cost
• Tar fraction • High pumping cost
• Poor atomization
Low H/C ratio • Biomass has low H/C ratio • Upgrading to hydrocarbons
is more difficult
Low miscibility • Highly oxygenated nature of • Does not mix with any
with hydrocarbons bio-oil hydrocarbons so integration into
a refinery is more difficult
Materials • Phenolic and aromatics • Destruction of seals and
incompatibility gaskets
Nitrogen • Contaminants in biomass feed • Unpleasant smell
• High nitrogen feed such as • Catalyst poisoning in
proteins in wastes upgrading NO in combustion
Phase separation or • High feed water • Phase separation
nonhomogeneity • High ash in feed • Partial phase separation
• Poor char separation • Layering
• Poor mixing
• Inconsistency in handling
• Storage and processing
(continued)

Characteristic Cause Effects
Poor distillation • Reactive mixture of degradation • Bio-oil cannot be distilled
products completely (maximum 50%
typically)
• Liquid begins to react below
100 °C and substantially
decomposes above 100 °C
Smell or odor • Aldehydes and other volatile • While not toxic, the smell is
organics (mostly from cellulose and often objectionable
hemicellulose)
Solids • Includes char, particulates from • Sedimentation
reactor such as sand (fluidizing • Erosion and corrosion
medium), particulates from feed • Blockage
contamination
Sulfur • Contaminants in biomass feed • Catalyst poisoning in
upgrading
Temperature • Incomplete reactions • Irreversible decomposition
sensitivity of liquid into two phases above
100 °C
• Irreversible viscosity
increases above 60 °C
• Potential phase separation
above 60 °C
Toxicity • Biopolymer degradation products • Human toxicity is positive
but small
• Eco-toxicity is negligible
Water content • Pyrolysis reactions • Complex effect on viscosity
• Feed water and stability
• Increased water lowers
heating value, density, stability,
and increase pH
• Affects catalysts
fast pyrolysis) or ex situ (catalytic upgrading of bio-oil vapors is performed after

pyrolysis). The summary of catalysts being used for bio-oil upgrading and the strat-
egies to design new catalysts with better efficiency and stability are described in
later sections.
14.4 I nfluence of Heat and Mass Transfer on the Bio-oil Yield

and Composition
It is difficult to systematically optimize a variety of factors including operating con-

ditions of the pyrolysis process (i.e., particle size of feedstock and operating tem-
perature) and the design of reactor for different types of biomass feedstocks to
achieve the desired yield and appropriate product distribution of bio-oil. Most of the
research is based on trying and testing different reactor configurations and operating
conditions for different biomass feedstocks (Bridgwater 2012). Different tempera-

tures, residence time, and particle sizes were tried and tested in several pyrolysis
reactors without much insight on how these operating conditions could affect the
transport phenomenon (i.e., heat and mass transport) inside the biomass particles.
These operating conditions could also affect numerous reactions taking place in the
condensed phase leading to the decomposition of biomass into char and bio-oil
(Ansari et al. 2018; Paulsen et al. 2013).
Due to the high temperature’s reactions coupled with heat and mass transport
effects, the high complexity of biomass feedstock composition and the extremely
fast reaction kinetics made it challenging to investigate fundamentals of pyrolysis.
Because there is the lack of insights into pyrolysis reactions, most of the theoretical
work, aimed at pyrolysis process design, used a lumped approach, where all the
reactions in the condensed phase are represented in the form of a few pseudo reac-
tions (Zhou et al. 2014). Kinetic parameters derived using such an approach were
empirical, and the models were only applicable to specific biomass pyrolysis system
and feedstock and did not have any predictive or interpretive capabilities for the
variety of biomass (Mayes et al. 2014; Seshadri and Westmoreland 2012). Therefore,
it is necessary to develop a comprehensive pyrolysis reaction network in the con-
densed phase and to combine it with heat and mass transport effects at particle level
to be able to predict the effects of operating variables and the reactor design on cel-
lulosic biomass decomposition at the particle level.
In principle, bio-oil derived from pyrolysis contains hundreds of compounds, which
can be broadly categorized into five main groups as follows (Ansari et al. 2018):
1. Anhydrosugar compounds comprising levoglucosan (LGA), levoglucosenone

(LGO), dianhydroglucopyranose (DAGP), and 1,6-anhydroglucofuranose
(AGF).
2. Furanic compounds consisting of 2-methylfuran, furfural, 5-methylfurfural,
2,5-dimethylfuran (DMF), 5-hydroxymethylfurfural (HMF), 2-furanmethanol,
furan, and furanone 2(5H).
3. Pyrans consisting of 2,3-dihydro-3,5-dihydroxy-6-methyl-4HPyran-4-one
(DHMDHP) and 1,5-anhydro-4-deoxy-d-glycerohex-1-en-3-ulose (ADGH).
4. Light oxygenates compounds collectively formed from acetic acid (AA),
1,2-cyclopentanedione (CPD), methylglyoxal (MG), formic acid (FA), glyoxal
(GL), hydroxyacetone (HAA), 2,3-butanedione (BD), and 2-hydroxy-3-
methyl-2-cyclopenten-1-one (CPHM).
The percentage of each compound governs the bio-oil composition, and it varies
significantly with the pyrolysis operating conditions, especially temperature and
feedstock size. Paulsen et al. (2013) have systematically showed the changes in the
yield of pyrolysis products, especially forming bio-oil, with respect to the biomass
(or cellulose) particle size and operating temperature. In the subsequent study,
Ansari et al. (2018) have succeed in decoupling the heat and mas transport in study-
ing the biomass pyrolysis by taking glucose as a model biomass compound. By
pyrolyzing two different sizes of glucose such as thin film, the influence of heat and
mass transport was eliminated, and in powdered form, the heat and mass transport
controlled the pyrolysis process. Fast pyrolysis of glucose thin film produced bio-oil
with a lower yield than it was observed in the glucose powder at the temperature
range between 300 °C and 500 °C, demonstrating the important role of heat/mass
transport in this process. Generally, the yields of noncondensable gases were similar
for both cases, but the observed amount of char was much higher in the case of
glucose thin film. The higher yield of char was because of some extent of re-
polymerization reactions taking place during glucose thin-film pyrolysis.
The yield of broader category of bio-oil compounds including furans, pyrans,
anhydrosugars, and light oxygenates also changed with pyrolysis temperature.
Within the bio-oil composition produced from the pyrolysis of glucose thin-film
samples, the amount of anhydrosugars decreased when the operating temperature is
increased, whereas an opposite increase was observed in the yield of light oxygenate,
and the number of furans and pyrans altered only slightly. The trend of produced
anhydrosugars and light oxygenate in derived bio-oil from the glucose powder pyrol-
ysis was similar to that of glucose thin film. Furans showed a marginal decrease in
their yields, while pyrans remained unchanged with an increase in the operating tem-
perature. At higher operating temperatures, anhydrosugars tend to convert into lighter
compounds via ring operating and fragmentation reactions. The uniform temperature
inside glucose thin film assisted anhydrosugars in further decomposition, which in
the case of glucose powders restricted because of the thermal gradient.
The insightful information gained from analyzing the product yields and com-
position of bio-oil obtained from powder and thin-film samples of glucose pyroly-
sis using the thin-plate spline interpolation method was helpful to optimize the
operating conditions of biomass pyrolysis process (Ansari et al. 2018). Figure 14.2
shows the yields of char, bio-oil, noncondensable gases, and different bio-oil com-
pounds (including levoglucosan, 5-hydroxymethylfurfural, furfural, furans, and
anhydrosugars). The large size of glucose particles (460–500 μm) and the higher
operating temperature (500 °C) maximized the noncondensable gases as shown in
Fig. 14.2a. When the transport is limited, the bio-oil yield remained maximum with
the glucose powders (500 μm) at 500 °C. The lowest yield of bio-oil was observed
at 300 °C in the pyrolysis of thin-film glucose as shown in Fig. 14.2b. The yield of
char yield exhibited an opposite trend to that of noncondensable gases/bio-oil and
reached the minimum at pyrolysis temperature of 500 °C and particle size around
500 μm (Fig. 14.2c).
For determining the quality of bio-oil or better product distribution, the maxi-
mum yield of furans could be obtained at the operating conditions with the particle
size of 300 μm and pyrolysis temperature of 500 °C (Fig. 14.2d). The amount of
5-hydroxymethylfurfural was maximized at 500 °C with particle size in the range of
200–400 μm, suggesting its production was competitive with other furans formation
in glucose–pyrolysis as shown in Fig. 14.2e. Another furanic compound, i.e., furfu-
ral, became highest at 400 °C and with particle size of 200–300 μm (Fig. 14.2f).
Finally, the formation of anhydrosugars and the major compound (e.g., levogluco-
san) (Lin et al. 2009) reached the maximum at 500 °C with the biomass particle of
460–500 μm (Fig. 14.2g, h). In summary, it is demonstrated that by varying the size
Fig. 14.2 Yields of bio-oil compositions versus pyrolysis temperature and feed particle size
(Ansari et al. 2018): (a) gases yield (% C), (b) bio-oil yield (% C), (c) char yield (% C), (d) furans
yield (% C), (e) HMF yield (% C), (f) furfural yield (% C), (g) anhydrosugars yield (% C), (h)
levoglucosan yield (% C)
of biomass particles and the operating temperature range, the yield of bio-oil and its
composition could be significantly changed. Such an approach for optimizing the
operating conditions of biomass pyrolysis (i.e., particle size and operating tempera-
ture) could help in obtaining the highest yield together with achieving the desired
composition of bio-oil produced from fast pyrolysis.
14.5 Fluidized Bed Reactor for Fast Pyrolysis Process
During the recent decades, numerous researches on biomass pyrolysis have focused
on the design of reactors for biomass pyrolysis, resulting in a development of many
different reactor designs such as fluidized bed reactor (Ly et al. 2019), fixed bed
(Mohanty et al. 2013), transported bed, ablative reactor (Auersvald et al. 2019), and
rotating cone reactor (Singbua et al. 2017). Among all reactors, fluidized bed reactor
provides better temperature control, particle mixing and residence times, high heat
transfer rates, and convenient industrial scaling-up (Bridgwater 2012; Guedes et al.
2018). The reactor is the central workhorse of a biomass pyrolysis process, which
contributes a small proportion of the capital cost of the pyrolysis system (less than
15%). The choice of pyrolysis reactor is guided by several parameters such as the
size of the installation, physicochemical properties of the feedstock, and the use of
the products.
Fluidized bed has a two-phase medium consisting of a dense phase, which is a
gas-particle emulsion, and a phase constituted by the gas bubbles passing through
the emulsion. In this type of reactor, the solid fuel is fluidized by introducing air at
high speed into a bed of inert materials (sand, olivine, etc.). The bed material plays
an important role in improving heat transfer rates. Moreover, fluidization is only
possible with smaller sized particles (2–5 mm), which generally requires prior
grinding of the biomass (Bridgwater 2007; Bridgwater and Peacocke 2000). At the
initial stage of pyrolysis, condensed-phase compounds (short-lived intermediates)
are formed within the short residence time in the fluidized bed reactor. Many com-
plex reactions could occur in this intermediate condensed-phase step, and subse-
quently result in the formation of solid char and volatile vapors. Char is separated
from the volatile matter using separating methods like cyclone separator. The vola-
tile products after being condensed at the later step form the bio-oil. If the vapor
phase temperature is more than 400 °C, it is desirable to quench rapidly to obtain the
maximum bio-oil yield.
Two main types of fluidized reactors are widely used for biomass pyrolysis such
as the bubbling bed and circulating beds. In a fluidized bed-type reactor, an inert gas
with high flow rate is used to fluidize the sand, providing a good particle mixing
with excellent heat transfer. Heat can be transferred to the biomass particles by cir-
culating hot gas around the reactor or by injecting hot inert gas through the reactor
(Bridgwater 2007). Bubbling fluidized bed is the most popular design for biomass
pyrolysis. Circulating fluidized beds also have the similar design to bubbling fluid-
ized bed reactors. However, the gas flow rate in circulating fluidized beds is inten-
tionally set high to carry all the particles out of the reactor compared to bubbling
fluidized beds where the bed material remains suspended in the reactor (Treedet and
Suntivarakorn 2018). The bed material is separated by gas cyclones, reheated in a
combustion chamber, and returned to the bottom of the pyrolyzer.
Recently, many researchers have studied the pyrolysis process using fluidized bed
reactors with different types of biomass feedstock (Eri et al. 2017; Park et al. 2019;
Suntivarakorn et al. 2018; Upadhyay et al. 2018). These researches aim to investigate
the effects of different parameters such as the biomass particle size, temperature,
residence time, and flow rate of fluidizing medium. Bubbling fluidized bed reactors
are mostly applied in those studies. In a study on the effect of fluidized bed materials
in the tulip tree pyrolysis using a bubbling fluidized bed-type reactor, Ly et al. (2019)
reported that the highest yield of bio-oil reached 49 wt% at 450 °C with nitrogen as
the fluidizing medium and silica sand as the fluidizing bed material. The bio-oil yield
reached 45 wt% at 400 °C using dolomite catalyst. Treedet and Suntivarakorn (2018)
developed a system that was able to produce highest bio-oil yield of 78.1 wt% at
480 °C. The particle size effect in the fluidized bed reactor has also been reported
(Septien et al. 2012; Shen et al. 2009). Shen et al. (2009) concluded that when the
average size of biomass particle was greater, the bio-oil yield was lower at the bed
temperature of 500 °C. It is generally accepted that to observe high biomass heating
rates, small particle sizes should be used.
Industrial developments in bubbling fluidized beds have been chosen by several
companies, including Dynamotive, which currently has units with a production
capacity range from 450 kg/h up to 250 tons/day (Pattiya 2018). Figure 14.3 pres-
ents the RTI pilot process, which can process 200–250 tons/day of biomass in
Guelph, Ontario, Canada, developed by Dynamotive Energy Systems (Radlein and
Quignard 2013). The advantage of this process is that it achieves high bio-oils yields
(72% for hardwoods and 65% for grasses). Many research units have also been
developed by Union Fenosa (Jendoubi 2011), Dynamotive, and Wellman (Radlein
and Quignard 2013). Some processes fail to scale up due to their low bio-oil yield,
low particle mixing, heat transfer rates, and design complexities (Pinheiro 2008).
The pretreatment of biomass to reduce oxygen content in bio-oil is carried out at
laboratory scales. Co-processing of bio-oil in fluid catalytic cracking unit (FCC) has
been used in some refineries. Pinho et al. (2015) demonstrated that most of the oxy-
gen in bio-oil was removed as water through the catalytic cracking, and the rest of
oxygen was accumulated in liquid product as phenolic compounds. Bio-oil could be
co-fed directly into a regular gasoil FCC feed up to 20 wt% without utilizing any
type of hydrodeoxygenation (HDO). Both cases partially upgraded bio-oil and raw
bio-oil with high oxygen content (50 wt%), and the co-processing would also be
feasible. Furthermore, through 14C isotopic analysis, Pinho et al. (2017) detected the
presence of renewable carbon in gasoline and diesel cuts, clearly demonstrating that
renewable carbon is not only transformed into coke, CO, and CO2 but also to refin-
ing liquid products with higher value. The carbon efficiency (conversion of carbon
to liquid products) was computed approximately to 30%, more than the values
found in literature (15–20%).
Fig. 14.3 One of the world’s largest industrial-scale fast pyrolysis plant with a biomass input of
200 ton/day by Dynamotive Energy Systems located at Guelph, Ontario, Canada, and schematic
representation of the RTI pilot process (Pattiya 2018)
Some issues must be considered when co-processing bio-oil in FCC unit:
1. To inject separately the fossil stream and the bio-oil at different reactor heights
into the reactor.
2. To prevent corrosion of the materials used for feed lines and bio-oil storage in
the FCC unit due to high acidity of the bio-oil.
3. The alkaline metals present in the bio-oil could destroy the structure and deac-
tivate the zeolite in the FCC catalyst. Therefore, higher make-up rates might
have to be utilized to ensure FCC equilibrium catalyst activity.
14.6 he Role of Molecular Modeling in Investigating

T
Biomass Pyrolysis
Several studies on the biomass pyrolysis mechanism have been performed in the last
decade. The state-of-the-art knowledge gained for the pyrolysis of lignocellulosic
biomass has been well reviewed in terms of experimental and kinetic modeling (Shen
et al. 2015; Wang et al. 2017). This section concerns an updated review of the most
recent molecular modeling works using quantum chemistry tool. Quantum chemistry
approaches offer a brilliant alternative way in providing insightful understanding into
the chemistry of reactions occurring in the fast pyrolysis at the micro- and molecular-
scale levels (Arora et al. 2018; Trinh et al. 2012, 2016, 2017; Varghese et al. 2016).
Since cellulose has a high polymerization structure, it is crucial to choose appro-
priate surrogate compounds for the modeling to study the mechanism of pyrolysis
process using quantum chemistry. Glucose is chosen as a basic monomer unit of
cellulose, and it has been popularly used for several mechanistic studies of glucose
pyrolysis. Seshadri and Westmoreland (2012) developed elementary-reaction path-
ways, i.e., β-d-glucopyranose using the theory level of UB3LYP/6–311++G(d,p). In
this work, different reactions pathways for the glucose ring-opening and reforma-
tion, retro-aldol condensation, ring contraction, tautomerization transformation
between keto-enol structures, and dehydration were evaluated.
Mayes et al. (2014) investigated the conversion of glucose in fast pyrolysis at
500 °C to 5-hydroxymethylfurfural using theoretical calculations based on density
functional theory (DFT) with the implementation of M06-2X/6-311+G(2df,p) the-
ory details. Moreover, this work also evaluated the role of the unimolecular glucose
dehydration and the transformation of levoglucosan to the pyranose and furanose
structures. Furthermore, the use of β-d-glucopyranose (the close ring structure) as
the model compound for cellulose pyrolysis was studied by Zhang et al. (2014) in
employing DFT simulations at theory level of B3LYP/6-31G(d,p). The reaction
pathways generated hydroxyacetaldehyde and acetol at around 126.8 °C and 1 atm
conditions. Hu et al. (2018) found that both mannose and glucose have the same
transformation pathways to produce 5-hydroxymethylfurfural and furfural and
some key intermediates such as d-fructose and 3-deoxy-glucosone.
Although several works have chosen glucose as model compound representative
of cellulose, this choice has serious limit concerning the fact that glycosidic bonds
are not presented in glucose (Mettler et al. 2012). Besides, the yields of the pyrolytic
products in glucose and their distribution are considerably different from those of
cellulose. Therefore, cellobiose and cellotriose are found more suitable to be used
as surrogate models in theoretical and modeling studies of cellulose fast pyrolysis.
Zhang et al. (2015) employed cellobiose as a cellulose model compound to investi-
gate the pyrolysis mechanism at a temperature range of 24.5–826.8 °C and use the
theory level of M06-2X/6-31+G(d,p). Several primary products of the depolymer-
ization reactions such as 5-hydroxymethylfurfural, hydroxyacetaldehyde, and levo-
glucosan were recognized. Furthermore, proton (H+) played a crucial role in
facilitating the glucosidic bonds cracking with the feasible reaction barrier of
146 kJ/mol at operation conditions of biomass pyrolysis.
Lu et al. (2018) performed fast pyrolysis of cellulose at 500 °C by DFT simula-
tions at the theory level of M06-2X/6-31+G(d,p) using surrogate model compounds
of both cellobiose and cellotriose. The first decomposition tends to produce impor-
tant characteristic chain ends such as levoglucosan end, acyclic d-glucose end,
reducing and nonreducing ends, unsaturated ends, and dehydrated units. In the sec-
ond decomposition, these two types of model compounds showed different behav-
ior in the final product formation. The authors also showed that levoglucosan is the
main product formed from all three basic units of cellulose. Ascopyrone P and
1-hydroxyl-3,6-dioxabicyclo-octan-2-one are noncompetitive products and rely to
the unsaturated end of cellulose. The acyclic d-glucose end consists in key compo-
nent for the formation of 5-hydroxymethyl furan, furfural, and hydroxyacetalde-
hyde. The dehydrated unit tends to form a certain amount of hydroxyacetaldehyde.
It is worthy to note that polymerization degree has significant influences on the
pyrolytic product distribution. The larger the polymerization degree, greater is the
amount of levoglucosan formed. The reason behind this is that the interior units
enhance the levoglucosan formation. This provides a way to control the selectivity
for the pyrolysis process to make specific products (Lu et al. 2018).
Lignocellulosic biomass usually contains from 15 to 35 wt% hemicelluloses (or
polyoses). These heteropolysaccharides present in the hemicellulose are more com-
plicated in structure than cellulose. The monosaccharide unit includes mainly pen-
toses (5-member aldoses such as xylose and arabinose) and hexoses (5-member
aldoses such as mannose, glucose, and galactose) and other saccharides with lower
content like fucose and rhamnose (Huang et al. 2016). There has been fewer studies
on hemicellulose pyrolysis modeling at the molecular level compared to cellulose.
Xylose is widely been chosen as a model compound for hemicellulose for mecha-
nistic investigation of pyrolysis.
Huang et al. (2016) studied the pyrolysis of xylose using DFT calculations at the
theory level of M06-2X/6-31++G(d,p). The authors found three major reaction
pathways among eight studied pathways. The first pathway consisted of the conver-
sion of xylose to acrylic containing carbonyl isomer, which could be able to process
via the ring-opening reaction with a reaction barrier of 189 kJ/mol. In the second
reaction route, xylose can be decomposed to generate ethanol with a much higher
barrier of 300 kJ/mol. Finally, in the third proposed pathway, xylose is activated via
the dehydration between the hydroxyl group attached to carbon C4 and the hydrogen
atom coordinated to carbon C5, forming the product anhydroxylopyranose with

computed reaction barrier energy of 295 kJ/mol. Overall, it is observed that the ring-
opening reaction is the most favored to initiate the pyrolysis of xylose.
Lu et al. (2016) employed B3LYP/6-31+G(d,p) DFT simulations to explore fast
pyrolysis mechanism for the formation of hydroxyacetaldehyde from β-d-
mannopyranose, β-d-glucopyranose, O-acetyl-β-d-xylopyranose, and β-d-
xylopyranose. The authors found that along with the pyrolysis of β-d-glucopyranose
compound, hydroxyacetaldehyde is essentially derived from different possible posi-
tions such as C3–C4, C1–C2, and C5–C6, which are initiated by the dissociation of
C–Oring bond characterized by transition state activation barrier of 178 kJ/mol.
Furthermore, the breaking of C2–C3 bond forming 1,2-ethenediol could be pro-
cessed via the retro-aldol reaction, and subsequently undergoes the tautomerization
into the hydroxyacetaldehyde with high selectivity from C1–C2. The β-d-
mannopyranose and β-d-xylopyranose have similar reaction mechanism with the
first studied component. The O-acetyl-β-d-xylopyranose has different behavior
compared to the other three compounds, in which it is shown that the hydroxyacet-
aldehyde is mainly obtained from C4–C5 positions, which is processed together with
the scission of the acetyl branch producing acetic acid (Lu et al. 2016).
Lignin is characterized by more complicated structures than the cellulose and
hemicellulose. The polymerization of three main structures of monolignols includ-
ing sinapyl alcohol, coniferyl, and p-coumaryl results in the formation of three cor-
responding structures of lignin units, i.e., syringyl lignin, guaiacyl, and p-hydroxyl
phenyl. These units are characterized with the interlinkages such as α-O-4, β-O-4,
β-1, and 5-5. Among those largest dominate interlinkages, β-O-4 and α-O-4 bonds
are presented with the highest proportions, and their contributions in the total link-
ages in lignin is 48–60% and 6–8%, respectively (Huang and He 2015).
Huang et al. (2014) employed DFT simulations at B3LYP/6-31G(d,p) details to
theoretically evaluate the pyrolysis of lignin containing the β-O-4 linkages using the
dimer structure of 1-phenyl-2-phenoxy-1,3-propanediol as a model compound.
They reported that the Cβ–O bond homolytic cleavage reaction was the most domi-
nating pathway with the lowest reaction barrier equal to 245 kJ/mol, whereas the
one of Cα–Cβ bond has the second lowest reaction barrier, i.e., 259 kJ/mol. Huang
and He (2015) investigated α-O-4 linkage dimer model pyrolysis employing the
theory level of B3LYP/6-31G(d,p) in their DFT simulations. The authors found that
the hemolytic Cα–O bond dissociation reaction (reaction barrier of 177 kJ/mol) was
the most preferred reaction pathway, whereas the O–CH3 bond homolytic cleavage
reaction (reaction barrier of 228 kJ/mol) and the one of Cα–Cβ bond (reaction barrier
of 267 kJ/mol) were less favorable being the weaker competitive routes in pyrolysis
mechanism of the studied model compound.
It is evident that the quantum chemistry modeling still occurs as an important
parameter allowing understanding the complicated reaction schemes of lignocellulosic
biomass at the molecular level. Although an enormous number of quantum chemistry
studies have been contributed to the biomass pyrolysis mechanism, there are still sev-
eral challenges. Many attempts can be made for predicting the preponderance of
Table 14.2 Different catalytic processes for bio-oil upgrading

Methods Catalyst References
Hydrogenation Ru/TiO2 Wang et al. (2016)
Ru/Fe3O4-SiO2 Cherkasov et al. (2017)
Hydrodeoxygenation • Metal sulfides (supported Mortensen et al. (2011), Si et al.
Co-MoS2 and Ni-MoS) (2017)
• Nobble metal catalyst
(supported Pd, Pt, Rh, Ru)
• Nonnoble metal catalysts
(supported Fe, Ni, Co, and W)
Catalytic cracking Zeolite (HZSM-5, HY, Adjaye and Bakhshi (1995a),
H-Mordenite, Silicalite, Adjaye and Bakhshi (1995b), Liao
SAPO-5, SAPO-11, MgAPO-36, et al. (2014), Mortensen et al.
etc.) (2011)
Catalytic Ion exchanged resin (732, NKC) Wang et al. (2010)
esterification Zeolite (medium-pore ZSM-5, Milina et al. (2014)
Faujasite)
Sulfated ZrO2–TiO2 Liu et al. (2015)
Catalytic steam Ni-Co/ and Ni-Cr/ Garcia et al. (2000)
reforming MgO-La2O3-α-Al2O3
Ni/Al2O3 Bimbela et al. (2013), Galdámez
et al. (2005)
Ni/MgO Wu and Liu (2011)
Supported Ni, Ru, or Rh Trane et al. (2012)
catalysts
Ni-Co/MgO Mei et al. (2016)
Ni/zeolite L, Ni/CeO2-zeolite L Bizkarra et al. (2019)
Ni/Al2O3, Ni/ZrO2, and Ni/MgO Santamaria et al. (2019)
reaction pathways, which form the representative oxygenated compounds from fast
pyrolysis and the possible interactions between these pathways.
14.7 Catalytic Bio-oil Upgrading
The quality and stability of crude bio-oil can be improved by removal of oxygen con-
tent that is present with high concentration. Several methods such as hydrogenation,
hydrodeoxygenation, catalytic cracking, esterification, emulsification, and steam
reforming have been extensively studied for the upgrading of bio-oil (Table 14.2).
After the catalytic upgrading, the properties and quality of bio-oil can be signifi-
cantly modified. In summary, each method of catalytic upgrading has its own advan-
tages and disadvantages that could be described as below:
1. Hydrogenation of unsaturated compounds and hydrodeoxygenation of oxygen-

rich organic compounds require a high pressure of hydrogen, special catalysts,
complex facilities, and high cost of the operation.
2. Catalytic cracking using a solid acid catalyst with high mechanical and thermal
stability such as zeolites converts oxygen-organic compounds to CO, CO2, H2O
and a hydrocarbon-rich high-grade liquid fuel. The catalyst for the catalytic
upgrading of bio-oils can have the following characteristics: (a) proper attrition
strength; (b) good chemical stability to be used in high temperature and corro-
sive environment; and (c) suitable mesoporosity of zeolite crystals to allow the
bio-oil molecules to access the catalytic acid sites located inside the pore and
permit the products to diffuse back out of the zeolite crystals.
3. The catalytic esterification can be used to neutralize bio-oil with high content
of carboxylic acids by alcohols (such as ethanol or methanol) and acid catalyst
in reactive distillation (Xiu and Shahbazi 2012). By adding these polar sol-
vents, the viscosity of the bio-oil also decreases that leads to better miscibility
with diesel fuel and higher volatility and heating value. Catalytic esterification
is also one of the most appropriate methods for the upgrading of bio-oil because
of the simplicity of the method and the low cost of alcohols.
4. Catalytic steam reforming of bio-oil recently is also an important upgrading
technology for converting into hydrogen. However, some oxygenated com-
pounds such as phenol cannot be completely converted. Carbon deposition on
nickel-supported catalysts, high reaction temperature that lead to the loss of
catalyst, and reactor corrosion are some disadvantages of this method.
5. The emulsification is used to produce homogeneous and stable fuel obtained
from bio-oil and diesel, which can be burned in existing engines. This a simple
method, but the obtained fuel can cause the corrosion of the injector nozzle
because of the presence of acidic compound.
Mortensen et al. (2011) and Tran et al. (2014) reported that the deoxygenation of
bio-oil by hydrodeoxygenation and catalytic cracking might be the most prospec-
tive options due to its economically feasible. Bio-oil can be upgraded either by cata-
lytic cracking over zeolite catalysts (oxygen removed as CO2 and water) at
atmospheric pressures and high temperatures (300–600 °C) (Cheng and Huber
2011; Jae et al. 2011; Mukarakate et al. 2014). This can also be done through cata-
lytic hydrodeoxygenation over metal catalysts (oxygen removed as water) like Ru,
Pt, Pd, Ni, Cu, Co, etc. in the presence of H2 (Nolte and Shanks 2017; Vispute and
Huber 2009; Vispute et al. 2010; Wildschut et al. 2009).
The changes in bio-oil properties before and after catalytic upgrading via hydrode-
oxygenation and zeolite cracking processes are presented in Table 14.3. Although the
quality of bio-oil can be improved, the catalytic cracking still suffers from a poor
quality of the upgraded bio-oil with O/C ratios higher than 0.6 and significant coke
formation due to the cleavage of C–C bonds. Due to the similarity between hydrode-
oxygenation and conventional hydrotreating and hydrodesulfurization processes used
in petroleum refineries, Mo-sulfide catalysts promoted with Co and Ni have been the
most widely used hydrodeoxygenation catalysts. However, the sulfided catalysts suf-
fer from rapid deactivation and require sulfur in the feed streams for activation, which
could lead to bio-oil product contamination. Catalytic hydrodeoxygenation produces
high H/C ratios with low oxygen content but requires high hydrogen pressures. Due
Table 14.3 The properties of bio-oil before and after catalytic upgrading (Mortensen et al. 2011)
Bio-oil Hydrodeoxygenation Zeolite cracking Crude oil
Upgraded bio-oil
Yoil (wt%) 100 21–65 12–28 –
YWaterphase (wt%) – 13–49 24–28 –
YGas (wt%) – 3–15 6–13 –
YCarbon (wt%) – 4–26 26–39 –
Oil characteristics
Water (wt%) 15–30 1.5 – 0.1
pH 2.8–3.8 5.8 – –
ρ (kg/L) 1.05–1.25 1.2 – 0.86
μ50°C (cP) 40–100 1–5 – 180
Higher heating value (MJ/ 16–19 42–45 21–36 44
kg)
C (wt%) 55–65 85–89 61–79 83–86
O (wt%) 28–40 <5 13–24 <1
H (wt%) 5–7 10–14 2–8 11–14
S (wt%) <0.05 <0.005 – <4
N (wt%) <0.4 – – <1
Ash (wt%) <0.2 – – 0.1
Atomic H/C 0.9–1.5 1.3–2.0 0.3–1.8 1.5–2.0
Atomic O/C 0.3–0.5 <0.1 0.1–0.3 0
to the limitations of the catalytic cracking process, most of the researches on catalyst
development have focused on the hydrodeoxygenation process.
A few other novel process is also being developed recently. A new method for
bio-oil upgrading using methane as a cheaper reductant instead of hydrogen for the
deoxygenation of guaiacol, a model compound in the lignin thermal degradation, on
Pt/C and Pt-Bi/C catalyst has been reported (Varma and Xiao 2017, 2018). In these
studies, Bi-promoter is used to prevent the coking or carbon deposition on the Pt/C
catalyst. However, there is still a long way of developing these processes to be com-
mercially applicable.
14.8 echanistic Study and State-of-the Art Computational

M
DFT Approach in Catalyst Design for Bio-oil Upgrading
One of the most challenging issue in upgrading of bio-oil is to design and develop
better catalysts, which can achieve the dual tasks. For example, the catalyst needs to
be efficient in decreasing the oxygen content and in the meantime being able to
facilitate the production of drop-in liquid fuels for blending as additives into conven-
tional gasoline fuels or directly utilizing as transportation fuels. The catalyst should
thus selectively break C–O bonds while preserving C–C bonds to form olefins/isoal-
kanes, which are some excellent fuel additives for gasoline. A good hydrodeoxygen-
ation catalyst needs to have appropriate surface oxophilicity (to facilitate C–O bond
cleavage) and moderate hydrogenation capability (to achieve selective hydrogena-

