PRNVZ01 Repositori Universitas Andalas

Advanced Biofuels and Bioproducts

James Weifu Lee
Editor

Advanced Biofuels
and Bioproducts

Editor
James Weifu Lee
Department of Chemistry and Biochemistry
Old Dominion University
Norfolk, VA, USA

ISBN 978-1-4614-3347-7
ISBN 978-1-4614-3348-4 (eBook)
DOI 10.1007/978-1-4614-3348-4
Springer New York Heidelberg Dordrecht London
Library of Congress Control Number: 2012939845
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Preface

The aim of this book is to provide the current status and development in the biomass
energy research field and report new and highly innovative technology concepts to
provide green/clean energy and control climate change. It will point out the potential benefits of these new technology concepts and the technical challenges that we
need to overcome to achieve the mission. This book could be helpful to a wide audience including not only energy and environmental scientists and engineers but also
industry and academia, teachers and students, and the general public including the
policy makers across the world. The book will address a variety of topics and technology concepts ranging from the latest development in smokeless biomass pyrolysis, Fischer–Tropsch hydrocarbons synthesis for biomass-derived syngas to liquid
transportation fuels, catalytic and selective pyrolysis of biomass for production of
fuels such as biodiesels and special chemicals such as levoglucosan and phenolic
compounds, biomass hydrothermal processing, biomethane and naturally occurring
hydrocarbon gas hydrates, to “cellulosic biofuels,” “electrofuels,” and photobiological
production of advanced biofuels (e.g., hydrogen, lipids/biodiesel, ethanol, butanol,
and/or related higher alcohols) directly from water and carbon dioxide. Advanced
bioproducts such as biochar that could bring significant benefits in helping control
climate change and sustainable economic development will also be covered. Each
chapter typically will describe a specific technology including its fundamental concept,
potential benefits, current status, and technical challenges. Therefore, this BioEnergy
sciences book will enable readers to quickly understand the up-to-date technical
opportunities/challenges so that the readers may also be able to somehow contribute

to this mission, since currently energy and environment (climate change) are such
huge and urgent issues to human civilization on Earth. Together, we can help overcome the challenges and build a sustainable future with clean renewable energy of
tomorrow.
Norfolk, VA, USA

James Weifu Lee

v

Acknowledgments

The editor, James Weifu Lee, would like to thank all of the nearly 100 authors and
a number of peer reviewers across the world for their wonderful contributions in support of this book project. The editing work of this book series was accomplished
using significant amounts of the editor’s spare time including his family time.
Therefore, the editor also wishes to thank his family for their understanding and
wonderful support.

vii

Contents

Part I Introduction and Brazil’s Biofuel Success
1

2

Introduction: An Overview of Advanced Biofuels
and Bioproducts ......................................................................................
James Weifu Lee

3

Sugarcane Ethanol: Strategies to a Successful
Program in Brazil....................................................................................
José Goldemberg

13

Part II

3

4

5

6

Smokeless Biomass Pyrolysis for Advanced Biofuels
Production and Global Biochar Carbon Sequestration

Smokeless Biomass Pyrolysis for Producing Biofuels and Biochar
as a Possible Arsenal to Control Climate Change ................................
James Weifu Lee and Danny M. Day
Oxygenation of Biochar for Enhanced Cation
Exchange Capacity..................................................................................
James Weifu Lee, A.C. Buchanan III, Barbara R. Evans,
and Michelle Kidder

23

35

Characterization of Biochars Using Advanced Solid-State
13
C Nuclear Magnetic Resonance Spectroscopy ...................................
Jingdong Mao, Xiaoyan Cao, and Na Chen

47

Biochar Fertilizer for Soil Amendment and Carbon
Sequestration ...........................................................................................
James Weifu Lee, Bob Hawkins, Xiaonian Li, and Danny M. Day

57

ix

Contents

x

7

8

Selection and Use of Designer Biochars to Improve Characteristics
of Southeastern USA Coastal Plain Degraded Soils.............................
J.M. Novak and W.J. Busscher

69

Biochar: A Coproduct to Bioenergy from Slow-Pyrolysis
Technology ...............................................................................................
Adriana Downie and Lukas Van Zwieten

97

9

Catalytic Pyrolysis of Biomass ............................................................... 119
Stefan Czernik

10

Selective Fast Pyrolysis of Biomass to Produce Fuels
and Chemicals ......................................................................................... 129
Xi-feng Zhu and Qiang Lu

11

Sub- and Supercritical Water Technology for Biofuels ....................... 147
Sandeep Kumar

12

Biomass to Liquid Fuel via Fischer–Tropsch
and Related Syntheses ............................................................................ 185
Y.T. Shah

13

Fischer–Tropsch Hydrocarbons Synthesis
from a Simulated Biosyngas ................................................................... 209
N. Escalona, R. García, and P. Reyes

14 To Synthesize Liquid Fuels on Precipitated Fe Catalyst
with CO2-Containing Syngas Gasified from Biomass .......................... 225
Wensheng Ning and Muneyoshi Yamada
Part III

Cellulosic Biofuels

15

Cellulosic Butanol Production from Agricultural Biomass
and Residues: Recent Advances in Technology .................................... 247
N. Qureshi, S. Liu, and T.C. Ezeji

16

Consolidated Bioprocessing ................................................................... 267
Jeffrey G. Linger and Al Darzins

17 The Synthesis, Regulation and Modification of Lignocellulosic
Biomass as a Resource for Biofuels and Bioproducts .......................... 281
Darby Harris, Carloalberto Petti, and Seth DeBolt
18

