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 Biofuels Production
and Processing Technology
 Biofuels Production
and Processing Technology

Edited by
M.R. Riazi and David Chiaramonti
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742

© 2018 by Taylor & Francis Group, LLC

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Library of Congress Cataloging-in-Publication Data

Names: Riazi, M. R., editor. | Chiaramonti, David, editor.

Title: Biofuels production and processing technology / [edited by] M.R. Riazi
& David Chiaramonti.
Description: Boca Raton : Taylor & Francis, a CRC title, part of the Taylor &
Francis imprint, a member of the Taylor & Francis Group, the academic
division of T&F Informa, plc, 2018. | Includes bibliographical references.
Identifiers: LCCN 2017013421| ISBN 9781498778930 (hardback) | ISBN
9781315155067 (ebook)
Subjects: LCSH: Biomass energy. | Chemical processes.
Classification: LCC TP339 .B54368 2018 | DDC 662/.88--dc23
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To Shiva, Touraj, and Nazly
and
To Michaela and Greta
Contents
Preface................................................................................................................................................xi
Editors..............................................................................................................................................xiii
Contributors......................................................................................................................................xv

Chapter 1 Introduction: Biofuel Production and Processing Technology......................................1

M.R. Riazi and David Chiaramonti

Chapter 2 Chemistry and Nature of Biofuels...............................................................................11

Maria Joana Neiva Correia, M. Margarida Mateus,
and Maria Cristina Fernandes

Chapter 3 Data on Biofuels Production, Trade, and Demand......................................................55

Daniela Thrän, K. Naumann, E. Billig, M. Millinger, K. Oehmichen,
D. Pfeiffer, and K. Zech

Chapter 4 Physicochemical Properties of Biofuels....................................................................101

B. Brian He and Zhidan Liu

Chapter 5 Raw Materials for Biofuels Production.....................................................................127

Jasvinder Singh and Jayati Trivedi

Chapter 6 Biofuels Production Processes and Technologies.....................................................153

Franziska Müller-Langer, Marco Klemm, and Jens Schneider

Chapter 7 Biofuels Characterization and Standard Methods for Quality Control.....................183

Martino Di Serio, Rosa Turco, Rosa Vitiello, and Riccardo Tesser

Chapter 8 Production of Bio-Oil................................................................................................199

Kevin M. Van Geem, Ismaël Amghizar, Florence Vermeire,
and Ruben De Bruycker

Chapter 9 Biodiesel Fuels: Properties and Quality....................................................................247

Paolo Bondioli

Chapter 10 Feasible Processes for Continuous Biodiesel Production from Multi-Feedstocks... 273
Naomi Shibasaki-Kitakawa and Toshikuni Yonemoto

vii
viii Contents

Chapter 11 Aviation Biofuels: Processes, Opportunities, Constraints, and Perspectives............295

David Chiaramonti and Luiz A. Horta Nogueira

Chapter 12 Liquid Hydrocarbon Biofuels from Lipids................................................................319

Alexander Asiedu and Sandeep Kumar

Chapter 13 Alcohol Fuels: The Biochemical Route....................................................................341

Elia Tomás-Pejó and Antonio D. Moreno

Chapter 14 Alcohol Fuels: The Thermochemical Route.............................................................361

Gnouyaro P. Assima, Ingrid Zamboni, and Jean-Michel Lavoie

Chapter 15 Production of Biogas and bioH2: Biochemical Methods...........................................415

Nuno Lapa, Elena Surra, Isabel A.A.C. Esteves, Rui P.P.L. Ribeiro,
and José P.B. Mota

Chapter 16 Production of Substitute Natural Gas: Thermochemical Methods............................461

Jürgen Karl and Michael Neubert

Chapter 17 Biogas Production from Biomass Wastes..................................................................487

Juan Antonio Melero, Fernando Martínez, Raul Molina, Yolanda Segura,
and Daniel Puyol

Chapter 18 Advances in Catalysts for Liquid Biofuel Production Processes..............................511

Vincenzo Russo, Riccardo Tesser, and Martino Di Serio

Chapter 19 Biorefineries: Biofuels, Biochemicals, and Bioproducts.......................................... 533

Isabella De Bari, Daniela Cuna, and Nicola Di Fidio

Chapter 20 Engine Performance: Biofuels versus Petrofuels......................................................569

Roberto Guimarães Pereira, Oscar Edwin Piamba Tulcan,
and Carlos Eduardo Fellows

Chapter 21 Life Cycle Assessment of Biofuel Production..........................................................587

Cristina de la Rúa Lope and Yolanda Lechón

Chapter 22 Economical Assessment of Biofuel Production........................................................613

B.A. McCarl, J.P.H. Jones, M. Kapilakanchana, M.Z. Wang, and G. Zhao
Contents ix

Chapter 23 Economic Assessment of Biodiesel Production........................................................641

Jorge Mario Marchetti and Mangesh R. Avhad

Chapter 24 Future Trends and Outlook in Biofuels Production..................................................663