tion) of the bio-oil derivatives to desired target products. Thus, hydrodeoxygenation
catalyst design requires an in-depth understanding of the metal–adsorbate interac-
tion. Bimetallic catalysts having dual functionalities or addition of promotors to
single metal catalysts can alter the electronic structure and properties and act as pos-
sible candidates for hydrodeoxygenation catalysis. Additionally, an insightful under-
standing on the underlying reaction chemistry is essential for rational catalyst design
and predicting product distributions and their corresponding selectivity.
The advent of supercomputers over the last decade has seen a significant improve-
ment in the computing technology. This has resulted in the advancement of tech-
niques and development of tools for understanding the chemical reaction at the
micro-level, i.e., at atomistic scales. A computational tool like density functional
theory (DFT) has been useful in establishing the electronic structure of catalyst sur-
faces and also in predicting reaction mechanisms, energetics, and chemical reactivity
for different reactions on these model catalyst surfaces (Mondal et al. 2016; Nandula
et al. 2015; Nihei et al. 2018; Sarkar et al. 2019; Singuru et al. 2016; Trinh et al.
2012, 2013, 2017, 2018; Varghese et al. 2016; Yang et al. 2015). The theoretical
insights gained from numerous computational studies are highlighted in this section,
which have thrown light on our understanding of the chemical reaction kinetics,
metal–adsorbate interactions, and developed structure activity relationships for the
catalytic hydrodeoxygenation of bio-oil derived from pyrolysis processes.
Although several experimental works on the catalytic upgradation of bio-oil have
been reported, very few have focused on understanding the underlying mechanisms
using theoretical tools. As discussed in the earlier sections, the bio-oil derived from
biomass pyrolysis is a complex mixture of aldehydes, ketones, furanic, and phenolic
compounds. The major challenge in developing metal–adsorbate interactions and
detailed reaction mechanism for bio-oil upgradation on a catalyst surface is the
choice of model compound, which could provide an accurate representation of the
real bio-oil. Model compounds like furfural, guaiacol, phenol, acetone, propanol,
p-cresol, m-cresol, ethanol, etc. have been widely used as representative compounds
in evaluating the hydrodeoxygenation on different metal surfaces (Chiu et al. 2014;
Gu et al. 2016; Mironenko and Vlachos 2016; Shi et al. 2015; Sitthisa et al. 2011b;
Vorotnikov et al. 2012; Wan et al. 2018). Among these, furfural and guaiacol have
gained the most attention due to the abundance of furanic and phenolic compounds
observed in the pyrolysis-derived bio-oil. Although model compounds may not give
a true representation of the hydrodeoxygenation of bio-oil, the insights gained could
be useful for predicting catalyst behavior of actual bio-oil. The difference in activity
of different metals toward hydrodeoxygenation can be broadly attributed to two fac-
tors, such as (a) nature of the metal–adsorbate interaction, i.e., orientation of adsorp-
tion and strength of adsorption, and (b) properties of the catalyst active site and
energetics of the hydrodeoxygenation mechanism.
Multiple theoretical investigations have examined the adsorption of bio-oil
model compounds on the transition metal surfaces. The most stable adsorption
configuration of bio-oil surrogate model compound on the catalyst is also one
of the important factor that control the selectivity/activity of the catalyst
(Banerjee and Mushrif 2018; Trinh et al. 2013, 2015, 2016, 2017). The DFT
studies have shown that furfural adopts two different adsorption configurations
such as (a) it is adsorbed on Cu surfaces via the O of the carbonyl group in a
η1(–O) structure (Shi et al. 2015; Sitthisa et al. 2011c), and (b) a η2(–C–O)
orientation, i.e., adsorption via both the ring and the carbonyl group favored on
Mo2C, Ni, Pt, Pd, and Ru surfaces (Banerjee and Mushrif 2017, 2018; Sitthisa
et al. 2011a, b; Vorotnikov et al. 2012).
A comparison of the furfural binding energies computed over different metal
surfaces in literature suggests that the strength of furfural adsorption follows the
trend, Mo2C(001) > Ru(001) > Ni(111) > Pd(111) ~ Pt(111) > Cu(111), correlating
to the corresponding activities of the catalysts. The η1(–O) orientation of adsorption
coupled with a low binding strength makes ring activation difficult on the Cu sur-
faces. In an opposite trend, the calculated furfural binding energy in the η2(–C–O)
configuration is a combination of the metal–ring and metal–carbonyl interaction
and the dominant interaction between the two is estimated from the furan binding
energies, which acts as a descriptor for metal–ring binding strength. The nature of
the binding interaction can give a rough estimation of the observed product distribu-
tions. For example, the strong metal–ring and the metal–carbonyl interaction on the
Ru surface would facilitate ring opened and C–O scission products, while the strong
interaction of the carbonyl group on the Mo2C surface results in very facile C–O
scission barrier leading to high methylfuran selectivity.
The catalyst activity and selectivity toward desired products can be further tuned
by the use of bimetallic catalysts, which either alter the adsorption strength (or sur-
face oxophilicity) or modify the orientation of adsorption (Jain et al. 2018; Sitthisa
et al. 2011a, b; Trinh et al. 2012; Wan et al. 2018). For example, the incorporation
of an oxophilic metal like Fe in Ni catalysts was found to stabilize furfural binding
on the NiFe surface, via a strong Fe–O interaction (Sitthisa et al. 2011a). The car-
bonyl C–O of furfural was elongated in the presence of Fe, which facilitated C–O
bond scission to form methylfuran and suppressed the decarbonylation of furfural to
furan. Theoretical studies have also shown the doping of boron onto Ni surfaces to
form a corrugated structure, which enhanced the furfural binding energies by
0.66 eV (Banerjee and Mushrif 2018; Trinh et al. 2016, 2017).
A lowering of furan yields and increase in furfuryl alcohol yields was observed
on Cu-modified Pd catalysts (Sitthisa et al. 2011b). The presence of Cu destabilized
the η2(–C–O) bonded furfural relative to the pure Pd surface, resulting in a decrease
in stability of the acyl species, which is an intermediate for furan formation. Jalid
et al. (2017) utilized a microkinetic modeling-based approach to determine the
activity toward C–O cleavage for ethanol on a stepped (211) surface of different
transition metals using carbon- and oxygen-binding energies as the descriptors. The
catalysts such as Ru, Rh, and Ni had high C- and O-binding energies and were
found to selectively produce methane via C–C cleavage, while Co, Ir, and Ni were
found to be ideal for C–O cleavage with high TOF for ethane. The abovementioned
studies show that adding suitable secondary adatoms to the monometallic catalyst
surface could modify the metal–adsorbate interaction to achieve desired products.
The principle of using bimetallic catalysts can be extended for replacing expensive
monometallic catalysts like Ru, which are highly active for hydrodeoxygenation of
bio-oil with cheaper catalyst formulations having similar metal–adsorbate interac-
tions to achieve desired product selectivity. However, metal–adsorbate interactions
may not be the only descriptor for catalyst reactivity, and the energetics of the reac-
tion on these modified surfaces need to be explored fully, to comprehend the cata-
lyst activity and selectivity.
Mechanistic investigations detailing the systematic progress from the reactant to
the product are required to explain the multiple product distributions that are
observed experimentally. Such an analysis would also be required for the design of
new, novel catalysts which can selectively produce the desired target products
(Trinh et al. 2012, 2017). The ability of computational tools like DFT in elucidating
the reaction mechanism and its energetics has led to numerous insights into catalyst
design and development. The reaction mechanism of model compounds like guaia-
col, furfural, and phenol has been studied on several different metal surfaces to
understand the activation behavior on the different surfaces.
The different bond-breaking or bond-forming pathways involved in the hydrode-
oxygenation of furfural include C–O cleavage, C–H cleavage, C–O hydrogenation,
C–C cleavage, Caryl hydrogenation, and Caryl–O cleavage as is illustrated in Fig. 14.4.
On Pd(111) surfaces, furfural hydrogenation to furfuryl alcohol proceeds via hydro-
genation of the O end of the carbonyl atom, with a highest barrier of 0.8 eV. On the
Fig. 14.4 Possible furfural activation pathways and possible products. Abbreviations: Methylfuran
MF, furfuryl alcohol FA, tetrahydrofurfuryl alcohol THFA, tetrahydrofuran THF, tetrahydrofurfu-
ral THFu, methyltetrahydrofuran MTHF (Banerjee and Mushrif 2017)
other hand, furfural decomposition to furan proceeds via C–H cleavage followed by
C–C cleavage with a highest barrier of 0.95 eV (Vorotnikov et al. 2012). CHx–O
(x = 0–2) scission of the carbonyl group had high activation barriers, thus making
methylfuran formation kinetically unfavorable on Pd surfaces. The effect of surface
H coverage and operating conditions on the reactivity of furfural was also explored
with DFT calculations (Wang et al. 2015). Furfural-binding configuration changes
from a flat to a “tilted” configuration with effective hydrogenation and decarbonyl-
ation barriers of 0.78 and 0.63 eV, respectively. This results in a reversal of the main
product selectivity from furan (at low H coverage limit at low H2 pressures) to fur-
furyl alcohol (at high H coverage limit at high H2 pressures).
Cai et al. (2015) investigated the structure sensitivity of furfural activation on dif-
ferent sites of Pt, including flat terrace site and under-coordinated site such as step and
corner sites. Both furfuryl alcohol and furan formation proceeded via a similar path-
way as that on Pd surfaces. Furfuryl alcohol formation was kinetically favored on the
terrace sites, i.e., Pt(111) surfaces with a highest barrier of 0.34 eV, while furan forma-
tion dominated at the corner sites (Pt55 cluster) with a highest barrier of 1.18 eV. On
Cu(111) surfaces, hydrogenation of the carbonyl group proceeds via the C atom first,
followed by the O atom to form furfuryl alcohol (Shi et al. 2015). However, CH2–O
scission (and subsequent hydrogenation to methylfuran) and hydrogenation to furfu-
ryl alcohol were found to have competitive barriers of 1.18 and 1.17 eV, respectively.
The experimentally observed furfuryl alcohol yields were attributed to the high H
coverage present on the Cu surfaces, which could favor furfuryl alcohol formation and
hinder methylfuran formation. The C–O scission always proceeded after hydrogena-
tion of the carbonyl group, and the direct scission of the carbonyl C–O was kinetically
limited on all the studied metal surfaces. All the above computational studies focused
on the formation of selected products like furan, methylfuran, and furfuryl alcohol and
did not provide a complete reaction pathway detailing all the possible products of
furfural activation (see Fig. 14.4). Such a reaction pathway analysis is especially use-
ful for developing micro-kinetic models, which evaluate surface coverages of the
intermediates and predict product selectivity.
The first detailed mechanistic studies for the activation of furfural on transition
metal Ni(111) and Ru(001) surfaces were performed recently in which the reaction
pathways resulting in the formation of different products like furfuryl alcohol, tet-
rahydrofurfuryl alcohol, furan, tetrahydrofuran, methylfuran, methyltetrahydrofu-
ran, diols, and alkanes were evaluated (Banerjee and Mushrif 2017, 2018). Nickel
catalysts show a strong product selectivity dependence with temperature. At lower
temperature, furans and furfuryl alcohol were obtained as the dominant products,
while higher temperatures favored furan and ring opened products. Banerjee and
Mushrif (2018) explained this unique behavior to be due to the surface H coverage
on Ni at different temperatures. At low temperatures, the adsorption of H on the Ni
surface is spontaneous, and therefore, a high surface H coverage is proposed, which
favors furfuryl alcohol formation and hinders ring activation.
At the certain high level of reaction temperature, the spontaneous adsorption of
H is no longer occurred, resulting in low H coverages, which favor furfural ring
opening and furan formation. On Ru surfaces, ring opening via a Cring–O cleavage
was found to be very facile with a barrier of only 0.66 eV making it the kinetically
favored first activation pathway for furfural (Banerjee and Mushrif 2017). The ring
opened moiety then undergoes successive C–O scissions (with barriers between 0.4
and 0.7 eV) and subsequent hydrogenations to form saturated alkanes as the domi-
nant products, in agreement with experimental observations. Except Ru, none of the
catalyst surfaces studied were successful in removing all the O-atoms from furfural.
The excellent capability of Ru toward hydrodeoxygenation of bio-oil as observed
via experiments was thus explained by the mechanistic studies.
Besides furfural, the reaction mechanism for hydrodeoxygenation of guaiacol,
m-cresol, p-cresol, and phenol has also been studied on Pt, Ru, and NiFe surfaces
(Chiu et al. 2014; Gu et al. 2016; Nelson et al. 2015; Shetty et al. 2017). The vapor
phase hydrodeoxygenation of guaiacol at low hydrogen pressures of ~1 bar leads to
phenol and catechol on Pt and phenol formation on Ru catalysts. On Ru, guaiacol
activation involves the step-wise dehydrogenation of the methoxy group followed
by a Calkyl–O and then Caryl–O cleavage to form phenol. Prior to the Caryl–O scission,
the catecholate radical (15 in Fig. 14.5) can either undergo hydrogenation at the O
end (to 14 followed by hydrogenation to catechol) or undergo a Caryl–O scission (to
17 followed by hydrogenation to phenol), with comparable activation barriers of 99
and 106 kJ/mol. However, the low reverse barriers in the former suggest (14) to be
an unstable species, which would dehydrogenate back to (15). As a result, catechol
formation is kinetically and thermodynamically less favored on the Ru surfaces.
Lee et al. (2015) studied guaiacol activation on Pt surfaces and proposed a similar
pathway as that on Ru surfaces to form a catecholate radical. However, hydrogenation
of this radical was kinetically favored with a barrier of only 0.29 eV relative to the
Caryl–O cleavage, which had a barrier of over 2 eV. Thus, catechol formation was
favored on the Pt surfaces. The phenol observed during hydrodeoxygenation of guaia-
col on Pt was proposed to form via a dehydroxygenation of catechol molecule on the
acidic Al2O3 sites of the Pt/alumina interface. Thus, hydrodeoxygenation of guaiacol
proceeded via a dehydrogenation of the methoxy group followed by Caryl–OH scission
on Pt and Ru surfaces and not by a direct demethoxylation or demethylation step.
A similar reaction mechanism has also been proposed for hydrodeoxygenation
of anisole on Pt, Ru, and Fe surfaces (Tan et al. 2017). Interestingly, mechanistic
studies on the hydrodeoxygenation of p-cresol to toluene on Pt surfaces revealed the
hydrodeoxygenation to proceed via 3–4 ring hydrogenations followed by a Caryl–
OH scission (Gu et al. 2016). Hydrogenation of the ring was found to lower the
Caryl–OH scission barriers. The hydrogenated complex then underwent a dehydroge-
nation step to form toluene as the dominant product. The importance of theoretical
calculations in understanding the mechanism for hydrodeoxygenation is further
highlighted as molecules with similar binding adsorbate geometries (p-cresol and
guaiacol here) behave differently on the same metal surface leading to different
product distributions.
Most of the above reaction pathway studies were evaluated for monometallic
catalyst surfaces, resulting in at least two dominant products (except for Cu). As
suggested earlier, the role of catalysts would be to produce the desired product/
products with high selectivity. In case of hydrodeoxygenation of bio-oil, the target
Fig. 14.5 Reaction network of hydrodeoxygenation of guaiacol on Ru(001) surface (Chiu

et al. 2014)
compounds include olefins, isoalkanes, etc. that can be easily blended with existing
transportation fuels. This can be achieved by using bimetallic catalysts, which can
either alter the electronic structure or affect the energetics of the reaction mecha-
nism (Le et al. 2016; Nguyen et al. 2014; Trinh et al. 2012).
A recent computational study explored the influence of doping boron onto Ni
surfaces to the product distribution (Banerjee and Mushrif 2018; Trinh et al. 2016).
On boron doped Ni surfaces, the barrier for furan formation decreased by ~0.6 eV,
relative to the Ni surface (Fig. 14.6a). The authors proposed that this enhanced
Fig. 14.6 Reaction energetics for (a) hydrodeoxygenation of furfural to furan on Ni and boron-
doped Ni surfaces (Banerjee and Mushrif 2018), and (b) hydrodeoxygenation of phenol to benzene
on NiMoP, FeMoP, and RuMoP (Jain et al. 2018)
catalytic activity could facilitate furan formation at lower reaction temperatures. A

combined theoretical and experimental study evaluated the activity of bimetallic
phosphides like FeMoP, RuMoP, and NiMoP for the hydrodeoxygenation of phenol
(Jain et al. 2018).
Three reaction pathways were proposed to explain the benzene and cyclohexane/
cyclohexene formation on FeMoP and NiMoP/RuMoP surfaces, respectively. The
direct deoxygenation pathway (DDO) proceeds via an attack of surface H with the
phenolic OH to form Ph-OH2, followed by a Caryl–OH2 bond cleavage in a concerted
step, while hydrogenolysis (RH-DO) and dehydration (RH-DEHYD) proceeded via
ring hydrogenation to form a saturated ring followed by C–O hydrogenolysis or
dehydration. The experimentally observed high benzene selectivity on FeMoP sur-
faces is due to the significantly low Caryl–O cleavage barriers (0.37 eV via DDO) and
high ring hydrogenation barriers (>1 eV via RH-DO) on the FeMoP surfaces mak-
ing DDO the dominant pathway to form benzene (Fig. 14.6b). On NiMoP and
RuMoP surfaces, ring hydrogenation is very facile with barriers <0.3 eV, suggesting
the RH-DO/RH-DEHYD pathways to cyclohexane/cyclohexene to be the dominant
pathways. Similar mechanistic studies on other bimetallic systems proposed in lit-
erature are presently lacking and need to be evaluated for a better understanding of
the underlying chemistry. Such reaction mechanism analysis can help propose sec-
ondary metals/adatoms, which may either suppress the formation of side reactions
or enhance the activity of the primary metal toward a route/pathway leading to
highly selective desired products.
In summary, this section highlights the importance of theoretical calculations for
understanding the catalyst reactivity on different metal surfaces. With the help of
numerous examples, an attempt is made to emphasize the importance of evaluation
of the metal–adsorbate interactions and mechanism and energetics of the reaction to
understand the underlying chemistry for a rational design of catalysts. Computational
studies for hydrodeoxygenation have, however, been largely limited to studies on
stable facets of monometallic systems. Under reaction conditions, catalysts have
defects and kink sites, which are likely higher active for the hydrodeoxygenation
reaction. In addition, a high hydrogen surface coverage is expected to be presented
on the catalyst surface under hydrodeoxygenation conditions. However, only a few
studies have evaluated the influence of H coverage to the reaction mechanism
(Banerjee and Mushrif 2018; Wang et al. 2015).
The development of novel catalysts would require a close collaboration between
computational scientists and experimentalists. In situ experimental studies can iden-
tify the nature of the actual active phase along with the dominant surface species
under reaction conditions and will help the computational scientists to model “real-
istic” catalyst surfaces under dynamic conditions. Such collaborations would help
in developing structure–activity relationships for different metal facets for multime-
tallic catalyst systems.
14.9 ignocellulosic Biomass Pretreatment and Reactions

L
Promoted by Ultrasound
Recently, the scientific community has been faced with major scientific hurdles in
the manufacturing of atom efficient chemical products from renewable bioresources
in the drive toward a sustainable economy. As a result, breakthrough technologies
can efficiently convert biomass to useful chemicals and fuels. In this section, the
utilization of low- and high-intensity ultrasound reactors for biomass conversions
will be reviewed and discussed. The advantages and disadvantages of employing
this unconventional activation technique in biomass conversions will also be dis-
cussed with its potential and prospects.
Many breakthrough technologies capable of efficiently circulating renewable
carbon-containing resources are an urgent task to produce atom efficient bio-based
commodities. However, due to the low thermal conductivity of biomass materials
that generates a barrier for mass and heat transfers, the conversion of concentrated
feeds of biomass remains a significant scientific challenge (Yunus et al. 2010; Zhao
et al. 2007). The use of ultrasound energy could provide an environment with unique
physicochemical properties to process the conversion of crude biomass feedstock.
Owing to the high corrosion and energy impact provided by the high-intensity ultra-
sound, biomass conversion coupling with ultrasound techniques can offer many
advantages such as easier fractionation, pretreatment, and the chemical conversion
of biomass materials. This could be facilitated under profoundly mild operation
conditions to eventually enhance the catalytic activity and reaction efficiency (He
et al. 2017; Shi et al. 2013).
The improvement of heat and mass transfer reactions is often observed during
ultrasound applications in biomass conversions (Moholkar et al. 2004). In heteroge-
neous catalytic systems, the enhancement in substrate–catalyst contact and accel-
eration in reaction rate and kinetics are also observed (Amaniampong et al. 2018c;
Suslick and Price 1999). Recent advances in the application of ultrasound for bio-
mass conversions have focused on the sono-assisted lignocellulosic pretreatment,
sonochemistry of carbohydrate compounds, extraction of natural products for phar-
maceutical applications (Baxi and Pandit 2012), transesterification and esterifica-
tion of fatty acids (Amaniampong et al. 2018c), and fermentation and pretreatment
of organic wastes (Shirsath et al. 2012). Despite this crucial advancement in the
application of unconventional activation techniques for biomass conversions, criti-
cal assessment of the reactions and pretreatments of biomass assisted by ultrasound
techniques to produce value-added chemicals and biofuels are required. This sec-
tion focuses on the judicious application of ultrasound for biomass conversions.
When ultrasound energy is applied to lignocellulosic biomass, the structural
integrity of the biomass material is greatly compromised via depolymerization of
the recalcitrant crystalline strong hydrogen bonding in the lignocellulosic network.
Biomass particle size attrition and reduction is greatly enhanced under ultrasonic
applications, leading to the ease of further conversions to other platform commodi-
ties. The application of high-intensity ultrasound with an average power rate of
3.0–10 W/mL to cellulosic materials can result in crushing of the particles and
crystalline grains of the biomass materials having particle size from micro to even
nano-ranges (Chen et al. 2011; Filson and Dawson-Andoh 2009). More interest-
ingly, Pinjari and Pandit (2010) also reported the success on the formation of nano-
fibrils from the milling of natural cellulose via hydrodynamic and ultrasound
cavitation. They observed that the particle size of the cellulosic grains was finally
reduced to 301 nm from the initial size of 1360 nm after hydrodynamic cavitation
under the process of 110-min sonication at the rate of 3.0 W/mL.
Sonication is also being used to obtain interesting results in the fractionation of
crude biomass and in the extraction of value-added compounds from raw biomass
such as polysaccharides and phenolic compounds (Filson and Dawson-Andoh
2009). The high-speed microjets and shockwaves generated from the ultrasonic
cavitation have great impacts in loosing and destroying the chemical linkages in the
lignocellulosic structure (Ashokkumar 2011). Amaniampong et al. (2017) reported
the successful conversion of glucose, a bio-derived substrate to glucuronic acid with
excellent yields (94%). This work was an important step in the production of rare
platform chemicals via the application of unconventional activation techniques. In
another work, Amaniampong et al. (2018a) investigated the glycosylation of con-
centrated feed of carbohydrates in alcoholic media. They reported an interesting
pyrolysis-like mechanism occurring at the gas–liquid interface, leading to the for-
mation of levoglucosan as intermediate for the oligomerization of carbohydrates.
Karnjanakom et al. (2015) reported a highest yield value of 80.3% for the hydro-
carbon formation via the upgrading of bio-oil obtained from ultrasound pretreated
cedar wood with 2.5 wt% Zn/Al2O3. A maximum bio-oil yield of 56 wt% was
obtained over ultrasound pretreated cedar wood as compared to 45 wt% bio-oil
from untreated cedar wood. Shi et al. (2013) utilized ultrasound as a pretreatment
tool which resulted in an enhanced efficiency of bio-oil formation from pure cellu-
lose liquefaction in hot-compressed water. Their results showed that the yield
(42 wt%) of bio-oil was significantly increased using the ultrasonic pretreatment. In
fact, emulsification and the mixing of bio-oil derived from lignocellulosic biomass
via fast pyrolysis process with diesel fuel forms emulsified oil faster and easier
under ultrasonic conditions, and this mixture fuel can be directly employed in exist-
ing engines (Li et al. 2010). This is because of improved phase contacts and mass
transfer effects.
Ultrasound intensification demonstrated beneficial and integrated applications in
biorefinery systems including the reactions and pretreatment of lignocellulosic
materials and other biomass-related reactions and pretreatment, such as preemulsi-
fication of bio-oil to prepare input materials for catalytic upgrading, liquefaction of
lignocellulosic biomass to crude bio-oil, and selective oxidation of biomass-related
substrates (oxygenates hydrocarbons such as sugars). Nonetheless, the utilization of
ultrasound in biomass conversions faces significant challenges that need to be inves-
tigated and addressed. The correct choice of ultrasound parameters and skillful use
of the reactor is desired to maximize energy output during its utilization. A proper
choice of solvent compatible to sonochemical reactions regarding biomass conver-
sions is crucial. The integration of ultrasound energy into biomass conversion and
downstream treatment has a bright and promising future, although further and dedi-
cated research studies are required.
14.10 Conclusions
This chapter demonstrated the biomass fast pyrolysis as a very promising alterna-
tive way to produce cleaner and sustainable fuel and reduce the reliance on fuel
from fossil resources. The liquid product obtained from the fast pyrolysis of bio-
mass, called bio-oil, should undergo catalytic upgrading before it can be used for
transportation purposes. Several methods to upgrade bio-oil are described along
with their corresponding advantages and disadvantages. One of the most widely
applied and most extensively studied approach for the catalytic upgrading of bio-oil
is the hydrodeoxygenation in which the oxygen-containing functional groups are
removed and replaced by hydrogen atoms. However, for this purpose of selectively
activating and breaking the C–O bonds while trying to maintain the C–C bonds
intact, processing knowledge base of petroleum industry may not be utilized for
hydrodeoxygenation of bio-oil, and therefore novel catalysts, solvents, and pro-
cesses need to be developed.
The importance of utilizing insights gained from theoretical calculations for a coher-
ent catalysts design with desirable properties such as high selectivity and activity for the
hydrodeoxygenation of bio-oil has been highlighted. The development of low-cost and
nonprecious metal catalysts, which selectively cleave the C–O bonds while preserving
the C–C bonds at low hydrogen pressures, could remain the major challenge for bio-oil
upgradation. Using DFT calculations, suitable descriptors like bond lengths, adsorbate
binding energies, etc. can be established for understanding chemical reactivity on differ-
ent catalyst surfaces. Such descriptors can be useful for proposing new multimetallic
catalyst systems and predicting their activity and/or selectivity toward hydrodeoxygen-
ation of bio-oil.
The catalyst activity can be enhanced by the addition of dopants/promotors to the
existing catalysts. Predicting the behavior of these doped catalyst systems could,
however, require an in-depth understanding of the energetics and mechanism of
hydrodeoxygenation of bio-oil. In addition, most of the catalytic activity is attrib-
uted to the presence of defect sites on the catalysts surface. A detailed in situ char-
acterization study of the catalyst under working conditions could help to model the
real catalytic surface under realistic surface coverages and accurately predict prod-
uct selectivity. Future work should also focus on improving our understanding of
hydrodeoxygenation by incorporating the effect of reaction conditions on the reac-
tivity at the molecular level. Finally, the application of sonochemical technique in
combination with catalyst design could make breakthrough developments in the
catalytic upgrading of bio-oil.
Acknowledgments Q.T. Trinh acknowledges the financial support by the National Research
Foundation (NRF), Prime Minister’s Office, Singapore, under its Campus for Research Excellence
and Technological Enterprise (CREATE) program. K.B. Ansari acknowledges the financial sup-
port from the Ministry of Singapore under the Academic Research Fund (AcRF) Tier-2 and
Nanyang Technological University (NTU) for its research facility. D.Q. Dao thanks the funding
from the Vietnam National Foundation for Science and Technology Development (NAFOSTED)
under the grant number 103.03-2018.366. P.N. Amaniampong and A. Drif are grateful to the
CNRS, the Ministry of Research and the Région Aquitaine-Limousin-Poitou-Charentes for their
financial support. The funding from the International Consortium on Eco-conception and
Renewable Resources (FR CNRS INCREASE 3707) and the Chair “TECHNOGREEN” is also
acknowledged.
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Heterogeneous Catalysis
in Hydroxymethylfurfural Conversion 15
to Fuels and Chemicals
Chanatip Samart, Thi Tuong Vi Tran,

Suwadee Kongparakul, Surachai Karnjanakom,
and Prasert Reubroycharoen
Abstract
Hydroxymethylfurfural is an important intermediate compound to produce
biomass-based fine chemicals. The conventional organic reactions including
oxidation, hydrogenation, reduction, and condensation can be used to transform
hydroxymethylfurfural to different intermediates of fine chemicals where
heterogeneous catalysts play significant roles. Furandicarboxylic acid,
2,5-dihydroxymethylfuran, 2,5-furandicarboxyamide, and 5-(hydroxymethyl)
furfurylamine are a few important value-added products obtained through oxi-
dation, selective hydrogenation, oxidative amidation, and reductive amination
of hydroxymethylfurfural, respectively. In addition, hydroxymethylfurfural is
a precursor to synthesize monomers of polyester and polyurethane.
Keywords
Hydroxymethylfurfural · Heterogeneous catalysis · Biomass · Fine chemicals ·
Biofuels
C. Samart (*) · S. Kongparakul

Department of Chemistry, Faculty of Science and Technology, Thammasat University,
Bioenergy and Biochemical Refinery Technology Program, Faculty of Science and
Technology, Thammasat University, Pathumthani, Thailand
T. T. V. Tran
Department of Chemistry, Faculty of Science and Technology, Thammasat University,
S. Karnjanakom
Department of Chemistry, Rangsit University, Pathumthani, Thailand
P. Reubroycharoen
Department of Chemical Technology, Chulalongkorn University, Bangkok, Thailand

356 C. Samart et al.
15.1 Introduction
Conventional fuels and petrochemical products are mostly derived from fossil
resources, which are on a verge of depletion. In addition, massive greenhouse gas emis-
sions and environmental pollution are also associated with their utilization. Accordingly,
the use of sustainable green chemistry approach has been considered for the design of
environmentally benign processes. Green carbon science was introduced to the chemi-
cal industries related with carbon processing, utilization, and recycling, including the
fuel and petrochemical industries (He et al. 2013). Waste plant biomass is an interesting
carbon source based on its renewable resource that consists mainly of the three differ-
ent components such as cellulose, hemicellulose, and lignin. Cellulose, a macromole-
cule of glucose units, is the main component of lignocellulosic biomass.
Glucose is mainly used as a building block for biomass-derived chemicals in
biorefinery process. On the other hand, hydroxymethylfurfural (HMF) and levulinic
acid (LA) are the key compounds in the biomass-based chemical platforms that can
be derived through the dehydration of glucose (Kucherov et al. 2018). To convert
glucose to chemical intermediates, resins, polymers, solvents, fuels, and other
value-added products, it is important to discover several catalytic thermochemical
and biochemical pathways. Many studies on HMF utilization have been published,
including fuel synthesis, chemicals, and polymers, while several organic reactions
related with HMF conversion have been presented in Fig. 15.1.
15.2 onversion of Hydroxymethylfurfural to Biofuels

C
and Fine Chemicals
Lignocellulosic biomass can be divided into the two groups of woody and agricul-
tural biomass, both differing in their chemical and structural composition (Nanda
et al. 2018). The non-woody biomass such as agricultural crop residues have gained
the most attention in HMF production due to the economic consideration of their
abundance and low cost. The cellulose content in agricultural biomass is in the
range of 30–50 wt%, in which the total annual cellulose availability is recently esti-
mated at over 700 million ton (Tye et al. 2016).
HMF is derived from lignocellulose biomass through a three-step mechanism, as
shown in Fig. 15.2, which includes (a) hydrolysis of cellulose to glucose, (b) isomeri-
zation of glucose to fructose, and (c) dehydration of fructose or glucose to HMF (Li
et al. 2019). Many catalytic systems can produce HMF with yields up to 70%. The
ionic liquid, especially metal halide system, uses Lewis acid catalysts for the dehydra-
tion of glucose to HMF, which can be performed under mild conditions. In such sys-
tems, higher HMF yields are generally achieved compared to autocatalytic systems,
which suffer from low HMF yield due to the formation of by-products such as levu-
linic acid and formic acid. This catalytic system was initially developed to increase the
HMF yield with a biphasic aqueous and organic mixture system where the reaction
takes place in an aqueous phase. The HMF product is later dissolved in the organic
layer resulting in a shift in the chemical equilibrium forward to produce more HMF
with yields approaching 79–81% (Binder and Raines 2009).
15
Fuel Solvent
C7 - C15 Alkanes
- -
Spice, cosmetic
Other (pharmaceutical,
pesticide, fungicide)
Heterogeneous Catalysis in Hydroxymethylfurfural Conversion to Fuels…
Chemical intermediates Resin, polymer
Fig. 15.1 Value-added derivatives and compounds from hydroxymethylfurfural

357
Hydrolysis Isomerization
Cellulose Glucose Fructose
Hydrolysis
HMF Levulinic acid

and so on
Fig. 15.2 Mechanism of hydroxymethylfurfural synthesis from cellulose
Various types of acids such as hydrochloric acid (HCl), sulfuric acid (H2SO4),
phosphoric acid (H3PO4), and formic acid (HCOOH) are applied in the conversion
of biomass into HMF in aqueous solutions. However, large amounts of corrosive
acidic wastes are produced from such processes, which require proper waste han-
dling and recycling technologies. Since the biphasic aqueous and organic mixture
are homogenous catalytic systems, the product separation, purification, and recov-
ery of acids are costly and challenging. Therefore, heterogeneous catalytic systems
using acid catalyst are interesting according to their ease of separation and recovery
process. Moreover, the heterogeneous catalysts can overcome the difficulty in the
recycling of homogeneous catalysts including the decrease in the amount of acidic
wastes from the processes.
Mesoporous materials such as Al-KCC-1 and acid-functionalized SBA-15 have
also been used to improve the HMF selectivity (>90%) (Shahangi et al. 2018; Wang
et al. 2019). Although highly efficient, HMF production rate is reported to be only
13% of the total world oil demand. Nevertheless, a less efficient but much faster
reaction could overcome this limitation (Perez et al. 2019). Therefore, HMF synthe-
sis still presents the highest potential and is already being applied in biomass-based
chemical industries.
15.3 Conversion of Hydroxymethylfurfural Through

Oxidation Reactions
Oxidation reaction is a technique for HMF transformation that results in the produc-
tion of dicarboxylic acids such as 2,5-furandicarboxylic (FDCA), which is formed
through the selective oxidation of HMF as shown in Eq. (15.1). The FDCA is then
used as a new precursor of bio-based polymers including polyethylene
2,5-furandicarboxylate (PEF), which possesses physical, mechanical, and thermal
15 Heterogeneous Catalysis in Hydroxymethylfurfural Conversion to Fuels… 359
properties superior to polyethylene terephthalate (PET) and acts as a potential

material for PET replacement in plastic industry. PEF is synthesized by the polym-
erization of the dimethyl ester of FDCA and ethylene glycol (EG), as shown in Eq.
(15.2). From an economic consideration, copper-based catalysts are used for the
oxidation of HMF. However, 2,5-diformylfuran (DFF) is the main product from
such reactions (Kucherov et al. 2018). A palladium-gold (Pd-Au) catalyst was intro-
duced for the oxidation of HMF to FDCA and achieved nearly 90% yield. The
synergistic interaction of the bimetallic catalyst played an important effect on HMF
oxidation activity (Xia et al. 2019).
(15.1)
(15.2)
(15.3)
For Au-based catalysts, the catalyst support also presented a significant effect on the
activity and selectivity in HMF conversion to FDCA due to the interaction between the
Au-based catalyst and catalyst support (Albonetti et al. 2015). Moreover, the morphol-
ogy of the catalyst support affected the growth of Au nanoparticles during the reaction
condition. The Au nanoparticles grew from 2.4 to 10.1 nm on the surface of Aerosil
(silica) (Masoud et al. 2018). Even though the precise metal catalyst can achieve high
yield and selectivity of HMF conversion to FDCA, researchers have tried to develop
low-cost catalysts such as copper or manganese with efficient catalytic properties
according to the economic concern. For example, the oxidation pair of CuCl/tertiary-
butanoic acid gave 50% yield of FDCA (Hansen et al. 2013), while the FDCA yield
was improved up to 98.6% by the use of needlelike CuO/Al2O3 fibers. The conversion
pathway of HMF to FDCA was through the oxidation of aldehyde and alcohol func-
tional groups present in HMF to DFF and 5-hydroxymethyl-2-furandicarboxylic acid
(HMFCA), respectively, as shown in Eq. (15.3) (Tirsoaga et al. 2018; Zhou et al. 2019).
On the other hand, the oxides of manganese acted as highly selective catalysts for
DFF formation with 97% selectivity (Chen et al. 2019; Tong et al. 2017). DFF can be
used as a substrate for various compounds in pharmaceuticals and as an antifungal
agent (Kucherov et al. 2018). The combination of Mn with Co as bimetallic catalyst
can convert HMF via oxidation to provide 71% yield of FDCA (Liu and Zhang 2016).
Among heterogeneous catalyst systems, to achieve an efficient PEF production, the
limitation of catalyst dispersion in the mixture is observed, which results in low pro-
ductivity and high energy consumption during the process (Kucherov et al. 2017).
To overcome the limitation of catalyst dispersion, an efficient shortcut route for
PEF synthesis from HMF-acetal with 1,3-propanediol (PD-HMF), which is stable
in concentrated aqueous solution (10–20 wt%), has been studied in an aerobic

oxidation system. The homogeneous and heterogeneous catalysts (e.g., PdCoBi/C
catalysts and CeO2-supported Au catalyst) have been used for anaerobic oxidative
esterification of HMF and HMF-cyclic acetal for FDCA synthesis (Kim et al. 2018;
Li et al. 2018a). A one-pot reaction system by aerobic oxidative esterification from
PD-HMF with methanol and ethylene glycol can be successfully converted to
methyl furan-2,5-dicarboxylate (MFDC) and bis(2-hydroxyethyl)furan-2,5-
dicarboxylate (HEFDC), which can further undergo self-condensation for high-
quality PEF synthesis.
15.4 Conversion of Hydroxymethylfurfural Through

Photocatalytic and Electrochemical Oxidation
Reactions
In addition to thermal conversion, the oxidation of HMF can also be attained by

electrochemical and photocatalytic-assisted oxidations. The selective oxidation of
HMF to FDCA was performed in aqueous solution in the presence of a cobalt thio-
porphyrazine catalyst (CoPz) when radiated with simulated sunlight to attain a
96.1% yield. The proposed mechanism is shown in Fig. 15.3. The catalyst adsorbed
sunlight and produced 1O2, which is a powerful oxidant that can oxidize HMF to
FDCA (Xu et al. 2017). In the case of HMF oxidation to DFF, polymeric carbon
nitride-hydrogen peroxide adducts were highly selective for DFF formation with an
obtained yield of 40–50% in aqueous media and natural sunlight. The mechanism
of HMF oxidation to DFF is shown in Eqs. (15.4)–(15.8) (Ilkaeva et al. 2018a, b).
(15.4)
(15.5)
(15.6)
(15.7)
(15.8)
For a green chemistry approach, electrochemical oxidation appears to be a

promising technique for the conversion of HMF to FDCA, because it can be
performed at ambient temperature and avoids the use of hazardous chemicals.
The electrochemical cell consists of the two compartments of anode and cathode
sides. The oxidation of HMF is performed at the anode side, whereas the cathode
CoPz
h g- C3N4
1O
HMF 2
FDCA
3O
2
CoPz*
g- C3N4
Fig. 15.3 Mechanism of photocatalytic oxidation of hydroxymethylfurfural
side presents hydrogen evolution as shown in Fig. 15.4. The product distribution was
significantly affected by the applied potential and the surface composition of elec-
trode. The oxyhydroxide on the surface of nickel (Ni) and cobalt (Co) presented a
highly efficient oxidation of HMF to FDCA. The proposed mechanism was that
HMF was oxidized with NiOOH at the electrode during the open circuit, while
NiOOH was reduced to Ni(OH)2. The Ni(OH)2 was then regenerated by linear sweep
voltammetry to NiOOH. In the case of CoOOH, it approached the same mechanism
as NiOOH (Latsuzbaia et al. 2018; Taitt et al. 2019). The reaction pathway proceeded
through the formation of HMFCA intermediate before undergoing oxidation to
obtain FDCA (Gao et al. 2018).
The electrochemical oxidation of HMF could be combined with hydrogen produc-
tion unit because the reduction of water occurred to produce hydrogen while HMF
was oxidized (Cha and Choi 2015). In addition, a Cu-based electrode was introduced
in the oxidation of HMF, which did not catalyze water oxidation as a side reaction.
Therefore, the Cu-based electrode performed with a wide potential window to oxidize
HMF without the side effect of water oxidation (Nam et al. 2018). The electrochemi-
cal oxidation was performed in an alkaline media as the FDCA product can be sepa-
rated in an acidic condition. Accordingly, the separation cost needs to be considered
for any large-scale process. Manganese oxide (MnO) could oxidize HMF under a low
pH to overcome the problem of FDCA separation where the FDCA could be formed
and precipitated simultaneously in an acidic medium (Kubota and Choi 2018). The
oxidation of HMF proceeds to FDCA as a major product that has the potential to
replace conventional terephthalic acid in PET polymerization. The FDCA can be
formed through thermal catalytic, photocatalytic, and electrochemical oxidations.
Although thermochemical conversion is still a cost-effective technology, the photo-
catalytic and electrochemical conversion have the advantage of being energy efficient
or using less hazardous chemicals, respectively.
e- e-
- +
H2
H2
FDCA H2
H2
HMF , H2O
Co-P/CF Co-P/CF
Fig. 15.4 Mechanism of electrochemical oxidation of hydroxymethylfurfural
15.5 Selective Hydrogenation of Hydroxymethylfurfural
The selective hydrogenation of HMF to 2,5-dihydroxymethylfuran (DHMF) is an attrac-

tive and important chemical platform that can be further transformed to other derivatives
such as 1,2,6-hexanetriol for medicament and cosmetics, 1-hydroxyhexane-2,5-dione for
polymer and solvent, and 3-hydroxymethylcyclopentanone for the synthesis of fragrances,
pesticides, and polymers (Hu et al. 2017). In addition, DHMF can further reduce to diol
tetrahydrofurandimethanol (THFDM), which was possibly used as a bio-based monomer
for polyesters or polyurethanes as shown in Eq. (15.9).
The selective hydrogenation of HMF has been reported using both homogeneous
and heterogeneous catalytic process. The hydrogenation catalyst should have a high
selectivity to minimize the formation of undesired products. Since HMF molecule
consists of a furan ring containing both aldehyde (HC=O) and alcohol (–OH) func-
tional groups, the selection of metal catalyst and ligand is a key role for catalytic
cycle in homogeneous hydrogenation of HMF. The metal salts of Ru, Rh, Ir, Re, and
Ni have been used as hydrogenation catalysts coupled with various types of ligands
such as N-heterocyclic carbene (NHC) ligands, phosphorus-based ligands, and aux-
iliary ligands (Cadu et al. 2018). By tuning the parameters, Ru-based catalysts with
nitrogen-containing ligands have shown the most active and selectivity for HMF
conversion to DHMF. Carbene ligands offered moderate activity and selectivity
with a preference for unsaturated backbones (for selectivity) and for bulky aromatic
substitution pattern (for conversion). However, there is some limitation for upscal-
ing to industrial production due to high catalyst amount required.
Heterogeneous catalysts including Pt, Pd, Ru, Ni, and Ir can perform selective
hydrogenation of HMF to DHMF where the metal species and support characteristic
significantly affected the catalyst activity. The DHMF yield was in the range of
34–89.3% (Cai et al. 2014). A zirconia-based inorganic-organic coordination poly-
mer was introduced in the catalytic transfer-based hydrogenation of HMF to DHMF
with a high catalytic efficiency giving a DHMF yield of 94%. The reaction pathway
followed the Meerwein-Ponndorf-Verley reaction (Hu et al. 2018) as shown in Eq.
(15.9). Chen et al. (2015) reported on the development of Pd supported on amine-
functionalized metal-organic frameworks (MOFs), high surface area, tunable pore
sizes, and controllable structures for metal supports.
The presence of free amine (–NH2) moieties in the frameworks played a key role for
the formation of uniform and well-dispersed palladium nanoparticles on the support.
The maximum DHMF yield achieved up to 96% with a full conversion of HMF using
3 wt% Pd loading over MOF support and operated at a 30 °C in aqueous medium. The
recycling of the fine particle of heterogeneous catalyst eases to separate by filtration or
centrifugation. However, the catalyst needs to form the certain shape for industrial
application to prevent the loss of solid catalyst during the process. To overcome separa-
tion issues of homogeneous and heterogeneous catalysts, the use of magnetic catalysts
is one of an interesting concept, which efficiently removed catalyst from reaction mix-
tures by applying an external magnetic field (Liu and Zhang 2016). The catalytic reac-
tion could be selective to the type of metal loading over magnetic nanoparticles.
(15.9)
Several authors have reported on the conversion of HMF to DHMF or further

reduction to THFDM by operating at pressurized hydrogen system (28–350 bar)
operated at high temperatures more than 100 °C using various precious metal
catalysts. However, there is another opportunity to convert HMF to DHMF by elec-

trochemical reduction with no hydrogen required. The reaction occurs in the cath-
ode compartment as shown in Fig. 15.5, where the electrode is covered by HMF and
its reduction intermediate. The electron transfer for the reduction of the intermedi-
ate to DHMF is shown in Eq. (15.10). This gives a 100% DHMF selectivity and a
Faradic efficiency of 100% (Roylance et al. 2016).
(15.10)
15.6 xidative Amidation and Reductive Amination