Genetic Modifications of Plant Cell Walls to Increase
Biomass and Bioethanol Production ..................................................... 315
M. Abramson, O. Shoseyov, S. Hirsch, and Z. Shani

19

Natural and Designed Enzymes for Cellulose Degradation ................ 339
Eva Cunha, Christine L. Hatem, and Doug Barrick

Contents

xi

Part IV Photobiological Production of Advanced Biofuels
with Synthetic Biology
20

Designer Transgenic Algae for Photobiological Production
of Hydrogen from Water ........................................................................ 371
James Weifu Lee

21

Designer Photosynthetic Organisms for Photobiological
Production of Ethanol from Carbon Dioxide and Water .................... 405
James Weifu Lee

22

Synthetic Biology for Photobiological Production of Butanol
and Related Higher Alcohols from Carbon Dioxide and Water ......... 447
James Weifu Lee

Part V Lipids-Based Biodiesels
23

Production of Biodiesel and Nontoxic Jatropha Seedcakes
from Jatropha curcas............................................................................... 525
Novizar Nazir, Djumali Mangunwidjaja, and M.A. Yarmo

24

Biofuels from Microalgae: Towards Meeting Advanced
Fuel Standards ........................................................................................ 553
Liam Brennan and Philip Owende

25

Bioprocess Engineering Aspects of Biodiesel and Bioethanol
Production from Microalgae .................................................................. 601
Ronald Halim, Razif Harun, Paul A. Webley,
and Michael K. Danquah

26

Closed Bioreactors as Tools for Microalgae Production...................... 629
Robert Dillschneider and Clemens Posten

27 Alternative Methods for the Extraction of Hydrocarbons
from Botryococcus braunii ...................................................................... 651
Chiara Samorì and Cristian Torri
28 Valorization of Waste Frying Oils and Animal Fats
for Biodiesel Production ......................................................................... 671
Teresa M. Mata, António A. Martins, and Nidia S. Caetano
29

One-Step Conversion of Algal Biomass to Biodiesel
with Formation of an Algal Char as Potential Fertilizer..................... 695
E. Adair Johnson, Zhanfei Liu, Elodie Salmon,
and Patrick G. Hatcher

Contents

xii

Part VI

Life-Cycle Energy and Economics Analysis

30

Process Economics and Greenhouse Gas Audit
for Microalgal Biodiesel Production...................................................... 709
Razif Harun, Mark Doyle, Rajprathab Gopiraj,
Michael Davidson, Gareth M. Forde, and Michael K. Danquah

31

Sustainability Considerations about Microalgae
for Biodiesel Production ......................................................................... 745
Teresa M. Mata, António A. Martins, Subhas K. Sikdar,
Carlos A.V. Costa, and Nidia S. Caetano

32

Life Cycle Assessment of Algae-to-Energy Systems ............................. 759
Andres Clarens and Lisa Colosi

Part VII

High-Value Algal Products and Biomethane

33

Cultivation of Arthrospira (Spirulina) platensis
by Fed-Batch Process .............................................................................. 781
João C.M. Carvalho, Raquel P. Bezerra, Marcelo C. Matsudo,
and Sunao Sato

34

Bioprocess Development for Chlorophyll Extraction
from Microalgae ...................................................................................... 807
Ronald Halim and Michael K. Danquah

35

Screening for Bioactive Compounds from Algae ................................. 833
Miguel Herrero, Jose A. Mendiola, Merichel Plaza,
and Elena Ibañez

36

Biogas Production from Algae and Cyanobacteria Through
Anaerobic Digestion: A Review, Analysis, and Research Needs ......... 873
Pavlo Bohutskyi and Edward Bouwer

37

Gas Hydrates as a Potential Energy Source: State of Knowledge
and Challenges ........................................................................................ 977
George J. Moridis, Timothy S. Collett, Ray Boswell,
Stephen Hancock, Jonny Rutqvist, Carlos Santamarina,
Timoth Kneafsey, Matthew T. Reagan, Mehran Pooladi-Darvish,
Michael Kowalsky, Edward D. Sloan, and Carolyn Coh

Contents

xiii

Part VIII Electrofuels
38

Electrofuels: A New Paradigm for Renewable Fuels ........................... 1037
Robert J. Conrado, Chad A. Haynes, Brenda E. Haendler,
and Eric J. Toone

39

Engineering Ralstonia eutropha for Production of Isobutanol
from CO2, H2, and O2 .............................................................................. 1065
Christopher J. Brigham, Claudia S. Gai, Jingnan Lu,
Daan R. Speth, R. Mark Worden, and Anthony J. Sinskey

40

Microbial ElectroCatalytic (MEC) Biofuel Production....................... 1091
Steven W. Singer, Harry R. Beller, Swapnil Chhabra,
Christopher J. Chang, and Jerry Adler

Index ................................................................................................................. 1101

Part I

Introduction and Brazil’s Biofuel Success

Chapter 1

Introduction: An Overview of Advanced
Biofuels and Bioproducts
James Weifu Lee

Abstract The field of advanced biofuels and bioproducts may play an increasingly
significant role in providing renewable energy and ensuring environmental health
for a sustainable future of human civilization on Earth. This chapter as an introduction for the book provides a quick overview of advanced biofuels and bioproducts
by highlighting the new developments and opportunities in the bioenergy research
& development (R&D) arena in relation to the global energy and environmental
challenges. The topics include: (1) Brazil’s sugarcane ethanol as an early and still
encouraging example of biofuels at a nationally significant scale, (2) smokeless
biomass pyrolysis for advanced biofuels production and global biochar carbon
sequestration, (3) cellulosic biofuels, (4) synthetic biology for photobiological
production of biofuels from carbon dioxide and water, (5) lipid-based biodiesels,
(6) life-cycle energy and environmental impact analysis, (7) high-value bioproducts
and biomethane, and (8) electrofuels.