Arnaldo Walter

Index...............................................................................................................................................681
Preface
The importance of biofuels in greening the transport sector in the future is unquestionable, given the
limited available fossil energy resources, the environmental issues associated with the utilization of
fossil fuels, and the increasing attention to security of supply. The initial idea on a new book came
from a meeting between one of us (MRR) and Allison Shatkin (managing editor at CRC) during the
2015 AIChE Annual Meeting held in Salt Lake City in November that year. The idea was pursued
with encouragement from the CRC managing editor and invitation for collaboration to leading sci-
entists in the field, which led to the completion of this book. Although an attempt was made to cover
all aspects of biofuels production and processing, this was certainly a difficult task, and probably
some topics received less attention than what they deserve. Readers may also find some overlaps
between the chapters, but these are minor, and each chapter focuses on a unique topic specific to
that chapter.
In completing this book, we are indebted to all distinguished authors who collaborated with us
and contributed to various chapters of the book. We are also grateful to a number of experts who
helped us in reviewing some chapters with their constructive comments and suggestions. Among
them, we are particularly indebted to George E. Anasontzis, Sergi Astals-Garcia, Neeraj Atray, Dina
Bacovsky, Joana Neiva Correia, Arnaldo Vieira de Carvalho, Martino Di Serio, Juan Antonio Melero
Hernández, Inmaculada Gomez Jimenez, Alfredo Juan, Dimitrios Komilis, Masato Kouzu, Nuno
Lapa, Jean-Michel Lavoie, Randy L. Maglinao, Franziska Müller-Langer, Ana Cristina Oliveira,
Eliseo Maria Ranzi, Marcos Sanchez Rodriguez, Vincenzo Russo, Jose Luis Sánchez, Joan Salvadó,
Martin Seemann, Elia Tomás-Pejó, Lee Keat Teong, Riccardo Tesser, Daniel Cardoso Vaz, and Jun
Zhu as they enthusiastically agreed to review some lengthy manuscripts.
We are also thankful to the Taylor & Francis Group for the publication of this book and in par-
ticular to Allison Shatkin, the managing editor, who was helpful and supportive at every stage of this
project, and her initial contacts and encouragement were instrumental in undertaking such a major
task. The work of Teresita Munoz, editorial assistant at CRC, and Deepa Kalaichelvan, project man-
ager at SPi Global, in reviewing and editing this manuscript is also appreciated.

M.R. Riazi
David Chiaramonti

xi
Editors
M.R. Riazi (www.riazim.com), who has a doctorate in chemical
engineering from Pennsylvania State University (Penn State), is the
author of 150 publications including six books in the areas of oil,
gas, coal, and biofuel characterization, production, and processing.
In addition, he has to his credit more than 100 conference presen-
tations. He has been invited to chair international conferences and
has conducted about 100 invited lectures and workshops and more
than 60 short courses for the petroleum industry in more than 40
countries. He has served as an assistant professor at Penn State as
well as a visiting professor/scholar in the Departments of Chemical
and Petroleum Engineering at the following universities: Illinois
(Chicago), Texas (Austin), Norwegian University of Science and Technology (Trondheim), McGill
(Montreal), Waterloo (Ontario), Wright State (USA), Sharif (Arya-Mehr University), IIT (Kanpur,
India), and Kuwait. He is also the managing director of the Petrogas firm based in Canada and the
chair of chemical engineering at Kuwait University. He is also the managing director of the Petrogas
firm based in Canada and a professor and former head of chemical engineering at Kuwait University.
He has been working on research projects related to hydrocarbon thermodynamics; gas processing; oil,
gas, and coal properties; enhanced oil recovery and heavy oil characterization; renewable energy; and
environmental issues funded by the American Petroleum Institute (API), U.S. Department of Energy,
U.S. National Science Foundation, GRI/Chicago, NSERC (Canada), Petrofina (Brussels), SINTEF
(Norway), as well as KPC, KFAS, KISR, KU, and KOTC (Kuwait). He is the founding editor and
editor-in-chief of IJOGCT as well as an associate editor of JPSE. As a result of his work, Dr. Riazi
has been honored with the following awards: Diploma of Honor from the U.S. National Petroleum
Engineering Society for Outstanding Contributions to the Petroleum Industry, KU Outstanding
Research and Teaching Awards (received from former Amir of Kuwait), and an elected Fellow of the
American Institute of Chemical Engineers (AIChE). He is a registered and licensed professional engi-
neer (P.Eng) in Ontario, Canada.

David Chiaramonti teaches biomass energy conversion tech-

nologies and processes at the University of Florence, where he
obtained his PhD in energy engineering. His major scientific
interest is on the production and use of biofuels—liquid, gas-
eous, and solid. His research works cover thermochemical bio-
mass conversion processes as well as liquid biofuel production
and use. He has published more than 140 scientific papers in
these areas, edited journal special issues, chapters in books and
studies, as well as articles in magazines. He is a member of the
editorial boards of peer-reviewed journals of the field, including
IJOGCT (Inderscience), Applied Energy (Elsevier), and Biomass
Conversion and Biorefinery (Springer). He is/has been chairman and member of steering, interna-
tional organizing, and scientific committees of various international conferences on biomass, bio-
energy, and bioproducts, member of IEA Task 39 (Liquid Biofuels) and 34 (Biomass Pyrolysis),
chairman of the scientific board of DBFZ, and member of other international organizations and
associations, such as the UN ICAO Committee on Aviation Environmental Protection/Alternative
Fuels Task Force and European Algae Biomass Association. His recent work on biofuels focused

xiii
xiv Editors

on policy development and market issues. He acted as a project manager and scientific responsible
in a large number of R&D&D projects, supported by the European Commission and Ministries and
private companies. He is the president of the not-for-profit research institution RE-CORD (funded
and participated in by the University of Florence and other public/private partners) that holds a
chemical laboratory dedicated to bioenergy and bioproducts and operates several innovative pilot/
demo plants for thermochemical and biochemical processing of biomass. In June 2017, he has been
awarded the Linneborn Prize for outstanding merit in biomass.
Contributors
Ismaël Amghizar Daniela Cuna
Laboratory for Chemical Technology Laboratory Agrifood Sustainability, Quality and
Ghent University Safety
Ghent, Belgium ENEA—Italian National Agency for New
Technologies, Energy and Sustainable
Alexander Asiedu Economic Development
Department of Civil and Environmental Brindisi, Italy
Engineering
Old Dominion University
Norfolk, Virginia Isabella De Bari
Laboratory Technologies and Processes for
Gnouyaro P. Assima Biorefineries and Green Chemistry
Faculty of Engineering ENEA––Italian National Agency for New
Department of Chemical and Biotechnological Technologies, Energy and Sustainable
Engineering Economic Development
Univeristé de Sherbrooke Rotondella, Italy
Sherbrooke, Quebec, Canada