O
of Hydroxymethylfurfural
HMF could serve as a versatile platform for producing various valuable chemi-
cals by the reaction with or formation of an amide. Nitrogen-containing com-
pounds including diamide are key intermediates of monomer synthesis and
pharmaceutics. Therefore, the production of biomass-based diamide has recently
gained more attention through the oxidative amidation of HMF, but the selectiv-
ity for the primary amide is still a challenge. The proposed mechanism of HMF
amidation is shown in Eq. (15.11). In this mechanism, the intermediate product
of 5-hydroxymethyl-2-furancarbonitrile is initially formed, which is then con-
verted to 2,5-dicyanofuran and 5-cyano-2-furancarboxamide, respectively, form-
ing 2,5-furandicarboxyamide.
e-
+
CB
e-
EF e-
EF
HMF
H+
O2/H2O hν
ν
h+
VB
Ag Cathode DHMF BiVO4-Photoanode
Fig. 15.5 Photo-electrochemical reduction of hydroxymethylfurfural (HMF) to

2,5-dihydroxymethylfuran (DHMF)
Alkali manganese oxide (α-MnO2/NaxMnO2) was introduced as a catalyst for

the oxidative amidation of HMF demonstrating nearly 85% yield of 2,5-dicyano-
furan. From a kinetic study, the hydration of 5-cyano-2-furancarboxamide was
found to be the controlling step (Li et al. 2017). The doping of cryptomelane with
different metals was investigated for the catalytic oxidative amidation of
HMF. Both the metal species and doping method played an important role on the
HMF amidation efficiency, and the yield of 2,5-dicyanofuran could be improved
up to 97% (Li et al. 2018b).
(15.11)
Nitrogen-containing carbon compounds were not only derived from the

o xidative amidation of HMF, but could also be prepared by reductive amination.
Here, the 5-(hydroxymethyl)furfurylamine (HMFA) product is a key compound in
pharmaceuticals and polymers synthesis. The reductive amination can generally be

performed with a precious metal catalyst (Pt and Pd) and excess liquid ammonia
following the reaction pathway shown in Eq. (15.12). The HMF was selectively
reacted with ammonia to an imine, and then the imine intermediate was converted
to HMFA through the reduction with hydrogen. However, nickel-based catalysts
have been reported to produce nearly the same HMFA yield as the precious metals
(Chen et al. 2018).
(15.12)
(15.13)
Equation (15.13) shows the direct reductive amination of 2,5-diformylfuran

(DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF). The presence of various
Ni-Raney catalysts has been previously reported (Le et al. 2015) where the acid-
treated Ni-Raney catalysts yielded 42.6% BAF in tetrahydrofuran/water mixture at
optimal reaction conditions. The electrochemical reductive amination is of interest
in the HMF conversion to amine derivatives of furan compounds because it requires
fewer chemicals in the system. Ethanolamine and water were used as the nitrogen
source and the reducing agent, respectively. The catalytic efficiency depends on the
electrode material and applied voltage. The electrical potential showed strong effect
on the desired product (Roylance and Choi 2016).
15.7 Polycondensation of Hydroxymethylfurfural
Polycondensation is the formation of complex esters via a condensation reaction

where small molecules such as water, alcohols, and hydrogen halides are eliminated
as the by-products. The polycondensation of HMF can be used to produce bio-based
polyesters and polyurethanes. Three different monomers have been prepared from
HMF such as 5,5′-bihydroxymethyl furil (BHMF), 5,5′-dihydroxymethyl furoin
(DHMFo), and bis[5-(hydroxymethyl)furan-2-yl)methyl]adipate (BHFA). These
monomers can be cross-linked to polyesters, linear polyesters, and poly(ester ure-
thane), which are insoluble fibers as shown in Eq. (15.14). The synthetic routes of
BHMF, DHMFo, and BHFA synthesis are presented in Eqs. (15.15) and (15.16),
where DHMF was synthesized by the self-condensation of HMF, while BHMF was
prepared by the selective oxidation of the sec-alcohol position in DHMFo to obtain
α-hydroxyketone. These monomers were then reacted with diacylchloride by a
polycondensation reaction to obtain the cross-linked polyester and linear polyester
as shown in Eqs. (15.17)–(15.19).
The BHFA could react with diisocyanates to produce polyurethane as shown
in Eq. (15.20) (Mou and Chen 2016). HMF is also a precursor of a bifunctional
furan monomer in the thermoplastics preparation. The degree of completion of

polycondensation and the mean length of the macromolecules are limited by the
equilibrium concentration of the reagents and reaction products (called as revers-
ible equilibrium polycondensation). Therefore, the polycondensation by-prod-
ucts must be removed to achieve an interesting chain length for its commercial
production.
(15.14)
(15.15)
(15.16)
(15.17)
(15.18)
(15.19)
(15.20)
15.8 Conclusions
Lignocellulosic biomass-based fine chemicals have gained in importance and

acceptance. The bio-based fine chemicals are expected to become a major industry
in the near future where HMF could serve as an important chemical platform. HMF
can be converted to a diverse range of chemicals through conventional organic
reactions. For example, FDCA formation, a monomer in the bio-based polymer, is
produced by the oxidation of HMF. The oxidation of HMF can be performed by
either thermochemical, photochemical, or electrochemical conversion. In addition,
DHMF, a precursor in pharmaceutics and cosmetics, can be obtained by the selec-
tive hydrogenation of HMF.
Electrochemical conversion can be applied for selective hydrogenation, while
the synthesis of nitrogen-containing compounds from biomass can be performed by
oxidative amidation and reductive amination where 2,5-furandicarboxyamide and
HMFA are key compounds obtained from the amidation and amination reactions,
respectively. However, HMF is not only a key intermediate of fine chemicals, but it
is also a monomer of bio-based polyester and polyurethane formed through poly-
condensation reactions. Therefore, the transformation of HMF via a catalytic system
in organic reactions to downstream products is an important area of research for the
next-generation of biomass-based fine chemical production.
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Conversion of Glycerol to Value-Added
Products 16
Parmila Devi and Ajay K. Dalai
Abstract
The dramatic increase in biodiesel production has increased the oversupply of glyc-
erol as a by-product. Low cost, ready availability, and surplus supply of glycerol is
a spectacular opportunity for chemical industry to utilize glycerol as feedstock for
production of high-value products. This chapter provides the information about dif-
ferent pathways available for conversion of glycerol into high specialty chemicals.
Various approaches and strategies have been developed by researchers to investigate
the effects of reaction parameters, i.e., nature and type of catalyst, reaction time,
temperature, pressure, and type of solvent, on glycerol conversion and product
selectivity. Based on the information provided in this chapter, researchers can select
a viable process for the conversion of waste glycerol into valuable commodities.
Keywords
Glycerol · Value-added products · Biodiesel · Esterification · Transesterification
16.1 Introduction
The increasing global energy demand, declining fossil fuel reserves, and associated
environmental concerns have stimulated the global interest in renewable sources of
energy. Biofuels and biomass are emerging as popular alternatives due to their vast
availability, nontoxic nature, and biodegradable properties. Biodiesel is convention-
ally produced from saponification and transesterification of vegetable oil (Ciriminna
P. Devi · A. K. Dalai (*)

Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon,
Saskatchewan, Canada

372 P. Devi and A. K. Dalai
et al. (2014) (Fig. 16.1)). In the saponification process, soap and glycerol are gener-
ated from hydrolysis of oil in presence of alkali salt. In the transesterification pro-
cess, methyl ester and glycerol are produced from reaction of triglycerides with
methanol or ethanol. Both of these processes concurrently generate large amounts
of glycerol (Gholami et al. 2014).
About 1 kg of glycerol is generated during the production of 10 kg of biodiesel
(Devi et al. 2018). In the last two decades, production of biodiesel has significantly
grown due to various governmental initiatives. Rapid development in the biodiesel
industry has led to the oversupply of crude glycerol in the market. The unavailabil-
ity of suitable method for the processing of crude glycerol has led to the drop in the
prices of crude glycerol. At the same time, the surplus amount of glycerol is gener-
ated as a by-product (Gholami et al. 2014; Devi et al. 2018). Owing to its limited
commercial applications, mainly in cosmetics, food, and pharmaceutical industries,
glycerol price dropped as low as $0.04–0.09/lb (Ciriminna et al. 2014). Therefore,
researchers across the globe are attempting to find ways to turn waste glycerol into
a profit.
Based on the predicted high growth rate of biodiesel production, it is expected
that the crude glycerol prices will further decline if the current market situation
continues. The economic feasibility of glycerol conversion to value-added product
is entirely dependent on the purity of glycerol, market price, and utility of the final
products. The current prices of pure glycerol are high compared to the crude glyc-
erol. Thus, the utilization of crude glycerol in glycerol catalytic conversion pro-
cesses is vital for attaining a sustainable and cost-effective production of products
with high market value. Given the high market value of chemicals obtained from
Fig. 16.1 Schematic process flow for the production of biodiesel

16 Conversion of Glycerol to Value-Added Products 373
Table 16.1 Current market prices of glycerol-based value-added products

Chemical Approximate Estimated US
Compound formula Chemical structure price ($/lbs) capacity (MMlbs)
Glycerol C3H8O3 0.04–0.5 251
Propionaldehyde C3H6O 0.5 401
Propionic acid C3H6O2 0.5–0.6 439
Glycidol C3H6O2 >$10,500 –
Allyl alcohol C3H6O 1.1 65
Acrylic acid C3H4O2 0.5–1.1 2779
Glycerol C4H6O4 406 –

carbonate
Solketal C6H12O3 – –
Tri-tert-butyl C15H32O3 – –
glycerol
catalytic conversion of glycerol, glycerol offers tremendous potential (Table 16.1).

Therefore, glycerol can be utilized as a feedstock for the manufacture of value-
added chemicals or products.
Until 2008, glycerol was mainly consumed in refined form in the chemical and
soap preparation industries. During 2009–2010, a sudden boom in biodiesel indus-
try resulted in an increased production of glycerol as by-product. The biodiesel
production market was at 37 billion gallons in 2016. Annually, the biodiesel market
is increasing by the growth of 42% indirectly generating about 4.1 billion gallons of
crude glycerol. Based on current market trends, the annual production of glycerol
will reach 41.9 billion liters by 2020 (Talebian-Kiakalaieh et al. 2018). The follow-
ing factors are triggering to the growth of global glycerol market:
1. Growth in food and beverage industries

2. Flourishing biodiesel industry
3. Optimistic approach of administrators toward environmentally friendly products
Crude glycerol is mainly used in animal feed, dust suppression, and deicing.
Recently, glycerol is reported to be used as an additive material and binder for bio-
mass pellets inducing hydrophobicity and heating value (Azargohar et al. 2019).
The chemical composition of crude glycerol obtained from biodiesel industry is
given in Table 16.2 (Ciriminna et al. 2014). Crude glycerol has substantial color
(yellow to dark brown), high salt and fatty acids, and high contents of toxic metha-
nol. Current technologies are not designed to use it directly and require expensive
refining for its further use.
Various researchers have developed processes for the transformation of glycerol
into marketable high-value chemicals/products using different approaches and
methodologies. In order to manage surplus glycerol glut and make biodiesel indus-
tries more cost-effective, it is necessary to convert glycerol into chemicals or value-
added products of higher price and larger market. In this chapter, several methods of
converting glycerol into value-added products are described, which include oxida-
tion, hydrogenolysis, dehydration, acetylation, etherification, esterification, polym-
erization, ammonification, chlorination, and carboxylation. The various intermediate
and final products during processing of glycerol using the abovementioned pro-
cesses are shown in Fig. 16.2.
16.2 Oxidation of Glycerol
Oxidation is a commonly used technique for the conversion of glycerol into dihy-
droxyacetone, hydroxypyruvic acid, formic acid, glycolic acid, etc. The glycerol oxi-
dation products have various applications in cosmetics, pharmaceutical, food,
detergents, dyeing, and chemical industries. Generally, heterogeneous noble metal
catalysts like Au-, Pt-, and Pd-based catalysts are used for the oxidation of glycerol.
Coupling of these catalysts with some green oxidant makes more sustainable system
for glycerol oxidation. Photocatalysts like TiO2, ZnO2, SiC, and CdS are another
most commonly used class of catalysts due to their low cost, high efficiency, and
nontoxic nature. Various researchers have investigated the effects of reaction condi-
tions and type of catalyst on glycerol conversion and product selectivity (Table 16.3).
Table 16.2 Typical compo- Components Typical composition (wt%)

sition of crude glycerol Glycerol 66–84
obtained from biodiesel
Methanol 24–38
industry
Ash 3–5
Water 0.9–3.1
Glycerides 0.4–2
Potassium ~0.2
FFAs 0.5–1
16 Conversion of Glycerol to Value-Added Products
Fig. 16.2 Various pathways for the transformation of glycerol into value-added chemicals and products
375
376
Table 16.3 Reaction conditions for the oxidation of glycerol to several by-products
Reaction parameters Selectivity (%)
Temperature Reaction Molar Catalyst Conversion
Catalyst (°C) time (h) ratio loading (%) DHA GLA LA TTA GCA FA OA References
Au-based 80 0.5 h 315 13.8 67.3 13.4 0.2 0.3 8.6 1.7 2.4 Yuan et al. (2015)
catalysts
Pt/CNTs 60 0.5 h 10 wt% 22 10.4 19.5 – 0.2 58.8 – 0.2 Ning et al. (2015)
Pt/O-CNTs 13 10.8 13.6 0.3 65.0 0.1
Pt/NCNTs 32 10.2 24.6 0.2 55.7 0.1
Pt/O-NCNTs 34 10.3 26.7 0.1 58.3 0.2
Ag/Al2O3 60 3h 4 0.5 g – 46.8 0 Skrzyńska et al. (2015)
Au/Al2O3 58.3 27.7
Pd/Al2O3 84.1 0.2
Pt/Al2O3 75.3 14.5
Abbreviations: dihydroxyacetone DHA, glyceric acid GLA, lactic acid LA, tartronic acid TTA, glycolic acid GCA, formic acid FA, oxalic acid OA, carbon nano-
tubes CNT
P. Devi and A. K. Dalai
It was found that the impurities present in crude glycerol could affect oxidation
process. Therefore, Skrzyńska et al. (2015) studied the synergetic and antagonistic
effects of various impurities (methanol, mineral salts, and organic sulfur deriva-
tives) on the oxidation process. Au catalysts show good activity in pure glycerol
oxidation, but the conversion rate was low for crude glycerol due to their sensitivity
toward mineral salts and organic sulfur derivatives. Pd was found to be the most
resistant toward methanol, mineral salts, and organic sulfur derivatives.
The effectiveness and efficiency of the catalyst can be changed by manipulating
the surface electronic properties, functionalities distribution, and deposition of
metal particles. Ning et al. (2015) studied the role of nitrogen and oxygen function-
ality of nitrogen-doped carbon nanotubes in oxidation of glycerol. It was found that
graphitic nitrogen interacts with Pt nanoparticles by electron transfer mechanism
and enhances the dispersion of Pt nanoparticles. However, the presence of oxygen-
containing groups reduces the donor–acceptor interaction.
Yuan et al. (2015) studied the oxidation of glycerol in the presence of Au-based
catalyst supported on MgO-Al2O3 materials using NaOH as the activation agent.
The acid–base property of the catalyst is reported to have strong effect on product
distribution depending on the molar ratio of Mg/Al in the catalyst. The high selec-
tivity of dihydroxyacetone was observed in acidic environment, while the selectiv-
ity of glyceric acid was found to be increased in basic environment. Similarly, other
researchers reported a significant catalytic activity (13–34%) of Pd/TiO2-, Pd-Ni/C-,
and Pd-Co/Au-based catalysts in alkaline solutions in comparison to methanol and
ethylene glycol (Su et al. 2009; Simoes et al. 2010; Rostami et al. 2015). Pd-Co/Au
catalyst was found very stable even after 200 cycles (Rostami et al. 2015).
16.3 Hydrogenolysis of Glycerol
1,2-Propanediol and ethylene glycol are the two major products produced from the
hydrogenolysis of glycerol. 1,2-Propanediol is prepared through selective hydroge-
nation of glycerol by the insertion of hydrogen molecule without attacking C–C
bond in glycerol. 1,2-Propanediol is mainly used in the production of pharmaceuti-
cal products, polymeric resins, cosmetic products, and paints. Previously, different
types of reaction schemes (gas or liquid phases) and pathways were reported for the
hydrogenation of glycerol to 1,2-propanediol. Casale and Gomez (1993) patented a
technique for hydrogenation of glycerol using copper and zinc catalysts in a tem-
perature range of 240–270 °C and at a pressure of 150 bar. The requirement of high
temperature and pressure conditions, low production efficiency, and low selectivity
to 1,2-propanediol limits the application of this method.
Several studies have been reported in the literature on usage of various transi-
tion metal catalysts such as Ni, Pt, Rh, Ru, Cu, and bimetallic systems (Pt-Ru).
Ruthenium has been reported as the most active catalyst for hydrogenation of
glycerol. The design of a bifunctional catalyst containing acidic/basic and metal
active sites is a crucial step for hydrogenation of glycerol to 1,2-propanediol.
Platinum catalysts with hydrotalcite and MgO as support exhibited good
conversion and higher 1,2-propanediol selectivity than Al2O3, H-ZSM5, and

H-beta (Yuan et al. 2010).
Hamzah et al. (2012) prepared a catalyst by the combination of Ru/TiO2 using
bentonite–TiO2 as the support. The activity of Ru/TiO2 catalyst was found to be
improved by the addition of bentonite due to proper dispersion of Ru particles on
catalyst surface that resulted in high activity of Ru/TiO2/bentonite for hydrogenoly-
sis of glycerol. The mechanism of hydrogenolysis of glycerol to 1,2-propanediol
depends on the reaction conditions (acidic/alkaline). In acidic conditions, hydroge-
nolysis of glycerol occurs in two steps, such as (a) dehydration of glycerol to acetol
and (b) hydrogenation of acetol to 1,2-propanediol (Alhanash et al. 2008; Furikado
et al. 2007; Miyazawa et al. 2007; Wang and Liu 2007). In alkaline conditions, the
reaction proceeds in three steps, such as (a) formation of glyceraldehyde from dehy-
drogenation of glycerol, (b) formation of 2-hydroxyacrolein from dehydration of
glyceraldehyde, and (c) formation of 1,2-propanediol from hydrogenation of
2-hydroxyacrolein (Feng et al. 2007, 2008; Maris and Davis 2007).
16.4 Dehydration of Glycerol
Acrolein is a key intermediate in the chemical synthesis industry and can be manufac-
tured from the dehydration of glycerol. The transformation of glycerol to acrolein is a
double dehydration reaction that proceeds via the formation of 3-hydroxypropional-
dehyde followed by 1-hydroxyacetone. Generally, liquid-phase dehydration and gas-
phase dehydration are used for the transformation of glycerol to acrolein. The poor
conversion of glycerol (15–25%) and low catalytic activity in the liquid-phase pro-
cesses limit its practical applications. Various studies have been reported on the appli-
cation of subcritical and supercritical conditions to improve the catalytic activity in
liquid-phase reactions. However, the application of severe reaction conditions during
subcritical and supercritical reactions leads to an increase in corrosiveness of the reac-
tor material and creates safety concerns (Ginjupalli et al. 2014; Dalil et al. 2015;
Alhanash et al. 2010). The gas-phase reactions are progressively used for the conver-
sion of glycerol to acrolein due to their high conversion efficiency (65–99%) and high
selectivity (Gholami et al. 2014).
Various solid acid catalysts including metal sulfates, metal oxides, metal phos-
phates, heteropolyacids (HPAs), and zeolites have been studied for gas-phase reac-
tions. The acid strength and textural properties of these catalysts determine their
efficiency and selectivity toward acrolein synthesis. Ginjupalli et al. (2014) found that
the catalytic activity in dehydration process was greatly affected by surface Lewis/
Brønsted acid sites of the catalysts. Lewis acid catalyst sites show high selectivity for
acetol due to the participation of –OH terminal of glycerol, while Brønsted acid sites
show higher selectivity for acrolein due to the participation of the secondary –OH
group of glycerol (Alhanash et al. 2010). Furthermore, strong acidity of the catalyst
promotes catalyst deactivation due to the deposition of carbonaceous species in its
micropores resulting in low activity on the catalyst surface (Ginjupalli et al. 2014).
The presence of oxygen promotes the formation of oxidation products like for-
mic acid, acetic acid, propionic acid, and carbon oxides (Dalil et al. 2015). The
reaction mechanism of glycerol dehydration in presence of WO3-TiO2 catalyst
involves various steps as shown in Fig. 16.3 such as:
1. Production of hydroxyacetone and 3-hydroxypropanal through loss of water

2. Formation of acrolein from dehydration of 3-hydroxypropanal
3. Retroaldol reaction of 3-hydroxypropanal leading to the production of formalde-
hyde and acetaldehyde
4. Formation of cyclic ethers from the reaction of formaldehyde with oxygen
16.5 Carboxylation of Glycerol
Carboxylation of glycerol produces glycerol carbonate and glycidol as the main

reaction product. Glycerol carbonate has various applications in chemical, pharma-
ceutical, agricultural, semiconductor, and cosmetic industry. The synthesis path-
ways and applications of glycerol carbonate are summarized in Fig. 16.4. It can be
produced from glycerol using direct and indirect pathways. Direct pathway involves
Fig. 16.3 Reaction mechanism for dehydration of glycerol using WO3-TiO2 catalyst
380
Fig. 16.4 Synthesis and applications of glycerol carbonate

carboxylation of glycerol using alkyl carbonates, urea, or CO2 as the carbonate

source, while indirect pathway includes glycerolysis, transesterification, and phos-
genation reaction.
Carboxylation of glycerol to glycerol carbonate using CO2 is carried out at ele-
vated temperature and pressure conditions in presence of catalyst (Aresta et al.
2006). The direct reaction of glycerol with urea is another method, but the require-
ment of strict reaction conditions (use of vacuum to evolve ammonia to start reac-
tion) and the production of side products (isocyanic acid and biuret) are the main
disadvantages associated with this process (Aresta et al. 2009). Many studies have
reported dimethyl carbonate as an alternative carboxylating agent (Table 16.4).
Carboxylation with dimethyl carbonate can be performed at milder conditions with-
out the production of problematic side products (Simanjuntak et al. 2011). The syn-
thesis of glycerol carbonate using indirect pathways like phosgenation and
transesterification is reported as the most industrially viable routes to achieve high
glycerol carbonate yield.
Several studies have reported the transformation of glycerol to glycerol carbon-
ate via transesterification using dialkyl carbonate (Kumar et al. 2012; Pan et al.
2012; Liu et al. 2013). A wide range of catalysts (homogeneous or heterogeneous
and acidic or alkaline) has been investigated for transesterification of glycerol.
Based on the literature, low catalytic activities for glycerol transesterification were
achieved using homogeneous and heterogeneous acidic catalysts due to the mass
transport limitations. On the other hand, homogeneous and heterogeneous basic
catalysts show high activity for transformation of glycerol to glycerol carbonate and
more than 90% glycerol carbonate yield. The main limitation of transesterification
process is the formation of glycidol due to decarboxylation of glycerol carbonate
(Devi et al. 2018; Algoufi et al. 2014). In addition, the maintenance of optimum
reaction conditions and design of suitable catalysts are the key parameters to achieve
high glycerol carbonate yield.
16.6 Acetylation of Glycerol
Acetylation of glycerol using acetic acid is gaining special attention due to the high
industrial importance of the final products. The products formed from glycerol acet-
ylation are monoacetylglycerol (monoacetin or MAG), diacetylglycerol (diacetin or
DAG), and triacetylglycerol (triacetin or TAG). Monoacetin is basically used in the
preparation of explosives, smokeless powder, and cosmetics. The mixture on mono-
acetin, diacetin, and triacetin can be used in printing inks, plasticizers, and softening
agents. Triacetin is of most industrial importance due to its application as an anti-
knock agent to improve the viscosity and cold flow properties of the biodiesel
(Khayoon et al. 2014). Additionally, triacetin meets the standards specification
(EN14214 and ASTM D6751) for flash point and oxidation stability, which makes
it product of high industrial importance (Gracia et al. 2009).
It is observed from the literature that strong acid catalysts perform best in acety-
lation of glycerol using acetic acid. Generally, the homogeneous catalysts like sul-
furic acid, hydrofluoric acid, or p-toluenesulfonic acid are used in acetylation
382
Table 16.4 Reaction conditions for conversion of glycerol to glycerol carbonate

Reaction parameters
Temperature Reaction time Molar Conversion
Catalyst (°C) (h) ratio Catalyst loading (%) Solvents References
Amberlyst 39 wet 75 1.5 5:1 6 wt% 6.2 DMC Ochoa-Gómez et al. (2009)
CaO 75 1.5 5:1 10 mol% 91.1
CaCO3 75 1.5 5:1 10 mol% 90.6
CaO 60 2 1:1 2 wt% 69 DMC Li and Wang (2011)
Calcium complex Ca(C3H7O3)2 60 3 2.5:1 8 mol% 95
CaO 75 0.5 2:1 3 wt% 90.2 – Simanjuntak et al. (2011)
Na2O 75 0.5 2:1 3 mol% 92.6
ZnO 75 0.5 2:1 0.5
MgO 75 3 2:1 10.2
CaO 35 1 2:1 0.5 wt% 81 EC Climent et al. (2010)
Al/Mg hydrotalcite 35 1 2:1 0.5 wt% 57 –
Al/Li hydrotalcite 35 1 2:1 0.5 wt% 85 –
Al/Ca hydrotalcite 35 1 2:1 0.5 wt% 87
K2CO3 73–75 3 3:1 4.5 wt% 97 DMC Rokicki et al. (2005)
Mg/Zr/Sr mixed oxides 90 1.5 5:1 0.1 wt% 94 Malyaadri et al. (2011)
Mg/Al/Zr mixed oxides 75 1.5 5:1 0.1 wt% 94
Mg/Al hydrotalcite 100 1 5:1 54 wt% 75 DMF Takagaki et al. (2010)
Mg/ 100 1.16 5:1 54 wt% 88 – Kumar et al. (2012)
Al hydrotalcite–hydromagnesium
Mg/Al hydrotalcite 100 2 3:1 10 wt% 65 – Liu et al. (2013)
Mg/Al hydrotalcite 130 8 21:1 2.16 g/g 84 DMSO Álvarez et al. (2012)
Zeolite (NaY) 70 4 3:1 54 wt% 77 DMF Pan et al. (2012)
KF/hydroxyapatite 78 0.83 2:1 3 wt% 99 – Bai et al. (2011)
K2CO3/MgO 80 2 2.5:1 1 wt% 99 – Du et al. (2012)
Abbreviations: dimethyl carbonate DMC, ethylene carbonate EC, dimethyl sulfoxide DMSO, dimethylformamide DMF
reactions (Kale et al. 2015). However, there are certain limitations associated with
the use of such catalysts due to their hazardous and corrosive properties. Recently,
many studies have reported the use of solid acid catalyst for acetylation of glycerol,
namely sulfated zirconia, sulfated activated carbon, sulfated mesoporous silica,
ionic liquids, heteropolyacids, and ion exchange resins (Table 16.5). However, cer-
tain limitations on the wide industrial application of these catalysts are related to the
functionalization of silicates catalysts, which is difficult and costly, and they have
low surface area, low thermal stability of zeolites and solubility of heteropolyacids
in polar media (Khayoon et al. 2014; Melero et al. 2007).
It is widely reported that acetylation of glycerol is an equilibrium reaction. In
addition, acetic acid is required in excess quantities to maximize the selectivity for
triacetin formation. Most of the studies reported low triacetin selectivity, and the
reaction mixture obtained from acetylation reaction contains all three types of ace-
tin (monoacetin, diacetin, and triacetin) (Melero et al. 2007; Zhu et al. 2013).
Rezayat and Ghaziaskar (2009) achieved 100% selectivity for triacetin using
Amberlyst-15 as the catalyst at very high glycerol-to-acetic acid molar ratio (1:24)
and 200 bar pressure. However, such high-pressure conditions with extremely high
molar ratio are not economically viable for industrial applications. On the contrary,
Liao et al. (2009) performed the acetylation in the presence of excess of glycerol (as
glycerol is a low-value product) using ion exchange resins as the catalysts. Several
authors worked on the hypothesis that equilibrium of the reaction shifts toward the
products by using an excess of glycerol, instead of an excess of acetic acid. Kale
et al. (2015) suggested that the addition of some external component (entrainer)
could be helpful to increase the selectivity of triacetin as the stoichiometric reaction
product. It was found that the removal of water using azeotropic distillation aids to
achieve high yield of triacetin.
Several studies have claimed better selectivity of triacetin in presence of acetic
anhydride as acylating reagent for acetylation of glycerol. Liao et al. (2009) reported
100% selectivity for triacetin with the Amberlyst-35 in the presence of acetic anhy-
dride. Similarly, Silva et al. (2011) reported 100% selectivity for triacetin using
glycerol-to-acetic anhydride molar ratio of (1:4) over zeolite, Amberlyst-15, and
niobium phosphate at 60 °C after 2 h. However, the use of acetic anhydride as the
acylating agent is not viable for industrial applications due to its higher cost and
associated health hazards (Silva et al. 2011).
16.7 Etherification of Glycerol
In etherification process, branched oxygen-containing compounds are formed from

the stepwise reaction occurring between the hydroxyl groups of glycerol and the
functional reactant groups such as alcohols (e.g., tert-butyl alcohol) or alkenes (iso-
butene). The product obtained from etherification reaction contains a mixture of
monoglyceride, diglyceride, and triglyceride due to the variation in reactivity of
hydroxyl groups of glycerol (Fig. 16.5). The oxygenate compounds obtained from
etherification of glycerol can be used as fuel additive. Glycerol tert-butyl ethers can
384
Table 16.5 Reaction conditions for acetylation of glycerol

Temperature Reaction time Molar Catalyst Conversion
Catalyst (°C) (h) ratio loading (%) Monoacetin Diacetin Triacetin References
Amberlyst-36 105 10 1:8 0.25 g 95.6 70.3 4.5 Dosuna-Rodríguez and
Amberlyst-15 95.3 70.3 2.5 Gaigneaux (2012)
Dowex resin-2 95.2 80.8 5.1
Dowex resin-4 94.8 71.6 4.2
Dowex resin-8 94.7 72.9 4.7
Ar-SBA-15 125 4 9:1 0.2 g 96 15 47 38 Melero et al. (2007)
F-SBA-15 90 14 50 36
Pr-SBA-15 80 17 44 39
Amberlyst-15 80 8 6:1 0.64 g 100 88.5 11.2 0.3 Kim et al. (2014)
HPMo/Nb2O5 87 81.8 17.5 0.7
SCZ 81 84.7 14.8 0.5
SO3H-SBA15 100 11.1 61.9 27.0
SO3H-cell 100 37.6 55.0 13.4
TPA3/ZrO2 100 6 6:1 0.15 g 80 60 36 4 Patel and Singh (2014)
TPA3/ 87 25 60 15
MCM-41
Amberlyst-15 105 10 6:1 5 wt% 100 0 12.3 83.9 Kale et al. (2015)
Amberlyst-70 100 0 7.5 87.6
STA/S11 100 1 55.5 35.8
Amberlyst-15 110 0.5 3:1 0.47 g 97 31 54 13 Gonçalves et al. (2008)
K-10 4.0 g 96 44 49 5
Niobic acid 6.3 g 30 83 - -
HZSM-5 1.6 g 30 83 10 0
PW2_AC 120 3 16:1 0.2 g 86 25 63 11 Ferreira et al. (2010)
Fig. 16.5 Etherification of glycerol using isobutene
be used as an alternative to ethyl tert-butyl ether as it helps to improve octane prop-

erties of gasoline. Other reaction products like di-tert-butylglycerols (DTBG) and
tri-tert-butylglycerol (TTBG) are reported to improve cold flow properties of the
fuel as valuable fuel additives to reduce the toxic emissions.
Homogeneous and heterogeneous catalysts (e.g., zeolites, mesoporous silica,
and metal oxides) can catalyze glycerol etherification. Generally, homogeneous
catalysts are not preferred due to their corrosive nature and difficulty to impossible
in recovery from reaction mixture and hence heterogeneous catalysts are preferred.
Heterogeneous acid catalysts including zeolites, ion exchange resins, and mesopo-
rous silicates are reported to be more active for etherification of glycerol (Izquierdo
et al. 2012). However, the application of heterogeneous catalysts is limited due to
their low selectivity and formation of secondary products. On the contrary, the high
product selectivity and higher etherification activity can be achieved using basic
heterogeneous catalysts (Table 16.6). Therefore, basic catalysts are usually pre-
ferred compared to the acidic catalyst (Melero et al. 2008; Klepacova et al. 2005).
The effects of different solvents (e.g., isobutene, dioxane, sulfolane, and dimethyl
sulfoxide) were investigated on etherification reaction, and highest conversion was
achieved using isobutene as solvent. Although isobutene is efficient in the etherifi-
cation of glycerol, its high cost and low selectivity and formation of secondary
products (e.g., isobutene oligomerization) are some disadvantages of this process.
Etherification of glycerol using tert-butyl alcohol is widely reported in the literature
(Frusteri et al. 2009; Chang and Chen 2011; Ozbay et al. 2010). In addition, oligo-
merization of isobutene can be prevented by the addition of tert-butyl alcohol to the
reaction mixture (Karinen and Krause 2006; Melero et al. 2008). However,
Table 16.6 Reaction conditions for etherification of glycerol
386

Temperature Reaction Molar Catalyst Conversion
Catalyst (°C) time (h) ratio loading (%) XMTBG XDTBG XTTBG Solvents References
Amberlyst-15 75 4 0.25 0.5 g 73 65 32 3 Isobutene González et al.
SBA-15 41 87 13 0 (2012)
SBA-15-Cs 98 39 56 5
SBA-15-Mw-S 99 9 55 36
BCC-S 393 K 4 4:1 5 wt% 70 42 20 (+) tert-Butyl Gonçalves et al.
alcohol (2016)
Amberlyst-15 90 8 4:1 7.5 wt% 100 8.5 59.6 21.2 Isobutylene Klepacova et al.
Amberlyst-35 100 7.6 59.3 29.8 (2005)
Zeolite H-Y 94.8 22.5 64.9 7.1
Zeolite H-beta 100 12.7 72.9 –
Amberlyst-15 60 8 4:1 7.5 wt% 95.9 13.2 55.8 16.6
Amberlyst-35 80.1 23.4 46.9 6.8
Zeolite H-Y 100 16.2 57.3 14.3
Zeolite H-beta 18.0 6.9 16.3 –
Amberlyst-35a 80 7 3 1g 95 Isobutene Karinen and
60 8 4 7.5 wt% 86 tert-Butyl Krause (2006)
alcohol
Spherical silica-supported 70 6 4 5.0 wt% 99 85 (+) tert-Butyl Beatrice et al.
perfluorosulfonic acid alcohol (2013)
A-15 70 6 4 7.5 wt% 78.9 71.6 27.7 0.5 tert-Butyl Cannilla et al.
H-730/ES70Y 34.1 79.8 19.3 0.9 alcohol (2014)
Amberlyst-15 89.4 8 4 7.3 wt% 72.3 0.509 mol 0.205 mol tert-Butyl Chang and
alcohol Chen (2011)
Propyl-SO3H/SiO2 85-95 3 1:10 10 wt% 90 60–70 20–30 tert-Butyl Drago et al.
alcohol (2013)
Abbreviation: mono-tert-butyl glycerol ethers MTBG, di-tert-butyl glycerol ethers DTBG, tri-tert-butyl glycerol ethers TTBG, black carbon from coffee ground
BCC treated with sulfuric acid
a
Reaction was performed at different reaction conditions using the same catalyst
tert-butyl alcohol-based etherification process has low selectivity for triethers when
compared to isobutene-based etherification process.
16.8 Acetalization of Glycerol
Acetalization of glycerol to ketal or acetal can be performed with aldehyde and

ketones. Highly branched oxygenated compounds with five-membered ring ketal
(2,2-dimethyl-[1,3]-dioxane-4-yl)-methanol and six-membered ring acetal
(2,2-dimethyl-dioxane-5-ol) are generally produced from acetalization of glycerol
using ketones. Acetals can be used as base in surfactant and as a precursor for manu-
facturing of 1,3-dihydroxyacetone and 1,3-propanediol (Umbarkar et al. 2009). It is
observed from the literature that glycerol acetalization reaction mixture contains
both five- and six-membered ring acetals. The fraction of five- and six-membered
acetals in acetalization reaction mixture can be controlled by varying the several
reaction parameters like temperature, aldehyde-to-glycerol molar ratio or ketone-to-
glycerol molar ratio, and the type of solvent used. Cesar et al. (2002) reported that
100% selectivity for five- and six-membered ring acetals is not achieved even under
supercritical conditions using acetone as the acetalization reagent. In contrast, very
high selectivity for six-membered ring acetals can be achieved using aldehyde-
based acetalization at higher temperatures (Pagliaro et al. 2007).
Acetalization of glycerol can be performed in the presence of homogeneous cat-
alysts like strong acids (sulfuric acid, hydrofluoric acid, hydrochloric acid, and
p-toluenesulfonic acid) (Frusteri et al. 2009). Kaufhold and El-Chahawi (1996) pat-
ented a procedure for acetal production using homogeneous catalyst in the presence
of water-soluble entrainer (hexane or pentane) in the temperature range of
25–75 °C. Acetalization of glycerol is a reversible process; therefore, water is con-
tinuously removed from reaction mixture to ensure the shift of reaction in the
desired direction. However, this process is not economically and environmentally
feasible due to the corrosive nature of acid catalyst.
Recently, many studies have reported the application of heterogeneous acid
catalysts to overcome the limitations associated with homogeneous catalysts
(Khayoo and Hameed 2013). Umbarkar et al. (2009) investigated the application of
MoO3/SiO2 catalyst prepared by sol–gel techniques for acetalization of glycerol
using aldehydes and obtained 78% conversion with very high selectivity (up to
100%) for six-membered acetal. Güemez et al. (2013) reported the conversion of
glycerol using n-butyraldehyde in the presence of Amberlyst-47 catalyst and
obtained mixtures of cyclic acetals as the main product. The selectivity of acetal-
ization process mainly depends on the actualization position of hydroxyl group in
glycerol molecule, which in turn depends on electronic and steric factors (Ferreira
et al. 2010). The typical reaction mechanism for acetalization of glycerol involves
the following steps: (a) formation of hemiketal, (b) removal of water molecule
through dehydration reaction, (c) formation of tertiary carbonium ion, and (d) for-
mation of ketal or acetal.
16.9 Polymerization of Glycerol
Polymerization of glycerol to polyglycerol is one way to expand the industrial

applications of glycerol. Polyglycerols are viscous, water-soluble, highly branched
compounds and can be synthesized from glycerol using two routes, especially (a)
etherification of glycerol and (b) glycerol condensation in the presence of excess
water (Gholami et al. 2014; Vila et al. 2012). The properties of polyglycerol esters
depend on the degree of esterification, length of polyglycerol chain, and molecular
weight of fatty acid (Clacens et al. 2002). Generally, it is difficult to control the
selectivity of polymerization process as the products contain mixture of polyglycer-
ols (monomers to hexamers). Diglycerol is a simplest polyglycerol, which is formed
by the condensation of two glycerol molecules. Furthermore, progressive condensa-
tion of glycerol molecules can lead to the formation of triglycerol, tetraglycerol,
pentaglycerol, and long-chain polyglycerol. Polyglycerols have many industrial
applications from the cosmetic industry to drug delivery. Polyglycerol esters can be
used in cosmetics, lubricants, food additive and as a surfactant (Guerrero-Urbaneja
et al. 2014). The polymerization of glycerol to polyglycerols using different cata-
lysts is widely reported in literature (Table 16.7).
Traditionally, epichlorohydrin is used as a starting material for the preparation of
polyglycerols in industrial processes, but the time-consuming multiple purification
steps make it an expensive process (Pérez-Barrado et al. 2015). Therefore, research-
ers are moving toward the alternative processes like catalytic etherification of glyc-
erol. Many studies have been reported in literature on polyglycerol synthesis using
different homogeneous (alkaline carbonates, Cs2CO3 and Na2CO3, and hydroxides,
NaOH, CsOH, and H2SO4) and heterogeneous catalysts (metal-impregnated MCM
and zeolites and mixed oxides). Catalytic activity of Na2CO3 in glycerol is better
than hydroxides due to its better solubility and high basicity (Bookong et al. 2015;
Barrault et al. 2004). Although homogeneous catalysts are more active than hetero-
geneous catalyst, low selectivity, corrosive nature, and difficulty in separation are
the factors that limit their applications.
The heterogeneous catalysts (mesoporous materials) have high selectivity for
low molecular weight oligomers like diglycerol and triglycerol due to their smaller
pore size. Several studies have been reported by the Barrault group on the use of
zeolitic and mesoporous catalysts for etherification of glycerol to polyglycerols.
Polyglycerols production from glycerol etherification involves complex reaction,
which makes difficult to control the degree of polymerization and leads to the for-
mation of undesirable side products. Generally, the formation of toxic acrolein is
reported at temperatures >200 °C due to double dehydration reactions (Ruppert
et al. 2008; Guerrero-Urbaneja et al. 2014). The mechanism of glycerol etherifica-
tion comprises the following steps: (a) protonation of –OH group of first glycerol
molecule, (b) protonated glycerol molecule nucleophilic attack hydroxyl group on
other glycerol molecules; (c) protonated glycerol molecule combined with other
glycerol molecules, and (d) release of water molecule.
Table 16.7 Reaction conditions for polymerization of glycerol
Catalyst Temperature (°C) Reaction time (h) Catalyst loading Conversion (%) Diglycerol Triglycerol References
MgAl-Na 220 24 300 mg 50 85 15 García-Sancho et al. (2011)
Cs (exchanged) 260 8 51 83 17 Clacens et al. (2002)
CsX (impregnated) 36 100 0
Cs25Al(20) 80 55 25
Cs-impregnated 260 2 wt% 80 75 25 Clacens et al. (2000)
MCM-41 90 40 23
La-incorporated 80 65 20
16 Conversion of Glycerol to Value-Added Products
MCM-41
Cs-exchanged X-zeolite
Amberlyst-15 60 8 68 Tseng and Wang (2011)
Amberlyst-35 70.9
Zeolite H-beta 64.9
Zeolite H-Y 88
389
16.10 Esterification of Glycerol
The production of polyglycerides using esterification of glycerol offers many prom-

ising industrial applications (Table 16.8). Particularly, monoglycerides are used as
food additive in food industry, personal care formulations, and pharmaceutical and
chemical industries. Generally, esterification reactions are performed out in homo-
geneous liquefied phase in a batch reactor. Acid catalysts (sulfuric acid, hydrochlo-
ric acid, and orthophosphoric acid) are used for the direct esterification of glycerol
with fatty acids at mild reaction temperature (Molinero et al. 2014).
Several reports are available on the use of microporous zeolites, mesoporous
silica, and porous carbon materials as catalysts for esterification of glycerol.
Mesoporous materials are found to be more efficient compared to microporous zeo-
lites in esterification of glycerol because the pores of mesoporous materials are
easily assessable by fatty acids and their esters (Sanchez et al. 2011). The porous
carbon materials produced from starch and polysaccharides are proven to be more
recalcitrant to the structural changes compared to mesoporous silica. Generally,
mesoporous are treated with alkyl sulfonic acid to impart acidic characters to the
catalyst. The presence of acidic R–SO3H groups is reported to increase the catalytic
activity of mesoporous silicates for esterification of glycerol (Jeenpadiphat et al.
2015). The concentration of methyl groups can affect the performance of the cata-
lyst for each fatty acid, and higher catalytic activity can be achieved by tuning the
methyl-to-sulfonic acid ratio (Díaz et al. 2000). The optimum balance between dif-
ferent parameters like catalyst acidity, pore size, specific surface area, and
Table 16.8 Value-added products from esterification of glycerol and their application
Products Structure Applications
Monoglycerol • Food industry
ester • Cosmetic industry
• Pharmaceutical and chemical industries
Diglycerol ester • Personal care formulations and fragrances