1 The Energy and Environment Challenges and Opportunities
The world currently faces a systematic energy and environmental problem of increased
CO2 emissions, decreased soil-carbon content, and global-climate change. To solve
the massive global energy and environmental sustainability problem, it likely requires
a comprehensive portfolio of R&D efforts with multiple energy technologies.

J.W. Lee (*)
Department of Chemistry & Biochemistry, Old Dominion University,
Physical Sciences Building, Room 3100B, 4402 Elkhorn Avenue, Norfolk, VA 23529, USA
Johns Hopkins University, Whiting School of Engineering,
118 Latrobe Hall, Baltimore, MD 21218, USA
e-mail: jwlee@odu.edu; JLee349@JHU.edu
J.W. Lee (ed.), Advanced Biofuels and Bioproducts, DOI 10.1007/978-1-4614-3348-4_1,
© Springer Science+Business Media New York 2013

3

4

J.W. Lee

The field of advanced biofuels and bioproducts, such as photosynthetic biomass
energy, may represent one of the major R&D areas that have the potential to provide
renewable clean energy, in additions to the other renewable energy technologies,
including nuclear energy, geothermal, wind, solar, and hydropower. Photosynthesis
captures more CO2 from the atmosphere than any other processes on Earth capture.
Each year, land-based green plants capture about 440 gigatons (Gt) CO2 (equivalent
to 120 GtC y−1) from the atmosphere into biomass [1]. That is, about one-seventh of
all the CO2 in the atmosphere (820 GtC) is fixed by photosynthesis (gross primary
production) every year. Theoretically, if there is a technology that could translate as
small as 7.5% of the annual terrestrial gross photosynthetic products (120 GtC y−1) to
a usable biofuel to substitute fossil fuels that would be sufficient to eliminate the
entire amount (nearly 9 GtC y−1) of CO2 emitted into the atmosphere annually from the
use of fossil fuels. The success of Brazil’s sugarcane ethanol reported in Chap. 2 has
demonstrated that with the advancement of science and technology and coupled with
proper policy support, it is possible for the field of advanced biofuels and bioproducts
to make a significant contribution to enrich the energy market at a national and/or
possibly global scale. Presently, ethanol from sugarcane replaces approximately 50%
of the gasoline that would be used in Brazil if such an option did not exist. Therefore,
Brazil’s sugarcane–ethanol success may be regarded as an early but still encouraging
example of biofuels at least at a national scale. However, understandably, Brazil’s
sugarcane–ethanol technology per se may or may not be applicable to the other parts
of the world such as the United States because of the differences in climates, crop
ecosystems, and various other factors. Development and deployment of other innovative biofuels technologies are essential to achieve the mission of renewable energy
production. The following highlights some of the bioenergy R&D areas that may be
of special significance.

2

Smokeless Biomass Pyrolysis for Advanced Biofuels
Production and Global Biochar Carbon Sequestration

Biomass utilization through smokeless (emission-free, clean, and efficient) pyrolysis is a potentially significant approach for biofuels production and biochar carbon sequestration at gigatons of carbon (GtC) scales. One of the key ideas here is
to use a biomass-pyrolysis process to produce certain biofuels and more importantly to “lock” some of the unstable biomass carbon such as dead leaves, waste
woods, cornstovers, and rice straws into a stable form of carbon―biochar, which
could be used as a soil amendment to improve soil fertility and at the same time,
to serve as a carbon sequestration agent, since biochar can be stable in soil for
thousands of years and can help retain nutrients in soil to reduce the runoff of fertilizers from agriculture lands that would otherwise pollute the rivers and water
bodies. This “carbon negative” approach, which was co-initiated by Danny Day of
Eprida Inc. and James Weifu Lee (the Editor) through their joint 2002 U.S. provisional patent application followed by a PCT application [2, 3], is now receiving

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Introduction: An Overview of Advanced Biofuels and Bioproducts