Mangesh R. Avhad Ruben De Bruycker

Faculty of Science and Technology Laboratory for Chemical Technology
Norwegian University of Life Sciences Ghent University
Drobakveien, Norway Ghent, Belgium
E. Billig
UFZ—Helmholtz Centre for Environmental Nicola Di Fidio
Research Department of Bioscience, Biotechnology and
Leipzig, Germany Biopharmaceutics
University of Bari “Aldo Moro”
Paolo Bondioli
Bari, Italy
INNOVHUB—Stazioni Sperimentali per
l’Industria
Division of Stazione Sperimentale Oli e Grassi Martino Di Serio
Milano, Italy Department of Chemical Sciences
University of Naples “Federico II”
David Chiaramonti
Napoli, Italy
Department of Industrial Engineering
University of Florence
and Isabel A.A.C. Esteves
LAQV-REQUIMTE
Renewable Energy Consortium for Research Departamento de Química
and Demonstration Faculdade de Ciências e Tecnologia
Florence, Italy Universidade NOVA de Lisboa
Caparica, Portugal
Maria Joana Neiva Correia
Department of Chemical Engineering
Centro de Recursos Naturais e Ambiente Carlos Eduardo Fellows
Instituto Superior Técnico Institute of Exact Sciences
Universidade de Lisboa Fluminense Federal University
Lisbon, Portugal Volta Redonda, Brazil

xv
xvi Contributors

Maria Cristina Fernandes Nuno Lapa

Department of Chemical Engineering LAQV-REQUIMTE
Centro de Recursos Naturais e Ambiente Departamento de Ciências e Tecnologia da
Instituto Superior Técnico Biomassa
Universidade de Lisboa Faculdade de Ciências e Tecnologia
Lisboa, Portugal Universidade NOVA de Lisboa
Caparica, Portugal
B. Brian He
Department of Biological Engineering
Jean-Michel Lavoie
University of Idaho
Faculty of Engineering
Moscow, Idaho
Department of Chemical and Biotechnological
Engineering
Luiz A. Horta Nogueira Univeristé de Sherbrooke
Campinas State University Sherbrooke, Quebec, Canada
Campinas, Brazil
and Yolanda Lechón
Universidade Federal de Itajubá Department of Energy
Itajubá, Brazil Centro de Investigaciones Energéticas,
Medioambientales y Tecnológicas
J.P.H. Jones Madrid, Spain
Resource, Energy, and Environmental
Economics
Zhidan Liu
RTI International
Department of Agricultural Structure and
Research Triangle Park, North Carolina
Environmental Engineering
College of Water Resources and Civil
M. Kapilakanchana Engineering
Bank of Thailand China Agricultural University
Bangkok, Thailand Beijing, People’s Republic of China

Jürgen Karl
Chair of Energy Process Engineering Cristina de la Rúa Lope
Department of Chemical and Biological Department of Energy
Engineering Centro de Investigaciones Energéticas,
Friedrich-Alexander-Universität Medioambientales y Tecnológicas
Erlangen-Nürnberg Madrid, Spain
Nuremberg, Germany
Jorge Mario Marchetti
Marco Klemm Faculty of Science and Technology
German Biomass Research Centre GmbH Norwegian University of Life Sciences
Leipzig, Germany Drobakveien, Norway

Sandeep Kumar Fernando Martínez

Department of Civil and Environmental School of Experimental Sciences and
Engineering Technology
Old Dominion University Universidad Rey Juan Carlos
Norfolk, Virginia Madrid, Spain
Contributors xvii

M. Margarida Mateus Michael Neubert

Centro de Recursos Naturais e Ambiente Chair of Energy Process Engineering
Instituto Superior Técnico Department of Chemical and Biological
Universidade de Lisboa Engineering
Lisboa, Portugal Friedrich-Alexander-Universität
Erlangen-Nürnberg
B.A. McCarl Nuremberg, Germany
Department of Agricultural Economics
Texas A&M University
College Station, Texas K. Oehmichen
German Biomass Research Centre GmbH
Juan Antonio Melero Leipzig, Germany
School of Experimental Sciences and
Technology
Universidad Rey Juan Carlos Roberto Guimarães Pereira
Madrid, Spain Department of Mechanical Engineering
Fluminense Federal University
M. Millinger Niterói, Brazil
UFZ—Helmholtz Centre for Environmental
Research
Leipzig, Germany D. Pfeiffer
German Biomass Research Centre GmbH
Raul Molina Leipzig, Germany
School of Experimental Sciences and
Technology
Universidad Rey Juan Carlos Daniel Puyol
Madrid, Spain School of Experimental Sciences and
Technology
Antonio D. Moreno Universidad Rey Juan Carlos
CIEMAT Madrid, Spain
Biofuels Unit
Madrid, Spain
M.R. Riazi
José P.B. Mota Petrogas
LAQV-REQUIMTE Montreal, Quebec, Canada
Departamento de Química
Faculdade de Ciências e Tecnologia and
Universidade NOVA de Lisboa Department of Chemical Engineering
Caparica, Portugal Kuwait University
Kuwait City, Kuwait
Franziska Müller-Langer
Department of Biorefineries
German Biomass Research Centre GmbH Rui P.P.L. Ribeiro
Leipzig, Germany LAQV-REQUIMTE
Departamento de Química
K. Naumann Faculdade de Ciências e Tecnologia
German Biomass Research Centre GmbH Universidade NOVA de Lisboa
Leipzig, Germany Caparica, Portugal
xviii Contributors

Vincenzo Russo Elia Tomás-Pejó

Department of Chemical Sciences Biotechnological Processes Unit
University of Naples “Federico II” IMDEA Energy
Napoli, Italy Madrid, Spain