• Plasticizer in polyvinyl alcohol films
• Manufacture of polyurethanes and
polyesters
Triglycerol ester • Cosmetic industry

• Food industry
methyl-to-sulfonic group ratio is necessary to obtain catalysts with improved cata-

lytic activity and selectivity for the desired products.
Various factors like surface area, adsorption, glycerol/fatty acid molar ratio,
swelling ratio, and catalyst acidity have strong effects on the catalyst activity and
selectivity toward the desired product (Pouilloux et al. 1999; Kotwal et al. 2011).
Water is generally considered as a limiting factor in esterification reaction. Therefore,
molecular sieve can be used as a water trap to increase the rate of reaction. Moreover,
adsorption and swelling pattern are also found to influence the reaction rate. Zhou
et al. (2013) reported that the length of fatty acid chain and the steric effect influence
the selectivity of the process and rate of reaction.
16.11 Chlorination of Glycerol
Chlorination of glycerol to dichlorohydrins and epichlorohydrin is an interesting

alternative. Epichlorohydrin has many industrial applications like chemical synthe-
sis of resins and synthetic elastomers, water purification process, and, in reinforce-
ment, intermediate for the synthesis of oligoglycerols and sizing agent in paper
industry. Several studies have reported the chlorination of glycerol to dichlorohy-
drin and subsequently to epichlorohydrin with gaseous hydrochloric acid
(Santacesaria et al. 2010). The products obtained from chlorination reaction are
1,3-chloro-2-propanol, 1,2-chloro-3-propanol, 1-chloro-2,3-pro-panediol, and
2-chloro-1,3-propanediol (Tesser et al. 2012). The mechanism of epichlorohydrin
synthesis involves two chlorination steps such as (a) chlorination of glycerol to
1-chloro-2,3-propanediol and 2-chloro-1,3-propanediol and (b) chlorination reac-
tion leading to the formation of 1,3-chloro-2-propanol and 1,2-chloro-3-propanol.
The chlorination reaction of glycerol and hydrochloric acid is traditionally cata-
lyzed by acetic acid, but the use of acetic acid as a catalyst has some disadvantages.
Acetic acid is volatile under high temperatures. Therefore, acetic acid is required to
be replaced by less volatile catalysts (e.g., glycolic acid, amino acid, and chlorotri-
methylsilane) to perform reactions at a higher temperature. Vitiello et al. (2014)
used a series of glycolic acid catalysts and amino acid series catalysts for chlorina-
tion of glycerol. The performance and selectivity of catalysts were found to depend
on pKa value and molecular structure (number of carboxylic groups) of the catalyst.
The glycolic acid series catalyst performed better than amino acid series catalysts in
terms of activity and selectivity. Escribà et al. (2009) investigated the production of
chlorohydrin esters using esterification–chlorination of glycerol using chlorotri-
methylsilane as the catalyst in the presence of classical or microwave heating. The
results showed that 2-chloro-1-(chloromethyl)ethyl esters can be obtained in high
quantity even at lower reaction temperatures without using any solvent addition.
16.12 Ammoxidation of Glycerol
Ammoxidation of glycerol is performed to produce acrolein and acrylonitrile. Based

on the number of steps involved, ammoxidation can be divided into two types, such
as direct ammoxidation and indirect ammoxidation. Acrolein can be directly pro-
duced from ammoxidation of glycerol. However, acrylonitrile is indirectly produced
from glycerol dehydration of acrolein followed by ammoxidation of acrolein to
acrylonitrile (Liebig et al. 2013). Usually, high temperature (270 °C) is required for
ammoxidation process.
Mono-oxides and mixed metal oxide-based catalysts (e.g., Mo, Sn, W, Zr, Al, P,
Ti, and Sn) are mainly used for the manufacture of acrylonitrile via ammoxidation
of glycerol (Bagheri et al. 2015). Liebig et al. (2013) performed the indirect ammo-
xidation of glycerol to acrylonitrile using dehydration and ammoxidation steps.
WO3/TiO2 catalyst was used for dehydration step, while Sb/V and Sb/Fe catalysts
were used for ammoxidation step. Sb/Fe catalysts were found to be highly selective
for acrylonitrile. The selectivity of acrylonitrile was found to rise with an increase
in reaction time due to the formation of FeSbO4 during the reaction. Similarly,
alumina-supported Sb/V catalyst was found to be highly active for the conversion of
glycerol into acrylonitrile under solvent-free microwave activation.
The acrylonitrile selectivity of more than 80% can be achieved using Sb/V cata-
lyst in microwave activation within short reaction times compared to conventional
thermal activation (Calvino-Casilda et al. 2009). It is reported that various kinds of
Sb–V–O structures can be obtained with the variation in Sb–V–O loading and the
method of impregnation. The oxidation state of the vanadium species in these
Sb–V–O structures significantly affects the catalytic behavior and selectivity toward
acrylonitrile (Golinska et al. 2010). The metal loading, chemical composition, and
morphology of the support are the key parameters affecting catalytic activity in
ammoxidation process.
16.13 Conclusions
Glycerol has emerged as a low-cost biodiesel industry by-product that has great
potential to be transformed into marketable value-added products. This chapter
highlights different potential reaction pathways for the catalytic conversion of glyc-
erol into value-added marketable fine chemicals. Interestingly, different kinds of
catalysts (homogeneous and heterogeneous) are explored for the conversion of
glycerol in a wide range of studies. However, few catalysts have shown long-term
stability without severe deactivation. Many researchers have provided information
about the optimization of experimental conditions to obtain high glycerol conver-
sion and good product selectivity, but majority of these experiments were limited to
batch reaction systems.
The time and temperature profiles of the catalytic reaction and product yield can
be significantly improved by the application of advanced reactors like ultrasonic,
microwave, membrane reactor, etc. A few studies are available on the usage of crude
glycerol for the manufacture of high market value chemicals. The utilization of
crude glycerol can provide new prospects on glycerol waste minimization and can
help in potential commercialization and industrialization of these processes.
Acknowledgments The authors are thankful for the financial support provided by the Agriculture
Development Fund (ADF), Saskatchewan and Canada Research Chair program.
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Recent Advances in Steam Reforming
of Glycerol for Syngas Production 17
Tan Ji Siang, Nurul Asmawati Roslan,
Herma Dina Setiabudi, Sumaiya Zainal Abidin,
Trinh Duy Nguyen, Chin Kui Cheng, Aishah Abdul Jalil,
Minh Thang Le, Prakash K. Sarangi, Sonil Nanda,
and Dai-Viet N. Vo
Abstract
Syngas, a mixture of carbon monoxide and hydrogen, has recently emerged as an
important intermediate feedstock in petrochemical industry and an efficient and
eco-friendly energy carrier to substitute petroleum-based fuels. Although methane
is conventionally employed as a main feedstock for syngas production via indus-
T. J. Siang
School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi
N. A. Roslan · H. D. Setiabudi · S. Z. Abidin · C. K. Cheng
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang,
Kuantan, Pahang, Malaysia
T. D. Nguyen · D.-V. N. Vo (*)
A. A. Jalil
School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi
Centre of Hydrogen Energy, Institute of Future Energy, Universiti Teknologi Malaysia,
Johor, Malaysia
M. T. Le
School of Chemical Engineering, Hanoi University of Science and Technology,
Hai Bà Trưng, Hà Nội, Vietnam
P. K. Sarangi
S. Nanda

400 T. J. Siang et al.
trial methane steam reforming process, a rising interest about the implementation
of glycerol for generating syngas is widely reported in literature due to its great
abundance, low cost, and hydrogen-rich content. This chapter summarizes the
recent progress in catalytic steam reforming of glycerol for s yngas yield in terms
of catalytic design using various supports and promoters and the manipulation of
operating variables. The mechanistic pathways and their fundamentally derived
kinetic models for expressing glycerol reaction rate and estimating associated
kinetic parameters are also comprehensively reviewed throughout this chapter.
Keywords
Glycerol · Glycerol steam reforming · Syngas · Hydrogen · Methane · Carbon
dioxide
17.1 Introduction
Since currently all aspects of the modern life, transportation and industrial produc-
tion, are heavily relying on petroleum-based energy, the fast and unavoidable
depletion of these main and nonrenewable fossil fuels is predictable in coming
decades (Nanda et al. 2015). In addition, the excessive combustion of oil-based
fuels leads to a significant increase in CO2 emissions, especially in the power and
transport industries contributing to around 266.7 metric tons per year in 2016
(EDGAR 2017). Hence, minimizing the undesirable CO2 emissions is crucial for
mitigating global warming mainly induced by the anthropogenic greenhouse gases.
In fact, the concerns on the security of energy supply and environmental issues have
driven the dependency of energy system from solids to liquid fuels and subsequently
toward other alternative gas sources. As seen in Fig. 17.1, about 90% of the world
energy supply could be eventually derived mainly from hydrogen by 2080.
Based on Fig. 17.1, hydrogen could emerge as one of the main energy sources to
substitute crude oil in the next centuries. Hydrogen is industrially separated from
syngas (a mixture of H2 and CO) produced from various processes through reform-
ing (Singh et al. 2018), gasification (Reddy et al. 2014; Nanda et al. 2016a; Okolie
et al. 2019), and electrochemical, photochemical, and biological routes (Nanda
et al. 2017b). Therefore, apart from utilizing other renewable energy sources,
namely solar energy, wind power, and biofuels, the global mitigation strategies are
currently focusing on the use of syngas as an alternative and sustainable source of
energy. In fact, syngas is extensively employed as important building blocks for
numerous petrochemical purposes, including crucial feedstocks for the production
of synthetic hydrocarbon fuels (Vo and Adesina 2011; Vo et al. 2012; Nanda et al.
2016b), methyl tert-butyl ether (Siang et al. 2018), methanol (Pham et al. 2019), and
ammonia (Schwengber et al. 2016; Inayat et al. 2019), while hydrogen is widely
used for high-temperature fuel cells and as an efficient energy carrier in hydrogen
cars (Holladay et al. 2009; Nanda et al. 2017a).
The current large-scale production processes of syngas are steam reforming of
methane (Arcotumapathy et al. 2015), autothermal reforming of methane, and
17 Recent Advances in Steam Reforming of Glycerol for Syngas Production 401
Fig. 17.1 Global energy system transition (1850–2150). (Adapted from Hefner III (1995) with
permission. Copyright 1995, Elsevier)
partial oxidation of methane (Minh et al. 2018; Siang et al. 2019). However, meth-
ane, a main constituent of natural gas, is also considered as a non-replenished energy
and can be used directly as fuel. Thus, the implementation of other biomass-derived
feedstocks such as ethanol (Bahari et al. 2016; Fayaz et al. 2019), ethylene glycol
(Jun et al. 2018), and glycerol (Arif et al. 2016) in the reforming processes has been
broadly considered in academic and industrial R&D to yield an eco-friendly syngas
product. Among biomass-based feedstocks, glycerol (C3H8O3), which is a highly
available by-product from industrial biodiesel production, has become increasingly
attractive as a hydrogen-containing feedstock for syngas production. In fact, the
global biodiesel production rate has substantially increased about 74.9 million met-
ric tons from 2000 to 2017 (Statista 2018), and the amount of unwanted glycerol
by-product is around 10 wt% of biodiesel productivity (Huang et al. 2018).
Additionally, the Food and Agriculture Organization predicted that as biodiesel pro-
duction attains 41 billion liters in 2020, approximately three million metric tons of
discarded glycerol would be generated (FAO 2015). The large amount of low-cost
glycerol co-generation is one of the main concerns in biodiesel industry although
glycerol is nonhazardous and easily handled and stored (Reddy et al. 2016). Thus,
the conversion of abundantly undesired glycerol to syngas is considered as an effi-
cient waste-to-wealth approach.
Syngas can be effectively produced from glycerol via various pathways such as
autothermal reforming (Hajjaji et al. 2014), partial oxidation (Wang 2010), dry
reforming (Tavanarad et al. 2018; Arif et al. 2017), steam reforming (Ghasemzadeh
et al. 2019), and supercritical water gasification (Nanda et al. 2018). Nevertheless,
glycerol steam reforming (GSR) is more preferred routes among the abovementioned
approaches since a higher hydrogen yield could be achieved from this method and
the industrial scale GSR production would not require much significant changes in
the current industrial hydrogen production process (Schwengber et al. 2016).
Moreover, GSR process has the potential to theoretically generate 7 mol of hydrogen
from 1 mol of glycerol. According to Eq. (17.1), 4 mol of hydrogen can be yielded
via the simple decomposition of 1 mol of glycerol. However, water-gas shift reaction
(Eq. 17.2) also occurs simultaneously during GSR:
C3H8 O3 3CO 4H 2 H 298

0
K 251 kJ / mol (17.1)
CO H 2 O CO2 H 2 H 0
298 K 41 kJ / mol (17.2)
Thus, a maximum of 7 mol of hydrogen can be produced from 1 mol of glycerol

in GSR, and the overall GSR process is given as follows:
C3H8 O3 3H 2 O 3CO2 7H 2 H 298

0
K 128 kJ / mol (17.3)
Along with glycerol decomposition (Eq. 17.1), numerous side reactions
(Eqs. 17.4–17.11) reportedly occur during GSR (Lin 2013):
3H 2 CO H 2 O CH 4 H 298
0
K 206 kJ / mol (17.4)
4H 2 CO2 2H 2 O CH 4 H 298
0
K 165 kJ / mol (17.5)
CH 4 CO2 2H 2 2CO H 298

0
K 247 kJ / mol (17.6)
H 2 CO2 H 2 O CO H 298
0
K 41 kJ / mol (17.7)
2CO Cs CO2 H 298

0
K 172 kJ / mol (17.8)
CH 4 Cs 2H 2 H 298
0
K 75 kJ / mol (17.9)
H 2 CO Cs H 2 O H 298
0
K 131 kJ / mol (17.10)
2H 2 CO2 Cs 2H 2 O H 298

0
K 306 kJ / mol (17.11)
In order to generate renewable syngas or hydrogen using glycerol as a main feed-

stock, the efficient scission of C–H and C–C bonds as well as maintenance of the
C–O bond to minimize carbon deposition is currently one of the main challenges in
large-scale production. From the above reasons, the right selection and development
of catalysts are extremely important in GSR in order to optimize glycerol conver-
sion, catalytic stability, and hydrogen yield. Thus, this chapter intensively discusses
various types of catalysts used in GSR. In addition, this article provides a clear
picture on catalyst design in GSR by examining the role of different active metals,
supports, and promoters as well as their synergic effects on catalytic performance
and stability. Besides, this chapter comprehensively reviews the influence of varied
operating conditions including reaction temperature, gas hourly space velocity, and
reactant feed composition in GSR. Finally, the current progress about kinetics and
mechanisms of GSR are also discussed in details.
17.2 Glycerol Steam Reforming Catalysts
Catalysts play a vital role in controlling the mechanistic path and product distribu-
tion of GSR via the cleavage of C–H, C–C, and O–H bonds amidst the glycerol
molecules (without changing C–O bonds) (Charisiou et al. 2018). Therefore, vari-
ous types of catalysts were suggested by researchers including monometallic, bime-
tallic, and trimetallic systems. The summary of recent catalysts used for GSR is
summarized in Table 17.1 and thoroughly reviewed in this section.
17.2.1 Active Metal Catalysts
Active metals play a vital role in the GSR whereby the dissociation of glycerol takes
place on these sites. Several metals have been used as active metals for metal-based
catalysts including the noble metals (Rh, Ru, Pt, and Ir) (Senseni et al. 2017), transi-
tion metals (Ni, Co, and Cu) (Papageridis et al. 2016; Kousi et al. 2016; Ramesh and
Venkatesha 2017; Demsash et al. 2018; Carrero et al. 2017; Dobosz et al. 2018;
Wang et al. 2018), and bi- or trimetallic catalysts (Ramesh and Venkatesha 2017;
Wang et al. 2018; Shejale and Yadav 2018).
Senseni et al. (2017) studied the GSR reaction over noble metal nanocatalysts
(Rh, Ru, Pt, and Ir) adopted on MgO-promoted Al2O3. At 300–600 °C, the catalytic
activity of GSR over the catalysts followed a sequence of Rh > Pt > Ru > Ir, while
hydrogen selectivity followed a sequence of Rh > Ir > Ru > Pt. Additionally, Rh
exhibited superior catalytic activity and stability with glycerol conversion of 100%,
hydrogen selectivity of 100%, and good longevity evaluation up to 20-h time-on-
stream (TOS). Superior catalytic performance of Rh catalyst was owing to its small-
est metal crystal size (1.28 nm), higher BET (Brunauer, Emmett, and Teller) surface
area (159 m2/g), and easier metal reduction as compared to the other catalysts.
Although noble metals exhibit higher activity and stability toward GSR, their high
expenditures may limit their commercial applications especially in industrial fields
(Papageridis et al. 2016). Thus, substantial efforts have been devoted to develop
transition metal-based catalysts.
Papageridis et al. (2016) used a constant loading (8 wt%) for Co, Cu, and Ni adopted
on γ-alumina (Al2O3) and tested for GSR. Results demonstrated the behavior and sta-
bility of GSR reaction following the sequence of Co/Al2O3 > Cu/Al2O3 > Ni/Al2O3.
The varying catalytic activity achieved by the catalysts was related to the acid-base
natures of the catalysts owing to the importance of a balanced acid-base distribution in
GSR. Ni/Al2O3 displayed relatively poor catalytic activity and stability owing to the
occurrence of dehydration, cracking, and polymerization reactions over the strong acid
Table 17.1 Summary of catalytic performance for recently employed catalysts in glycerol steam reforming
404
Initial performance Final performance

Steam/ Glycerol H2 CO CO2 Glycerol H2 CO CO2
glycerol GHSV conversion selectivity selectivity selectivity TOS conversion selectivity selectivity selectivity
Catalysts ratio T (°C) (L/gcat/h) (%) (%) (%) (%) (h) (%) (%) (%) (%) Da (%) References
Supported catalysts
8%Ni/γ-Al2O3 4/1 600 50 78.2 61.0 57.9 34.5 20 10.8 85.1 56.0 43.7 86.2 Papageridis
et al. (2016)
8%Co/γ-Al2O3 4/1 600 50 63.3 55.1 64.8 31.3 20 23.9 68.5 82.7 16.8 62.2 Papageridis
et al. (2016)
8%Cu/γ-Al2O3 4/1 600 50 54.3 54.6 73.9 23.7 20 21.0 71.9 77.8 22.3 61.3 Papageridis
et al. (2016)
10%Ni/γ-Al2O3 4/1 600 57 95.1 93.8 8.4 86.1 55 29.5 27.6 7.4 22.3 68.9 Kousi et al.
(2016)
Ni/γ-Al2O3 3/1 650 10000b 58.7 66.7 4.8 25.1 24 54.3 69.4 4.2 25.0 7.5 Ramesh and
Venkatesha
(2017)
10%Ni/γ-Al2O3 12/1 650 10b 99.9 58.7 13.5 21.9 24 78.0 37.9 36.2 14.0 21.9 Demsash
et al. (2018)
7%Co/SBA-15 6/1 600 7.7 92.3 61.7 – – 50 91.3 – – – 1.1 Carrero et al.
(2017)
7.5%Co/HAp 9/1 800 6 99.1 74.8 – – 6 94.2 51.5 – – 4.9 Dobosz et al.
(2018)
10%Ni/ATP 9/1 600 9619b 67.0 61.9 49.4 45.7 30 19.8 84.3 53.1 34.2 70.4 Wang et al.
(2018)
T. J. Siang et al.
10%Ni/Al2O3/CeO2 12/1 650 10b 99.9 59.9 11.5 22.8 24 94.4 49.9 22.6 17.1 5.5 Demsash
et al. (2018)
Promoted catalysts
16.8%La-promoted 4/1 600 57 64.8 66.3 6.9 57.0 20 36.2 36.6 7.9 27.3 44.1 Kousi et al.
Ni/γ-Al2O3 (2016)
10%Mo7%CeAl 15/1 500 9.2 64.9 57.8 18.2 21.6 10 62.4 54.3 23.3 19.1 3.8 Mitran et al.
(2016)
8.5%Ce-promoted 6/1 600 7.7 99.8 70.7 – – 50 49.2 – – – 50.7 Carrero et al.
Co/SBA-15 (2017)
10%Ce-promoted 9/1 800 6 99.1 79.5 – – 6 98.8 56.2 – – 0.3 Dobosz et al.
Co/HAp (2018)
1%Ru-promoted 12/1 650 10b 100 65.0 9.2 23.9 24 99.5 65.2 11.1 21.8 0.5 Demsash
Ni/Al2O3/CeO2 et al. (2018)
Bimetallic or trimetallic catalysts
LaNiO3 3/1 650 10000b 59.9 65.3 3.1 27.9 24 59.2 65.2 4.1 27.1 1.2 Ramesh and
Venkatesha
(2017)
LaNiO3 (E)c 3/1 650 10000b 68.8 68.0 3.6 26.4 24 66.7 67.5 4.6 25.2 3.1 Ramesh and
Venkatesha
(2017)
5%Ni-5%Co/ATP 9/1 600 9619b 70.5 58.2 61.6 53.8 30 60.0 71.2 42.7 54.3 14.9 Wang et al.
(2018)
5%Ni-5%Cu/ATP 9/1 600 9619b 75.2 61.6 56.3 47.4 30 48.0 74.9 55.7 45.9 36.2 Wang et al.
(2018)
(continued)
17 Recent Advances in Steam Reforming of Glycerol for Syngas Production
405
406
Initial performance Final performance

Steam/ Glycerol H2 CO CO2 Glycerol H2 CO CO2
glycerol GHSV conversion selectivity selectivity selectivity TOS conversion selectivity selectivity selectivity
Catalysts ratio T (°C) (L/gcat/h) (%) (%) (%) (%) (h) (%) (%) (%) (%) Da (%) References
5%Ni-5%Zn/ATP 9/1 600 9619b 67.9 62.0 40.2 60.0 30 62.6 67.2 41.0 60.9 7.8 Wang et al.
(2018)
10%Ni-10%Cu/ 6/1 500 3120b 66.2 96.1 – – 15 80.7 80.1 – – – Shejale and
La2O3-MgO (CP)d Yadav
(2018)
10%Ni-10%Co/ 6/1 500 3120b 60.0 88.8 – – 15 66.6 68.7 – – – Shejale and
La2O3-MgO (CP)d Yadav
(2018)
a
Degree of catalyst deactivation, D (%) = [1 – (final glycerol conversion/initial glycerol conversion)] × 100%
b
GHSV (gas hourly space velocity) unit is h−1
c
Catalyst was prepared with ethylenediaminetetraacetic acid
d
CP and IP represent the corresponding coprecipitation and impregnation methods
T. J. Siang et al.
sites-rich catalyst’s surface. On the contrary, the relatively good p erformance of Co/
Al2O3 was probably due to the enhanced acidity nature of the catalyst upon the addition
of Co via the transformation of intrinsic weaker acid sites to stronger acid sites.
Regarding the product distribution, Ni/Al2O3 has the highest potential in producing the
gaseous products via GSR than Co/Al2O3 and Cu/Al2O3, which might be owing to its
higher ability in promoting the rupture of C–C bond. The application of Ni/Al2O3 in
GSR was also reported by other researchers (Ramesh and Venkatesha 2017; Demsash
et al. 2018; Kousi et al. 2016) at different operating conditions as listed in Table 17.1.
For overcoming the drawbacks of Ni-derived catalysts, several studies have
reported the combination of Ni-based catalysts with the second and/or third metals
to form bimetallic or trimetallic catalysts, respectively. Wang et al. (2018) studied
the performance of monometallic Ni- and bimetallic Ni-M (M = Zn, Co, or Cu)-
based attapulgite (ATP) catalysts in GSR. The catalytic results revealed relatively
better hydrogen yields and glycerol conversions for all bimetallic catalysts than
monometallic Ni/ATP catalyst, which significantly associated with the improved
strength of metal-support interaction upon the inclusion of the second metals.
Stronger metal-support interactions in bimetallic catalysts inhibited the coke depo-
sition and metal sintering. As compared, Ni-Cu/ATP showed superiority in terms of
hydrogen yield and glycerol conversion in GSR than Ni supported on Co/ATP and
Zn/ATP catalysts. This was owing to the greater particle size of 12.2 nm and higher
reducibility for Ni-Cu/ATP, which resulted in its outstanding performance. In terms
of catalytic stability, deactivation resistance followed the order of Ni-Zn/
ATP > Ni-Co/ATP > Ni-Cu/ATP > Ni/ATP. Ni-Zn/ATP exhibited long-term stability
for GSR, which can be credited to its outstanding anti-sintering ability proven from
the smallest crystal size of spent catalyst.
On the contrary, Shejale and Yadav (2018) compared the catalytic performance
of trimetallic catalysts, Ni-Cu/La2O3-MgO and Ni-Co/La2O3-MgO in GSR. Both
catalysts demonstrated satisfactorily stability over 15-h TOS, and Ni-Cu/La2O3-
MgO marked higher glycerol conversion and hydrogen selectivity than Ni-Co/
La2O3-MgO. The high performance of Ni-Cu/La2O3-MgO can be explained by the
presence of Cu, which triggered dehydrogenation reaction in parallel with high
water-gas shift reaction, subsequently resulting in higher hydrogen production. In
addition, the combination of both Mg and Cu triggered the formation of an elec-
tronic effect on the active Ni phase and therein limited the formation of coke deposi-
tion. Moreover, the larger surface area and more homogeneous Ni distribution also
contributed to the higher hydrogen production in Ni-Cu/La2O3-MgO.
In addition to Ni-based catalyst, perovskite-type oxide catalysts have attracted
great attention for GSR owing to their special characteristics. Ramesh and Venkatesha
(2017) compared the performance of Ni/Al2O3 with Ni-based perovskite prepared
with and without template, denoted as LaNiO3(E) and LaNiO3, respectively. As com-
pared, LaNiO3 and LaNiO3(E) perovskite catalysts performed better catalytic perfor-
mance and stability than Ni/Al2O3. The superiority of perovskite catalysts (LaNiO3(E)
and LaNiO3) compared with Ni/Al2O3 was due to the smaller NiO nanoparticle sizes
formation, easier NiO reduction, and moderately weak acid sites, which prevented
the filamentous carbon deposition, metal sintering, and deactivation.
17.2.2 Catalyst Supports
Catalyst support plays a significant role in the GSR since it facilitates the dissocia-
tion of water into –OH groups, thus triggering the migration of the species to the
active metal sites where COx and H2 are formed (Charisiou et al. 2018). In addition,
support enhances the stabilization of the metal particles at elevated reaction tem-
peratures (Charisiou et al. 2018). Several types of supports have been used in GSR
in an effort to determine the most favorable physicochemical properties including
acid-base properties and metal-support interaction. Alumina (Al2O3) is one of the
most widely adopted catalyst supports in GSR owing to its excellent physicochemi-
cal attributes and thermal endurance. According to literature, Ni/Al2O3 was mainly
populated with strong acid sites, and these sites play a significant factor in the GSR
(Papageridis et al. 2016; Kousi et al. 2016; Ramesh and Venkatesha 2017; Demsash
et al. 2018). However, the adoption of Al2O3 as support triggered catalyst deactiva-
tion as a result of coke deposition and catalyst sintering. At strong acid sites of
Al2O3, the coke formed can be related with cracking, dehydration, and polymeriza-
tion reactions, while sintering can be explained by the gradual transformation of
Al2O3 to crystalline phase within the reaction.
To overcome the limitation related with the Al2O3-adopted catalysts, several
researchers reported on the potential of mesoporous silica as catalyst support for
GSR. Carrero et al. (2017) explored the performance of Co/SBA-15 in GSR. SBA-
15 has several interesting characteristics including significantly high surface area
and uniform pore size dispersion, which may obstruct the agglomeration of large
metal and catalyst deactivation by metal sintering. 7%Co/SBA-15 exhibited good
activity in GSR with glycerol conversion of 92.3% and 1.08% degree of catalyst
deactivation during 50-h TOS.
Dobosz et al. (2018) examined the catalytic behavior of Co-based calcium
hydroxyapatite (HAp) in GSR. HAp with a chemical formula of Ca10(PO4)6(OH)2
possesses a high thermal stability, mesoporous structure, and acid-based character-
istics. The catalytic activity study showed that an efficient transformation of glyc-
erol into reforming products was achieved by 7.5%Co/HAp with glycerol conversion
of 99.1% and hydrogen selectivity up to 74.8% at 800 °C.
Wang et al. (2018) discovered the potential of attapulgite (ATP) as supports for
Ni-based catalyst. ATP, commonly known as polygorskite, is a kind of hydrated
magnesium aluminum silicate clay mineral ((H2O)4(Mg,Al,Fe)5(OH)2Si8O20·4H2O)
covered with reactive hydroxy groups. Its lath or fibrous morphology is formed as
its upper and lower parts are integrated by octahedral magnesium/aluminum/iron
atoms layer in sixfold coordination structure and its structure was constituted by the
Si-O tetrahedra parallel double-strand. ATP possesses excellent properties, includ-
ing high surface area, superb thermal/mechanical properties, and silanol-based
chemistry surface. Ni/ATP displayed good activity in GSR with glycerol conversion
of 67% and hydrogen selectivity of 61.9% at 800 °C.
Several researchers have reported the potential of mixed oxides as support mate-
rials. Demsash et al. (2018) explored the catalytic activity of GSR over 10%Ni/
Al2O3/CeO2. The results showed that Ni supported on Al2O3/CeO2 exhibited good
activity and stability owing to the greater enhancement in catalytic properties than
that of single oxide, Al2O3. In fact, 10%Ni/Al2O3/CeO2 exhibited glycerol conver-
sion of 99.9% and hydrogen selectivity of 59.9% at 650 °C.
17.2.3 Promoters
Various oxides, which are mostly alkaline earth or lanthanide oxides, have been used
as promoters for improving the resistance of Ni-based catalysts toward metal sinter-
ing and coking. The presence of promoter is anticipated to promote the high longev-
ity of Ni particles at elevated reaction temperature and increase NiO particles
reducibility. Kousi et al. (2016) explored the potential of lanthanide oxide (La2O3) as
a promoter for Ni/γ-Al2O3. They found that the addition of La2O3 facilitated the reac-
tant conversions to gas-phase products. In addition, La2O3 played an important role
in hindering the carbonaceous species formation by interacting La2O3 with CO2 to
form intermediate La2O2CO3 species. However, Ni/La2O3/γ-Al2O3 did not offer a
higher stability than Ni/γ-Al2O3 owing to its poorer textural properties. This circum-
stance can be claimed on the formation of LaAlO3 phase as a result of the detrimental
impact by the addition of La2O3 onto Al2O3 support and severe calcination at 900 °C.
Mitran et al. (2016) explored the combination of two metal oxides (CeO2 and
MoO3) on Al2O3 for GSR. The combination of 7%Ce with 10%Mo resulted in the
most selective catalyst toward GSR owing to the synergetic interaction between Ce
and Mo. The high activity of GSR over MoCe7Al was closely related to Ce addition
that was able to alter the phase of Mo species from tetrahedral molybdena to octa-
hedral molybdena, thus contributing to the enhancement of both activity and hydro-
gen selectivity for MoCe7Al. In contrast, Carrero et al. (2017) investigated Ce
addition as a promoter for Co/SBA-15 in GSR. Within 5-h TOS, the introduction of
Ce induced better glycerol conversion compared with Co/SBA-15, especially at
600 °C. The superiority of Co-based Ce/SBA-15 over Co/SBA-15 was owing to the
higher strength interactions amidst Co and Ce/SBA-15. At 600 °C, Co-Ce/SBA-15
yielded higher H2 and CO2 products than Co/SBA-15 as high redox properties of Ce
ameliorated water reactivity and oxygen mobility and thus facilitated water-gas
shift reaction.
Dobosz et al. (2018) compared the hydrogen production via GSR by using the
calcium hydroxyapatite (HAp)-supported cobalt (Co/HAp) and cobalt-cerium cata-
lysts (Ce-promoted Co/HAp) at 800 °C. During the reaction, the individual selectiv-
ity of hydrogen and glycerol conversion declined along the TOS for Co/Hap, while
the glycerol conversion for Co-Ce/HAp remained stable within 6-h TOS. The Ce
addition improved the glycerol conversion, hydrogen selectivity, and stability of
Co-Ce/HAp by suppressing the growth or sintering of Co particles. The lower sus-
ceptibility of Co-Ce/HAp to sintering was relatively associated with strong interac-
tion amidst Ce and Co species.
Demsash et al. (2018) performed GSR activities using Ni/Al2O3, Ni/Al2O3/CeO2,
and Ru-promoted Ni/Al2O3/CeO2. As evidenced, Ru-promoted Ni/Al2O3/CeO2 demon-
strated better and more stable catalytic behavior than Ni/Al2O3 and Ni/Al2O3/CeO2. Ni/
Al2O3, Ni/Al2O3/CeO2, and Ru-promoted Ni/Al2O3/CeO2 maintained their stabilities

for 7 h, 17 h, and 24 h, respectively. Highest hydrogen selectivity (88.6%) versus ther-
modynamic selectivity (95.9%) was marked by Ru-promoted Ni/Al2O3/CeO2, and it
was found to restrict the formation of by-products such as CO and CH4. This phenom-
enon can be credited to the parallel water-gas shift side reaction (CO + H2O(g) ↔
CO2 + H2) and methane reforming processes (CO2 + CH4 → 2H2 + 2CO; CH4 + H2O
⇌ CO + 3H2) that consumed the corresponding CO and CH4. Moreover, it can be noted
that Ru-promoted Ni/Al2O3/CeO2 catalyst enhances metal dispersion and NiO reduc-
ibility, which are favorable for GSR.
17.3 ffects of Operating Conditions on the Performance