5

increased attention worldwide [4, 5], especially since certain related studies have
also indicated the possibility of using biochar as a soil amendment for carbon
sequestration [6–9].
Chapter 3 provides an overview of this smokeless biomass-pyrolysis approach
for producing biofuels and biochar as a possible arsenal to control climate change.
For the immediate future, application of this biochar producing biomass-pyrolysis
approach to turn waste biomass into valuable products could likely provide the best
economic and environmental benefits. Globally, each year, there are about 6.6 Gt
dry matter of biomass (3.3 GtC) such as crop stovers that are appropriated but not
used. Development and deployment of the smokeless biomass pyrolysis technology could turn this type of waste biomass into valuable biochar and biofuel products. Even if assuming that only half amount of this waste biomass is utilized by
this approach, it would produce 0.825 GtC y−1 of biochar and large amounts of
biofuel (with a heating value equivalent to that of 3,250 million barrels of crude
oil). By storing 0.825 GtC y−1 of biochar (equivalent to 3 Gt of CO2 per year) into
soil and/or underground reservoirs alone, it could offset the world’s 8.67 GtC y−1 of
fossil fuel CO2 emissions by 9.5%, which is still very significant. So far, there are
no other technologies that could have such a big (GtC) capacity in effectively capturing and sequestering CO2 from the atmosphere. Therefore, this is a unique
“carbon-negative” bioenergy technology system approach, which in the perspective of carbon management is likely going to be more effective (and better) than the
nuclear energy option, since the nuclear-power energy system is merely a carbonneutral energy technology that could not capture CO2 from the atmosphere. This is
true also in comparing the “carbon-negative” smokeless biomass-pyrolysis
approach with any other carbon-neutral energy technologies, including solar photovoltaic electricity, geothermal, wind, and hydropower, and all carbon-neutral
biofuel technologies such as cellulosic biofuels, photobiological biofuels from carbon dioxide and water, lipid-based biodiesels, and electrofuels, which are also covered in this book. Consequently, nuclear energy and any other carbon-neutral
energy technologies all cannot reverse the trend of climate change; on the other
hand, the smokeless biochar-producing biomass-pyrolysis energy system approach,
in principle, could not only reduce but also could possibly reverse the climate
change. Therefore, this “carbon-negative” smokeless biomass-pyrolysis approach
clearly merits serious research and development worldwide to help provide clean
energy and control climate change for a sustainable future of human civilization on
Earth [10].
Chapter 4 reports an invention on partial oxygenation of biochar for enhanced
cation exchange capacity, which is one of the key properties that enable biochar to
help retain soil nutrients to reduce fertilizers runoff from agriculture lands and to
keep water environment clean. Chapter 5 describes chemical structural characterization of biochars using advanced solid-state 13C nuclear magnetic resonance spectroscopy, which is scientifically important in understanding the chemistry and
application of biochar materials. As reported in Chap. 6, one of the ideas is to use
biochar particles incorporated with certain fertilizer species such as ammonium
bicarbonate and/or urea, hopefully to make a type of slow-releasing fertilizer.

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J.W. Lee

Use of this type of biochar fertilizer would place the biochar carbon into soil to
improve soil fertility and, at the same time, store (sequester) carbon into the soil and
subsoil earth layers to achieve carbon sequestration. Chapter 7 discusses selection
and use of designer biochars to improve characteristics of Southeastern USA
Coastal Plain degraded soils while Chap. 8 describes biochar as a co-product to
bioenergy from slow-pyrolysis technology.
There are significant progresses and scientific understanding in the arts of biomass
pyrolysis. Chapter 9 reports the arts of catalytic pyrolysis of biomass for the production of both biofuels and biochar while Chap. 10 describes the selective fast pyrolysis
of biomass to produce fuels and chemicals. As reported in Chap. 11, it is also possible to produce advanced biofuels and biochar through hydrothermo processing of
biomass.
To avoid negative impact on air quality with such a large (GtC)-scale operation
required to achieve the envisioned global biochar carbon sequestration, the biomass-pyrolysis process technology must be smokeless (emission-free, clean, and
efficient). Therefore, it is essential to fully develop a smokeless biomass-pyrolysis
process to achieve the mission. One of the possible productive ways to achieve the
smokeless (emission-free, clean, and efficient) feature is by converting the pyrolysis
syngas “smoke” into clean energy such as liquid transportation fuel. Currently, there
are a number of Fischer–Tropsch processing technologies [11, 12] that could be
helpful for conversion of biomass-derived syngas into advanced (drop-in-ready)
liquid biofuels, such as biodiesel, to replace petroleum-based transportation fuels.
Chapter 12 describes the fundamentals of the biomass-to-liquid fuel process technologies via Fischer–Tropsch and related syntheses. Chapter 13 reports Fischer–
Tropsch hydrocarbons synthesis from a simulated biosyngas while Chap. 14
describes Fischer–Tropsch synthesis of liquid fuel with Fe catalyst using CO2containing syngas that can be produced from biomass pyrolysis.

3

Cellulosic Biofuels

Chapter 15 reports cellulosic butanol production from agricultural biomass and
residues: recent advances in technology while Chap. 16 describes the technology
concept of consolidated bioprocessing of lignocellulosic biomass for biofuels production. The research opportunity here is the possibility of converting vast amount
of lignocellulosic plant biomass materials such as cornstover, wheat straw, switchgrass, and woody plant materials into usable biofuels such as ethanol and/or butanol.
Recently, bisabolane has also been identified as a terpene-based advanced biofuel
that may be used as an alternative to D2 diesel [13]. This field of cellulosic biofuels
has been active for more than 25 years and it still remains a hot topic because of its
significant potential. One of the major challenges is known as the “lignocellulosic
recalcitrance” which represents a quite formidable technical barrier to the costeffective conversion of plant biomass to fermentable sugars. That is, because of the

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Introduction: An Overview of Advanced Biofuels and Bioproducts

7

recalcitrance problem, lignocellulosic biomasses (such as cornstover, switchgrass,
and woody plant materials) could not be readily converted to fermentable sugars to
make ethanol or butanol without certain pretreatment, which is often associated
with high processing cost. Despite more than 25 years of R&D efforts in lignocellulosic biomass pretreatment and fermentative processing, the problem of recalcitrant lignocellulosics still remains as a formidable technical barrier that has not yet
been fully eliminated so far. This problem is probably rooted from the long history
of natural plant evolution; plant biomass has evolved effective mechanisms for
resisting assault on its cell-wall structural sugars from the microbial and animal
kingdoms. This property underlies a natural recalcitrance, creating roadblocks to
the cost-effective transformation of lignocellulosic biomass to fermentable sugars.
Therefore, one of the R&D approaches is to unlock the sugars by re-engineering the
cell wall structure through molecular genetics. Chapter 17 describes the synthesis,
regulation, and modification of plant cell wall carbohydrates (lignocellulosic biomass) as a resource for biofuels and bioproducts while Chap. 18 reports genetic
modifications of plant cell walls to increase biomass and bioethanol production.
Other approaches include but are not limited to developing more effective pretreatment, enzymes, and microorganisms that could help convert the biomass materials
into biofuels. Chapter 19 reviews the structural features of cellulose and cellulose
degrading enzymes and describes the technology concept of designer enzymes/cellulosomes for cellulose-based biofuels production.