Jens Schneider Jayati Trivedi

German Biomass Research Centre GmbH Biofuels Division
Leipzig, Germany Indian Institute of Petroleum
Dehradun, India
Yolanda Segura
School of Experimental Sciences and
Oscar Edwin Piamba Tulcan
Technology
Department of Mechanical Engineering and
Universidad Rey Juan Carlos
Mechatronics
Madrid, Spain
National University of Colombia
Bogotá, Colombia
Naomi Shibasaki-Kitakawa
Department of Chemical Engineering
Tohoku University Rosa Turco
Sendai, Japan Department of Chemical Sciences
University of Naples “Federico II”
Jasvinder Singh Napoli, Italy
Biofuels Division
Indian Institute of Petroleum Kevin M. Van Geem
Dehradun, India Laboratory for Chemical Technology
Ghent University
Elena Surra Ghent, Belgium
LAQV-REQUIMTE
Departamento de Ciências e Tecnologia da
Florence Vermeire
Biomassa
Laboratory for Chemical Technology
Faculdade de Ciências e Tecnologia
Ghent University
Universidade NOVA de Lisboa
Ghent, Belgium
Caparica, Portugal

Riccardo Tesser Rosa Vitiello

Department of Chemical Sciences Department of Chemical Sciences
University of Naples “Federico II” University of Naples “Federico II”
Napoli, Italy Napoli, Italy

Daniela Thrän Arnaldo Walter

UFZ—Helmholtz Centre for Environmental Mechanical Engineering Faculty
Research Department of Energy
German Biomass Research Centre GmbH University of Campinas
Campinas, Brazil
and
Department of Bioenergy M.Z. Wang
Institut Bioenergies Systeme Department of Agricultural Economics
University of Leipzig Texas A&M University
Leipzig, Germany College Station, Texas
Contributors xix

Toshikuni Yonemoto K. Zech

Department of Chemical Engineering German Biomass Research Centre GmbH
Tohoku University Leipzig, Germany
Sendai, Japan
G. Zhao
Ingrid Zamboni Department of Agricultural Economics
Faculty of Engineering Texas A&M University
Department of Chemical and Biotechnological College Station, Texas
Engineering
Univeristé de Sherbrooke
Sherbrooke, Quebec, Canada
 1 Biofuel Production and
Introduction

Processing Technology
M.R. Riazi and David Chiaramonti

CONTENTS
1.1 Introduction................................................................................................................................1
References...........................................................................................................................................9

1.1 INTRODUCTION
The term “biofuel” refers to a liquid or gaseous transport fuel, such as ethanol, biodiesel, hydropro-
cessed vegetable oils and lipids, upgraded bio-pyrolysis oil (bio-oil), or biogas-derived biomethane,
produced from biomass and renewable resources, such as lignocellulosic plants, starch or sugar crop
plants, and the organic fraction of municipal or industrial wastes. The term “bioliquid” is instead
used to indicate a liquid fuel used for energy purposes other than for transport, including electricity
and heating and cooling, produced from biomass. As energy resources from fossil fuels (such as
oil, natural gas, and coal) are being depleted or discouraged due to the associated greenhouse gas
(GHG) emission and impact on global climate, the production and use of sustainable biofuels is
considered crucial to fully deploy potential energy resources in the future. The International Energy
Agency (IEA) projected that petroleum resources will be depleted around 2060. According to the
IEA, currently about 2% of world energy needed for transportation is being produced from bioen-
ergy. It is expected this figure will be increased to 27% by 2050 (IEA, 2016). The U.S. biodiesel
production increased from 343 million gal in 2010 to 1.278 billion gal in 2014, an increase of 272%
during this 5-year period (AgMRC, 2016). The World Economic Forum in Davos recommended that
515 billion dollars a year be spent globally on clean energy development (including sustainable
biofuels) between now and 2030 (Russia Today, 2009). Lowering CO2 emission and increasing world
energy security represent further cornerstones of biofuels in a global sustainable energy scenario.
Main feedstocks for the production of biofuels include lignocellulosic biomass, starch, sugar, lipids,
and wet biomass. Major products from these feedstock materials include syngas, bio-oil, bioalcohols,
hydroprocessed vegetable oil, biodiesel, glycerol and biomethane, and pyrolysis oil as an intermediate
energy carrier to be further upgraded downstream into transport fuels. Processes that may be used to
convert the feedstocks into the products may include gasification, pyrolysis, liquefaction, fermenta-
tion, hydroprocessing, and transesterification.
Biofuels are often classified into four groups: first, second, third, and fourth generations. First-
generation biofuels (also called conventional biofuels) are those produced from food-based land-
using feedstocks such as sugar, starch, and lipids/fats. The main criticisms against this type of biofuel
relate to their rather limited average biofuel yields per hectare and the potential negative impact on
food production, as they require agricultural land for their production. Nevertheless, examples of
efficient and sustainable biofuel production chains through conventional (i.e., first-generation) tech-
nologies also exist, as it is, for instance, the case of sugarcane chain in Brazil, or other sustainable
crops in Europe, or the integrated production of food and fuel and the development of innovative