E
of Glycerol Steam Reforming
A systematic understanding of the impacts of process variables on catalytic perfor-

mance is enormously essential for catalyst development (Wang et al. 2018); optimi-
zation of GSR in terms of activity, yield, and selectivity (He et al. 2010); as well as
the derivation of comprehensive kinetic models (Bobadilla et al. 2015; Menezes
et al. 2018). As a result, a wide range of studies regarding the role and contribution
of process parameters (viz., temperature, gas hourly space velocity (GHSV), and
steam/glycerol feed ratio) on GSR performance have been extensively conducted to
determine their correlations with reaction activity and stability. The following sec-
tions discuss the detailed and recent findings about the effect of process variables on
catalytic GSR performance and desired product distribution. The influence of steam/
glycerol ratio, reaction temperature, and GHSV on glycerol conversion, selectivity,
and H2/CO ratio over various supported catalysts is also summarized in Table 17.2
for comparison purpose.
17.3.1 Effect of Reaction Temperature
Based on the stoichiometric GSR reaction (see Eq. 17.3), every mole of glycerol
reactant consumed theoretically yields 7 mol of hydrogen as the product. However,
the presence of other parallel side reactions such as glycerol dehydrogenation,
hydrogenolysis of glycerol, CO methanation, and CO2 methanation could result in
the loss of H2 selectivity and yield. As GSR possesses endothermic nature, its cata-
lytic activity is favored by rising reaction temperature, while the degree of undesired
side reactions could be controlled effectively by the manipulation of reaction tem-
perature. From the above reasons, the selection of suitable reaction temperature is a
fundamental and important factor requiring detailed investigation to limit unfavor-
ably concomitant side reactions and concurrently improve the GSR activity.
In the evaluation of catalytic GSR stability at various temperature regions for Ni
supported on Al2O3, CeO2, and SiC with the corresponding acidic, basic, and neutral
attributes, Kim and Woo (2012) observed that increasing temperature from 300 °C
to 500 °C could lead to an improvement in glycerol conversion around 76–83% and
Table 17.2 Influence of process variables on the performance of glycerol steam reforming over different catalysts
Operating conditions Glycerol Selectivity or yield (%)
Steam/glycerol Temperature GHSV (L/ conversion H2/CO
Catalyst ratio (°C) gcat/h/) (%) CH4 H2 CO CO2 ratio References
Ni/Al2O3 6/1 300–500 33.3a 20.1–92.7 – – – – 1.3–4.9 Kim and Woo
(3–9)/1 400 33.3a 46.4–73.0 – – – – 2.7– (2012)
12.7
Ni/CeO2 6/1 300–500 33.3a 20.3–87.3 – – – – 1.0–4.8 Kim and Woo
(3–9)/1 400 33.3a 50.5–87.7 – – – – 2.5–6.4 (2012)
Ni/SiC 6/1 300–500 33.3a 15.9–93.7 – – – – 1.0–1.7 Kim and Woo
(3–9)/1 400 33.3a 65.7–95.2 – – – – 1.3–1.8 (2012)
Ni/ATP 9/1 500–700 9619b 45.0–65.3 15.3–8.8 20.8–61.8 45.5–53.0 39.2–38.2 1.8–2.2 Wang et al.
Ni-Co/ATP 9/1 500–700 9619b 50.8–78.0 5.1–2.5 50.9–65.5 30.0–43.0 64.9–54.5 2.9–3.2 (2018)
Ni-Cu/ATP 9/1 500–700 9619b 60.6–73.4 1.9–0.6 44.4–64.0 35.3–45.1 62.8–54.3 3.3–3.0
Ni-Zn/ATP 9/1 500–700 9619b 63.2–73.1 3.8–0.8 39.8–63.0 30.3–39.7 65.9–59.5 2.6–3.6
NiNbAl 1/2 450–650 300,000b 7.37–81.9 0.8–2.9c 4.3–44.3c 6.2–41.9c 2.5–36.9c – Menezes et al.
(5–2)/1 450 500,000b 73.0–6.8 0.3–1.0c 6.2–2.7c 4.4–3.6c 5.0–0.8c – (2018)
1/3 500 200,000– 97.0–26.0 2.9–0.3c 33.9–6.4c 29.1–4.4c 28.7–5.9c –
500,000b
MoCe7Al 15/1 400–500 9.2d 15.5–65.5 – 22.4–58.3 33.9–16.5 14.0–21.7 – Mitran et al.
(9–20)/1 500 9.2d 32.8–83.9 – 29.0–65.6 24.6–18.8 17.9–12.3 – (2016)
15/1 500 6.4–12.9d 67.7–57.5 1.1–2.1 60.0–55.5 14.5–19.3 23.3–22.7 –
(continued)
411
412
Operating conditions Glycerol Selectivity or yield (%)

Steam/glycerol Temperature GHSV (L/ conversion H2/CO
Catalyst ratio (°C) gcat/h/) (%) CH4 H2 CO CO2 ratio References
3%Pt/C 46/1 225 10,000– 45.2–22.6 3.3–2.4 41.5–51.8 73.6–85.0 3.9–5.5 – Wei et al.
30,000b (2015)
3%Pt–3%Re/C 46/1 225 25,000– 59.4–18.8 1.8-0 45.2–56.4 72.9–83.4 6.1–5.8 –
153,000b
Ni/CeZrO 24/1 500–700 36 94.0–100 5.1–13.4 76.7–33.9 29.2–59.7 66.4–28.8 – Shao et al.
(6–18)/1 600 36 80.9–92.8 4.7–4.8 62.7–71.9 44.1–35.7 51.3–61.4 – (2014)
NiSn/AlMgCe 12/1 600–750 100 63.0–82.0 – 18.0– – – 2.0-4.5 Bobadilla et al.
49.0c (2015)
(20–8)/1 750 100 91.0–76.0 – 63.1– – – –
39.9c
12/1 750 50–100 – 7.8–7.2 60.2–56.2 8.7–19.6 25.3–15.7 –
Co–Ni/HTls 4/1 500–600 100 – 2.1–1.7 98.0–95.7 0.1–3.1 0–1.4 – He et al. (2010)
(3–9)/1 575 100 – 66.9–7.9 97.7–98.9 43.2–18.8 35.5–30.7 –
a
LHSV (liquid hourly space velocity) unit is h−1
b
GHSV unit is h−1
c
Yield value (%)
d
GHSV based on glycerol feed
T. J. Siang et al.
enhance H2/CO ratio by up to 41–73% as shown in Table 17.2. This observation was
ascribed to the endothermic nature of GSR inducing the facilitation of C–H, C–C,
and C–O bonds cleavage at rising reaction temperature (Kim and Woo 2012).
Additionally, in a thermodynamic study of GSR, Chen et al. (2011) found that CH4
production decreased, while the amount of H2 and CO enhanced with increasing
temperature, suggesting the excessive H2 formation may be generated not only from
GSR and water-gas shift reaction but also from methane steam reforming (MSR), in
which methane intermediate product is converted to valuable hydrogen.
Wang et al. (2018) synthesized bimetallic Ni-M (M:Co, Cu, or Zn) supported on
attapulgite (ATP) and examined their catalytic performance for GSR at varying tem-
perature from 500 °C to 700 °C with steam/glycerol ratio of 9 and atmospheric pres-
sure. Similar findings from Kim and Woo (2012) were reported for the role of
reaction temperature. Increasing temperature from 500 °C to 700 °C has a positive
effect on the bond cleavage of glycerol molecule, hence enhancing GSR activity.
Interestingly, it is also reported that the selectivity of methane possessed an opposite
trend with hydrogen selectivity, suggesting that methane by-product originated from
glycerol decomposition during GSR process was converted to hydrogen via MSR.
17.3.2 Effect of Gas Hourly Space Velocity
As one of the most important process variables in heterogeneous catalytic system,

the impact of GHSV on catalytic performance of GSR is rigorously assessed to
achieve the independence of GSR activity from mass and heat transfer limitations
and optimize the performance of catalysts with respect to conversion, H2 yield, and
H2/CO ratio. Bobadilla et al. (2015) prepared a bimetallic NiSn/AlMgCe catalyst for
catalyzing the GSR reaction at various GHSV values and 750 °C. They reported that
the growth in GHSV from 50 to 100 L/gcat/h adversely decreased hydrogen selectiv-
ity from 60.2% to 56.2% and decreased catalytic stability reasonably owing to the
thermal cracking of glycerol to carbonaceous species clogging the active sites.
According to Wang et al. (1997), the glycerol decomposition reportedly occurs
before reaching catalyst bed, and few glycerol compounds (without thermal crack-
ing) successfully access active sites for catalytic surface reaction. Hence, Bobadilla
et al. (2015) proposed that GSR is a catalytic system in which glycerol is thermally
decomposed to carbon deposition on active metal sites and the steam gasification of
these species to gaseous products (viz., CH4, C2H4, CO, H2, and CO2) subsequently
occurs to prevent catalyst from deactivation. From the abovementioned reasons,
high GHSV could not provide enough residence time for thoroughly gasifying
deposited carbon from glycerol decomposition to the desired H2 and CO products as
well as protect active sites from carbonaceous species.
Menezes et al. (2018) examined the impacts of operating parameters on GSR by
Ni-supported Al2O3 and Nb2O5. They found that rising GHSV values led to a signifi-
cant decline in glycerol conversion from 97% to 26% in agreement with findings of
Bobadilla et al. (2015). As reported by Menezes et al. (2018), coke formation was
the main factor accounted for the drastic drop in GSR activity. They also suggested
that the formation of carbonaceous species preferred at low GHSV led to the
suppression of hydrogen formation, while the liquid by-products were dominant at
high GHSV since the feed rate of glycerol was too excessive on catalytic bed to be
converted to gaseous products.
17.3.3 Effect of Reactant Partial Pressure
At high reaction temperature, GSR could inevitably encounter glycerol thermal

cracking side reaction leading to the blockage of active sites with deposited carbon.
Therefore, scrutinizing the impact of reactant partial pressure (or water/glycerol
ratio) on GSR activity, stability and hydrogen selectivity is appreciably vital for
kinetic investigation and industrial applications. Shao et al. (2014) prepared Ni/
CeZrO via coprecipitation method and assessed its catalytic performance for GSR
at 600 °C and varied water/glycerol ratios ranging from 6 to 18. They observed that
glycerol conversion increased from 80.9% to 92.8% with increasing water/glycerol
ratio from 6:1 to 18:1 owing to decreasing glycerol feed composition. In addition,
increasing water/glycerol ratio reportedly favored water-gas shift reaction because
a substantial rise in H2 and CO2 selectivity was evident while CO selectivity experi-
enced a considerable drop. Interestingly, a comparative stability with desired cata-
lytic performance was achieved when a water/glycerol ratio of 6 was employed,
indicating this ratio could be appropriate for carbon removal and enhanced the GSR
activity by retaining catalytic active sites (Shao et al. 2014).
A similar behavior was also observed by Mitran et al. (2016) for their assessment
of GSR over MoCeAl catalyst at water/glycerol ratios of 9–20 and temperature of
500 °C. Glycerol conversion was considerably increased up to 83.9% with growing
water/glycerol ratios, rationally because of the reducing glycerol concentration in
feed. With increasing water/glycerol ratio, the selectivity of both CO and CO2
declined substantially, whereas the rise in H2 selectivity was observed. Although
hydrogen formation rate could be facilitated with an excessive steam content in
feedstock, the employment of extreme water/glycerol ratios could induce an exten-
sive energy prerequisite for evaporating a large amount of water into steam. Thus,
from an economic perspective, it is crucial to achieve a balance between GSR per-
formance and operating cost for sufficient energy supply (Bobadilla et al. 2015).
17.4 Mechanisms and Kinetics of Glycerol Steam Reforming
The comprehensive reaction rate expressions for heterogeneous catalytic reactions

are fundamentally essential for the prediction of consumption rate, reactor design,
and scale-up in commercialized industrial applications. Indeed, the intrinsic cata-
lytic features play a key role in the establishment of the mechanism-derived reaction
rate expressions. Thus, kinetic studies of glycerol steam reforming have arisen to be
one of the main concerns in both industrial and academic realms in recent years, and
several studies about GSR mechanism and kinetics have been lately reported in
literature. In general, GSR kinetics reportedly include empirical power law model
and mechanistic-based models, namely Langmuir-Hinshelwood-Hougen-Watson
(LHHW) and Eley-Rideal (ER) models.
The implementation of power law model for the rough calculation of reaction
order and apparent activation energy for reactant consumption and product forma-
tion is widely conducted owing to its simplicity. In fact, the experimental GSR reac-
tion rates measured at varied reaction temperature and reactant partial pressure are
conventionally fitted to the simple power law model (see Eq. 17.12) without the
prerequisite of determining mechanistic pathways and rate-controlling step in order
to estimate the associated model parameters:
rC3H8O3 kPC3H8O3 PH2O (17.12)
where −rC3H8O3 and k are the corresponding glycerol reaction rate and reaction rate
coefficient, whereas Pi (with i: C3H8O3 or H2O) denotes the reactant partial pressure.
In addition, α and β signify the reaction order of C3H8O3 and H2O, respectively.
Table 17.3 summarizes the calculated activation energy of glycerol consumption
and reaction orders corresponding to glycerol and steam reactants from the GSR
power law models. Adhikari et al. (2009) conducted GSR on Ni/CeO2 with the
excessive presence of water in comparison with glycerol concentration. As a result,
they could use a simplified power law model excluding the effect of steam concen-
tration to capture experimental glycerol consumption rates at varying reaction tem-
perature of 600–650 °C and reported glycerol reaction order and activation energy
were around 0.23 and 103.4 kJ/mol, correspondingly (Table 17.3). An analogous
power law expression was also proposed by Dave and Pant (2011) for GSR over
Ni-ZrO2/CeO2. A lower activation energy for glycerol conversion of 43.4 kJ/mol
was reported, whereas the glycerol reaction order was observed as 0.3.
Additionally, in the kinetic investigation of GSR over Ni-Mg-Al-based catalysts,
Wang et al. (2013) developed a GSR pseudo-nth order model, which was only asso-
ciated with the concentration of glycerol, for capturing the consumption rate of
glycerol. They also reported that depending on catalysts employed, glycerol activa-
tion energy could vary from 37.8 to 131.6 kJ/mol. In addition, glycerol reaction
order of unity was verified with the highest accuracy and best fitness for describing
glycerol reaction rate.
Unlike aforementioned literature, the undeniably significant role of steam in
GSR was also taken into account for power law models in other studies. Cheng et al.
(2010a) employed Co-Ni/Al2O3 for GSR at varied operating conditions of 500–
550 °C and 1 atm. The fitting of their experimental data for product formation rates
including H2, CO2, CO, and CH4 into a power law equation using nonlinear regres-
sion based on Levenberg-Marquardt algorithm revealed that partial pressure of
steam possessed a great effect on CH4, H2, CO, and CO2 formation rates. Apart from
CO, the production rates of CH4, H2, and CO2 increased with rising steam partial
pressure since positive reaction orders with respect to steam partial pressure were
observed for the formation of these species. The negative value of steam reaction
order toward CO formation possibly suggested the competitive H2O adsorption
occupying active sites for generating CO product or loss of CO via simultaneous

water-gas shift side reaction, particularly at steam-rich environment. Cheng et al.
(2010a) also reported that for glycerol reaction rate, the fractional orders were esti-
mated as 0.25 and 0.36 for the corresponding glycerol and steam reactants, while
the activation energy for glycerol conversion was computed as about 63.3 kJ/mol on
Co-Ni/Al2O3 catalyst. In the study of GSR over Ni/Al2O3, Cheng et al. (2011) found
relatively similar activation energy values for H2 and CO2 product formation as well
as glycerol reactant consumption ranging from 60 to 61.8 kJ/mol. These results
could indicate that the direct GSR pathway involving the reaction between glycerol
and water was the predominant step accounting for H2 and CO2 production.
Although the empirical power law model is able to provide an initiate conjecture
of overall activation energy and reaction order for each reactant involved, this sim-
ple model fails to yield the accurate estimation of associated model parameters over
a wide-ranging feedstock composition. Additionally, the power law model only
complies with statistical criteria and does not obey or reflect the inherent GSR
mechanisms. Hence, other fundamentally mechanism-derived reaction rate expres-
sions, namely ER and LHHW models, are widely used for verifying the best fitness
of obtained experimental data to the proposed kinetic models. Based on the degree
of fitness and thermodynamic criteria, the most appropriate kinetic model could be
determined and hence contributing to the confirmation of intrinsic GSR reaction
steps on catalyst surface.
In the inspection of GSR over Ni/CeO2 synthesized via precipitation deposition
method, Pant et al. (2011) proposed an ER kinetic model, in which the molecularly
adsorbed glycerol on catalyst surface could react with water in gas phase followed
by decomposition into various intermediates as the rate-determining step (see
Eq. 17.13) in Table 17.4. By fitting experimental GSR consumption rates to the
proposed ER kinetic model, the overall GSR activation energy was estimated at
around 36.5 kJ/mol.
Table 17.3 Summary of kinetic parameters computed from GSR power law models on several
catalysts
Activation energy, Ea Reaction order
Temperature (kJ/mol) α β
Catalyst (°C) Glycerol Glycerol Water References
Ni/CeO2 600–650 103.4 0.23 0 Adhikari et al. (2009)
Ni/Al2O3 450–550 60.0 0.48 0.34 Cheng et al. (2011)
Co/Al2O3 450–550 67.2 0.08 0.40 Cheng et al. (2010b)
Co-Ni/ 500–550 63.3 0.25 0.36 Cheng et al. (2010a)
Al2O3
Ni-ZrO2/ 600–700 43.4 0.30 0 Dave and Pant (2011)
CeO2
Ni-Mg-Al 400–600 131.6 1 0 Wang et al. (2013)
Ce-Ni/ 550–650 62.9 0.45 0 Demsash and Mohan
Al2O3 (2016)
Cheng et al. (2011) used Ni/Al2O3 catalyst for GSR and detected the existence of
both basic and acidic sites on catalyst surface via the corresponding CO2 and NH3
temperature-programmed desorption runs. Thus, they proposed a dual-site GSR
mechanism (see Fig. 17.2) involving molecular glycerol adsorption and dissociative
water adsorption on two various active sites. Additionally, the surface reaction
between these adsorbed glycerol and water is assumed as a rate-determining step.
Based on this suggested mechanism, a LHHW model was derived as given in Eq.
(17.14) of Table 17.4 and adequately captured the consumption rate of glycerol as
well as satisfied all associated statistical and thermodynamic standards.
However, it is well-known that heterogeneous catalytic reactions could alter its
mechanistic pathway to different routes depending on the type and attributes of
catalysts employed. For example, in the study of bimetallic Co-Ni/Al2O3 for GSR,
Cheng et al. (2010a) proposed 12 different GSR mechanisms based on single-site or
dual-site ER and LHHW mechanism as they found the existence of acidic and basic
Brönsted sites on catalyst. The statistical and thermodynamic discrimination for
these 12 derived GSR kinetic models was conducted and proved that the LHHW
kinetic model (Eq. 17.15) in Table 17.4, involving the molecular adsorption of both
glycerol and steam reactants on 2 distinct active sites, was the most suitable model
with the best fitness to the experimental glycerol reaction rate data. Thus, the activa-
tion energy for glycerol consumption was further computed from this model as
about 69.36 kJ/mol.
17.5 Conclusions
In general, GSR reaction depends on the nature of the catalyst that consists of active
metal and support. Active metals are responsible for the dissociation of glycerol
molecules. Meanwhile, supports are crucial in activating the dissociation of water
into –OH groups as well as promoting the species to migrate toward the active metal
species whereby the COx and hydrogen are formed. In addition, supports stabilize
the metal particles at elevated reaction temperature under steam.
For active metal selection, transition metals have attracted considerable attention
owing to its availability and low price. Nickel is the most popular active metal cata-
lyst in GSR among transition metals, even though it is prone to coking issues. In
order to address the challenge of coke issues from nickel, bimetallic catalysts are a
suggestive solution. In the bimetallic system, a ratio of the constituents’ metals is
considered as a crucial factor in order to produce more active bimetallic catalyst as
compared to the corresponding monometallic catalyst. Additionally, reported litera-
tures indicated that the adoption of alkaline earth or lanthanide oxides aided in dis-
persing the active metal particles reinforced the metal-support interactions, balanced
acid-base strength and density distribution, and thus improved the performance of
catalysts (glycerol conversion, hydrogen production, and stability) toward GSR.
In addition, appropriate support selection must be done considering its textural
and chemical attributes to boost the active metal particles dispersion, facilitate the
metal-support interaction, minimize metal sintering, stimulate the reduction of the
Table 17.4 LHHW and ER kinetic expressions for catalytic glycerol steam reforming
418
Catalyst Assumption Mechanism Kinetic model Eq. no. Ref.

Ni/ Decomposition of K1
(17.13) Pant
CeO2 molecularly adsorbed C3H8 O3 S1 C3H8 O3 S1 et al.
glycerol with water (2011)
forming k1k2 PC3H8O3 PH2O
K2 rC3H8O3
intermediates as RDS C3H8 O3 S1 H 2 O C3H10 O 4 S1 k1k2 PC3H8O3
k1 k1PC3H8O3 k2 PH2O
k3
k3
C3H10 O 4 S1 Intermediates RDSa
k1b k
K4 K1 ; K2 2
Intermediates H 2 CO2 S1 k1 k2
Ni/ Surface reaction of (17.14) Cheng
Al2O3 dual-site molecularly et al.
adsorbed glycerol krxn PC3H8O3 PH2O (2011)
and dissociatively C3H8O3 + S1 ↔ C3H8O3 − S1 rC3H8O3
adsorbed water as 1 K C3 H 8 O 3 PC3H8O3 1 K H2O PH2O

RDS
krxn = 1.33 × 10−7 mol/s/m2/kPa
K H2O 0.043 kPa 1

K C3H8O3 0.00056 kPa 1
H2O + 2S2 ↔ OH − S2 + H − S2
C3H8O3 − S1 + H − S2 → CH2OHCHOH − S1
+ CHOH − S2 + 2H2 (RDS)
CHOH − S2 → CO − S2 + H2
CH2OHCHOH − S1 + H − S2 → CH2OH − S1
+ CH3O − S2
CH2OH − S1 + S2 → CH2 − S1 + OH − S2
T. J. Siang et al.
CH2 − S1 + H − S2 → S2 + CH3 − S1
CH3 − S1 + H − S2 → S2 + CH4 + S1
CH3O − S1 + S2 → H − S2 + CH2O − S1
CH2O − S1 + S2 → H − S2 + HCO − S1
HCO − S1 + S2 → H − S2 + CO − S1
CO − S1 ↔ S1 + CO
CO − S1 + OH − S2 ↔ CO2 + H − S2 + S1
H − S2 + H − S2 ↔ H2 + 2S2
Co- Dual-site molecular (17.15) Cheng
Ni/ glycerol and water et al.
krxn PC3H8O3 PH2O
Al2O3 adsorption with rC3H8O3 (2010a)
surface reaction of C3H8O3 + S1 ↔ C3H8O3 − S1 1 K C 3H 8 O 3 PC3H8O3 1 K H2O PH2O

adsorbed reactants as
RDS krxn = 5.57 × 10−7 mol/s/m2/kPa
K H2O 0.0369 kPa 1
K C3H8O3 0.283 kPa 1

H2O + S2 ↔ H2O − S2
C3H8O3 − S1 + H2O − S2 → CH2OHCHOH − S1
+ HCOO − S2 + 2H2 (RDS)
COO − S2 → H − S2 + CO2
CH2OHCHOH − S1 + H − S2 → CH3O − S2
+ CH2OH − S1
H2OH − S1 + S2 → OH − S2 + CH2 − S1
CH2 − S1 + H − S2 → S2 + CH3 − S1
(continued)
419
420

CH3 − S1 + H − S2 → S2 + CH4 + S1
CH3O − S1 + S2 → H − S2 + CH2O − S1
CH2O − S1 + S2 → H − S2 + HCO − S1
HCO − S1 + S2 → H − S2 + CO − S1
CO − S1 ↔ S1 + CO
CO − S1 + OH − S2 ↔ H − S2 + S1 + CO2
2H − S2 ↔ H2 + 2S2
a
RDS represents the rate-determining step, while S is the available active site on catalyst surface. S1 and S2 indicate two different active sites of catalysts
b
ki and k−i are the corresponding adsorption and desorption rate constants, while Ki is the adsorption equilibrium constant and krxn is GSR reaction rate constant
T. J. Siang et al.
Fig. 17.2 Mechanistic steps in glycerol steam reforming reaction

catalyst, and, most importantly, reduce or resist the carbonaceous species formation.
It is proposed that developing the synergistic effects of suitable metals composition
with the proper selection of supports can successfully synthesize favorable catalysts
toward GSR. Moreover, the research on catalysts that can remain stable at GSR
operating conditions and particularly more practical, eco-friendly, and economical
in industrial scale applications are highly needed for commercialization.
The examination of GSR operating parameters such as reaction temperature,
GHSV, and reactant partial pressure could establish the optimal GSR operation con-
ditions for various desired targets, namely glycerol conversion, hydrogen yield, H2/
CO ratio, and stability. Apart from power law model, ER and LHHW models are
broadly proposed based on GSR mechanisms with the assumption of varied rate-
determining steps depending on catalyst types. Hence, glycerol reaction rate and
Arrhenius parameters are adequately captured and estimated, respectively. However,
the isotopic studies and other investigations about in situ chemisorption of both
glycerol and steam reactants are crucial in future work for further validating the
mechanistic GSR pathways and derived GSR kinetic models.
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Conversion of Biogas to Syngas via
Catalytic Carbon Dioxide Reforming 18
Reactions: An Overview
of Thermodynamic Aspects, Catalytic
Design, and Reaction Kinetics
Doan Pham Minh, Ahimee Hernandez Torres,

Bruna Rego de Vasconcelos, Tan Ji Siang,
and Dai-Viet N. Vo
Abstract
Biogas production has continuously increased worldwide during the last decades.
Nowadays, heat, electricity, and biomethane production are the main utilization
of biogas at large-scale industrial processes. The research and development on
biogas valorization is currently related to synthesis gas production via reforming
process, since syngas allows obtaining various chemicals and fuels of high-added
value. However, biogas reforming is a complex process, which implies various
reactions in parallel, and needs high temperature (>800 °C) to obtain high meth-
ane conversion. The development of a highly-performing catalyst, which must be
active, selective, thermally stable, and resistant to solid carbon formation on its
surface, is crucial. This chapter is devoted to an update of the thermodynamic
aspect of biogas reforming under different conditions. This chapter
D. Pham Minh (*) · A. H. Torres

Université de Toulouse, IMT Mines Albi, Centre RAPSODEE, UMR CNRS 5302,
Albi, France
B. Rego de Vasconcelos
Department of Chemical and Biotechnological Engineering, Université de Sherbrooke,
Sherbrooke, Québec, Canada
T. J. Siang
School of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Johor, Malaysia
D.-V. N. Vo

428 D. Pham Minh et al.
also reviews recent significant works related to catalyst design as well as kinetic
and mechanistic studies of biogas reforming processes.
Keywords
Biogas · Dry reforming of methane · Tri-reforming of methane · Catalyst · Kinetic
study
18.1 Introduction
The green alternatives to fossil fuel have been constantly developed in order to
reduce the greenhouse gas emissions. One of the possible solutions is related to
biogas, which is considered as a renewable energy source to replace conventional
fuels to produce heat, electricity, and chemicals. Biogas is obtained from the decom-
position of organic matter under anaerobic conditions (absence of oxygen). The
main feedstocks for biogas production include energy crops (e.g., sunflower, wheat
grain, sugar beet, etc.), agricultural residues, animal manure, municipal solid waste
(MSW), industrial wastes, wastewater, and sewage sludge. These feedstocks con-
tain mostly complex organic compounds, which are degraded by microorganisms
under the absence of air through four main steps, such as hydrolysis, acidogenesis,
acetogenesis or dehydrogenation and methanation (Jaffrin et al. 2003; Weiland
2010; Mudhoo 2012; Pullen 2015). The hydrolysis of complex polymers into oligo-
mers and monomers (e.g., sugars, amino acids, fatty acids) takes place in the first
step. These oligomers and monomers are then degraded into volatile fatty acids
(>C2), acetate, and hydrogen. The volatile fatty acids are later converted into ace-
tate, H2, and CO2 by acetogenic bacteria. Finally, acetate, H2, and CO2 produce CH4
through methanation. This multi-step transformation needs specific conditions
including the absence of air (anaerobic condition), uniform temperature, optimum
nutrient supply, optimum and uniform pH (Kaparaju and Rintala 2013).
From the technical point of view, large-scale biogas production can be done in an
anaerobic digestion plant or in a landfill site, leading to the formation of digested
gas and landfill gas, respectively. The size of these bioreactors varies from some
cubic meters to several thousand cubic meters (Persson et al. 2009; Mudhoo 2012;
Pullen 2015; Di Maio et al. 2018). Depending on the reactor design, feedstock used,
and operational conditions, the composition of biogas can vary. However, biogas
typically contains mostly CH4, CO2, H2, N2, O2, light hydrocarbons, water vapor,
and some pollutants (hydrogen sulfide, ammoniac, siloxanes, and organometallic
complexes) (Persson et al. 2009; Pullen 2015; Mudhoo 2012; Kvist and Aryal 2019;
Hoo et al. 2018; Eklund et al. 1998; Biogas Renewable Energy 2019). The digested
gas generally contains more CH4 (50–75 vol%) and less CO2 (30–40 vol%) than
landfill gas (CH4: 35–65 vol% and CO2: 15–50 vol%). Landfill gas contains varying
amounts of N2 (5–40 vol%) and O2 (0–5 vol%) while the digested gas generally
contains <2 vol% of these gases. This is due to the difficulty of sealing control in
landfill sites during landfill gas recovery. Thus, the lower heating value (LHV) of
the digested gas (5.5–7.5 kwh/Nm3) is higher than that of landfill gas (around 4.4
kwh/Nm3) (Okonkwo et al. 2018; Persson et al. 2009).
18 Conversion of Biogas to Syngas via Catalytic Carbon Dioxide Reforming… 429
Biogas production worldwide continuously increases during the last decades.

According to IRENA (2017), the worldwide installed capacity for biogas produc-
tion increased from 6323 MW in 2007 to 15,752 MW in 2016. Europe represents
the highest biogas production capacity with 10,533 MW in 2016 or 66.9% followed
by North America with 2639 MW or 16.8% in the same year. In Europe, the top-five
biogas producers are, in descending order, Germany, UK, Italy, France, and
Netherlands (Achinas et al. 2017). In addition, Scarlat et al. (2018) predicted that
biogas production in Europe would still increase with the similar rate during the
next years.
Among different feedstocks, MSW is particularly interesting because of its spe-
cific characteristics. MSW is generated by households and includes various types of
organic and inorganic wastes, which are mostly food waste, waste paper, cardboard,
wood, plastic, rubber, and glass. However, it should be noted that the following
wastes are not considered as MSW sources, e.g., municipal wastewater sludge,
industrial wastes, automobile bodies, combustion ash, or construction and demoli-
tion debris. According to Kaza et al. (2018), the worldwide MSW production is
predicted to increase from 2.01 billion tons in 2016 to 3.04 billion tons in 2030,
mostly due to population explosion and urbanization. MSW composition largely
depends on the income of each country. In high-income countries, MSW contains
less food waste but more paper and cardboard wastes (from packaging), more rub-
ber and leather (from used tires, clothes, and accessories) compared to low-income,
lower-middle, and upper-middle income countries (Kaza et al. 2018). An example
of the typical MSW composition in the United States is presented in Table 18.1. The
total organic biomass content represents 69.5 wt% illustrating the high potential of
biogas generation from MSW.
Up-to-date, the MSW collection is different from each country. In high-income
countries, most of the MSW is collected (~100% for both urban and rural zones).
This collection rate is lower in other countries, around 85%, 71%, and 45% from
urban municipalities in upper-middle, lower-middle, and low-income countries,
respectively. In contrast, 45%, 33%, and 26% of MSW are obtained from the rural
municipalities in the upper-middle, lower-middle, and low-income countries, respec-
tively. Thus, the effort is still needed for improving MSW collection in these coun-
tries. The MSW management by landfill technique is also different from each
country. In several developing countries of low and lower-middle income, and
Table 18.1 MSW composition in the United States (Themelis and Ulloa 2007)
Biomass components Weight % Petrochemical components Weight %
Paper/board 36.2 Plastics 11.3
Wood 5.8 Rubber, nylon, etc. 3.7
Yard trimmings 12.1 –
Food scraps 11.7 –
Cotton, wool, and leather 3.7 –
Total biomass 69.5 Total man-made 15
Reprinted from Renewable Energy 32 (2007) 1243–1257, Themelis NJ, Ulloa PA, Methane gen-
eration in landfills, pp. 1246, Copyright (2006), with permission from Elsevier
particularly in rural zone, MSW is still burnt in open atmosphere without considering
the pollution impacts, technical specification of waste treatment. MSW in some
developing countries is treated in open dumping sites without leachate treatment and
biogas recovery. In developed countries, sanitary landfill sites are used, which are
equipped with lining systems for leachate and biogas recovery, geo-membrane for
securing underground water, covering and drainage systems (Youcai and Ziyang
2017). More research is invited to improve the valorization of biogas generated by
landfill sites in the world.
18.2 Biogas Utilization and Valorization
18.2.1 Heat and Electricity Production
Biogas mainly contains CH4 and CO2 together with other compounds (e.g., water
vapor, N2, O2, H2S, NH3, and siloxanes). One of the primary valorization techniques
is the production of heat and electricity. Biogas production in rural areas can be
directly used for cooking, household heating, and street lightening without purifica-
tion or upgrading. This is largely applied in developing countries with the financial
incentives by local governments to boost cost-effective waste recycling, local income,
and simple utilization (Yasmin and Grundmann 2019; Clemens et al. 2018; Pradhan
and Limmeechokchai 2017; Aziz et al. 2019; Khalil et al. 2019; Mittal et al. 2018).
In large-scale urban regions, biogas can be used as a fuel for producing heat and elec-
tricity. Biogas utilization is found in the following aspects (Kaparaju and Rintala 2013):
1. Production of heat and/or steam using a boiler.

2. Production of electricity combined with waste heat recovery (combined heat
power).
3. Production of heat, steam and/or electricity and cooling using a micro-turbine.
4. Production of electricity using a fuel cell.
It is worth mentioning that raw biogas must be purified before its utilization in an
engine to removal pollutants like sulfur-, nitrogen- and chlorine-containing com-
pounds, siloxanes, etc. (Kaparaju and Rintala 2013). In general, the requirement for
biogas purification can be classified as follows: fuel cell > gas engine, gas turbine
and micro-turbine > stirling engine > boiler (Kaparaju and Rintala 2013).
18.2.2 Biomethane Production
Biogas can also be upgraded into biomethane having the quality of natural gas. This
biomethane can be then injected to the gas grid. This valorization way is nowadays
commercialized in several countries. The pollutants and CO2 must be removed from
biogas to increase CH4 content to at least 80 vol% (Elfattah et al. 2016). Different
methods are available for biogas upgrading including water scrubbing, chemical
scrubbing, biological absorption, pressure swing adsorption, membrane separation,
and cryogenic technology, although each technology has its own advantages and
disadvantages (Khan et al. 2017; Sahota et al. 2018; Angelidaki et al. 2018).
Water scrubbing is a simple method with low operation cost and allows CH4 recov-
ering of more than 80%. However, it requires high energy and water consumption, and
has high corrosion risk because of the dissolution of acid gas like hydrogen sulfide.
Chemical scrubbing is faster and more efficient, but also more expensive than water
scrubbing. Adsorption needs specific operational conditions of pressure, temperature,
and adsorbent to reach high efficiency (Pertiwiningrum et al. 2018). According to
Angelidaki et al. (2018), the applied commercial technologies for biogas upgrading
are as follows: water scrubbing > chemical scrubbing ~ membrane separation > pres-
sure swing adsorption > other technologies. As previously presented, France is in the
top-five biogas producers in Europe. The number of biomethane injection stations to
the gas grid in France was 37 in June 2017, which has increased to 87 in May 2019
with a total production of 1382 GWh/year (GRDF 2019).
18.2.3 Syngas Production
Synthetic gas (or syngas—a gas mixture rich in CO and H2) is well known as a ver-
satile platform gas to produce various chemicals and fuels, e.g., methanol, light
hydrocarbons, gasoline, diesel, waxes, and alcohols (Brown 2011; Puigjaner 2011;
Abdoulmoumine et al. 2015; Liu et al. 2010; Shah 2017; Asimakopoulos et al. 2018;
Abdulrasheed et al. 2019). The commercial syngas is produced from fossil resources,
e.g., coal, natural gas and heavy hydrocarbons by catalytic steam reforming process
(Schildhauer and Biollaz 2016; Liu et al. 2010; Shah 2017). Biogas, mainly contain-
ing CH4 and CO2, can be used as a renewable feedstock for syngas production.
Syngas production by catalytic steam reforming of biogas has been deployed at
large-scale facilities. In the case of the VABHYOGAZ project in France, purified
landfill gas was reformed with a molar ratio of steam/water around 4:1 to produce
syngas, which is similar to the conditions of natural gas reforming, according to Eq.
(18.1). This syngas was later transformed into hydrogen by the water-gas shift pro-
cess (Grouset and Ridart 2018; Nanda et al. 2017). However, the large excess of
steam makes the process highly intensive in energy because the reforming takes
place around 900 °C. Current research on biogas reforming into syngas is focused
on catalytic dry reforming and tri-reforming processes.
As previously mentioned, biogas mainly contains CH4 and CO2. This gas mix-
ture can be transformed into syngas according to Eq. (18.2) which is the chemical
reaction of dry reforming of methane (DRM). In this process, CO2 is the principal
oxidizing agent of the reforming of the CH4 molecule. However, biogas generally
contains more CH4 than CO2. In addition, water vapor and oxygen are generally
present in biogas and can play the role of oxidizing agents in the steam reforming
(Eq. 18.1) and partial oxidation (Eq. 18.3) of methane. The combination of three
reactions, steam reforming, dry reforming, and partial oxidation of methane consti-
tutes the process of tri-reforming of methane (TRM) (Eq. 18.4) (Table 18.2).
Table 18.2 Methane reforming reactions and side reactions

Reaction Equation
Steam reforming CH4 + H2O ↔ 3H2 + CO (∆H°298 = 206.3 kJ/mol) Eq. (18.1)
Dry reforming CH4 + CO2 ↔ 2H2 + 2CO (∆H°298 = 247 kJ/mol) Eq. (18.2)
Partial oxidation CH4 + 0.5 O2 ↔ 2H2 + CO (∆H°298 = − 30.6 kJ/mol) Eq. (18.3)
Tri-reforming xCH4 + yH2O + zCO2 + tO2 ↔ uH2 + vCO Eq. (18.4)
Water-gas shift CO2 + H2 ↔ CO + H2O (∆H°298 = 41 kJ/mol) Eq. (18.5)
Methane cracking CH4 ↔ C(s) + 2H2 (∆H°298 = 75 kJ/mol ) Eq. (18.6)
Boudouard reaction 2CO ↔ C(s) + CO2 (∆H°298 = − 175 kJ/mol) Eq. (18.7)
Carbon gasification C(s) + H2O ↔ CO + H2 (∆H°298 = 131 kJ/mol) Eq. (18.8)
Carbon partial C(s) + 0.5 O2 ↔ CO (∆H°298 = − 110.5 kJ/mol) Eq. (18.9)
oxidation
Carbon combustion C(s) + O2 ↔ CO2 (∆H°298 = − 393.5 kJ/mol) Eq. (18.10)
Biogas reforming into syngas is accompanied by several side reactions