4

Synthetic Biology for Photobiological Production
of Biofuels from Carbon Dioxide and Water

This multidisciplinary R&D area involves synthetic biology and genetic transformation
of photosynthetic organisms to create designer transgenic organisms that can photobiologically produce biofuels such as hydrogen, lipids/biodiesel, ethanol, butanol,
and/or other related higher alcohols (e.g., pentanol and hexanol), or hydrocarbons
directly from water and carbon dioxide. Chapter 20 reports inventions on creating
designer algae for photobiological production of hydrogen from water. In wild-type
algae, there are four physiological problems associated with the proton gradient
across the algal thylakoid membrane, which severely limit algal hydrogen production.
These technical issues are: (1) accumulation of a proton gradient across the algal
thylakoid membrane, (2) competition from carbon dioxide fixation, (3) requirement
for bicarbonate binding at photosystem II (PSII) for efficient photosynthetic activity,
and (4) competitive drainage of electrons by molecular oxygen. As reported in
Chap. 20 one of the key inventions here is the genetic insertion of a proton channel
into the algal thylakoid membrane to simultaneously eliminate all of the four transthylakoid proton gradient-associated technical problems for enhanced photoautotrophic hydrogen production.

8

J.W. Lee

In addition to the designer proton-channel algae, Chap. 20 describes a further
invention on creating designer switchable PSII algae for robust photobiological
production of hydrogen from water splitting, which can eliminate all the following
three molecular oxygen (O2)-associated technical problems: (4) competitive drainage
of electrons generated from photosynthetic water splitting by molecular oxygen,
(5) oxygen sensitivity of algal hydrogenase, and (6) the H2–O2 gas separation and
safety issue. Use of the two inventions (two US patents): (I) designer proton-channel
algae [14] and (II) designer switchable PSII algae [15], may enable efficient and
robust photobiological production of hydrogen with an enhanced yield likely more
than ten times better than that of the wild-type.
This designer-algae synthetic biology approach can be applied not only for
hydrogen production, but also for the production of other advanced biofuels of
choice, such as ethanol and/or butanol, depending on specific metabolic pathway
designs [16, 17]. Chapter 21 reports inventions on application of synthetic biology
for photobiologically production of ethanol directly from carbon dioxide and water
while Chap. 22 describes the methods of creating designer transgenic organisms for
photobiological production of butanol and/or related higher alcohols from carbon
dioxide and water. One of the key ideas here is to genetically introduce a set of
specific enzymes to interface with the Calvin-cycle activity so that certain intermediate product such as 3-phosphoglycerate (3-PGA) of the Calvin cycle could be converted immediately to biofuels such as butanol. The net result of the envisioned total
process, including photosynthetic water splitting and proton-coupled electron transport for generation of NADPH and ATP that supports the Calvin cycle and the
butanol production pathway is the conversion of CO2 and H2O to butanol
(CH3CH2CH2CH2OH) and O2 as shown in (1). Therefore, theoretically, this could be
a new mechanism to synthesize biofuels (e.g., butanol) directly from CO2 and H2O
with the following photosynthetic process reaction:
4CO2 + 5H 2 O → CH 3 CH 2 CH 2 CH 2 OH + 6O2

(1)

This photobiological biofuel production process completely eliminates the
problem of recalcitrant lignocellulosics by bypassing the bottleneck problem of
the biomass technology. Since this approach could theoretically produce biofuels
(such as hydrogen, ethanol, butanol, related higher alcohols, and/or hydrocarbons/
biodiesel) directly from water and carbon dioxide with high solar-to-biofuel energy
efficiency, it may provide the ultimate green/clean renewable energy technology for
the world as a long-term goal. According to a recent study [18] for this type of direct
photosynthesis-to-biofuel process, the practical maximum solar-to-biofuel energy
conversion efficiency could be about 7.2% while the theoretical maximum solar-tobiofuel energy conversion efficiency is calculated to be 12%.
The designer algae approach may also enable the use of seawater and/or groundwater for photobiological production of biofuels without requiring freshwater or
agricultural soil, since the biofuel-producing function can be placed through molecular
genetics into certain marine algae and/or cyanobacteria that can use seawater and/or

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Introduction: An Overview of Advanced Biofuels and Bioproducts

9

certain groundwater. They may be used also in a sealed photobioreactor that could
be operated on a desert for the production of biofuels with highly efficient use of
water since there will be little or no water loss by evaporation and/or transpiration
that a common crop system would suffer. That is, this designer algae approach could
provide a new generation of renewable energy (e.g., butanol) production technology
without requiring arable land or freshwater resources, which may be strategically
important to many parts of the world for long-term sustainable development.
Recently, certain independent studies [19, 20] have also applied synthetic biology in
certain model cyanobacteria, such as Synecoccus elongatus PCC7942, for photobiological production of isobutanol and 1-butanol.
Furthermore, the designer algae approach may be applied for enhanced photobiological production of other bioproducts, including (but not limited to) lipids,
hydrocarbons, intermediate metabolites, and possibly high-value bioproducts such
as docosahexaenoic acid (DHA) omega-3 fatty acid, eicosapentaenoic acid (EPA)
omega-3 fatty acid, arachidonic acid (ARA) omega-6 fatty acid, chlorophylls, carotenoids, phycocyanins, allophycocyanin, phycoerythrin, and their derivatives/
related product species.