1
2 Biofuels Production and Processing Technology

crop rotation schemes. These shortcomings stimulated the development of second-generation bio-
fuels, which are mainly produced from nonfood feedstocks such as straw, bagasse, forest and agri-
cultural residues, and purpose-grown energy lignocellulosic crops. Nevertheless, the “land use”
issue remains a key element to make these biofuels advanced according to the current European
Union (EU) legislation, with the use of residues clearly promoted before agricultural land-consum-
ing crops. Third-generation biofuels are based on the production and conversion of algal biomass
and are presently under extensive research to maximize yields and lower production costs. Fourth-
generation biofuels are carbon-negative ones and are still in the research and development stage for
direct conversion of solar energy into fuel using cheap and widely available raw materials (Aro,
2016). At present time, more than 99% of biofuel production relates to first- and second-generation
biofuels, which are the topics covered in this book. A schematic of possible biorefinery processes
is shown in Figure 1.1 (from Chapter 19). Details on biofuel classifications, types, and chemical
compositions of raw materials and products are given in Chapter 2. The chapter also briefly reviews
various processing technologies for the conversion of different raw biomaterials to various products.
Statistical data on production of biofuels, trade, and demand are presented in Chapter 3. Global
production and consumption of various types of biofuels in different parts of the world over the last
15 years is also presented in this chapter. Estimation of biomass potential over the next three decades
until 2050 is presented as well. Economy of biofuel production, price change with time, and com-
parisons with fossil fuels are discussed with extensive data and 36 figures along with environmental
issues and GHG mitigation potential of biofuels.
Process development and design/operation of units for the production of biofuels largely depend
on the physiochemical properties of the raw materials as well as the products for each process. In
addition, safety and utilization of biofuels require certain properties and specifications. These prop-
erties are discussed in Chapter 4 for biogas, biohydrogen through the fermentation process, liquid
biofuels such as bio-oil from woods, as well as solid biofuels and biomass raw materials. Elemental
analysis (C, H, O, S, N, etc.); content of major elements in solid fuels (Al, Ca, Fe, Mg, P, K, Si, Na,
and Ti) and minor elements; standard test methods; measurement of heating value; specifications for
liquid biofuels as recommended by American Society for Testing and Materials (ASTM) standards
for physical properties such as flash point, Ca and Mg contents, alcohol control, water and sediment
contents, viscosity, density, ash, cloud point, carbon residue, acid number, oxidation stability, glyc-
erin content, and P, Na, and K contents; thermal stability; as well as distillation data are presented
in Chapter 4.
As said, a wide range of raw materials can be used to produce biofuels through different pro-
cesses. Availability of feedstocks in different parts of the world is an important factor in choosing the
most appropriate local options for biofuel production. This is the topic covered in Chapter 5, which
discusses various types of raw materials, including sugar and starch energy corps, grass, oil crops,
palm oil, soybean oil, jatropha curcas oil, croton nut oil, cocoa, rubber tree waste, industrial waste,
forest residues, animal wastes, rice straw, wood-like residues, and other types of biomass that can
be used as potential raw materials for biofuel production. A large amount of crop residues remains
unused or burnt in the fields. In the absence of adequate collection mechanism, a considerable quan-
tity of urban waste is disposed of without any utilization, while its disposal by burning contributes
to increase the environmental pollution, as noted in Chapter 5.
A general overview of processes for the production of different types of biofuels under various
geographical locations and environments as well as the classification of production routes such
as physicochemical, biochemical, or thermochemical conversions is presented in Chapter 6. In
this chapter, the process information and technology characteristics of the most important biofuel
options are discussed, providing fundamentals for the following chapters in this book that deal
with much more details. Processes such as transesterification, fermentation and digestion (anaerobic
fermentation), and hydrothermal (carbonization, liquefaction, and gasification), pyrolytic (carbon-
ization, slow or flash pyrolysis), electrochemical, and gas to liquid (Fischer–Tropsch [FT] process)
processes are among the many processes analyzed in this chapter for various types of biofuels and
 Organic residues Starch Sugar Lignocellulosic Lignocellulosic Marine Oil-based
Grasses Oil crops
and others crops crops crops residues biomass residues

Grain Straw
Straw
Separation Fractionation and/
Pretreatment Pressing/
Introduction

or pressing disruption

Lignin
Fiber Gasification
separation
Organic juice
Pyrolysis, Oil
HTU
Hydrolysis

Syngas
Anaerobic Extraction
Pyrolytic liquid
digestion C6 sugars C5 sugars

Water gas
Separation
shift

Hydrogenation/
Biogas Methanization upgrading
Chemical
Upgrading Fermentation Combustion reaction
Chemical
reaction
Esterification
Upgrading
Steam
reforming
Water
H2 electrolysis

Chemical
Legend reaction

Feedstock Chemical Thermochemical

process process

Platform Mechanical/ Biochemical

physical process processes Chemicals and Synthetic biofuels Polymers and Animal
Biomethane Biomaterials Food
building blocks (FT, DME...) resins feed
Material Energy products
products
Link among biorefinery pathways Electricity
Fertilizer Bio-H2 Bioethanol Glycerin Biodiesel
and heat

FIGURE 1.1 General schematic of biorefineries for both energy-driven and product-driven categories. (From IEA, Bioenergy: Sustainable biomass supply chains for
biorefineries—IEA task 42 update, Fourth International Forest Biorefinery Symposium, Maria Wellisch, Agriculture and Agri-Food Canada, Montréal, Quebec, Canada,
February 3, 2014, http://www.iea-bioenergy.task42-biorefineries.com/upload_mm/3/9/d/0b150a14-ebfe-49b5-bad5-daaa507b065f_IEA%20Task%2042%20Feb%20
3