(Eqs. 18.4–18.7), which have an important impact on methane conversion and syn-
gas selectivity as well as catalyst stability. This chapter is focused on the thermody-
namic aspects, catalytic design, and reaction kinetics of dry- and tri-reforming of
methane. The study of the thermodynamic equilibrium allows determining the limit
of a given chemical process under defined conditions of temperature, pressure, and
initial composition. The common method of the thermodynamic equilibrium calcu-
lation is based on the minimization of Gibbs free energy (Faungnawakij et al. 2007;
Nikoo and Amin 2011; Néron et al. 2012).
Nikoo and Amin (2011) have detailed the basis of this method for the dry reform-
ing of methane. Chemical compounds at both gas and solid phases have been con-
sidered. The solid considered in this process is related to solid carbon formed during
the reaction. The gaseous molecules considered include CH4, CO2, CO, H2, water
vapor, methanol, ethylene, ethane, and dimethyl ether (Nikoo and Amin 2011). In
the literature, work has been devoted to the thermodynamic study of dry- and tri-
reforming of methane (Song and Pan 2004; Faungnawakij et al. 2007; Nikoo and
Amin 2011; Jafarbegloo et al. 2015; Abdullah et al. 2017; Pham Minh et al. 2018a,
b; Cao et al. 2018; Chein et al. 2017; Chein and Hsu (2018); Rahnama et al. 2014;
Diez-Ramirez et al. 2016; Rego de Vasconcelos (2016)). Similar conclusions have
been obtained by these studies. This section summarizes the main characteristics of
each process.
18.3 Dry Reforming of Methane
For dry reforming of the methane process, Fig. 18.1 shows the amounts of different
species in equilibrium from an equimolar mixture of CH4 and CO2 (1 mole for each
molecule) at 1 and 16 atm. These results were obtained by ASPEN Plus software on
the principle of Gibbs free energy minimization described elsewhere (Nikoo and
Amin 2011). When the gas mixture is set at 1 atm, solid carbon (C(s)) and water
vapor are strongly favored below 700 °C. On the other hand, H2 and CO are pre-
dominant above 700 °C. The conversion of CH4 and CO2 as well as the selectivity
Fig. 18.1 Thermodynamic equilibrium of a gas mixture initially composed of 1 mol of CH4 and
1 mol of CO2 at (a) 1 atm and (b) 16 atm
of H2 and CO are significantly favored above 900 °C. However, catalyst thermal
sintering can occur at this high temperature, which is considered as irreversible
catalyst deactivation. Therefore, the design of a thermally stable catalyst is a main
challenge of dry reforming of methane. Another characteristic of the dry reforming
process is related to solid carbon formation (Eqs. 18.6 and 18.7).
Wang and Lu (1996) have shown that the upper limit of the Boudouard reaction
is equal to 700 °C while the lower limit of the methane cracking reaction is equal to
557 °C. Theoretically, there is no temperature range wherein solid carbon formation
could be absent. Therefore, dry reforming catalyst must be not only thermally stable
but also resistant to solid carbon formation. The formation of solid carbon can be
reduced by increasing the molar ratio of CO2/CH4. By keeping the temperature at
700 °C and the total pressure at 1 atm, Rego de Vasconcelos (2016) showed that no
solid carbon is formed when the molar ratio of CO2/CH4 is equal to 2.5/1. However,
increasing this ratio also favors the formation of water vapor and slightly decrease
the H2 amount.
Dry reforming of methane produces more gaseous molecules than the initial gas-
eous reactants (Eq. 18.2). Thus, increasing pressure does not favor this reaction.
This decreases CH4 and CO2 conversion as well as H2 and CO selectivity while
increases the selectivity in water vapor and solid carbon (Nikoo and Amin 2011;
Rego de Vasconcelos 2016; Abdullah et al. 2017; Jafarbegloo et al. 2015).
Figure 18.1b illustrates the equilibrium amount of an equimolar mixture of CH4 and
CO2 when the total pressure is set at 16 atm. At 1000 °C and 16 atm, the unreacted
CH4 and CO2 amounts are 11.1 and 8.8%, respectively, which are much higher than
those at 1000 °C and 1 atm (<1%).
18.4 Tri-reforming of Methane
Tri-reforming process combines steam, dry reforming, and partial oxidation of

methane. According to Eq. (18.4), CH4 can be reformed by varying amounts of
water vapor, CO2, and O2. Song and Pan (2004) have proposed a concept of
tri-reforming of methane starting from natural gas (CH4 and CO2 source) and flue
gas (CO2, O2, and water vapor) wherein various mixtures of CH4, CO2, O2, and
water vapor were considered. Pham Minh et al. (2018a, b) have also simulated vari-
ous mixtures of landfill gas with water vapor. From the energetic point of view,
partial oxidation of methane is exothermal (Eq. 18.3), thus heat from this reaction
reduces the energy consumption of the global tri-reforming process (Chein and Hsu
2018). Furthermore, by varying the feeding composition, the molar ratio of H2/CO
can be varied, which is favorable for the downstream application of syngas (Song
and Pan 2004). Above 750 °C and at 1 atm, the tri-reforming process generally has
higher CH4 conversion, higher molar ratio of H2/CO and lower solid carbon amount
compared to simple dry or steam reforming (Song and Pan 2004).
Figure 18.2 shows the thermodynamic equilibrium of a mixture initially com-
posed of 2 mol of CH4, 1 mol of CO2, 1 mol of water vapor, and 0.1 mol of O2 at 1
and 16 atm. The sum of oxidizing agents (O2, CO2, and water) is in excess for com-
pletely converting methane into syngas according to Eq. (18.1–18.3). The composi-
tion of this mixture is obtained from the addition of water vapor to a purified landfill
gas having the molar ratio of CH4/CO2/O2 of 2/1/0.1. At the total pressure of 1 atm,
high temperature of at least 800 °C is required to selectively convert this mixture to
syngas. Under these conditions, solid carbon could be prevented. In addition,
increasing the pressure to 16 bar has negative impacts on reaction conversion and
selectivity. At this pressure and 1000 °C, CH4 conversion only reaches 86.3%.
From the thermodynamic point of view, both dry- and tri-reforming of methane
are strongly influenced by the initial feeding composition, temperature, and total
pressure. The gas mixture containing more oxidizing agents (e.g., water, CO2, and
O2) than the stoichiometric amounts favors CH4 conversion. High temperature also
favors CH4 conversion and syngas selectivity because of the endothermicity of
steam and dry reforming of methane. On the other hand, high pressure is unfavor-
able considering the stoichiometric coefficients of methane reforming reactions.
Fig. 18.2 Thermodynamic equilibrium of a gas mixture initially composed of 2 mol of CH4, 1
mol of CO2, 1 mol of water vapor, and 0.1 mol of O2 at (a) 1 atm and (b) 16 atm
18.5 Catalysts Development
The development of an active and stable catalyst is one of the key points necessary
for the implantation of biogas reforming technologies at large-scale operations.
Catalyst deactivation related to carbon deposition, sulfur poisoning, and catalyst
sintering is one of the biggest issues related to catalytic performance. Therefore,
researches have focused on the development of more resistant catalysts using, for
example, combination of different active metals, new supports, and promoters.
Studies developed through the years on this area have shown that the performance
of the catalysts mainly depends on the active metal used on the nature of the sup-
port, on the metal-support interaction as well as on other features, such as metal
particle size and catalyst surface area. The following topics will discuss the recent
advances in catalyst design and application in dry- and tri-reforming of biogas.
18.5.1 Catalysts in Dry Reforming of Methane
Noble metal-based catalysts have been reported as highly active and stable catalysts
for dry reforming of biogas with only low amounts of coke formation (Papadopoulou
et al. 2012). The main reasons related to the coke resistance of these catalysts are the
small equilibrium constants for the decomposition of CH4 as well as the carbon dis-
solution into their lattices (Papadopoulou et al. 2012). These findings were reported
by Rostrup-Nielsen and Hansen (1993) when they compared the performance of
different noble metals catalysts (Ru, Ir, Pd, Pt, and Rh) on dry reforming of methane
at temperatures varying between 500 °C and 650 °C. Their results showed that
ruthenium (Ru) and rhodium (Rd) had the best catalytic performances with high
selectivity for carbon-free operation, thus proving the high coking resistance.
Similarly, Hou et al. (2006) evaluated the performance of several noble metals (Ru,
Pd, Pt, and Ir) doped on alumina (α-Al2O3) catalysts in the dry reforming of methane
reaction at 950 °C. The results proved the coking resistance and the stability of these
noble metal catalysts with CH4 and CO2 conversions higher than 84%. The follow-
ing order of performance was observed: Rh > Ru > Ir > Pd > Pt. The less efficient
performance of the Pd- and Pt-based catalysts was related to the metal particles
sintering at high temperature.
Despite the high activity and stability of noble metal-based catalysts, their high
cost and low availability render them unattractive for industrial-scale uses. Transition
metals have become a suitable alternative due to their low cost, high availability, and
good activity in the dry reforming reaction (Pakhare and Spivey 2014). Nickel-
based catalysts are often studied since they are already used for advanced reforming
process at industrial scale, such as steam reforming (Eq. 18.1). Goula et al. (2015)
investigated the performance of Ni/Al2O3 catalysts with nickel (Ni) loadings vary-
ing between 8 and 16 wt% on the biogas reforming reaction. The authors reported
that the catalysts with lower nickel loading exhibited higher specific surface area
and low nickel particles than the catalysts with high nickel loadings, which was
related to the coverage of the internal surface area by the nickel species adsorbed on
the alumina active sites. However, the authors reported that the nickel loading had
no direct effect on the catalytic performance. In this case, the preparation method
showed to be the most influencing parameter since it had a direct impact on the
reducibility of the nickel species and thus on the overall performance of the cata-
lysts. The 16 wt% Ni/Al2O3 catalyst prepared by incipient wetness impregnation
method showed the best catalytic performance at 750 °C with CH4 and CO2 conver-
sions equaled to 69.1% and 88.3%, respectively.
Despite their low cost and proven catalytic activity, transition metal-based cata-
lysts have been repeatedly reported as more prone to deactivation due to carbon
deposition than noble metal-based catalysts (Pakhare and Spivey 2014). Kroll et al.
(1997) showed Ni/SiO2 as a better performing catalyst in the dry reforming reaction
at 700 °C showing CH4 conversion of 93% during the first hours of reaction.
However, the catalyst quickly deactivated after less than 10 h of reaction due to
carbon deposition. Hence, recent studies have focused on improving the catalytic
properties of transition metal-based catalysts.
Bi-metallic catalysts using a combination of two transition metals or between
transition metals and noble metals have been tested to improve the catalytic proper-
ties of the catalysts. Among the various combinations of transition metals used,
nickel (Ni) and cobalt (Co) are by far the most investigated combination due to the
synergy between these two metals as well as to the property of cobalt of decreasing
the rate of coke formation (Estephane et al. 2015). The influence of cobalt addition
to the performance of Ni/ZSM5 catalyst on dry reforming reaction at temperatures
ranging from 600 °C to 800 °C was investigated by Estephane et al. (2015). The
authors suggested that the cobalt presence could help oxidizing the carbon species
close to the catalytic sites, thus increasing the stability of the catalyst. The best cata-
lytic result was obtained using a Ni/Co ratio equal to 1:2. This catalyst exhibited
CH4 and CO2 conversion equal to 80% and 85%, respectively, at 800 °C, proving the
good catalytic performance of this bi-metallic catalyst.
Similar results were achieved by Xu et al. (2009). The addition of cobalt signifi-
cantly increased the catalytic performance of the Ni/La2O3-Al2O3 catalyst. The
authors reported CH4 and CO2 conversions equal to 93.7% and 94%, respectively, in
biogas reforming at 800 °C and 290 h when a bi-metallic catalyst with a Ni/Co
molar ratio equal to 7:3 was used. Besides carbon deposition, sulfur poisoning also
leads to catalyst deactivation during biogas reforming. Recent studies have shown
that the use of bi-metallic catalysts could improve the sulfur resistance of the cata-
lysts. Sapountzi et al. (2018) showed that doping Ni/GDC (gadolinia-doped ceria)
catalyst with 2.3 wt% of gold (Au) hindered the formation of strongly bonded sulfur
components by producing an Au-Ni alloy.
The textural and chemical promoters have also been used to improve the catalytic
performance of the catalysts. According to Jang et al. (2019), promoters are usually
used to enhance the textural properties of the catalysts, which helps preventing or
delaying sintering of the active phase. Chemical promoters provide new active sites or
enhance chemical properties, such as basicity and redox property, which prevent car-
bon formation (Jang et al. 2019). San José-Alonso et al. (2011) investigated the use of
potassium (K) and strontium (Sr) on the performance of Co/Al2O3 on CO2 reforming
of CH4 at 700 °C. The authors reported that the Co/Al2O3 catalyst showed CH4 and
CO2 conversions of 73% and 82%, respectively. The percentage of deposited carbon
was 0.53%. When this catalyst was doped with 1 wt% K or 1 wt% Sr, CH4 and CO2
conversions decreased to about 15%. The percentage of deposited carbon also
decreased, achieving 0.08% when K was used. The main reason for the decrease in the
CH4 conversion was related to the partial coverage of the active sites for CH4 decom-
position and to the ability of the catalyst to gasify the carbon species.
Ceria (Ce) has also been reported to improve the coke resistance of the catalysts.
Daza et al. (2010) investigated the effect of Ce addition and loading on Ni/Mg-Al
catalyst on dry reforming at 700 °C. The addition of 1 wt% of Ce to the catalyst was
responsible for increasing CH4 conversion from 34.9% to 88.3%. The authors
reported that Ce addition increased the reducibility and the total basicity of the cata-
lyst, which was responsible for the increase in the catalytic activity. However,
increasing Ce content from 1 to 10 wt% did not have an influence on the catalyst
activity but it greatly hindered the formation of coke deposits. The catalyst doped
with Ce was stable in the reaction conditions during 100 h of reaction.
18.5.2 Catalysts in Tri-reforming of Methane
As presented in the previous sections, tri-reforming is a synergetic combination

between dry reforming, steam reforming, and partial oxidation. Hence, it is not sur-
prising that the catalytic systems used in the tri-reforming process are similar to
those used in the other advanced reforming process and face similar problems, such
as low stability due to coke deposition and metal sintering. However, the tri-reforming
process is a much more complex process due to the presence of three oxidizing
agents (e.g., O2, CO2, and H2O), requiring a catalyst capable of adsorbing and activat-
ing all three reactants efficiently as well as to withstand the highly oxidizing atmo-
sphere. The following topics will briefly present the recent advances in catalyst
development for this process as well as the efforts for scaling up the technology.
Nickel supported on conventional catalytic supports, such as Al2O3, ZrO2, SiO2, and
CeO2 is the most studied active metal. However, these catalysts may behave differently
in tri-reforming conditions mainly due to their re-oxidation by the oxygen in the feed,
which leads to their deactivation (Amin et al. 2015). Majewski and Wood (2014) inves-
tigated the performance of Ni/SiO2 core shell catalyst in steam reforming of methane
in tri-reforming conditions at 750 °C. The authors reported that changing the percent-
age of each oxidizing agent (O2, CO2, and H2O) in the feed mixture had a different
impact on the performance of the catalyst. Increasing the amount of oxygen in the feed
mixture increased the CH4 conversion to 90% but did not improve the H2/CO ratio in
the produced syngas. When steam was not present in the feed, CO2 conversion increased
to 90%, but CH4 conversion decreased. When steam was added with a CH4/H2O ratio
of 1:0.5, the H2/CO ratio of the syngas decreased from 2.5 to 1.5 and coke deposition
increased from 5 mg gcat−1 up to 99 mg gcat−1. These results show the potential of Ni/
SiO2 core-shell catalyst in the tri-reforming process. However, it also highlights the
complexity to maintain high reactants’ conversion and good catalyst stability.
The role of the support in tri-reforming is also not yet defined and further stud-
ies to correlate the physicochemical properties of the catalysts to their perfor-
mance are still needed. Different supports have been used to prepare catalysts for
tri-reforming reaction, including CeO2 (Pino et al. 2011), TiO2 (Jiang et al. 2007),
ZrO2 (Si et al. 2012; Singha et al. 2016; Anchieta et al. 2019), MgAl2O4 (Lino
et al. 2019), and SiC (García-Vargas et al. 2014a, 2014b, 2015b). In attempt to
investigate the influence of different support materials on the performance of
nickel-based catalysts, Kumar et al. (2019) prepared different catalysts using
Al2O3, ZrO2, MgO, CeO2-ZrO2, SBA-15, and TiO2 as the supports and evaluated
their performance in tri-reforming at 800 °C and with a feed composition of CH4/
CO2/H2O/O2/N2 of 1:0.23:0.46:0.07:0.28. The authors reported that Ni/Al2O3 had
the best catalytic performance in the test conditions used with CH4, H2O, and CO2
conversion rates equal to 8.72 × 10−1 mmol gcat−1 s, 4.2 × 10−2 mmol gcat−1 s, and
2.31 × 10−2 mmol gcat−1 s, respectively. However, Ni/CeO2-ZrO2 and Ni/ZrO2
showed better stability against oxidation, due to their redox and oxophilic proper-
ties, respectively. On the other hand, Ni/MgO and Ni/TiO2 catalysts showed only
very low CH4 and CO2 conversion rates since they presented a very low degree of
reducibility. The authors concluded that small Ni particles with high dispersion,
high degree of reducibility, strong metal-support interaction as well as high con-
centration of basic sites on the surface of the catalyst are crucial for the good cata-
lytic performance of the catalysts.
García-Vargas et al. (2014b) investigated the performance of Ni/Al2O3 and Ni/
CeO2 catalysts in tri-reforming conditions at 800 °C. The best catalytic result was
obtained using Ni/CeO2 catalyst, showing CH4 and CO2 consumption rates around
8 and 3 mol s−1 gNi−1, respectively, which was explained by its basic properties. Ni/
Al2O3 showed the lowest CH4 and CO2 conversion rates due to the formation of
NiAl2O4 phase, thus decreasing the reducibility of the catalyst. Pino et al. (2011)
have found that Ni/CeO2 (5 wt%) catalysts prepared by flaming combustion at
350 °C were highly active and selective in tri-reforming of methane at 800 °C with
methane conversion up to 93%. The addition of La slightly increased the catalytic
performance of these catalysts.
Singha et al. (2016) investigated Ni/ZrO2 catalysts synthesized by hydrothermal
method in the reforming of different mixtures containing CH4, CO2, water vapor,
and oxygen at 500–800 °C. In most of the case, CH4 conversion likely linearly
increased with the reaction temperature while the molar ratio of H2/CO varied in
narrow range of 1.7–2.0. The optimal Ni content was found at 4.8 wt%, explained
by the dependency of Ni particle size on Ni content. At 800 °C, this catalyst was
found very active and stable with reactants’ conversion close to 96–98% for 100 h
of reaction time. This catalytic performance was mostly explained by the formation
of metal nanoparticles strongly interacted with the support.
During the last decade, much work has been devoted to the design of a per-
forming catalyst for biogas reforming, e.g., dry- and tri-reforming. Nickel has
been found as the most appropriate active metal for these processes. Such a cata-
lyst is generally constituted of (a) a thermally stable support at 700–1000 °C, (b)
highly dispersed metal particles (<40 nm), (c) strong metal-support interaction,
and (d) controlled basicity. The addition of promoters could also improve catalyst
performance. Despite encouraging results, large pilot application of dry- and tri-
reforming is still limited.
18.5.3 Catalyst Supports
Besides the active metal and promoters, the nature of the support also plays a sig-
nificant role in the performance of the catalysts. Catalyst supports provide mechani-
cal and thermal stability to the catalysts and confer high specific surface area,
leading to high metal dispersion, which favors the CH4 adsorption and dissociation
(Papadopoulou et al. 2012). Moreover, strong metal-support interaction is respon-
sible for the high stability of the metal particles during the reaction, which will
prevent sintering and coking (Jang et al. 2019). Other support features, such as
basic-acid characteristics and oxygen storage capacity also play an important role in
the overall performance of the catalysts (Mohamedali et al. 2018).
Al2O3 is one of the support materials most used for reforming applications due to
its low cost and high mechanical and thermal stability (Papadopoulou et al. 2012).
Mo et al. (2015) recently investigated the application of Ni/Al2O3 porous catalysts
in dry reforming of CH4. The catalyst synthesized by hydrolysis-deposition method
had high specific surface area of 477 m2/g and small nickel particles of about 7 nm,
which ensured high CH4 and CO2 conversions of around 95% during 10 h of time
on stream. However, depending on the synthesis method used, large metal particles
(>10 nm) or even phases difficult to reduce, such as nickel aluminate can be formed,
thus decreasing the performance of the catalyst. The acid sites present in this sup-
port rendered the alumina-based catalysts more prone to deactivation by carbon
deposition.
Hydrotalcite-like materials containing aluminum (Al) and magnesium (Mg)
have been intensively investigated for dry reforming applications mainly due to
their basic character, which improve coke gasification to their high surface area and
to the presence of di and trivalent cations that leads to a homogeneous distribution
of the active phase in the matrix (Dębek et al. 2015). de Vasconcelos et al. (2018a)
recently investigated the performance of MgAl hydrotalcite-based catalysts doped
with Ni and with MgO loads varying from 0 wt% to 70 wt% in the dry reforming
reaction at 700 °C. The authors reported that the catalyst with an MgO loading of
70 wt% presented the best catalytic performance with CH4 and CO2 conversions
around 80% during 50 h of time on stream as well as the lowest deactivation rate of
about 0.004% h−1. The catalytic performance of this catalyst was related to the pres-
ence of strong basic sites that favored the carbon gasification during the reaction.
Moreover, a NiO-MgO solid solution was formed, which stabilized the active phase
and prevented its sintering.
Rare earth-based supports, specially ceria, have been also been studied due to its abil-
ity to enhance the availability of hydroxyl (OHads) and surface oxygen (Oads) species,
which controls the formation of carbon deposits (Papadopoulou et al. 2012). Wolfbeisser
et al. (2016) studied the dry reforming reaction over ceria- zirconia-
supported Ni
catalysts at 600 °C. The authors reported that the presence of Ce did not improve the
catalytic stability of the catalyst. However, it considerably increased its stability but hin-
dering the formation of filamentous coke. The authors further reported that the influence
of ceria strongly depends on the catalyst synthesis method, which can affect the pres-
ence of surface oxygen species and of oxygen vacancies. These factors are crucial for
the carbon removal at the metal/support surface.
Ceria/zirconia-based supports have been investigated by many authors (Djinovic
et al. 2012, 2015; Aw et al. 2014a, b, 2015; Djinovic and Pintar 2017). Solid solu-
tions of ceria/zirconia with high specific surface area, high oxygen storage capacity,
and high interaction with nanoparticles of nickel and cobalt as active metals have
been found as the main factors responsible for high catalytic performance in dry
reforming of methane. These catalysts strongly limited the formation of coke during
dry reforming reaction. However, water has been usually found as byproduct with
high selectivity (up to 20% in the gas mixture at the reactor outlet) (Aw et al. 2015),
suggesting that the designed catalyst favors reversed water-gas shift reaction.
Finally, hydroxyapatite (HAP, chemical formula: Ca10(PO4)6(OH)2) has also
been found as a new promising catalyst support for the dry reforming of methane
(Boukha et al. 2007, 2019; de Vasconcelos 2016; de Vasconcelos et al. 2018a, c;
Phan et al. 2018). Hydroxyapatite-supported metals catalysts (e.g., Pt, Ni, and Co)
have been found active, selective, and stable in dry reforming reactions and are
competitive compared to catalysts prepared from conventional supports like Al2O3
and MgAl2O4 (de Vasconcelos et al. 2018a). The performance of hydroxyapatite in
this reaction could be explained by a high thermal stability, a controlled acido-
basicity via the molar ratio of Ca/P, and a good cation exchange capacity allowing a
strong support-metal interaction between metal nanoparticles and hydroxyapatite
surface (de Vasconcelos 2016; Boukha et al. 2019).
18.6 Kinetic Models and Mechanism Aspects
In this section, an overview of reaction mechanisms and kinetics for dry- and tri-
reforming of methane are systematically discussed. Understanding the inherently
catalytic mechanisms and establishing comprehensive kinetic models for precisely
predicting the consumption and formation rates of the corresponding reactants and
products are crucial for catalyst design, process optimization, and reactor fabrica-
tion and scale-up.
18.6.1 Kinetics of Dry Reforming of Methane
Dry reforming of methane is widely known as a highly endothermic reaction,

which is thermodynamically favored at high reaction temperature (Aramouni et al.
2018). However, at such high reaction temperature, dry reforming is also accompa-
nied by several parallel side reactions such as CH4 decomposition, which provoke
carbonaceous deposits leading to catalytic deactivation (Pakhare and Spivey 2014;
Kawi et al. 2015; Bian et al. 2017). Therefore, the understanding of fundamental
dry reforming mechanism is crucial for kinetically resisting carbonaceous forma-
tion and simultaneously enhancing syngas yield as well as H2 selectivity. Generally,
the mechanistic pathways for syngas production from dry reforming of methane
can be summarized into four major mechanisms, such as: (a) dissociative CH4
adsorption, (b) dissociative CO2 adsorption, (c) formation of hydroxyl groups, and
(d) oxidation and desorption of intermediate species. The comprehensive review
for these main dry reforming mechanisms is provided as follows:
1. Dissociative CH4 adsorption: The dissociation energy for CHx-H bonds in CH4
reactant on the catalyst surface is mainly reliant on the intrinsic attributes of
active phases and CH4 dissociation step is widely recognized as the rate-
determining step in dry reforming of methane (Tang et al. 2014; Horn and
Schlögl 2015). In particular, CH3 species are adsorbed on the top of active metal
atoms, whereas CH2 species are adsorbed in the middle of two active metal
atoms also referred as bridged adsorption (Tang et al. 2014).
2. Dissociative CO2 adsorption: CO2 adsorption and dissociation are dependent on
surface structure and structural defects of catalysts (Aramouni et al. 2018). In
fact, this process can occur through three routes including C-only coordination,
O-only coordination (in which an active metal surface is bonded with two
O-atoms), as well as C and O coordination (wherein C and O atoms are adsorbed
on catalyst surface meanwhile another O atom is left to expose) (Papadopoulou
et al. 2012; Guharoy et al. 2018).
3. Formation of hydroxyl groups: Numerous dry reforming kinetic studies reveal
that the water-gas shift (WGS) reaction nearly reaches equilibrium, indicating
the rapid rate of associated surface reaction. The adsorbed H species from H2
spillover on active metal surface reportedly migrate to support and subsequently
react with adsorbed O-species to form hydroxyl groups. However, this process is
unfavorable at high temperature beyond 800 °C (Papadopoulou et al. 2012;
Bobadilla et al. 2017).
4. Oxidation and desorption of intermediates: The adsorbed CHx species on active
sites, denoted as S-CHx, could react with surface oxygen leading to the formation
of S-CHxO and/or S-CO groups. Several proposed pathways for CO formation
reportedly include the generation of intermediate S-CHxO species and reduction
of carbonates (formed by adsorbed CO2) by surface carbon species. In general,
the formation and/or decomposition of S-CHxO species to H2 and CO gases are
recognized as the rate-determining step (Papadopoulou et al. 2012; Jiang et al.
2017; Das et al. 2018).
In general, the kinetic models typically employed in dry reforming of methane

can be mainly categorized into empirical power law, Langmuir Hinshelwood-
Hougen Watson (LHHW), and Eley Rideal (ER) models. Amongst these kinetic
models, the practical and most simple power law model, as provided in Eq. (18.11),
is commonly used since it is regarded as one of the easiest computational models for
estimating the pertinent reaction parameters.
−rCH4 = kPCH
m
4
n
PCO 2
(18.11)
where k and Pi (i: CO2 or CH4) are the corresponding apparent rate constant of
CH4 and partial pressure of reactants, while m and n represent the reaction orders for
the corresponding CH4 and CO2 reactants, and –rCH4 is the CH4 reaction rate.
The simplicity of power law model, which does not require the full understand-
ing of elementary dry reforming reaction steps since this model is not derived from
mechanistic pathways has made it to be extensively employed in many studies for
approximate kinetic parameters estimation. As the power law model is not based on
the surface mechanism of dry reforming of methane, this model is slightly inaccu-
rate and inappropriate for the investigation of wide-ranging feedstock compositions
in comparison with other mechanism-based kinetic models. Nevertheless, this
empirical model is advantageous for providing an initial guess of reactants’ power
constants and apparent activation energy, Ea (kJ mol−1). These useful parameters can
be used for the justification of catalytic activity and comparison purpose among
reported catalysts in literature.
Table 18.3 lists the computed reaction orders of CH4 and CO2 reactants and CH4
activation energy obtained via power law model for numerous catalysts in recent
dry reforming studies. Ayodele et al. (2016) found that CH4 and CO2 reaction orders
were 3.66 and 0.35, respectively, with the apparent CH4 activation energy of 96.4 kJ/
mol on the La2O3-supported cobalt catalyst in dry reforming of methane. The higher
CH4 reaction order than that of CO2 could indicate the larger dependence on CH4
partial pressure for CH4 dissociative adsorption. In addition, they found that the
great oxygen storage capacity of La2O3 support supplied mobile lattice oxygen to
enhance coke gasification from the catalyst surface. This evolution reasonably
explains the low CH4 activation energy (96.4 kJ/mol) on Co/La2O3 compared to
other catalysts such as Pt/ZrO2 (Wei and Iglesia 2004) and Ni/α-Al2O3 (Cui et al.
2007) with Ea of 100.56 and 106.84 kJ/mol, correspondingly.
In the kinetic study of dry reforming of methane over SmCoO3 perovskite cata-
lyst, Osazuwa et al. (2017) found similar activation energy values for CH4 and H2
whereas CO2 activation energy was reportedly close to that of CO. Thus, they sug-
gested that H2 and CO formation rates were mainly affected by the corresponding
CH4 and CO2 consumption rates. Karam and Hassan (2018) used SBA-15 supported
Ni catalysts for dry reforming of methane and found that the activation energies of
reactants (e.g., CH4 and CO2) were smaller than those of products (e.g., H2 and CO),
indicating that the formations of H2 and CO via surface reaction between adsorbed
species are the rate-determining step.
As previously mentioned, the empirical power law models cannot elucidate the
involvement of inherent elementary steps on surface reaction during dry reforming
of methane since these models are mainly reliant on statistical criteria and could
yield untrue kinetic parameter values. Hence, ER and LHHW models are broadly
implemented to capture reactant consumption rates and product distribution in dry
reforming as they are derived from the intrinsic mechanistic reaction steps. In the
dry reforming study of Ru or Pt loaded TiO2, Singh and Madras (2016) found that
the typical peaks belonging to CO2 adsorption were not detected but CO2 in the gas
Table 18.3 Kinetic parameters obtained via power law models for dry reforming on various catalysts
Reaction order
Apparent CH4 activation energy, Ea (kJ/Mol) m n
Catalyst Temperature (°C) CH4 CH4 CO2 References
Co/La2O3 650–750 96.4 3.66 0.35 Ayodele et al. (2016)
Ir-Ni/SBA-15 580–620 26.4 1.54 0.69 Karam and Hassan (2018)
Ni/SBA-15 580–620 35.1 0.99 0.97 Karam and Hassan (2018)
Ni0.07Mg0.93O 500–700 84.0 1 – Zhou et al. (2018)
Ru0.003Ni0.067Mg0.93O 500–700 92.0 1 – Zhou et al. (2018)
Ru0.07Mg0.93O 500–700 74.0 1 – Zhou et al. (2018)
SmCoO3 700–800 41.0 1.15 0.33 Osazuwa et al. (2017)
18 Conversion of Biogas to Syngas via Catalytic Carbon Dioxide Reforming…
443
444
Table 18.4 Representatives of LHHW and ER kinetic expressions for dry reforming of methane
Catalyst Assumption Mechanistic pathways Kinetic model Eq. No. Refs.
Pt/TiO2 Molecularly adsorbed K1
(18.12) Singh
CH4 with the k2 K1K 3 K 4 PCO2 PCH4 and
CH 4 + S∗ ↔ CH 4 − S −rCH4 = 2
dissociation of CH4 as k2 K 3 K 4 PCO + PCO (
+ 1 + K1PCH4 K 3 K 4 PCO2) Madras
RDS CH 4 − S → 2H 2 + C – S ( RDS∗ ) (2016)
K3
C – S + CO2 + S ↔ 2CO – S
K4
2CO – S ↔ 2S + 2CO
NiCeMgAl CO2 and CH4 K1 4 8

(18.13) Bao
dissociative adsorption CH 4 + S ↔ CH 4 − S K14 K 24 K 34 K 44 K 64 K 74 PCH P4
4 CO2 
C1  et al.
−rCH4 = k5 4  
and the removal of K2 PCO P6  DEN  (2017)
2 H2
adsorbed C species by CH 4 − S + 4S ↔ C – S + 4H – S
adsorbed OH as RDS K3
K1K 2 K 62 PCH4 PH02.5
DEN = 1 + K1PCH4 + + + K 3 PCO2
CO2 + S ↔ CO2 – S PH22 K 60.5
K4
0.5
CO2 – S + H – S ↔ CO – S + OH – S PCO K3 K 4 K 7 PCO2 PH2
k5
+ +
K7 K 60.5 PCO
C – S + OH – S → CO – S + H – S ( RDS)
K6
2 H – S ↔ H 2 + 2S
K7
CO – S ↔ CO + S
D. Pham Minh et al.
La2RhZr2O7 CO2 and CH4 K1
(18.14) Pakhare
dissociative adsorption k2 K 4 PCO PH2 et al.
CH 4 + S ↔ CH 4 − S −rCH4 = (
PCH4 1 + K1PCH4 )
and CH4 dissociation k2 K1 K 3 K 5 K 6 PCO PH2 PCO2 (2014)
as RDS CH 4 − S → C – S + 2H 2 ( RDS)
K3
CO2 + S ↔ CO2 – S
K4
CO2 – S ↔ O – S + CO
K5
H2 + O – S ↔ S + H2O
K6
C – S + H 2 O ↔ S + CO + H 2
∗
S and RDS represent the corresponding active site and the rate-determining step, whereas Ct is the total number of active sites
18 Conversion of Biogas to Syngas via Catalytic Carbon Dioxide Reforming…
445
phase was observed in in-situ Fourier transform infrared spectroscopy (FTIR) stud-
ies. In addition, adsorbed CH4 species on catalyst surface were evidenced suggest-
ing that dry reforming of methane over the abovementioned catalysts followed the
ER mechanism. Thus, an ER kinetic model was proposed with the assumption of
molecularly adsorbed CH4 on active site and the subsequent CH4 dissociation as the
rate-determining step as shown in Eq. (18.12) of Table 18.4. The dissociated carbon
species were further reacted with CO2 in the gas phase to yield CO gas. This derived
ER model demonstrated an excellent validation with experimental data.
Bao et al. (2017) examined NiCeMgAl catalyst for dry reforming of methane and
developed an LHHW kinetic model (Eq. 18.13 in Table 18.4) based on the assump-
tion of irreversibly adsorbed carbon gasification by surface –OH species as a rate-
determining step and consideration of the significant contribution of the reverse
water-gas shift reaction. Both CO2 and CH4 reactants were also assumed to adsorb
dissociatively on the same active site of catalyst. The fitting of CH4 consumption
rate data to the derived kinetic model showed a high correlation coefficient of 0.97,
indicative of satisfactory projection for dry reforming reaction rate.
In the kinetic and mechanistic studies of dry reforming of methane over
La2RhZr2O7 pyrochlores, Pakhare et al. (2014) conducted the deuterium kinetic iso-
tope experiments with the employment of CD4 during dry reforming and revealed
that the rate-determining step was CH4 activation or dissociation on active sites.
Hence, an LHHW model involving dissociative CH4 adsorption as a rate-determining
step (Eq. 18.14 in Table 18.4) was proposed and in line with the obtained experi-
mental data of kinetic and transient pulsing measurements.
18.6.2 Kinetics of Tri-reforming of Methane
Tri-reforming of methane is typically a synergistic combination of multiple reac-

tions involving steam reforming of methane (SRM), dry reforming of methane, and
partial oxidation of CH4 (Song and Pan 2004). However, the kinetic and mechanistic
studies of tri-reforming of methane are comparatively less than other reforming
reactions owing to its complexity with the highest number of concomitant side reac-
tions. Thus, mechanistic and kinetic investigation of tri-reforming of methane would
turn out to be a crucial and alluring research area in the coming years.
The fundamental understanding of mechanism-derived kinetics is still vague and
fewer studies have been carried out for tri-reforming of methane. Song and Pan
(2004) conducted the first kinetic study of tri-reforming of methane over Ni-based
catalysts. To identify the varied CO2 conversion rate associated with reactant partial
pressures, an empirical power rate law (Eq. 18.15) was simplified by retaining the
CH4 and O2 partial pressures as constants. Therefore, the contribution of CH4 and O2
partial pressures would be reflected by other model parameters:
 − E app  α β
− ri = A exp   PCO2 PH2 O (18.15)
 RT 
where −ri, Eapp, and A are the corresponding CH4 or CO2 reaction rates, apparent
activation energy, and pre-exponential factor. PH2O and PCO2 are the partial pressure of
H2O and CO2 reactants, whereas α and β are reaction orders belonging to CO2 and
H2O, respectively. The computed values of kinetic parameters obtained from Eq.
(18.15) for tri-reforming of methane over different Ni-based catalysts are summa-
rized in Table 18.5. From the experimental data and computational results, Song and
Pan (2004) observed the negative reaction order values for H2O reactant during the
fitting of CO2 consumption rates to the abovementioned power law model (Eq. 18.15)
for all catalysts. This observation indicated the competitive adsorption between H2O
and CO2 on the catalyst surface for reacting with CH4 to yield H2 and CO. As a result,
an increase in PH2O reasonably reduced the rate of CO2 consumption. As seen in
Table 18.5, reaction orders also varied considerably depending on catalysts employed.
To intrinsically scrutinize the interaction between catalyst surface and CO2 mol-
ecule with respect to mechanistic steps, they also employed a simplified LHHW
model, which was derived from dry reforming side reaction for minimizing the
intricacy of tri-reforming of methane. These mechanistic steps including the adsorp-
tion of CH4 and CO2 reactants as well as surface reaction are provided in Table 18.6.
As seen in the simplified kinetic model, the interaction between catalyst surface and
CO2 molecules was the major factor accounting for the equilibrium CO2 adsorption
constant, i.e., K2. The enhancing interaction of CO2 with catalyst surface would
provoke an increase in the number of adsorbed CO2 species at high PCO2. Hence,
these adsorbed CO2 species occupied most of active sites available for CH4 adsorp-
tion, thereby inducing a drop in CH4 consumption rate. This could be indicative of
negative CO2 reaction order.
In the assessment of Ni-Mg/β-SiC at varied temperature and reactant feed ratios
for tri-reforming of methane, García-Vargas et al. (2015b) observed that methane
partial oxidation with the rapid achievement of full conversion was the predominant
process among other concomitant main reactions since oxygen reactant was virtu-
ally absent in gaseous effluent from tri-reforming of methane. Based on this obser-
vation, a kinetic model merely in association with steam reforming, dry reforming,
and water-gas shift reaction was proposed for capturing the individual rate of these
reactions (see Table 18.7). The apparent activation energy of steam reforming, dry
Table 18.5 Kinetic parameters obtained from simplified power law model for tri-reforming of
methane by Song and Pan (2004)
Kinetic parameters Ni/Al2O3 Ni/MgO Ni/MgO/CeZrO
Effect of PCO2
α, CH4 0.79 –0.87 0
α, CO2 1.90 0.53 0.98
Effect of PH2O
β, CH4 –0.06 –0.64 0.03
β, CO2 –1.57 –2.59 –1.08
Apparent activation energy, Eapp (kJ/mol)
CO2 247.0 160.1 165.7
CH4 69.1 219.6 67.4
Table 18.6 Tri-reforming of methane mechanistic steps for LHHW model proposed by Song and
Pan (2004)
Elementary steps Kinetic model
Adsorption of reactants
kK1K 2 PCH4 PCO2
K1
−rCH4 =
CH 4 + S ↔ CH 4 − S
(1 + K P )
2
1 CH 4 + K 2 PCO2
K2
CO2 + S ↔ CO2 − S
Reaction on catalysts surface
k
CH 4 − S + CO2 − S → 2H 2 + 2CO + 2S ( RDS )
Note: k and S represent the rate constant and accessible active sites, respectively
Table 18.7 Kinetic expressions and estimated parameters for steam reforming, dry reforming,
and water-gas shift reaction side reactions of tri-reforming of methane (García-Vargas et al. 2015a)
Reactions Kinetic parameters Kinetic models
Steam reforming of
methane (SRM) E a1 = 74.7 kJ/mol  PH3 2 PCO 
rSRM = k1PCH4  1 − 
 K SRM PCH PH O 
 4 2 
k10 = 85.8 mol s−1 kPa−1
 −26830 
 