5

Lipid-Based Biodiesels

Biodiesel is a mixture of fatty acid alkyl esters obtained typically by transesterification
of triglycerides from vegetable oils, algal lipids, or animal fats. Transesterification
of the lipid feedstocks is already a quite well-established chemical engineering
process with a multiple-step reaction, including three reversible steps in series,
where triglycerides are converted to diglycerides, then diglycerides are converted to
monoglycerides, and monoglycerides are then converted to esters (biodiesel) and
glycerol (by-product). One of the major challenges is to cost-effectively produce large
quantities of lipids that can be readily harvested for biodiesel fuel production.
One of the approaches is to produce vegetable oils through Jatropha plantation.
Chapter 23 reports the production of biodiesel and nontoxic jatropha seedcake from
Jatropha curcas. The highest potential in biodiesel production probably resides in
algae. The bio-oil (lipids) content for some of the algae can be upto 30–60% of its
dry biomass, which energy density is at least as high as coal. Chapter 24 provides a
quite comprehensive review of biofuels from microalgae towards meeting the
advanced fuel standards. Chapter 25 discusses the bioprocess engineering aspects of
biodiesel and bioethanol production from microalgae while Chap. 26 describes the
arts of closed photo-bioreactors as tools for biofuel production. Chapter 27 reports
extraction of hydrocarbons from Botryococcus braunii while Chap. 28 describes
valorization of waste oils and animal fats for biodiesel production. Chapter 29
reports a single-step direct thermo-conversion of algal biomass to biodiesel with the
formation of an algal char as potential fertilizer.

10

6

J.W. Lee

Life-Cycle Energy and Environmental Impact Analysis

To assess a new energy technology before considering its implementation, it is
essential to perform a life-cycle analysis on its total energy efficiency and environment impact, including both its potential benefits and risks. A viable energy technology should have a significant net energy gain or a carbon footprint reduction
based on its objective life-cycle analysis. Chapter 30 reports the process economics
and greenhouse gas audit for microalgal biodiesel production. Chapter 31 discusses
the sustainability considerations about microalgae for biodiesel production while
Chap. 32 reports a life-cycle assessment for algae-to-energy systems.

7

High Value Bioproducts and Biomethane

Use of biomass technology can produce high-value products also. For example, certain cyanobacteria and green algae have been used as human foods, sources for vitamins, proteins, fine chemicals, and bioactive compounds. Chapter 33 reports fed-batch
cultivation of Spirulina platensis, which can be used as high-value health nutrient
supplement. Chapter 34 discusses the bioprocess development for Chlorophyll
extraction from microalgae while Chap. 35 reports the screening methods for bioactive compounds from algae. Fermentation of biomass for methane production represents another important bioresource for biofuel production and waste management.
Chapter 36 provides a comprehensive review on algae/biomethane production.
Methane hydrates created from biomass at the bottom of the vast oceans and in certain
permafrost regions may represent another significant resource that could hopefully be
explored for utilization in the future as well. Chapter 37 reports methane hydrates on
its current status, resources, technology, and potential.

8

Electrofuels

Electrofuels is a newly created biofuel technology concept that may have significant
potential in producing transportation fuel from non-biomass feedstocks such as
CO2, H2, and/or electricity. One of its key features is the application of certain
chemolithoautotrophic organisms with synthetic biology to synthesize biofuel(s),
such as butanol through fixation of CO2 using H2 and/or electrons as a source of
reductant. Potentially, this approach could become quite attractive for biofuels production, since large quantities of inexpensive electricity (thus H2 from electrolysis
of water) and CO2 feedstock could foreseeably become available in the near future.
With advanced photovoltaic cells, the solar-to-electricity energy conversion
efficiency can now reach more than 20%. A solar electricity-based electrofuel
process with certain chemolithoautotrophic CO2 fixation pathways [21] could have
a combined solar-to-biofuels energy conversion efficiency higher than that of a

1

Introduction: An Overview of Advanced Biofuels and Bioproducts

11

photosynthesis-based biofuel technology. Therefore, the electrofuels approach merits
serious exploration also. In 2009, the United States Department of Energy (DOE)
Advanced Research Projects Agency-Energy (ARPA-E) created the electrofuels
program to explore the potential of non-photosynthetic autotrophic organisms for
the conversion of durable forms of energy to energy-dense, infrastructure-compatible
liquid fuels. Chapter 38 reports the US DOE/ARPA-E Electrofuels program efforts,
including its rationale, approach, potential benefits, and challenges. Chapter 39 discusses the motivations and the methods used to engineer Ralstonia eutropha to produce the liquid transportation fuel isobutanol from CO2, H2, and O2; and Chap. 40
reports the development of an integrated Microbial-ElectroCatalytic (MEC) system
consisting of R. eutropha as a chemolithoautotrophic host for metabolic engineering
coupled to a small-molecule electrocatalyst for the production of biofuels from CO2
and H2, which extends well beyond biomass-derived substrates.