2014%20MW%20Montreal.pdf.)
4 Biofuels Production and Processing Technology

feedstocks. In addition, mechanical pretreatment and feedstock preparation (pressing, washing, and
drying) as well as the final product treatment of produced biofuels such as gas cleaning and condi-
tioning are examined in Chapter 6.
Chapter 7 discusses standards and quality of various biofuels in conjunction with properties
discussed in Chapters 4 and 9. The principal documents for quality determination are subdivided
into three groups—regulations, standards, and codes—and discussed in detail in this chapter. The
chapter begins with the introduction of the various standard organizations in the United States and
the EU, followed by regulations issued by governments for safety in the use of biofuels. Biofuels’
quality specifications according to ASTM standards in the United States are introduced. Similarly,
the quality specifications according to EN test methods for biofuels use in the EU are presented.
These specifications include impurities and limits of concentrations according to various fuel quality
standards in addition to important properties, such as acidity, appearance, and conductivities.
Chapter 8 discusses the production of bio-based hydrocarbons and chemicals (such as alkenes
and aromatics) using biomass feedstocks. The focus has been on the introduction of commercial and
industrialized processes using both thermochemical and catalytic conversions, with description of
process conditions, reactor design, and kinetic models. Triglycerides and fatty acids are converted to
bio-derived hydrocarbons through hydrodeoxygenation and catalytic cracking/isomerization, while
lignocellulosic materials are converted through fractionation, fast pyrolysis, torrefaction, or gasifica-
tion (to maximize syngas) to bio-oil, biochar, or biogas (syngas). Syngas is then converted to liquid
hydrocarbons through the Fischer–Tropsch process or other catalytic steps. Bio-derived hydrocar-
bons can then be converted into aromatics or alkenes through a steam cracking process. Torrefaction
is an anaerobic thermal process that converts biomass into a kind of coal-like material (torrefied bio-
mass) with higher energy density than the original feedstock. In this process, heating of biomass is
carried out in the absence of oxygen: the weight loss is nearly 30%, while energy loss is about 10%.
While torrefaction maximizes the yield of solid carbonaceous material, fast pyrolysis maximizes the
yield of condensable organic molecules, and gasification maximizes the yield of noncondensable
gases as explained in this chapter.
Besides bioethanol, biodiesel has been the most widely used biofuel in the world and especially
in Europe since the 1990s. Biodiesel is a mixture of different types of fatty acid methyl esters
(FAMEs) that could be used in diesel engines as neat fuel, but in actual applications it is blended at
low percentages (e.g., 7% max in Europe). Physical properties of FAME biodiesel are closer to those
of conventional fossil diesel fuel than the initial feedstock (vegetable oils, lipids). For example,
the density of FAME biodiesel at 20°C is about 880 kg/m3, while the density of fossil-type diesel
is about 830 kg/m3. Similarly, the cetane number of FAME biodiesel is 56, while that of diesel is
about 50. Chapter 9 is devoted entirely to the discussion of the production, properties, and quality of
biodiesel as the most widely used biofuel in Europe for transportation. The chapter reviews various
types of feedstock materials and corresponding processes to produce biodiesel, followed by chemi-
cal and physical properties of biodiesel for quality control, including oxidation stability, cold prop-
erties, density and viscosity, vapor pressure and heating value, solubility, hygroscopicity, biological
contamination, interfacial tension, flash point, cetane number, corrosivity, acidity, water content,
carbon residue, and chemical composition. In addition, factors that affect processing (including
separation of contaminants) and related problems as well as handling of effluents are also discussed
in this chapter. A comparison between the quality and the characteristics of biodiesels produced in
the United States and Europe is finally presented.
Chapter 10 is also devoted to biodiesel production, which increased from 3.4 million tonnes in
2015 to 25 million tonnes in 2016. As said, biodiesel is a mixture of fatty acid methyl esters, and
it is mainly produced from lipid feedstocks that consist of various glycerides and free fatty acids.
Different technologies for the production of biodiesel, various feedstocks (such as rice bran oil and
jatropha oil), various catalysts, and production routes are discussed, followed by a comparison of
the quality of produced biodiesel with recommended standards and specifications by international
standard organizations. In addition, a novel process that uses cation- and anion-exchange resins for
Introduction 5

continuous production of biodiesel is presented. Some laboratory data for production of biodiesel
from an automated pilot-scale process using cheap feedstocks are also discussed in this chapter.
Aviation represents a key and growing sector for transportation, differently from road trans-
ports, that can implement a variety of GHG emission reduction measures to mitigate the impact on
climate change (such as intermodality, shift to electrical transport, pool car, and biomethane). The
major option for aviation is certainly represented by the substitution of conventional fossil fuels
with cleaner fuels, for example, biofuels and renewable low-carbon fuels. Production of aviation
biofuel through different feedstocks and processes is presented in Chapter 11. The authors initially
review the status of global commercial biofuel flights and carriers, providing also an overview of
the future scenario of CO2 emissions from aviation. Feedstock and pathways to aviation biofuels
are then introduced and discussed, taking into account the peculiar characteristics of this paraf-
finic fuel and its particular operational conditions. A special focus is given to describe the complex
ASTM certification process, a fundamental element in order to use a new fuel in commercial flights,
which involves a large number of technical phases and stakeholders (such as original equipment
manufacturers [OEMs]). The concepts of technology and fuel readiness levels are also introduced in
the chapter, which is then concluded with the analysis of the main opportunities and barriers to the
introduction of aviation biofuels in the market.
Chapter 12 discusses the production of liquid hydrocarbons from lipids mainly derived from
plants or animal fats. Lipids are a group of heterogeneous, water-insoluble, and organic molecules
and primarily consist of triacylglycerols and fatty acids. Triglycerides are the main elements of
lipids (animal fats and vegetable oils) that consist of a glycerol molecule attached to three fatty
acid molecules. The chapter reviews nature and characteristics of lipids and various processes (i.e.,
transesterification and hydroprocessing of lipids, catalysts, process optimization, etc.) for conver-
sion of these materials into biofuels. The fuels derived from nonfood-based lipid biomass such as
waste fats, oils, greases, and nonfood plant-derived oils grown on marginal lands are being viewed
as cost-competitive options to produce biofuels. Environmental and economic issues associated with
the technology of converting lipids to liquid hydrocarbons are also discussed in this chapter.
Chapter 13 discusses the production of bioalcohols from solid biomass (lignocellulose) through
biochemical routes such as the fermentation processes. Most common alcohol biofuels are mainly
biomethanol, bioethanol, and biobutanol; however, so far bioethanol is the most widely used biofuel
in the transportation sector. There is no chemical difference between biologically produced and
chemically produced alcohols, and efforts are underway to develop and optimize the biochemical
processes for the production of alcohol fuels by means of microorganisms. Methanol can also be
produced by methanotrophic bacteria under aerobic conditions. Emerging routes such as anaerobic
oxidation of methane to obtain higher conversion efficiencies are also reviewed in this chapter.
Chapter 14 discusses the production technology of alcohol fuels through thermochemical route.
Thermochemical conversion processes involve the treatment of renewable carbon substrates with
a limited amount of an oxidizing agent (i.e., air, steam, or oxygen) for the production of a mixture
composed of a solid (biochar), a liquid (bio-oil), and a gas (syngas), as already previously discussed.
The chapter begins with discussing the gasification process of biomass, followed by its utilization
for alcohol production. Production of methanol, ethanol, propanol, butanol, isobutanol, tert-butanol,
and higher alcohols is described here. The chapter is concluded with a discussion on ethical con-
cerns regarding biofuel production, especially regarding biomass sources, quantity, and supply.
Production of biogas (mainly methane, CO2, and other trace gases) and biohydrogen through
biochemical routes (microbial degradation of organic matter in anaerobic conditions) is discussed in
Chapter 15. Biogas is a suitable energy vector for electricity and heat production, while its upgrad-
ing to biomethane allows for gas injection and use as a transport fuel. Biomethane (CH4 > 97% v/v)
production is discussed in the last section of this chapter. As several other sustainable biofuel pro-
duction routes, biogas generates various environmental and social benefits, namely, organic waste
reduction and valorization, reduction of GHG emissions, global warming mitigation, reduction of
the dependency on fossil fuels, renewability, contribution to achieve targets on renewable energy,
6 Biofuels Production and Processing Technology