K SRM = 1.198 × 1017 e T 
Dry reforming of
methane (DRM) E a2 = 77.8 kJ/mol  PH22 PCO
2

rDRM = k 2 PCH4  1 − 
 K DRM PCH PH O 
 4 2 
k 02 = 71.0 mol s−1 kPa−1
 −31230 
 
K DRM = 6.780 × 1018 e T 
Water-gas shift
reaction (WGS) E a3 = 54.3 kJ/mol  PH O PCO PCO2 
rWGS = k 3  2 − 
 PH K WGS 
 2 
k 30 = 149.9 mol s−1 kPa−1
 2078 
 −2.029 
K WGS = 10 T 
reforming, and water-gas shift reaction is 74.7, 77.8, and 54.3 kJ/mol, respectively,
and the kinetic models show a relatively good fitness to experimental data with
mean deviations from 10.8% to 19.4%.
Unlike the kinetic expressions suggested by García-Vargas et al. (2015a), Chein
et al. (2017) proposed that different kinetic rate models involved steam reforming,
reverse CO2 methanation (RCM), and water-gas shift reaction (Table 18.8) since they
found that the presence of H2O induced a great influence on tri-reforming reaction
rate in their parametric investigation. They also reported that in the absence of water,
Table 18.8 Kinetic rate models for steam reforming, reverse CO2 methanation, and water-gas
shift reactions in tri-reforming of methane (Chein et al. 2017)
Reactions Kinetic rate models
Steam reforming of
methane (SRM) k1  PH3 PCO 
2.5 
PCH4 PH2O − 2 
PH2  K SRM 
rSRM =
DEN 2
 −26830 
 
K SRM = 1.198 × 1023 e T 
 −240100 
 
k1 = 3.711 × 1017 e RT 
K H2O PH2O
DEN = 1 + K CH4 PCH4 + K CO PCO + K H2 PH2 +
PH2
Water-gas shift reaction

(WGS) k2  PH2 PCO2 
 PH2O PCO − 
PH2  K WGS 
rWGS = 2
DEN
 4400 
 
K WGS = 1.767 × 10 −2 e T 
 −67130 
 
k 2 = 5.431e RT 
Reverse CO2 methanation

(RCM) k3  PH42 PCO2 
 P P 2
− 
PH3.25  4 2 
CH H O
K RCM 
rRCM =
DEN 2
KRCM = KSRMKWGS
 −24390 
 
k 3 = 8.96 × 1016 e RT 
Note: Denominator DEN
dry reforming of methane became the predominant reaction inducing a low H2/CO
ratio of 1, while steam reforming of CH4 was the main reaction with the absence of
CO2 reactant.
As partial conclusion, this section presents a comprehensive review on various
kinetic models derived from the respective rate-determining step in association with
different proposed mechanistic steps. Many kinetic models were widely reported
into three forms, namely power law, ER, and LHHW models. The power law models
could provide empirical reaction orders to reveal the dependence of reaction activity
on reactant partial pressure. However, it could not reflect the essential influence fac-
tor of rate-determining step toward catalytic activity with respect to mechanistic
pathway. Thus, numerous rate-determining steps presented in LHHW and ER mod-
els have been suggested for predicting the consumption rate of reactants. Generally,
these rate-determining steps involve C–H bonds cleavage in CH4 molecule on metal,
dissociation of oxidizing agent (e.g., O2, CO2, or H2O) on metal or support, formation
of intermediate species and decomposition, oxidation of carbonaceous species, and
several other parallel reactions. To implement the dry reforming and tri-reforming
technologies for industrial application, the best-fit kinetic modeling associated with
the intrinsic dry reforming and tri-reforming mechanism is indispensable for effi-
ciently designing the catalyst system and optimizing the reactor design.
18.7 Industrial Applications
Despite the interest in scaling up this technology, problems related to catalyst activ-
ity and stability still need to be solved to advance the readiness level of this process.
To the best of our knowledge, only very few reports are available on the literature
regarding the scale-up of dry reforming of methane. Rego de Vasconcelos and
Lavoie (2018) recently reported the scale-up of a dry reforming technology com-
bined with renewable electricity. In this case, an electrified fixed-bed reactor is used
in combination with steel wool as a catalyst. The tests performed showed CH4 and
CO2 conversions equal to 100% over 200 h of time on stream. The advantages of
this approach are the very low cost and the good catalytic performance of the cata-
lyst as well as the use of renewable electricity to provide the energy to the reaction.
The technology evolved from bench scale with capacity of treating less than 1 L/
min of a mixture containing CH4 and CO2 to a pilot capable of treating 40 L/min of
the same gaseous mixture. The technology developed is compatible for biogas, tail
gas, and natural gas.
The Linde Group has also claimed the development of an innovative dry reform-
ing process that convert large volumes of CO2 into syngas using a nickel-based cata-
lyst, which has been tested for more than 1000 h (Linde 2019). Besides CH4 and
CO2, water is also used in this process to prevent catalyst deactivation by coke for-
mation (Tullo 2016). The Linde Pilot Reformer research facility is located at Pullach
(Germany) and is currently under scale up for commercial application.
Steam reforming of natural gas has been deployed at large industrial scale. This
technology can be transposed to the reforming of landfill gas, as the case of the
VABHYOGAZ3 project, financed by ADEME in France (ADEME 2016). This
project aims to design a complete production chain of liquid hydrogen production
from landfill gas containing up to 60% of CH4. Landfill gas is firstly reformed into
syngas at around 900 °C, with a large excess of steam (molar ratio of steam/methane
of around 4:1). In fact, the landfill gas used in this project containing CH4, CO2, and
O2 is fed together with steam to the reforming catalytic reactor. The syngas is then
converted into a mixture rich in H2 and CO2 by water-gas shift reaction. Pure hydro-
gen (99.99%) is obtained by the pressure swing adsorption process, which is then
compressed to 350–700 bar into liquid hydrogen for injection in hydrogen-fueled

vehicles. CO2 obtained from the pressure swing adsorption process is valorized by
producing sodium bicarbonate for flue gas treatment. The current production unit
developed by the industrial partners of this project has a capacity of 10 kg of liquid
hydrogen per day (ADEME 2016; Pham Minh et al. 2018a, b). The consortium of
this project can deploy production units of 80–800 kg of liquid hydrogen per day
from landfill gas with competitive cost of liquid hydrogen versus other production
ways (e.g., electrolysis of water).
18.8 Conclusions
Biogas production from biological degradation of biomass and biowaste continu-

ously increases worldwide. Heat and electricity production from biogas have been
largely deployed. Current research and development on biogas valorization mostly
consists in the production of value-added chemicals via biogas reforming. Both dry-
and tri-reforming processes need high temperature (e.g., 800–1000 °C) and low
pressure (e.g., atmospheric pressure) to reach high methane conversion. The utiliza-
tion of a performing catalyst is indispensable to obtain exploitable reaction rate and
good syngas selectivity. The main criteria of such a catalyst include high thermal
stability, high coke resistance, high activity, and stability. Nickel is the most appro-
priate active metal for biogas reforming, while various supports have been found
suitable. Significant efforts have also been devoted to kinetic and mechanism stud-
ies of dry- and tri-reforming processes. This is mandatory for reactor design for
further deployment of these processes at large-scale.
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Opportunities for Biodiesel
Compatibility as a Modern Combustion 19
Engine Fuel
Swarup Kumar Nayak, Purna Chandra Mishra, Sonil Nanda,

Biswajeet Nayak, and Muhamad Mat Noor
Abstract
This chapter summarizes the feasibility of effective utilization of biodiesel in mod-
ern vehicle engines. The parameters discussed in this chapter include diesel engine
characterization and diagnostics including performance, emissions, and combus-
tion behavior. The lifecycle and economic analyses with future scope of biodiesel
are also described. From the review, it is conferred that a huge proportion of bio-
diesel is produced from edible vegetable oils, which is a threat to the food supply.
Biodiesel sources are focused upon non-edible oils and other feedstocks that do not
compete with the food crops. Therefore, the selection of appropriate feedstock is
essential to confirm the low-cost production of biodiesel. Concerning the engine
characteristics and combustion diagnostics, it can be ensured that biodiesel
improves engine performance and emission characteristics with little engine modi-
fications such as injection timing, pressure, exhaust gas recirculation, etc. The
review holds well on the possibility of using biodiesel in diesel engines, but still it
is not economically viable and needs more research and technology advancements
to make it competitive with other conventional fuels in the market.
S. K. Nayak · P. C. Mishra (*)

School of Mechanical Engineering, Kalinga Institute of Industrial Technology (KIIT
University), Bhubaneswar, Odisha, India
S. Nanda
B. Nayak
Department of Mechanical Engineering, Einstein Academy of Technology and Management,
Bhubaneswar, Odisha, India
M. M. Noor
Faculty of Mechanical Engineering, Universiti Malaysia Pahang, Pekan, Pahang, Malaysia

458 S. K. Nayak et al.
Keywords
Biodiesel · Transesterification · Greenhouse gas emissions · Engine performance
· Non-edible oil
19.1 Introduction
Energy has turned into an essential component of humankind to keep the monetary
development and maintain an exclusive requirement of livelihood and living wage.
It is envisaged that the world could require more than half of the energy that is being
utilized now by the year 2030, of which a significant portion may be utilized by
rapidly developing countries like India and China (Shahid and Jamal 2011; Atabani
et al. 2012; Nanda et al. 2015). The worldwide transportation and energy utilization
is foreseen to increase by a standard of 1.8% every year by 2035 (USEIA 2010).
Despite the fact that fossil fuel tends to abide by the best antecedent of vitality, the
oil contribution in the world market is foreseen to decrease only at a small fraction
from 35% in 2007 to 30% in 2035 (Shahid and Jamal 2011; USEIA 2010). It is
accepted that the environmental degradation and ecosystem imbalance are currently
the most important problems faced by the world related to fossil fuel extraction and
utilization (Rana et al. 2018, 2019). It is anticipated that nearly 8 billion metric tons
of CO2 could be discharged into the environment until 2035 due to rapid industrial
development and globalization (Atabani et al. 2011).
Globally, the transportation sector represents roughly 22% of aggregate CO2
emissions in 2008 (Atabani et al. 2011). On-road transportation contributes to
around 10% of the worldwide greenhouse gas (GHG) emissions (Nayak et al.
2017a, b). GHGs mainly consist of CO2, CH4, CO, CO, NOx, CO, and aerosols. In
2008, roughly 30% of the U.S. GHG emissions originated from the transportation
part. Thus, transportation sector is the second largest source of GHG emissions in
the United States (Sharma and Singh 2009). According to the current appraisals, oil
reserves in India can continue for the next 20–25 years. Recently, the per capita
emission of CO2 in India has increased from 0.5 to 1.7 metric tons per year.
Biofuels seem to be promising in terms of reducing the dependency on fossil fuels
and mitigating the GHG emissions (Nanda et al. 2017). Lignocellulosic biomasses
such as agricultural crop residues and woody biomass can be effectively converted to
biofuels such as biodiesel, bio-oil, bioethanol, biobutanol, biohydrogen, biomethane,
synthesis gas, etc. (Nanda et al. 2014, 2016). Biodiesels are produced as monoalkyl
esters of long-chain fatty acids derived from vegetable oils, animal fats, and alcohols
with or without using a catalyst (Nayak et al. 2017a; Reddy et al. 2018). Compared
to fossil diesel, biodiesel produces negligible emissions of SOx, CO, CO2, particulate
matter, and hydrocarbons. More free oxygen leads to complete combustion and
reduced emission (Nayak et al. 2017b). The increasing cost of edible vegetable oils
is one of the major concerns for many Asian countries. There is a need for dedicated
feedstock research and identification of superior biomass species, which could pro-
duce appreciable quality and quantity of biodiesel.
19 Opportunities of Biodiesel Compatibility as a Modern Combustion Engine Fuel 459
The main motivation behind this chapter is to discuss the evolution of next-
generation biodiesel and its compatibility in modern diesel engines with complete
analysis of performance, emission, combustion, engine durability, and wear and tear
analysis. After a comprehensive literature survey, it was viewed that minimal infor-
mation is available on the usage of next-generation biodiesel in the modern or
hybrid diesel engines. Hence, the objective of the present chapter is to display an
extensive report on:
1. Biodiesel evolution and its compatibility in present diesel engines without any
engine modification.
2. Synthesis of the available literature and summarize the opportunities and
challenges.
3. Experimental data quantifying the performance, emissions, and combustion
analysis of biodiesel.
19.2 Biodiesel Properties and Measurement Methods
Biodiesel standards are being prescribed globally to maintain its quality in the
competitive market. Since biodiesel is mostly derived from oil seeds, some stan-
dard specifications are laid down to meet the fuel quality to ensure better fuel
performance without any significant engine modification. Biodiesel produced
from various feedstocks must adhere to the specifications laid down by the
International Biodiesel Standard. In 2008, American Standards for testing materi-
als (ASTM) published new biodiesel blend specification standards, which include
ASTM 6751-3. Similarly, several other countries also published their own stan-
dards such as for European Union (EN 14214), Germany (Deutsches Institut für
Normung), Czech Republic (Czech State Norm), India (Bureau of Indian
Standards), and Italy (Italian National Standards Institute).
Some of the general parameters to determine the quality of biodiesel are density
(g/cm3), viscosity (mm2/s), flash point (°C), fire point (°C), cetane number, carbon
residue (%), iodine number, methanol/ethanol (mass %), acid value (mg KOH/g),
ash content (w/w %), cloud point (°C), pour point (°C), etc., which also depend
upon the type of feedstock selected and free fatty acid (FFA) composition (Demirbas
2007; Karmakar et al. 2010; Atadashi et al. 2011; Lin et al. 2011). Some general
parameters published by different nations for testing the quality of biodiesel are
depicted in Table 19.1. A synopsis of physicochemical properties of biodiesel
derived from various feedstocks is shown in Table 19.2.
Viscosity is an imperative property of biodiesel because it leads to poor atomiza-
tion of air-fuel mixture in the combustion chamber. Kinematic viscosity of liquid
fuel is measured at 40 °C as per the specifications given in ASTM D445. Generally,
kinematic viscosity of biodiesel is higher than that of diesel due to its significant
molecular mass and chemical structure. High viscosity may lead to cold starting
problem, which increases mechanical stress on the fuel and injection pump system
and affect the fuel delivery qualities. High viscosity has greater impact on fuel
Table 19.1 Typical specification of biodiesel in the United States and European countries
Diesel (ASTM
D975) Biodiesel
EN 14214–2008 ASTM D6751
Test Test
Properties Units method Limits method Limits Test method Limits
Flash point °C D975 60–80 EN Min. D93 Min. 125
ISO 100
3679
Cloud point °C D975 –15 to – – D2500 −3 to −13
−5
Pour point °C D975 −35 to – – D97 −15 to
−15 −17
Cetane – D4737 46 EN Min. 50 D613 Min. 47
number ISO
5165
Density (at kg/m3 D1298 810– EN 850– D1298 880
15 °C) 850 ISO 890
3675
Viscosity (at mm2/s D445 2–5 EN 3–5 D445 1.9–6.0
40 °C) ISO
3104
Acid number mg – – EN Max. D664 Max. 0.5
KOH/g ISO 0.5
14104
Cold filter °C D590 −9 EN – D6371 Max. 5
plugging point ISO
14214
Oxidations mg/L D2274 26 EN Min. – –
stability ISO 3.5 h
14112
Carbon % m/m D4530 0.2 EN Max. D4530 Max. 0.05
residue ISO 0.4
10370
Sulfated ash % mass – – EN Max. D874 Max. 0.002
content ISO 0.02
3987
Ash content % mass D482; 99/0.04 EN 500 mg/ D−/2709 0.005 vol%
Water and D2709 ISO kg
sediment 12937
Free glycerine % mass – – EN Max. D6584 Max. 0.02
ISO 0.03
14105
Total % mass – – EN 0.24 D6584 0.25
glycerine ISO
14105
(continued)

Diesel (ASTM
D975) Biodiesel
EN 14214–2008 ASTM D6751
Test Test
Properties Units method Limits method Limits Test method Limits
Phosphorus % mass – – EN 0.001 D4951 Max. 0.01
ISO
14107
Carbon wt% D975 14 – – PS1 21 76
Hydrogen wt% D975 – – – PS1 21 11
Oxygen wt% – – – – PS1 21 10
Total mg/kg D22624 – EN 23 D5452 25
contamination ISO
12662
Boiling point °C – – – – D7398 100–600
Saponification mg – – – – D5558 Max. 350
value KOH/g
References: Çelikten et al. (2010), Shameer et al. (2016), Saba et al. (2016)
atomization, i.e., on fuel droplet size and injector spray geometry during injection.
The maximum allowable viscosity limit for biodiesel as per ASTM D445 is
1.9–6 mm2/s. Density of liquid is measured as per specification given in ASTM
D1298 and EN ISO 3675/12185. The density of biodiesel varies with feedstocks
and it is generally greater than fossil diesel.
Fire point is an extension of flash point in a way that reflects the condition at
which vapor burn continuously for more than 4 s. Fire point is generally higher than
flash point by 10–15 °C. The flash point and the fire point of the test fuel blends are
measured as per the ASTM D93-66 standard and EN ISO 3697 (Xue et al. 2011;
Nayak and Mishra 2018). Flash point of biodiesel is generally more than 150 °C
while it is only 55–65 °C for diesel (Nayak and Mishra 2019). Poor cold flow proper-
ties lead to blockage in pipelines and pumps eventually prompting to fuel starvation.
There are no specific standards derived to measure cold flow properties. Hence, every
country can focus on its own particular limits depending upon the local climatic
conditions. From the literature, it is revealed that biodiesel experiences certain nega-
tive effects of cold flow properties, which are much higher than that of diesel.
Pour point is the lowest temperature at which the fuel becomes semi-solid and
loses its flow characteristics. Therefore, it is the measurement of minimum tempera-
ture at which the fuel can flow. The pour point is always lower than the cloud point.
Both cloud point and pour point are measured by utilizing the ASTM D2500, EN
ISO 23015, and D97 standards. Biodiesel has higher pour point and cloud point than
fossil diesel (Xue et al. 2011).
Cold filter plugging point (CFPP) is the minimal temperature during which a
particular volume of diesel can still go through a standardized filtration device in a
particular period at specific conditions. This parameter is vital because in cold
weather conditions, if CFPP is high then it will plug the fuel flow in pipelines,
Table 19.2 Typical physicochemical properties of biodiesel derived from various feedstocks
Calophyllum Camelina Canola
Jatropha inophyllum Madhuca Mesua Rubber sativa sativa
Fuel properties FAME FAME FAME FAME FAME FAME FAME
Density at 879.5 888.6 874 898
15 °C (kg/m3)
Viscosity at 4.8 g 7.724 3.98 6.2 5.81 4.15 4.42
40 °C (cSt)
Cetane 51.6 51.9 65 54 52.8
number
Iodine 104 85
number
Calorific 39.23 36.8 42.23 36.5
value (MJ/kg)
Acid 0.4 0.76 0.41 0.01 0.31 0.01
neutralization
value (mg
KOH/g)
Pour point 2 6 3 −8 −4 −9
(°C)
Flash point 135 151 208 112 130 >160 >160
(°C)
Cloud point 2.7 38 – – 4 3 −3.3
(°C)
Cold filter 0 – – – −3 −7
plugging
point (°C)
Water and <0.005 – – 0.035 – <0.005 <0.005
sediment
content
(vol%)
Ash content 0.012 0.026 0.01 0.01 –
(w/w %)
Sulfated ash 0.009 – – <0.005 <0.005
(m/m %)
Free 0.006 – – 0.002 0.006
glycerine
(m/m %)
Total 0.1 0.232 – – 0.08 0.114
glycerine
(m/m %)
Conradson 0.025 0.434 0.02 0.25 0.075 0.03
carbon
residue, 100%
(mass %)
References: Çelikten et al. (2010), Shameer et al. (2016), Saba et al. (2016)
pumps, or engines affecting their performances. CFPP is measured by using the

ASTM D6371 procedures (Demirbas 2007).
Oxidation stability is a chemical reaction, which occurs by combination of the
oxygen with lubricating oil. It is one of the main considerations that aides survey the
nature of biodiesel. Oxidation occurs because of the vicinity of unsaturated fat
chains, which quickly respond with the oxygen when it is exposed to air (Zuleta and
Rios 2012). Chemical composition of biodiesel makes it more vulnerable to oxida-
tive deterioration in comparison to that of diesel. Oxidation leads to an increase in
the oil’s viscosity and deposition of varnish and sludge. ASTM D6751 and EN
14214 standards use the Rancimat method (EN ISO 14112) to measure oxidation
stability (Demirbas 2007; Zuleta and Rios 2012).
The cetane number is the evidence of the ignition capacity of fuel to auto-ignite
rapidly after being injected. Better ignition quality of fuel is associated with a higher
cetane number, which is one of the most important parameters for biodiesel quality.
Higher cetane number shows a shorter time between the ignition and the start of fuel
infusion into the combustion chamber (Nayak and Mishra 2019). The cetane num-
ber of diesels is 47 min for ASTM D613 and 51 min for EN ISO 5165 (Nayak and
Mishra 2018). Biodiesel has a cetane number more than diesel, which brings higher
combustion efficiency (Demirbas 2007).
Fatty acids are usually derived from triglycerides, and when they are in free form,
i.e., not attached to any other molecules, they are called free fatty acid (FFA). The
FFA are important source of fuel because when processed they yield large amount of
adenosine triphosphate (ATP). More the amount of fatty acid, higher is the acid
value. Generally, acid value is measured in terms of mg KOH/g of fatty acid methyl
ester (FAME), which is measured by utilizing ASTM D664 and EN 14104 standards.
Higher acid value results in the corrosion of the fuel supply system. Therefore, the
acid value is approved to a maximum of 0.5 mg KOH/g (Zuleta and Rios 2012).
A specific amount of heat is released from the combustion of a specific quantity
of fuel. Moisture content is one of the important parameters for determining the
heating value of oils (Karmakar et al. 2010). Minimum heating value of biodiesel is
about 35 MJ/kg as per the EN 14213 standards but there are still no specifications
laid down by ASTM D6751 and EN 14214. The iodine value indicates the degree of
unsaturation of the vegetable oils. A high degree of unsaturation leads to a higher
chemical reactivity. The deposition to polymerized vegetable oils with low iodine
value has lower value of carbon residue and higher oxidation stability. The test
method used for determining the iodine value of biodiesel is ASTM D5768 (Lin
et al. 2011; Karmakar et al. 2010).
19.3 Biodiesel Engine Performance and Characteristics
Most of the studies available from literature review are on the performance and
emission characteristics of biodiesel-fueled diesel engine by determining the brake
thermal efficiency (BTE), brake specific fuel consumption (BSFC), exhaust gas
temperature (EGT), and emission parameters on basis of CO2, CO, NOx,
Table 19.3 Engine specifications for testing of biodiesel performance
464
Number of Brake power Speed Compression Displacement Cooling

Engine model cycles (kW) (rpm) ratio (m3) system References
DI engine 1 – – – – Air Devendra et al. (2015)
TDI engine 6 135 2500 – 5900 Water Satputaley et al. (2017)
Kirloskar TV1 1 5.2 1500 – 661 Water Pradhan et al. (2016)
ADCR CRDi 4 85 3700 17.5:1 2636 Water Işık et al. (2017)
engine
Isuzu 4HF1 4 88 1800 19:1 4334 Water Mikulski et al. (2016)
NWK 22 4 18 1500 17:1 2400 Water Jayaprabakar and Karthikeyan
(2016)
DJC type DI 4 12 1800 19:1 – Air Lei et al. (2016)
engine
Kirloskar AV1 1 3.7 1500 16.5:1 553 Water Atmanli (2016)
4 stroke WC, DI 1 7.4 1500 19.5:1 – Water Lahane and Subramanian
engine (2015)
4 stroke AC, DI 1 4.4 1500 19.5:1 – Water Gopal et al. (2014)
engine
4 stroke AC, DI 6 81 2600 17.5:1 – Air Sanli et al. (2015)
engine
4 stroke WC, DI 4 89 2000 16.4:1 – Water Tüccar et al. (2014)
engine
S. K. Nayak et al.
19
4 stroke AC, DI 1 7.08 2400 18:1 – Air Tan et al. (2017)

engine
4 stroke WC, DI 1 3.5 1500 17.5:1 – Water Kakati and Gogoi (2016)
engine
4 stroke AC, DI 1 3.09 3800 18:1 – Air Al-lwayzy and Yusaf (2017)
engine
4 stroke WC, DI 1 5.9 1500 17.5:1 – Water Ramalingam et al. (2016)
engine
Note: Direct injection DI engine, Brake power BP, Turbocharged direct injection engine TDI, Common rail direct injection CRDi
Opportunities of Biodiesel Compatibility as a Modern Combustion Engine Fuel
465
hydrocarbons, and smoke opacity (Çelikten et al. 2010). Engine performance is an

indication of the degree of efficiency for the fuel engine to accomplish the conver-
sion of the chemical energy contained in the fuel into the mechanical and kinetic
energy. The various diesel engines used by different researchers are listed in
Table 19.3. The engine brake power (BP) consists of two elements such as the brake
mean effective pressure (BMEP), i.e., the force available to work and the speed at
which it is working. Therefore, the output of the engine can be increased either by
increasing the speed or BMEP. Table 19.4 summarizes the comprehensive review of
various biodiesel varieties and their engine performance.
Satputaley et al. (2017) during their experimentation on direct injection (DI)
engine fueled with microalgal methyl ester reported an increment of about 4.4%
BSFC in contrast to conventional diesel fuel at the load of 5.15 kW. This might be
because microalgal methyl ester conveys lower heating value. Thus, more amount
of fuel is being consumed to provide it the power output. Pradhan et al. (2016)
investigated a novel method for preparing biodiesel from waste oil, thereby fabricat-
ing a new infrared radiator reactor. Their experiments depicted a higher value of
BSFC of 6.3% and 7.9% for both B10 and B20 blends, respectively, in contrast to
diesel at optimal loading condition of 8 N. However, at the peak load, B100 depicted
lower fuel consumption than other test fuels.
Waste cooking oil is a potential feedstock for biodiesel production (Reddy et al.
2016; Nanda et al. 2019). Işık et al. (2017) during their investigation upon direct
injection engine using waste cooking oil and n-butanol found that B20 blend of
n-butanol had lower BSFC in contrast to B20 blend of waste cooking oil. Such a
trend of lower fuel consumption for B20 was observed due to the presence of higher
concentration of oxygen. This also results in lowering the cylinder wall tempera-
ture, thereby hampering the combustion behavior of n-butanol fuel. Mikulski et al.
(2016) conducted their experimentation upon a common rail direct injection (CRDi)
engine using swine lard biodiesel. From the analysis, it was seen that BSFC for B25,
B50, and B75 blends were higher by 3.2%, 8.5%, and 13.8%, respectively, in con-
trast to diesel fuel. It was also seen that the fuel conversion efficiency (FCE) for all
B25, B50, and B75 blends were found to be lesser, i.e., 1.6%, 4.8%, and 7.8%,
respectively, than that of diesel fuel. The reason for such a trend was due to the
lower heating value and reduced ignition delay. Jayaprabakar and Karthikeyan
(2016) investigated the diesel engine using rice bran biodiesel blends by varying the
injection timing from 23°bTDC until 26°bTDC. From the experimentation, it was
clear that rice bran blends depicted higher BTE than other test fuels because of its
higher heating value with advanced injection timing.
19.4 Emission Characteristics from Biodiesel-Fueled Engines
Hydrocarbon emissions take place when the fuel molecules inside the combustion
chamber do not burn completely or burn partially. Hydrocarbons along with oxides
of nitrogen (NOx), CO, and CO2 deplete the ozone layer and are the chief cause of
global warming and smog formation in urban areas. CO is a product of incomplete
19
Table 19.4 Review of comparative engine performance in edible plant oil, biodiesel, and fossil diesel
BSEC (kg/
Test condition Biodiesel BTE (%) BSFC (kg/kWh) kWh) EGT (°C) BP (kW) References
Constant speed; Algae (B20) 5%↓ for 0.35 kg/kWh↓ – – – Devendra et al.
injection timing (20°, 20°bTDC at for 20°bTDC at (2015)
23° and 26°) 4.3 kW 4.3 kW
Emission test cycle Microalgae (B100) 1.67%↑ 9.79 g/kWh↑ – – 0.12 kW↓ Satputaley et al.
(2017)
Constant speed; load Microalgae (B100) 2%↓ at 2 kg 4.4%↑ 5 MJ/kWh at – – Pradhan et al.
(0–18 kg) step of 2 kg load 2 kg↑ (2016)
Constant speed; Waste cooking oil 2%↓ Avg. 50 g/kWh↑ – – – Işık et al. (2017)
variable load (28, 84, (B100)
140, 196 and 224 nm)
Constant speed; Waste cooking oil 2% at 75 g/kWh at – – – Jayaprabakar and
variable load (2, 3.3 (B20) 4.6 kW↓ 4.6 kW↑ Karthikeyan
and 4.6 kW) (2016)
Constant speed; Waste fry oil (B100) 1.89%↑ 8.64%↑ – – – Lei et al. (2016)
variable load (1, 3.6
and 9 kW)
Constant speed; Waste mustard oil 2% at 2 N↓; 0.0015 kg/kWh – – 6% at Atmanli (2016)
variable load (2, 4, 6 (B100) 6% at 8 N↓ at 2 N↑; 8 N↑
and 8 kW) 0.001 kg/kWh at
8 N↑
Constant speed Biodiesel-diesel blends 3.2%↓ – Higher for – – Lahane and
(1500 rpm) biodiesel Subramanian
blend (2015)
Constant speed; Waste cooking oil 3.6% at high 0.5 g/kWh at – – – Gopal et al. (2014)
variable load methyl ester
load ↓ optimum load ↑

(continued)
467
468
BSEC (kg/
Test condition Biodiesel BTE (%) BSFC (kg/kWh) kWh) EGT (°C) BP (kW) References
Variable speed Waste fry oil Higher for 0.2 g/kWh↑ – – – Sanli et al. (2015)
(1100–1700 rpm) pure esters
Variable speed Diesel-algae; biodiesel- – 0.46 g/kWh↑ – – 2.26%↓ Tüccar et al.
(1200–2800 rpm) butanol blends (2014)
Variable speed Diesel-biodiesel- 8.9%↓ for all 3.2% at full load – – – Tan et al. (2017)
(1600–2400 rpm) bioethanol blends condition ↑
Variable load Kutkura fruit seed oil Avg. 4% Slightly lower for – – – Kakati and Gogoi
max.↑ B20 blend ↓ (2016)
Variable speed Microalgae (Chlorella Avg. 5.7% 10.2%↑ for all – 6.1%↓ at full – Al-lwayzy and
(1770–3800 rpm) protothecoides) max.↑ blends at full load Yusaf (2017)
biodiesel load
Variable load Annona biodiesel with Avg. 3% at 8.8%↑ – Slightly higher – Ramalingam et al.
1,4-dioxane fuel optimal load ↑ for all additive (2016)
additive blends
Note: Brake thermal efficiency BTE, Brake power BP, Brake specific energy consumption BSEC, Brake specific fuel consumption BSFC, Exhaust gas tempera-
ture EGT, Decreasing trend ↓, Increasing trend ↑
S. K. Nayak et al.
combustion or partial oxidation of carbon present in the fuel. These vehicular emis-
sions are currently one of the most extensive and extending metropolitan environ-
mental problems (Ramalingam et al. 2016).
Satputaley et al. (2017) during their experimentation on a direct injection engine
fuelled with microalgal methyl ester depicted a reduction in hydrocarbon emission
for about 2% in contrast to diesel and other test fuels for all load conditions. The
reason for such a trend was due to the enhanced cetane number of microalgal methyl
ester blends. Satputaley et al. (2017) also showed a reduction of about 38 ppm for
microalgal oil while 22 ppm for microalgal methyl ester upon loading condition of
5.15 kW. However, according to most of the reports there is an increase in NOx emis-
sion as depicted in Table 19.5. Moreover, considering the emission analysis, a reduc-
tion of CO emission (27%↓) was found upon 5.15 kW of load. This might be due to
high oxygen content in the prepared test fuel, thereby converting CO into CO2.
Jayaprabakar and Karthikeyan (2016) investigated a diesel engine using rice bran
biodiesel blends and microalgae oil by varying injection timing from 23°bTDC to
26°bTDC. From their experimentation, it was revealed that hydrocarbon emission
lowered by 5% for both test fuel blends. This was because of high oxygen concen-
tration in biodiesel, which improved the process of combustion for advanced injec-
tion timing. They conducted their experimentation upon a CRDi engine using swine
lard biodiesel. From their analysis, it was seen that B25 blend depicted similar
trends in contrast to diesel fuel considering the fuel conversion efficiency of the
mean value 1.7%. Moreover, B50 (4.8%↓) and B75 (7.3%↓) provided lower hydro-
carbon emissions in comparison to diesel fuel. The reason for this reduction in fuel
conversion efficiency was reported because of the lower calorific value of swine lard
biodiesel blends.
Atmanli (2016) carried out the experimentation on comparative analysis of
diesel-waste oil biodiesel with propanol, n-butanol, and 1-pentanol blends in a
direct injection engine. The results depicted higher hydrocarbon emission for pure
biodiesel for about 78.9%↑ more than conventional diesel fuel for all load condi-
tions. Moreover, the blending of n-butanol and 1-pentanol with biodiesel by 20%
depicts lower hydrocarbon emission of 17.4% and 17.6%, respectively. However,
the addition of propanol of 20% to biodiesel blend enhanced hydrocarbon emission
by 35.4% in contrast to other test fuel blends. The results also depicted an increment
of CO emission of about 33.8% for waste oil biodiesel in contrast to conventional
fuel. Moreover, the addition of propanol, n-butanol, and 1-pentanol to waste oil
blends enhanced CO emissions more around 39.9%, 38.3%, and 12.7%, respec-
tively, in comparison to that of diesel fuel. According to the literature, there is a
decrease in CO emission as shown in Table 19.5.
Pradhan et al. (2016) investigated a novel method for preparing biodiesel from
waste oil by fabricating a new infrared radiator reactor. Their experiment demon-
strated low hydrocarbon emissions of 16.3%↓ for B10 biodiesel blends in contrast
to other test fuels. This was due to enhanced combustion for waste mustard oil
blends. The experiment depicted lower CO emissions of 75%↓ at low loads and
70.3%↓ at peak load conditions. Işık et al. (2017) during their experimentation
stated an addition of both waste cooking oil and n-butanol of 10% with conventional
Table 19.5 Comparative studies on engine exhaust emissions from biodiesel and conventional fuel
470
Particulate
Test condition Biodiesel NOx CO2 CO Hydrocarbons Smoke matter Reference
ETC test cycle Microalgae 2.57 g/kWh↑ – 0.215 g/ 0.03 g/kWh↓ – – Panwar et al.
(B100) kWh↓ (2010)
Constant speed; Microalgae 38 and – 27%↓ Approx. 2% for Approx. – Zhu et al. (2011)
variable load (B100) 22 ppm↓ all load ↓ 5%↓
(0–18 kg) in
steps of 2 kg
UDC/NEDC Animal fat 14 ppm↑ – – – – Agarwal and Dhar
(15, 30, 50 and (B50) (2013)
100 km/h)
Constant speed; Animal fat 140 ppm and – 17.7% at low Avg. 8.9% at 200 mg/s at Vedharaj et al.
variable load residue (B100) minimum load ↓ 1500 rpm↑ low load ↓ (2014)
(1–5 kW) in load ↑
steps of 1 kW
Constant speed; Waste chicken 16% at full 2.5%↑ 12%↓ Avg. 9.2%↑ – Hwang et al.
variable load fat (B100) load (2014)
(150, 300, 450
and 600 nm)
2 speeds (1500; Swine lard 12.6% at Avg. 0.3%, Avg. 27%, 7.3% at – Nayak and
3000 rpm); (B25; B50 and 1500 rpm↑ 1.8% and 38% and 37% 1500 rpm↓ Pattanaik (2014)
variable load B100) 13.5% at at 1500 rpm↓
(50, 100 and 1500 rpm↑
150 nm)
Variable speed Trout oil (B10; 40 ppm for Avg. 1%, 3% Avg. 19%, 45% at 40% for – Dhar and Agarwal
(900–2700 rpm); B20, B40 and B20↑ and 6% at 25% and 30% 3000 rpm↓ B10↓ (2014)
constant load B50) 3000 rpm↓ at 3000 rpm↓
Variable speed; Waste cooking 32.5 ppm for 2% for 3600 Avg. 40% for Low for all – – Sharma and
constant load oil (B100) 1200 rpm↑ at full load ↓ 3600 rpm at speed at 50% Murugan (2015)
full load ↑ and 100% loads
S. K. Nayak et al.
19
Constant speed; Waste cooking 8.7%↑ 2%↑ 11.8% for 29% for full load 7% for – Karthikayan et al.
variable load oil (B10) low and ↓ peak load ↓ (2015)
medium load
↓
Constant speed; Waste cooking Avg. 18.3%↑ – Avg. 31%↓ Avg. 57%↓ Approx. – Dhar and Agarwal
variable load oil (B100) 10% for (2015)
low and
medium
loads ↑
Constant speed; Waste cooking Avg. 6.5%↑ Avg. 13.3%↑ Avg. 46.1%↑ Avg. 23.5% for – – Senthil et al. (2016)
variable load oil (B75) B50↑
Variable speed Waste fry oil Avg. 11.3%↑ Avg. 2.08%↑ Avg. 22.3%↓ Avg. 29.36%↓ – – Gangil et al. (2016)
(100, 1400 and (B100)
1700 rpm)
Constant speed; Waste cooking 9.01%↑ 9.09%↓ 10.5%↓ 10% at 4.6 kW↑ – – Sanjid et al. (2016)
variable load (2, oil (B20)
3.3 and 4.6 kW)
Constant speed; Waste fry oil Avg. 1.68%↓ – Avg. 12.7%↑ Avg. 78.9%↑ – – Dharma et al.
variable load (1, (B100) (2016)
3.6 and 9 kW)
Constant speed; Waste mustard 29% at 2 N↑ 30% at 2 N↓ 75% at 2 N↓ 16.3% at 2 N↓ – – Lalvani et al.
variable load (2, oil (B100) (2016)
4, 6 and 8 kW)
Constant speed; Fish oil 0.5 g/kWh↑ Approx. 8 g/ Approx. 8 g/ Approx. 0.5 g/ – 64 mg/m3 at Kim et al. (2016)
variable load (B100) kWh at low kWh at low kWh at low load peak load ↓
and high load and high load ↓
↓ ↓
(continued)
471
472
Particulate
Test condition Biodiesel NOx CO2 CO Hydrocarbons Smoke matter Reference
Constant speed; Fish oil Avg. 5.2%↓ Avg. 33.7%↓ Avg. 33.7%↓ Avg. 26.2%↓ Avg. 3%↑ – Tamilselvan and
variable load (B100) Nallusamy (2015)
Variable speed Mahua and Approx. Avg. 16.24%↓ Avg. Avg. 19.8%↓ Avg. 10%↓ – Acharya et al.
(1000– Jatropha 10 ppm↑ 16.24%↓ (2017a)
2500 rpm); biodiesel
constant load blends
Constant speed Biodiesel- 42.8%↑ – Avg. Avg. 57%↓ 17.4%↓ – Acharya et al.
(1500 rpm) diesel blends 0.005%↓ (2017b)
Constant speed; Waste cooking 20% for full – Avg. 45.5%↓ Avg. 24.2%↓ Avg. 9.3%↓ – Lee et al. (2017)
variable load oil methyl load ↑
ester
Variable speed Waste fry oil 28% at Avg. 13.3%↑ Avg. 10.5%↓ 24.2%↓ – – Srithar et al. (2017)
(1100– 1500 rpm↑
1700 rpm)
Variable speed Diesel-algae 18.3% at – 14%↓ Avg. 8.1%↓ Avg. – Sivaramakrishnan
(1200– blend; 2000 rpm↓ 44.9%↓ (2018)
2800 rpm) biodiesel-
Butanol blends
Constant speed; Micro algae – – Avg. 43.3%↓ Avg. 17.7%↓ Avg. 40%↓ – Mahalingam et al.
variable load methyl ester (2018)
Variable speed Ceiba 20% at 11.11%↓ – 12%↓ – – Nayak et al. (2014)
pentandra 1500 rpm↑
Note: European transient cycle ETC, Particulate matter PM, Hydrocarbons HC, Urban driving cycle UDC, New European driving cycle NEDC
S. K. Nayak et al.
fuel resulting in higher hydrocarbon emissions (10%↑) more than conventional die-
sel fuels for all load conditions. Moreover, the addition of 20% waste cooking oil
and n-butanol resulted in lower hydrocarbon emissions. This was because of low
heating value, short ignition delay, and higher oxygen content of biodiesel in con-
trast to conventional diesel fuel.
19.5 Conclusions
This critical review of different biodiesel varieties including edible oils, non-edible
oils, and animal fats summarized their physicochemical properties, engine perfor-
mance, and emissions. The major problem associated with plant oil is its higher
viscosity than diesel, which affects the spray characteristics leading to improper
combustion. The biodiesel engine brake power may also fluctuate depending upon
the type of feedstock and oil extraction process. The emissions of CO, hydrocar-
bons, and smoke reduce considerably but NOx generally increase because of higher
oxygen concentration in biodiesel. Many techniques have been undertaken to
improve the performance and emission characteristics of biodiesel like preheating,
blending, emulsification, transesterification, pyrolysis, hydrocracking, thermal
cracking, etc. Some reports also revealed modification in engine design and con-
figuration like injector pressure, injection timing, additional combustion chamber,
and exhaust gas recirculation to increase biodiesel efficiency. More research and
development will determine the large-scale commercial utilization of biodiesel in
the newer vehicles at a global scale.
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Current Advancements in Microbial Fuel
Cell Technologies 20
Latika Bhatia, Prakash K. Sarangi, and Sonil Nanda
Abstract
With the increase in global energy utilization and expected deficits in crude
oil supply, there is an extensive and prompt enthusiasm in developing alterna-
tive green sustainable energy sources. In the recent years, the utilization of
biomass-based energy in terms of fuel or power has become an imperative
requirement on a global scale to enhance the environmental sustainability.
Organic wastes are considered as the main feedstock for bioenergy and elec-
tricity production. Microbial fuel cells are enthralling bioelectrochemical
devices that utilize microbial biomass as the main catalytic source to convert
organic waste matter into electrical energy. Recent advancements in microbial
fuel cells in terms of structural modification, substrates utilization, modes of
operation, supplementation of different microbial communities, overcoming
limitations, and exploring new applications toward clean environment are
critically described in this chapter. The role of eukaryotic microorganisms in
microbial fuel cells is discussed. The perspectives of different microbial spe-
cies and their biocatalytic activities to generate electrical energy from organic
wastes along with future scope and possibilities are also critically reviewed.
This chapter provides glimpses of the technological advancements and utili-
ties of the microbial fuel cells.
L. Bhatia
Department of Microbiology and Bioinformatics, Atal Bihari Vajpayee University,
Bilaspur, Chhattisgarh, India
P. K. Sarangi (*)
S. Nanda