References
1. Geider RJ, Delucia EH et al (2001) Primary productivity of planet earth: biological determinants
and physical constraints in terrestrial and aquatic habitats. Glob Chang Biol 7(8):849–882
2. Day DM, Lee JW (2004) The production and use of a soil amendment made by the combined
production of hydrogen, sequestered carbon and utilizing off gases containing carbon dioxide.
PCT Int Appl WO 2004037747 A2:58
3. Day DM, Evans RJ, Lee JW, Reicosky D (2005) Economical CO2, SOx, and NOx capture from
fossil-fuel utilization with combined renewable hydrogen production and large-scale carbon
sequestration. Energy 30:2558–2579
4. Marris E (2006) Sequestration news feature: black is the new green. Nature 442:624–626
5. Lehmann J (2007) Commentary: a handful of carbon. Nature 447:143–144
6. Gundale MJ, Thomas H, DeLuca TH (2007) Charcoal effects on soil solution chemistry and
growth of Koeleria macrantha in the ponderosa pine/douglas fir ecosystem. Biol Fertil Soils
43:303–311
7. Solomon D, Lehmann J, Thies J, Schafer T, Liang B, Kinyangi J, Neves E, Petersen J, Luizao
F, Skjemstad J (2007) Molecular signature and sources of biochemical recalcitrance of organic
C in Amazonian Dark Earths. Geochim Cosmochim Acta 71:2285–2298
8. Lehmann J, Gaunt J, Rondon M (2006) Bio-char sequestration in terrestrial ecosystems:
a review. Mitig Adapt Strat Glob Chang 11:403–427
9. Adriana ED, Zwieten LV, Smernik RJ, Morris S, Munroe PR (2011) Terra Preta Australis: reassessing the carbon storage capacity of temperate soils. Agric Ecosyst Environ 140:137–147
10. Lee JW, Hawkins B, Day DM, Reicosky DC (2010) Sustainability: the capacity of smokeless
biomass pyrolysis for energy production, global carbon capture and sequestration. Energy
Environ Sci 3(11):1695–1705
11. Hamelinck CN, Faaij PC, den Uil H, Boerrigter H (2004) Production of FT transportation fuels
from biomass; technical options, process analysis and optimisation, and development potential. Energy 29:1743–1771
12. James OO, Mesubi AM, Ako TC, Maity S (2010) Increasing carbon utilization in Fischer–Tropsch
synthesis using H2-deficient or CO2-rich syngas feeds. Fuel Process Technol 91:136–144
13. Peralta-Yahya PP, Ouellet M, Chan R, Mukhopadhyay A, Keasling JD, Lee TS (2011)
Identification and microbial production of a terpene-based advanced biofuel. Nat Commun.
doi:10.1038/ncomms1494
14. Lee JW (2011) Designer proton-channel transgenic algae for photobiological hydrogen
production. US Patent No. 7,932,437 B2

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15. Lee JW (2010) Switchable photosystem-II designer algae for photobiological hydrogen
production. U.S. Patent No. US 7,642,405 B2
16. Lee JW (2011) Designer organisms for photosynthetic production of ethanol from carbon
dioxide and water. US Patent No. 7,973,214 B2
17. Lee JW (2009) Designer organisms for photobiological butanol production from carbon
dioxide and water. PCT International Publication No. WO 2009/105733 A2
18. Robertson DE, Jacobson SA, Morgan F, Berry D, Church GM, Afeyan NB (2011) A new dawn
for industrial photosynthesis. Photosynth Res 107:269–277
19. Lan EI, Liao JC (2011) Metabolic engineering of cyanobacteria for 1-butanol production from
carbon dioxide. Metab Eng 13:353–363
20. Atsumi S, Higashide W, Liao JC (2009) Direct photosynthetic recycling of carbon dioxide to
isobutyraldehyde. Nat Biotechnol 27(12):1177–1182
21. Berg IA, Kockelkorn D, Ramos-Vera WH, Say RF, Zarzycki J, Hügler M, Alber BE, Fuchs G
(2010) Autotrophic carbon fixation in archaea. Nat Rev Microbiol 8:447–460

Chapter 2

Sugarcane Ethanol: Strategies to a Successful
Program in Brazil
José Goldemberg

Abstract Presently, ethanol from sugarcane replaces approximately 50% of the
gasoline that would be used in Brazil if such an option did not exist. In some aspects,
ethanol may represent a better fuel than gasoline and to a great extent a renewable
fuel contributing little to greenhouse gas emissions in contrast with fossil-derived
fuels. Production of ethanol increase from 0.6 billion liters in 1975/1976 to 27.6
billion liter in 2009/2010. Although production costs in 1975/1976 were three times
higher than gasoline prices in the international market, such costs declined dramatically thanks to technological advances and economics of scale becoming full
competitive (without subsidies) with gasoline after 2004. This was achieved through
appropriate policies of the Brazilian government. These policies and the rationale
for them as a strategy to reduce oil imports are discussed here with the possibilities
of replication in other countries.