and job creation as outlined by the authors of the chapter. Biogas production can be carbon neutral,
as the carbon in biogas comes from organic matters in nature, and should be connected to sustain-
able farming practices (in particular, crop rotations favoring sustainable soil management).
The chapter begins with the full description of the anaerobic digestion (AD) processes and the
bacteria groups involved in the process. Factors affecting the process such as temperature, pH,
retention time, C/N ratio, chemical oxygen demand (COD), and organic load rate to the bioreactor
as well as monitoring operational parameters are discussed, followed by biogas properties and uses.
A comparison between biogas production facilities in Europe and the rest of the world is presented,
followed by authors’ discussion on the challenges ahead in this field. The second part of the chapter
is devoted to analyze the production of hydrogen through biochemical processes using lignocellu-
losic biomass feedstock. Alternative processes for hydrogen production comprise all the biological
technologies, in which different microorganisms are able to produce H2 through a variety of meta-
bolic pathways. The chapter also briefly reviews various methods for hydrogen production through
different routes, including the use of fossil fuels, and discusses the advantages/disadvantages of
various methods. The last part of the chapter discusses upgrading of produced biogas to biomethane
and purification technologies.
Chapter 16 discusses the production of substitute natural gas (SNG, mainly methane) from
biomass through thermochemical methods. At present, the most widely used process to produce
biomethane is through AD and separation, as covered in the preceding chapter. In particular, agricul-
tural residues are converted into methane-rich gas by microorganisms in large fermenters. However,
these microorganisms do not convert lignin or lignocellulosic materials, and therefore, the whole
conversion of woody biomass and other lignocellulosic residues requires thermal conversion pro-
cesses. Pyrolysis processes aim at the production of liquid bio-oil, while gasification processes aim
at producing biogas: as the reactions are endothermic ones, they require high temperatures, typically
well above 700°C, with the presence of air or steam as an oxidizing agent. The heat required for the
process may come from partial combustion of biomass materials or indirect heating. The product of
a high-temperature low-tar gasification process is syngas, which is mainly composed of hydrogen
and carbon monoxide. Syngas can be converted to biomethane through catalytic processing, and
the product is also called synthetic (or substitute) natural gas. The methanation reactions are highly
exothermic ones and may generate temperatures above 600°C; cooling is thus necessary to avoid
damages to catalysts (such as nickel). This also represents an opportunity for heat recovery through
steam generation. Methanation of syngas through biological processes is a new trend in SNG pro-
duction using microorganisms, a topic that is also covered in this chapter. For both processes, reactor
type, operating conditions, and efficiencies of processes as well as future challenges are examined
in detail in this chapter.
Discussions on the production of biogas/biomethane from biomass materials continue in Chapter
17; however, this chapter is focused on the production of biogas from biomass wastes, which has
received great attention by researchers and entrepreneurs in recent years. Special attention is given to
novel and low-cost pretreatments of sewage sludge to enhance methane production and the integra-
tion of biohydrogen production and methanogenesis in multiple systems. The chapter also reviews
methods of improving efficiencies of AD processes for the production of biogas. Some innovative
technologies for pretreatment of sewage sludge to improve the efficiency of the anaerobic processes
are introduced in this chapter. These innovative pretreatments are based on the use of special chemi-
cals, which considerably promote anaerobic activity. Production of biohydrogen gas through dark
fermentation, photo-fermentation, and bio-photolysis processes is discussed, and the chapter ends
with a section on future trends in this area.
Due to the importance and role of catalysts in many biofuel production processes, Chapter 18
is entirely devoted to recent developments in this field. Briefly, as discussed in previous chapters,
biodiesel can be produced from transesterification of triglycerides in the presence of methanol,
bio-gasoline from catalytic cracking of triglycerides, green diesel from catalytic decarboxylation
and hydrogenation of triglycerides, bioethanol from catalytic fermentation of biomasses, and
Introduction 7