478 L. Bhatia et al.
Keywords
Microbial fuel cells · Biofuels · Bioenergy · Microorganisms
20.1 Introduction
In the recent years, an exponential increase in the energy utilization around the
world is observed due to rapid industrialization and urbanization both in develop-
ing and developed countries (Nanda et al. 2014b, 2015a). Fossil fuels not only
result in atmospheric pollution due to massive greenhouse gas emissions but also
cause global warming, climate change, and threat to many natural ecosystems
(Nanda et al. 2016). Many notable efforts have been made to explore convincing
strategies in resolving the energy crisis by focusing on a variety of renewable
sources such as solar, wind, tidal, geothermal, and waste biomass (e.g., lignocel-
lulosic biomass, cattle manure, industrial effluents, food waste, waste cooking oil,
etc.) (Nanda et al. 2013, 2015a, b, 2016a, b, 2019). The fuel cells are much recent
approaches generating energy involving metal catalysts of high value (Rahimnejad
et al. 2012a). There are many benefits associated with fuel cells, a major among
them being zero emission of greenhouse gases (viz. SOx, NOx, CO2, and CO).
However, fuel cells also pose some disadvantages such as being expensive and
generating high microbial biomass (Rahimnejad et al. 2015).
Biological fuel cell works on the principles of electrochemistry and physics
along with the involvement of living organism that performs catalytic redox activity.
There are two types of biological fuel cells, namely enzymatic fuel cell (EFC) and
microbial fuel cell (MFC). Enzymatic fuel cells produce electrical energy with the
aid of selective enzymes that work as a catalyst toward redox reactions, whereas
microbial fuel cells generate electricity from organic compound with the aid of
electroactive microorganisms (Santoro et al. 2017). In other words, MFCs are a
form of renewable devices that hold the potential to transform chemical energy into
electricity involving a variety of electrochemically active bacteria. In MFCs, a broad
spectrum of carbon sources including organic substrate or even pollutants in waste-
water are oxidized by electrochemically active bacteria, thereby transferring the
generated electron to anodes.
Microbial fuel cells involve anaerobic metabolism of electrochemically active
bacteria for electricity generation. These electrochemically active bacteria consume
low-grade waste or organic pollutants that are too wet to be burned, thereby making
the MFC technology highly advantageous. The breakdown of biomass is an impor-
tant process for the production of target products by utilizing microorganisms and
their enzymes. There are some contrasting features of MFCs over conventional low-
temperature fuel cells such as biotic electro-catalyst at anodic side, near-ambient
operating temperature (15–45 °C), utilization of complex biomass as anodic fuel,
neutral pH condition, and low environmental impacts (He et al. 2005; Larrosa-
Guerrero et al. 2010; Borole et al. 2011; Tremouli et al. 2016; Tee et al. 2017). The
biotechnological implementation and computational tools are continuously making
20 Current Advancements in Microbial Fuel Cell Technologies 479
remarkable impact to overcome the critical issues of process engineering in MFCs.

The chapter makes an overview of the recent progress and application of MFCs.
20.2 Brief History of Microbial Fuel Cells
The history of electricity generation by microorganisms is believed to be initially

performed by Potter in 1910 (Potter 1911). However, such findings were not well
established because of having only the only concept of electron transport by micro-
organisms from cellular metabolism process, which is also regarded as extracellu-
lar electron transfer. Over the time, many researchers attempted biocatalytic
electricity generation. When the idea of current and power generation was estab-
lished through the addition of electron acceptor, real advancements came out on
this context. After significant development of MFC reactors during the late 1990s
by utilizing wastewater as the substrate, the real progress on this technology
started. Later years also witnessed many researches enhancing the overall energy
output and efficiency of MFCs. Diversification was achieved by modifying the
architecture of basic integrals like the electrodes or by researching with a variety
of solutions or electrolyte being used.
Several strategies were framed to augment the comprehensive output and the
electricity production efficiency. Many researchers globally have worked on the
configuration and modification of the basic components of MFCs such as electrodes
and utilized solution or fuel. In 2005, another alteration for augmenting electron
transmission tool directly by extracellular conductive connections was discovered.
Additionally, research sphere of MFCs broadened in 1999 when it was noticed that
mediator was not an essential part within MFCs (Rahimnejad et al. 2015).
During the last decade, MFCs have established great attention among research-
ers and academicians globally being a novel technology toward a sustainable and
renewable production of energy (Du et al., 2008). The electrochemical actions of
microorganisms play vital roles for conversion of waste organic residues into
electrical energy through oxidation and electron transfer. The first generation of
MFC was based on the principle of electron mediators. In this type of MFC,
direct transfer of electrons by microorganisms to anode was not possible, which
necessitated the requirement of external electron acceptors. The focus of such
type of MFC is the implementation of electron mediators by acceptance of elec-
trons of bacterial origin and then subsequently releasing these electrons to the
anode. Such mediator-assisted electron transfer process has some limitations of
toxicity and instability (Du et al. 2007). Thus, with further research, second-
generation MFCs were developed to increase the mediator-less electron transfer
(Kim et al. 2002; Chaudhuri and Lovley 2003). Shewanella putrefaciens,
Geobacteraceae sulfurreducens, Geobacteraceae metallireducens, and
Rhodoferax ferrireducens are few examples of active bacteria used in MFCs
(Kim et al. 2002; Bond and Lovley 2003; Holmes et al. 2004; Crittenden et al.
2006; Liu et al. 2007).
20.3 Process Mechanism of Microbial Fuel Cells
The microorganisms divert the electrons generated from the substrate for their met-
abolic requirement along with migration toward the anode. This process demands
efficiency for sustainable generation of power. Depending on the mode of electrons
transportation to the anode, MFCs can be classified into two groups, especially
mediator-using MFCs and mediator-less MFCs (Pant et al. 2010). Some synthetic
exogenous mediators are neutral red, methylene blue, and 2-hydroxy-1,4-
naphthoquinone. The incorporation of exogenous mediators could help in this sce-
nario if they are stable and non-toxic. The employment of native electron shuttles
generated by the microorganisms can also circumvent the problem of electron flow.
The secondary metabolites can be employed for MFC applications, as they are
potential redox mediators. These metabolites are potential reversible electron accep-
tors as they carry electrons from bacterial cell to an anode. The way the chambers
of anode and cathode are assembled, it classifies MFC prototype into either single-
chambered (Fig. 20.1) or double-chambered (Fig. 20.2).
MFCs are described by biological and electrochemical parameters. The
substrate-loading rates in continuous systems are biological parameters, whereas
power density and cell voltage are chief electrochemical parameters. There are
several factors influencing the performance of MFCs, a few of which include the
following (Rahimnejad et al. 2015):
1. Oxygen supply and its consumption in cathode chamber.

2. Substrate oxidation in anode chamber.
3. Electron shuttle from anode compartment to anode surface.
4. Proton exchange membrane permeability.
Fig. 20.1 A single-chambered microbial fuel cell

There are many electrochemically active bacteria acting as MFCs. These bacteria
possess extracellular electron transport mechanism that helps transport of electron.
Thus, these microorganisms can produce electricity from various energy sources.
When microorganisms start metabolizing organic matter inside an anaerobic anode
chamber, they generate the free electrons and protons. The electrons travel through
the electron transport chain releasing energy, which supports microbial survival and
metabolism. These electrons reach external terminal electron acceptors (resistor)
toward the cathode through several extracellular electron transport mechanisms,
thereby generating voltage. There is aerobic cathode chamber where protons are
diffused simultaneously via the selective proton exchange membrane.
Water molecules are produced in this chamber due to the reduction of oxygen by
electrons and protons, thereby completing the charge balance. This technology has
proven itself as one of the optimal methods to undergo simultaneous bioremediation
and power generation (Wang et al. 2014). Elevated endogenous secretion of pyocya-
nin mediators could be achieved by chemical alterations of the insulating interface
junction across the cellular membrane of Escherichia coli (Hou et al. 2013) and
genetically engineered Pseudomonas aeruginosa (Wang et al. 2013), thereby enhanc-
ing the power output in these MFCs. Human urine has also been explored as a source
of energy for small-scale stacked MFCs (Ieropoulos et al. 2013). The performance of
MFCs can be further enhanced by employing extracellular electron transport pro-
cesses for better understanding of microbial species interactions.
Earlier studies have revealed that Pseudomonas sp. are prominent members of
microbial population used in MFCs. These bacteria produce phenazine-based
Fig. 20.2 A double-chambered microbial fuel cell

mediators that relocate electrons to the electrode. Brevibacillus sp. PTH1 is found
along with Pseudomonas sp. in an acetate-fed MFC. Pseudomonas sp. CMR12a
produces a significant amount of phenazine-1-carboxamide (PCN) and biosurfac-
tants in the anode of MFCs. Pseudomonas sp. CMR12a_Reg is a regulatory mutant
that is unable to synthesize PCN. The supernatants of this mutant did not show the
above improvement effects. When rhamnolipids were used as biosurfactants at the
concentration of 1 mg/L along with purified PCN, it enhanced the generation of
electricity by Brevibacillus sp. PTH1. Brevibacillus manifests the ferric iron reduc-
tion that is supplied as goethite (FeOOH) with concomitant oxidization of acetate,
thereby achieving transfer of electron extracellularly. This effect was missing when
PCN was added alone. The possibilities indicate that this synergy of bacteria is a
prominent mechanism in the anodic electron transfer of an MFC, thus aiding
Brevibacillus sp. PTH1 to acquire its supremacy (Pham et al. 2008).
20.4 Microorganisms Used in Microbial Fuel Cells
MFCs are potential sources for the generation of clean energy as well as for pollut-
ants remediation. The microbial system in anode has a potential to oxidize a broad
spectrum of organic substrates including organic pollutants found in wastewater. In
this process, the generation of electrons and its transfer to inertial solid electrodes
occurs, thereby making it feasible to generate electricity from chemical energy
(Osman et al. 2010). MFCs can also be used as biosensors and in secondary fuel
production (Das and Mangwani 2010). Geobacter, Shewanella, Pseudomonas, and
E. coli are a few examples of electrochemically active bacteria holding the potential
to transfer electrons to electrodes. Table 20.1 presents different substrates and
microorganisms used in MFCs.
P. aeruginosa has attracted enormous attention as it holds the potential to gener-
ate pyocyanin that acts as highly redox-active endogenous electron shuttles (Shen
et al. 2014). Pseudomonas possesses metabolic versatility and can be isolated from
soil, water, petroleum spills, and natural habitats. P. aeruginosa holds the potential
to produce significant compounds like antibiotics, siderophores, surfactants, etc. Its
diverse metabolic activity and utility in waste treatment has attracted the attention
of researchers toward P. aeruginosa. In addition, P. aeruginosa is a source of vari-
ous phenazine derivatives that are electrochemically active. Many factors regulate
the biosynthesis of phenazine, which include cell density, nature of the carbon
sources as well as concentrations of oxygen, iron, and phosphate. Phenazines play
a vital role in anaerobic conditions as they support bacterial growth by generating
energy. Phenazines also aid in the maintenance of redox homeostasis.
The mixed microbial communities in MFCs are beneficial because they are more
stable and easy to be maintained than the MFCs having only a single pure culture of
electrochemically active bacteria. Except the exoelectrogens, fermentative strains of
Bacteroidetes and Firmicutes constitute a part of the consortia and are unanimously
present in abundance in mixed community MFCs. Hence, it is a matter of impor-
tance to investigate the community structure for mixed-community MFCs.
Table 20.1 Different substrates and microorganisms used in microbial fuel cells
Maximum
power or
Type of current
Substrate Type of inoculum MFCs produced References
1,2-dichloroethane Microbial consortia Two- 0.008 mA/ Pham et al.
from acetate- chambered cm2 (2009)
enriched MFC MFC
Acetate Pre-acclimated Cube- 0.8 mA/cm2 Logan et al.
bacteria from MFC shaped (2007)
chamber
MFC
Arabitol Pre-acclimated Single- 0.68 mA/cm2 Catal et al.
bacteria from MFC chambered (2008)
air cathode
MFC
Azo dye with glucose Mixture of aerobic Single- 0.09 mA/cm2 Sun et al.
and anaerobic chambered (2009)
sludge air cathode
MFC
Carboxymethylcellulose Co-culture of Double- 0.05 mA/cm2 Ren et al.
Clostridium chambered (2008)
cellulolyticum and MFC
Geobacter
sulfurreducens
Cellulose particles Pure culture of MFC with 0.02 mA/cm2 Rezaei et al.
Enterobacter carbon cloth (2009)
cloacae anode
Ethanol Anaerobic sludge Double- 0.025 mA/ Kim et al.
from wastewater chambered cm2 (2007)
plant aqueous
cathode
MFC
Furfural Pre-acclimated Single- 0.17 mA/cm2 Luo et al.
bacteria from anode chambered (2010)
of a ferricyanide- air cathode
cathode MFC MFC
Galactitol Pre-acclimated Single- 0.78 mA/cm2 Catal et al.
air cathode
MFC
Glucose Mediator-less Double- 28 mW/m2 Rahimnejad
Saccharomyces chambered et al.
cerevisiae MFC (2012b)
Glucose Mediator-less Air cathode 3 mW/m2 Sayed et al.
Saccharomyces MFC (2012)
cerevisiae
(continued)

Maximum
power or
Type of current
Glucose Mixed bacterial Single- 0.70 mA/cm2 Catal et al.
culture of chambered (2008)
Rhodococcus and air cathode
Paracoccus MFC
Glucose Methylene Double- 150 mW/m2 Ganguli and
blue-mediated chambered Dunn (2009)
Saccharomyces MFC
cerevisiae
Glucose Methylene Double- 1500 mW/m2 Ganguli and
blue-mediated chambered Dunn (2009)
Saccharomyces MFC
cerevisiae
Landfill leachate Leachate and Double- 0.0004 mA/ Greenman
sludge chambered cm2 et al. (2009)
MFC
Mannitol Pre-acclimated Single- 0.58 mA/cm2 Catal et al.
air cathode
MFC
Microalage Chlorella vulgaris Single- 0.2 mA/cm2 Velasquez-
chambered Orta et al.
air cathode (2009)
MFC
Phenol Mixed aerobic Double- 0.1 mA/cm2 Luo et al.
activated sludge and chambered (2009)
anaerobic sludge MFC
Ribitol Pre-acclimated Single- 0.73 mA/cm2 Catal et al.
air cathode
MFC
Sodium formate Anaerobic digested Double- 0.22 mA/cm2 Ha et al.
fluid from a sewage chambered (2008)
treatment plant MFC
Sodium fumarate Pure culture of Stainless 2.05 mA/cm2 Dumas et al.
Geobacter steel (2008)
sulfurreducens cathode
Sorbitol Pre-acclimated Single- 0.62 mA/cm2 Catal et al.
air cathode
MFC
Starch Clostridium Double- 1.3 mA/cm2 Niessen
butyricum chambered et al. (2004)
MFC
(continued)

Maximum
power or
Type of current
Sucrose Anaerobic sludge Double- 0.19 mA/cm2 Behera and
from septic tank chambered Ghangrekar
mediator (2009)
less MFC
Synthetic wastewater Mediator-less Air cathode 25.5 mW/m2 Raghavulu
Saccharomyces with et al. (2001)
cerevisiae graphite
plate anode
Synthetic wastewater Anaerobic mixture Double- 0.005 mA/ Kargi and
with molasses and urea from wastewater chambered cm2 Eker (2007)
plant MFC
Xylitol Pre-acclimated Single- 0.71 mA/cm2 Catal et al.
air cathode
MFC
Xylose Mixed bacterial Single- 0.74 mA/cm2 Catal et al.
culture chambered (2008)
air cathode
MFC
Xylose and humic acid Domestic Double- 0.06 mA/cm2 Huang and
wastewater chambered Angelidaki
MFC (2008)
Direct-ethanol fuel cell (DEFC) is a type of fuel cell, which requires ethanol as the
feedstock. Short-chain alcohols are vital category of next-generation biofuels,
which can be produced through fermentative pathways (Nanda et al. 2014a, 2017a).
Pseudomonas putida has proven itself as a diverse microorganism for biofuels
production as it is catabolically diverse and has accomplished metabolism and elab-
orated resilient power to assorted toxic materials (Udaondo 2012). P. putida pos-
sesses features like adaptable metabolism, immense innate resilience to noxious
materials, and flexibility of metabolic engineering. Therefore, it has appeared to be
a distinguished microorganism for high-output yield of next-generation biofuels.
Moreover, P. putida gains attention as a promising and potential organism for etha-
nol formation at an industrial scale as it possesses important characteristics such as:
(a) native elaborated protection to various stressors, which includes solvents, (b)
susceptibility to genetic modification, (c) competence to multiply rapidly, and (d)
generally recognized as safe (GRAS) (Martins dos Santos et al. 2004).
When the biosynthetic pathway from C. acetobutylicum was imposed in P.
putida, the latter gained the potency to produce n-butanol (Nielsen 2009). As
P. putida also possesses the capacity to degrade n-butanol, it becomes vital to
knock out the analogous genes to enhance n-butanol production (Cuenca

2016). Moreover, the engineered strain of P. putida has the ability to grow
under anaerobic conditions and employed in two-phase liquid extraction sys-
tems (Schmitz 2015; Basler et al. 2018).
P. putida strains are robust to utilize efficiently a wide range of carbon sources
ranging from aliphatic to aromatic hydrocarbons. P. putida can be employed for
biofuels production from lignocellulosic materials as it has been genetically modi-
fied for aromatic compounds formation from lignin (Johnson and Beckham 2015;
Vardon et al., 2015). Lignin is a cross-linked phenylpropane polymer that binds
cellulose and hemicellulose together in lignocellulosic biomass (Fougere et al.
2016; Rana et al. 2018). Bacterial ligninolytic systems as compared to fungal sys-
tem are more specific in action.
P. putida has proven to be an efficient biocatalyst after being engineered
to support the formation of a broad spectrum of compounds such as
polyketides, non-r ibosomal peptides, rhamnolipids, aromatics, and non-aro-
matics (Loeschcke and Thies 2015). Many strains of Pseudomonas possess
the potential to efficiently utilize numerous industrial products and solvents
as the sole source of carbon. Moreover, it can also tolerate high amount of
toxic aromatic compounds (Basler et al. 2018).
Prema et al. (2015) researched on the production of biofuel using waste papers
from P. aeruginosa. Cellulose structure (the main constituent of paper) was lysed
into simple fermentable sugar. As a result, about 40% fermentable sugar was
obtained after hydrolysis. P. aeruginosa converted starch of waste paper substrate
into simple fermentable sugar. The saccharification was followed by the simultane-
ous fermentation of sugars to ethanol. Pseudomonas, Enterobacter, and Bacillus are
reported to efficiently express transesterification activity. Pseudomonas fluorescens,
Pseudomonas cepacia, and Rhizomucor miehei possess enzymes to support trans-
esterification activity (Escobar-Niño et al. 2014). Roman et al. (2017) produced
ethyl esters from coconut oil and ethanol by employing chitosan-entrapped lipase
produced by P. fluorescens.
Growing energy crops is associated with intensive utilization of fertilizers and
pesticides, which lead to many negative impacts on the environment. Microalga is
one of the competent organisms in biofuel production as it provides immense bio-
mass productivity, tremendous aggregation of lipids, huge sequestration of CO2,
ability to thrive in wastewater and no competition to agricultural lands (Yadav et al.
2019). A consortia of plant growth-promoting rhizobacteria (PGPR) such as
Pseudomonas, Azospirillum, Bacillus, Rhodococcus, and Acinetobacter found in
activated sludge are found to effectively support and flourish the growth of microal-
gae (Nanda and Abraham 2011, 2013). This can be mediated by two means, i.e.,
combining microalgae and bacteria cultivation in a single process or pretreating
wastewater with bacteria before going for microalgal farming in isolated processes.
Pretreating wastewater with bacteria provides more supportive situations for the
growth of microalgae.
20.5 Major Applications for Microbial Fuel Cells
The metabolic system of bacteria is employed in MFCs for the generation of

electricity by utilizing a broad spectrum of organic substrates. Marine sedi-
ments are needed to be explored to provide current for low power devices. A
thorough understanding of microbiology, synthetic biology, fluid dynamics,
and thermodynamics associated with the system could help in improving MFC
technology. Some researchers are unfolding efficient MFC technology, which
could lead to an efficient and complete degradation of wastes and toxic chemi-
cals while producing clean electricity.
20.5.1 Wastewater Treatment and Electricity Generation
Wastewater treatment is in priority in applying MFC. Microorganisms possess

exclusive metabolic assets because of which they hold immense potential to
be employed in MFCs either as a pure culture or as consortia. Sewage sludge,
food processing wastewater, and swine wastewater are some of the substrates
rich in organic matter capable of feeding a wide spectrum of microorganisms
employed in MFCs. Enormous amounts of growth promoters are found in
MFC substrates that have the potential to accelerate the growth of active
microorganisms employed in wastewater treatment. The energy demand on
treatment plants could diminish because of simultaneous operation of bioen-
ergy generation and waste bioremediation.
20.5.2 Biosensors
Organic content can be calculated in wastewater by its biological oxygen demand

(BOD) using conventional methods. Many methods are not found suitable to control
biological wastewater treatment processes and its on-line monitoring. MFC is a
potential of BOD sensor. It is feasible to accurately measure BOD value at a broad
spectrum of the concentration range of organic contents present in wastewater. With
the aid of MFC-based biosensor, it is possible to monitor organic matter, toxicity,
and microbial activity in various environments (Davila et al. 2011; Stein et al. 2011).
20.5.3 Secondary Fuel Production
The generation of secondary fuels like hydrogen has also been conducted through
MFC. In this operation, proton and electron generated in the anodic chamber move
to cathode, which then react with oxygen to form water. Thermodynamic principles
do not favor the generation of hydrogen or it can be said that it is a tough process for
a cell to convert proton and electron into hydrogen. The generation of hydrogen
demands an enhancement in external potential applied at the cathode that can
circumvent the thermodynamic barrier because of which proton and electron gener-
ated in the anodic reaction chamber join at the cathode to form hydrogen. MFC is
an ecofriendly producer of hydrogen than that of the classical method of glucose
fermentation (Nanda et al. 2017b). Wagner et al. (2009) reported hydrogen and
methane production by using modified microbial electrolytic cells with increased
external potential at the cathode.
Microbial electrolysis cell (MEC) is another modified version of MFCs, which
supports the energy-rich production of chemicals (Call and Logan 2008, Rozendal
et al. 2009; Wagner et al. 2009). Sediment bioremediation is supported when envi-
ronments like river, lake, and marine systems apply MFCs technology (He et al.
2007; Donovan et al. 2008; Mathis et al. 2008). With the aid of microbial desalina-
tion cell (MDC), a modified version of MFC, it is now possible to curtail the salinity
of brackish water or seawater along with the generation of electrical power from
organic matters (Cao et al. 2009; Mehanna et al. 2010; Chen et al. 2012).
20.6 Current Advancements in Fuel Cell Technologies
The U.S. space program boosted MFC development in 1960s as a feasible technol-
ogy for the disposal of organic wastes for space flights that could simultaneously
generate power. There are many aspects on which MFC technology has been
explored such as feasible implementation, anode and cathode performances, variety
of substrates used in MFCs, etc. MFCs have been explored as a novel way of elec-
tricity generation along with bioremediation of wastes. Electricity production via
MFC technology has gained momentum after the origin of phototrophic MFC and
solar-powered MFC. Microbial electrolysis cell that has an anoxic cathode with
elevated external potential is the manifestation of recent alterations in MFCs tech-
nology (Bullen et al. 2006).
It is important to note that electrochemically active bacteria play a prominent
role in generating power in MFCs as they possess the ability to generate electrons
during metabolism and transfer these electrons via its cell membrane to the anode.
Hence, genetic engineering of the electrochemically active bacteria is becoming a
key area of current research along with electrode material modification, operation
parameters optimization, and scale-up of the reactor.
Recent decades have witnessed a significant improvement in MFC technology.
However, many hindrances block the scale-up and practical application of this tech-
nology. Along with these challenges, MFCs have faced two impediment problems
in power generation. Firstly, the power produced in MFCs and concentrations of
substrate are directly related, although in a momentous role in each system. The
generation of power is obstructed if the substrate concentration exceeds a specific
value. Secondly, high internal resistance is another issue that needs to be tackled as
it utilizes a significant amount of power produced in MFCs, thereby restricting the
MFC output.
The concept of design of sediment-type microbial fuel cell (SMFC) is because
detritus of plant and animal and anthropogenic organic materials generate soil and
sediments where the organic carbon content varies from 0.4 to 2.2 wt%.
Exoelectrogens can consume these materials, thereby liberating electrons that are
then directly transported outside the cell. SMFC has an anode ingrained in the
anaerobic sediment and linked through an electrical circuit and a cathode electrode
dangled in overlying water (Xu et al. 2015).
Power production and organic load removal are the thrust areas that have been
focused on optimizing MFC performance for several decades. These efforts have
been fruitful in terms of rapid improvement with power generation in multiple mag-
nitudes as it was a few decades back. However, the usage of cheap and sustainable
materials for the MFCs fabrication needs attention, which will not only help in cost-
effective scaling-up but also subside the problem of accumulation of toxic wastes
generated from old electronic components, plastics, and batteries.
The reliance on artificial mediators is also one of the obstacles that needs to
be overcome. Few chemicals aid in moving electrons from within the bacterial
cell to the surface of anodes such as neutral red, methylene blue, and thionine.
However, many a times these chemical mediators are not required as the micro-
bial species could direct conductance. The current focus has shifted toward
exploring cost-effective and easily available materials that could lead to an
advancement in MFC technology.
Platinum and other catalysts are replacing the cathode electrode. There are a few
materials that are comparatively cheaper than platinum and therefore provide a
competitive advantage (Cheng and Wu 2013). Another component that needs to
grab focus is the ion exchange membrane (IEM). Liquid feedstock is used in MFCs
in the anode, which has a potential to carry charged ions like protons. Hence, the ion
exchange membrane is not prerequisite if there is physical or electrochemical sepa-
ration between the anode and cathode. One of the simple methods is the complete
removal of the membrane from the MFC (Logan et al. 2007).
Membrane-less MFCs are cost-effective approach as it curtails the reactor
cost. The demerit associated with this approach is that oxygen diffuses toward
the anode electrode and there is a need to place the electrodes a certain distance
apart. This would also permit electrodes to be placed closely while stopping a
high flux of oxygen to the anode. Microporous filtration membranes, canvas,
nylon-infused membrane, and paper are a few examples of reported porous mate-
rials. These cost-effective materials have been intensively studied for their capac-
ity to enhance power generation along with their feasibility for field application.
Ceramic is one of the most dependable and trusted porous materials that can be
employed in MFCs (Zhuang et al. 2009).
The ambient environment is a prerequisite for MFC to operate as it works
on the metabolism of mesophilic microorganisms that survive in lower and
ambient temperatures. In this aspect, MFCs differ from the solid-oxide fuel
cell (SOFCs). The use of ceramics as a material also helps MFCs to operate at
extreme conditions proving as a suitable material for MFCs. The parameters
like the clay type, porosity, wall thickness, and density can be customized for
a target application. Moreover, adaptation can be brought in clay material to
enhance microbial colonization (Winfield et al. 2013).
20.7 Conclusions
Microbial fuel cells are bioelectrochemical devices where chemical energy stored
in organic waste substrates is transformed into electrical energy by utilizing the
biocatalytic microorganisms. MFC is an ideal, renewable, and sustainable approach
not only to treat organic wastes but also for electricity generation. MFCs can be
with the mediator and mediator-less MFCs based on the movement of electrons
produced by electrochemically active bacteria from the media to the anode. It also
suffices the production of secondary fuel along with the bioremediation of lethal
compounds. There is a huge spectrum of anaerobic bacteria involved in the reduc-
tion of contaminants, thereby transferring electrons to a solid electrode and gener-
ating electricity in MFCs.
The recent years have witnessed the expansion in the scope of MFCs, thereby
broadening its potentials from electricity production toward other specialized
applications. MFC technologies are optimal ways to approach the production
of renewable energy while remediating the pollutants. Significant efforts are
made to enhance the performance and efficiency of MFCs while reducing the
operating costs so that large-scale application of MFCs is feasible. Further
advancements in microbial metabolism in MFC systems as well as MFC appli-
cations at a much larger scale are important.
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Sonil Nanda

Prakash Kumar Sarangi

ISBN 978-981-15-1803-4 ISBN 978-981-15-1804-1 (eBook)

© Springer Nature Singapore Pte Ltd. 2020

The pretreatment procedures, enzymatic hydrolysis and microbial fermentation of

process parameters on hydrothermal liquefaction to improve the bio-oil yield.

This chapter provides insights on the technological advancements and utilities of

Saskatoon, Saskatchewan, Canada Sonil Nanda

1 Growth of Biofuels Sector: Opportunities, Challenges,

9 A Review of Thermochemical and Biochemical Conversion

18 Conversion of Biogas to Syngas via Catalytic Carbon Dioxide

About the Editors

Sonil Nanda is a Research Associate at the

Dai-Viet N. Vo is the Director of the Center of

Prakash K. Sarangi is a Scientist with specializa-

Sumaiya Zainal Abidin Faculty of Chemical and Natural Resources Engineering,

Paula Zaghetto de Almeida Departamento de Bioquímica e Imunologia,

R. Mahesh Department of Biosciences and Bioengineering, Indian Institute of

Nurul Asmawati Roslan Faculty of Chemical and Natural Resources Engineering,

N. Arun · A. K. Dalai (*)

© Springer Nature Singapore Pte Ltd. 2020 1

Globally, the consumption of renewable and low-carbon biofuels is on rise owing to

The sustainable biorefining of biomass can also result in the production of a

1.2 Biofuel Scenario in Canada and the World

Fig. 1.5 Production of biomethanol from carbohydrate biomass by gasification (Reproduced

studies done by several international organizations such as USEPA, Stockholm

1.3  olicies and Their Impacts on the Success of Advanced

Table 1.5 (continued)

Table 1.5 (continued)

Table 1.5 (continued)

1.4 Outlook for a Sustainable Future

Energy can be considered as the most influential commodity in supply-demand con-

Table 1.6 (continued)

modification of cell metabolism may be essential. However, a risk-based assess-

The microalgae-based biofuels processes still need techno-economic analysis

generally overlooked owing to the limitations in availability of literature support-

Thiago Machado Pasin, Paula Zaghetto de Almeida,

T. M. Pasin · P. Z. de Almeida · A. S. de Almeida Scarcella · J. da Conceição Infante ·

© Springer Nature Singapore Pte Ltd. 2020 23

Table 2.1 Comparative production of crops in different countries

Due to the various possible sources of lignocellulosic biomass, this chapter is

2.2 Composition of Lignocellulosic Biomass

Cellulose (23–50 wt% of the dry matter of lignocellulosic biomass) is a linear

processes involving glucose. Mannan is the second most abundant component of

2.3  ommonly Available Agricultural Crop Residues

2.3.1 Barley and Coffee Residues

2.3.2 Sugarcane, Maize, Rice, and Wheat Residues

bioethanol and the accumulation of biomass for second-generation bioethanol pro-

2.3.4 Oil Palm Residues

2.3.5 Potato Residues

2.3.6 Soybean Residues

The soybean (Glycine max) is known to be widely cultivated because of its

2.4 Enzymatic Saccharification of Lignocellulosic Residues

Endo-β-1,4-glucanases (EC 3.2.1.4) hydrolyze the glycosidic bonds mainly at

2.4.2 Auxiliary Activity 9 Enzyme and Swollenin Protein

Auxiliary activity 9 (AA9) enzyme is a fungal lytic polysaccharide monooxygenase

Hemicellulases are classified as the class of enzymes responsible for depoly-

hydrolysis of β-1,4-glycosidic linkages. Exo-β-1,4-xylosidase (EC 3.2.1.37) or

2.4.4 Pectin-Degrading Enzyme System

2.4.5 Delignifying Enzymes

Saskatoon, Saskatchewan, Canada Sonil Nanda

1 Growth of Biofuels Sector: Opportunities, Challenges,

9 A Review of Thermochemical and Biochemical Conversion

18 Conversion of Biogas to Syngas via Catalytic Carbon Dioxide

1.2 Biofuel Scenario in Canada and the World

1.3 olicies and Their Impacts on the Success of Advanced

1.4 Outlook for a Sustainable Future

2.2 Composition of Lignocellulosic Biomass

2.3 ommonly Available Agricultural Crop Residues

2.3.1 Barley and Coffee Residues

2.3.2 Sugarcane, Maize, Rice, and Wheat Residues

2.3.4 Oil Palm Residues

2.3.5 Potato Residues

2.3.6 Soybean Residues

2.4 Enzymatic Saccharification of Lignocellulosic Residues

2.4.2 Auxiliary Activity 9 Enzyme and Swollenin Protein

2.4.4 Pectin-Degrading Enzyme System

2.4.5 Delignifying Enzymes

2.5 ioconversion of Biomass to Second-Generation

2.6 Pretreatment of Lignocellulosic Biomass

2.7 Obtaining an Enzymatic Consortium

2.8 ermentation for the Production of Second-Generation

3.2 Conversion of Ethanol to Small Oxygenates

3.2.2 Acetic Acid and Ethyl Acetate

3.3 Conversion of Ethanol to Hydrocarbons

4.2 Dehydration of Ethanol

4.2.1 Diethyl Ether Production

C H OH C2 H 4 H 2 O H 298 44.9 kJ / mol (4.1)

2C2 H 5 OH C2 H 5 OC2 H 5 H 2 O H 298 25.1 kJ / mol (4.2)

4.2.2 Ethylene Production

4.2.3 Propylene Production

CH 2 CH 2 CH 3 CH CHCH3 2CH 3 CH CH 2 (4.3)

4.3 Oxidation of Ethanol

4.3.1 Ethylene Oxide Production

4.3.2 Acetic Acid Production

4.4 Steam Reforming of Ethanol and Dehydrogenation

4.4.1 Steam Reforming of Ethanol to Hydrogen

CH 3 CHO H 2 O 2CO 3H 2 (4.10)

4.4.2 Dehydrogenation of Ethanol

4.4.2.2 Ethyl Acetate

C2 H 5 OH CH 3 COOH CH 3 COOC2 H 5 H 2 O (4.12)

C2 H 4 CH 3 COOH CH 3 COOC2 H 5 (4.13)