1

Introduction

Sugarcane has been cultivated in Brazil since the sixteenth century and more recently
the country became the largest producers of sugar accounting for approximately
25% of the world’s production. The production of ethanol has been small but
starting in 1931 the Government decided that all the gasoline used in the country
(mostly imported) should contain 5% of ethanol from sugarcane. This was done to
benefit sugar producing units when faced by declining prices of sugar in the
international market which notoriously fluctuate over the years (Fig. 1).
Around 1970 the sugar industry in Brazil was stagnated, processing only 70–80
million tonnes of sugarcane per year mainly due to Government policies of
guaranteed prices to producers: when the international price of sugar was low the
J. Goldemberg (*)
University of São Paulo, Institute of Eletrotechnics and Energy, São Paulo, Brazil
e-mail: goldemb@iee.usp.br
J.W. Lee (ed.), Advanced Biofuels and Bioproducts, DOI 10.1007/978-1-4614-3348-4_2,
© Springer Science+Business Media New York 2013

13

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J. Goldemberg

Fig. 1 World refined sugar price—1983/2007

government purchased the sugar at prices that satisfied the producers. Competition
and modernization were thus discouraged; each producer had a quota and therefore
few concerns about losing money. Sugar producers did not plan in the long run and
usually produced strictly what they considered attractive in a given year. Since the
price of sugar in the international markets varies significantly over time, as seen in
Fig. 1, such lack of planning frequently left them out of the market when prices
suffered strong fluctuations [1].
The solution proposed at that time by Ministry of Industry and Commerce [2]
was to expand production regardless of the prices of sugar and use the excess production (when prices were low) to produce ethanol which was more expensive to
produce than gasoline. One of the drivers for that was the need to eliminate lead
components from gasoline (lead tetraethyl) which was imported saving thus foreign
currency. Such ideas did not prosper until the oil crisis of 1973: the cost of oil went
suddenly from US$ 2.90 per barrel to US$ 11.65 per barrel. The import bill with oil
(80% of which was imported) skyrocketed from 600 million dollars in 1973 to 2.5
billion in 1974, approximately 32% of all Brazilian imports and 50% of all the hard
currency that the country received from exports.

2 The Expansion of Ethanol Production
Under these conditions the Government decided to accelerate ethanol production
thorough decree 76,593 of November 14, 1975 which is really the birth certificate
of the Brazilian “Alcohol Program.” The idea was to reduce gasoline consumption

2

Sugarcane Ethanol: Strategies to a Successful Program in Brazil

15

Fig. 2 Ethanol and sugar
production—Brazil
1970–2008

and therefore decrease oil imports. Production goals were set at three billion liters
of ethanol in 1980 and 10.7 billion liters in 1985.
This decree determined that very generous financing terms were to be offered to
entrepreneurs through Government banks1 and that the price of ethanol should be on
a parity with sugar 35% higher than the price of 1 kg of sugar.2
The decree made the production of ethanol and the production of sugar equally
attractive to the entrepreneurs. This opened the way for the increase in the production of ethanol which happened indeed as seen in Fig. 2.
Production increased from 600 million liters/year in 1975/1976 to 3.4 billion liters
per year in 1979/1980. This corresponded to 14% of the gasoline used in 1979.

3 The Expansion of Ethanol Consumption
In principle, therefore the problem of increasing ethanol production was solved. The
remaining problem was to make sure that the ethanol produced was consumed.
The Government solved the problem using two instruments [1]:
• Adopting mandates for mixing ethanol to gasoline. Up to 1979, the mixture of
ethanol in the gasoline increased gradually to approximately 10% which required
small changes in the existing motors. In 1981, ethanol consumption reached 2.5
billion liters.
The interest to be paid on these loans was lower than the rate of inflation which resulted in a negative real interest rate.
2
Theoretically one can produce 0.684 L of ethanol with 1 kg of sugar which is fairly close to the
value established by the decree 76,593.
1

16

J. Goldemberg

Fig. 3 Learning curve for ethanol production from sugarcane in Brazil. Source: Refs. [8, 9]

• Setting the price of ethanol paid to producers at 59% of the selling price of
gasoline (which was more than twice the cost of imported gasoline). The high
price of gasoline has been used for a long time by the Government as a method
of collecting resources to subsidize diesel oil. Parts of such resources were then
used to subsidize ethanol.
Subsidies of approximately one billion dollars per year on the average over the
30 years were needed to sustain the program. These subsidies were removed gradually and in 2004 the price paid to ethanol producers was similar to the cost of gasoline in the international market as seen in Fig. 3.

4 Technologies for Ethanol Use
Decree 76,593 and its consequences were adopted purely for economic reasons.
Only in 1978 it become evident through work of university groups [2] that ethanol
for sugarcane was very close of being a renewable energy source (except for the
minor ingredients of pesticides, fertilizers, and some diesel oil needed for its production). All the energy for the process of crushing the sugarcane, fermenting and
distillation originated in the bagasse of the sugarcane. The ratio of the energy contained in a 1 L of ethanol to the energy of fossil origin used in the process was
approximately 4.53 to 1 when the first evaluation was carried out [3]. Today, evaluations are showing that the rate is even better (8 to 1) due to the significant agricultural and industrial efficiency improvements [4, 5]. Impressive productivity gains of
3% per year over 30 years have been achieved. As an example, Fig. 4 gives the
growth of sugarcane agriculture productivity in different regions of Brazil, from
1977 to 2009, indicating an increase of 51% in the period.

2

Sugarcane Ethanol: Strategies to a Successful Program in Brazil

17

90.00

Productivity (ton/hectare)

80.00
70.00
60.00
50.00
40.00
São Paulo

30.00

Center - South

20.00

North - Northeast
10.00
Brazil
−
1975

1980

1985

1990

1995

2000

2005

2010

2015

Year

Fig. 4 Evolution of the sugarcane productivity in Brazil. Source: Ref. [10]

The second oil shock in 1979 led the Government to the drastic move to
introduce cars with motors designed to operate exclusively with hyd