bio-oil-derived hydrocarbons from catalytic pyrolysis and processing of biomasses. All these path-
ways involve catalytic reactions, and therefore catalysts play a key role in the rate of reaction, prod-
uct quality, as well as operational conditions in the reactor. Both base (such as NaOH and KOH)
and acid (such as Lewis acid) catalysts can be used for biodiesel production. The performances of
the homogeneous Lewis acid catalysts can be improved by using suitable complexing agents as dis-
cussed in the chapter. The use of heterogeneous catalysts such as CaO, ZnO, SrO, and MgO for the
production of different biofuels is discussed along with their characteristics, deactivation, and sepa-
ration methods after the reaction. Application of many other types of catalysts (Ti/Al2O3, HTiNbO3,
TiO2, V2O5); zeolite-type catalysts for bio-gasoline production, Pd/C, H3PO4, Ni(Mo), and Co(Mo);
and noble metal catalysts for green diesel production is discussed in this chapter, providing informa-
tion on their performance under different operational conditions. Methods for catalysts loading, sup-
porting materials, and their specific application in each process are given in this chapter. A summary
of both base and acid heterogeneous catalysts tested for the transesterification reaction with related
drawbacks is presented at the end of the chapter.
Chapter 19 discusses biorefineries for the production of biofuels, biochemicals, and bioprod-
ucts. As a general approach, a biorefinery aims at converting various types of biomass feedstocks
(e.g., starch, oilseeds, lignocellulosic biomass, and algae) into a range of value-added products and
chemicals (e.g., food, feed, fibers, lubricants, solvents, fuels, and monomers such as lactic acid)
as well as bioenergy. The energy required to operate a biorefinery plant can be generated from
unconverted residues/coproducts and waste streams to make it an energy-self-sufficient industrial
complex. Among others, the classification of biorefineries can be based on the energy-driven or
product-driven approach. In energy-driven biorefineries, the industrial plants are oriented toward
energy products such as biofuels or bioenergy, while in product-driven biorefineries the plants are
mostly oriented toward value-added chemicals and materials. Although the main objective of the
chapter is to present energy-driven biorefineries, the second class of biorefineries is also introduced.
Similar to petroleum refineries, biorefineries are plants composed of a series of units for feed treat-
ment, separation, conversion, and finishing processes as shown in Figure 1.1 with details presented
in Chapter 19. A photo of a large-scale commercial biorefinery plant for the production of sustain-
able advanced biofuels located in Crescentino, Italy, by Biochemtex/Mossi & Ghisolfi Group, is
shown in Figure 1.2.

FIGURE 1.2 The Beta Renewables commercial lignocellulosic ethanol biorefinery plant in Crescentino,
Italy, developed by Biochemtex/Mossi & Ghisolfi group. (Courtesy of Beta Renewables, Crescentino, Italy.)
8 Biofuels Production and Processing Technology

Regarding biofuels, a further fundamental issue is to assess their behavior when used in com-
mercial engines, for instance, to compare performance of biodiesel versus conventional fossil diesel
(produced from petroleum) when used in a diesel engine. This is the topic of Chapter 20 that presents
experimental results on the performance of biodiesel in ignition engines as well as engine emissions
when fossil diesel or biodiesel is used. The authors indicate that biodiesel derived from coconut oil,
palm oil, and canola oil can be successfully applied in compression ignition engine blending with
diesel up to 20% of vegetable oil. Coconut oil, palm oil, and canola oil can also be converted into
biodiesel and used in compression ignition engines neat or blended with diesel in various propor-
tions. The study was made with different blends of vegetable oil–diesel and biodiesel–diesel, up to
20% biodiesel mixed with regular diesel. The use of vegetable oil in low percentage may decrease
specific fuel consumption and as a result decrease in the emission of NO, NOx, CO, CO2, and SO2
pollutants.
Further discussion on the environmental implications from the use of biofuels in the transporta-
tion sector is presented in Chapter 21 under the topic of life cycle assessment (LCA) of biofuel pro-
duction. LCA is a methodology for estimating and assessing the environmental impacts caused by
the whole life cycle of a product. Although the use of biofuels may result in GHG mitigation effects,
it can also present some negative impacts on the environment, with concerns on their potential to
create agricultural boundaries’ expansion at the global level and associated GHG emissions. Some
experts, for instance, have expressed concerns on the impact of biofuel production and the related
water use. With population growth and limited supply of fresh water, high demand on some biofuels
may complicate their overall sustainability. In order to evaluate the environmental impacts from
biofuels supply chain, LCA has been accepted as the most appropriate method. Chapter 21 aims at
presenting the LCA method, highlighting the most relevant issues in its application to biofuels and
reviewing the most significant studies in this field.
The economic aspects of biofuel production are examined in Chapter 22. Competitiveness of
biofuels in the transport fuel market depends on existing policy, feedstock availability, market condi-
tions, and substitution characteristics. Increase in fuel demand, production cost, and trade conditions
will all affect fuel prices and market penetration for biofuels. Literature on economic aspects of bio-
fuels is vast and diverse, and the authors of this chapter review this mainly in terms of four aspects:
(1) feedstock use, availability, and cost; (2) issues regarding the ability to sustain biofeedstock pro-
duction; (3) relationship to conventional fuel and fuel markets; and (4) socioeconomic effects.
Technological progress is a key factor influencing the economic performance of biofuel produc-
tion, and for the case of biodiesel production, it is discussed in detail in Chapter 23. Production
costs from different routes to produce biodiesel using different raw materials are discussed in this
chapter. The techno-economic assessment for biodiesel production has become of high relevance to
make critical decisions under uncertainties that are essential for the successful implementation of
the process on an industrial scale. The economic aspects of using different triglycerides- and non-
triglycerides-based lipid biomass for biodiesel production are thoroughly discussed in this chapter.
A detailed analysis of variables and technologies affecting the production cost of biofuel is pre-
sented. These variables include feedstock, process type, operating conditions, and degree of purifi-
cation that may have impacts on the cost of produced biofuel. Finally, the payback period and return
on the investment are calculated versus biofuel price for biodiesel and some other biofuels.
The last chapter of this book (Chapter 24) is devoted to an expert’s views on future trends and
outlook in biofuel production. Biofuels, as stated in this chapter, are examples of modern biomass
thanks to higher efficiency of the conversion process or sustainability. Bioenergy has a significant
potential for mitigating GHG emissions, provided the resources are developed sustainably and effi-
cient systems are used. Because of this potential contribution, biofuels have been promoted in recent
years in different countries but the actions on fostering modern bioenergy also aim at reducing
the dependence on fossil fuels, supporting local economy, and offering better life conditions in
rural areas. Future bioenergy systems should be based on perennial crops, the use of residues, and
advanced conversion processes. Future perspectives of biofuels will either depend on improvements
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