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Biofuel and Biorefinery Technologies 8
Meisam Tabatabaei
Mortaza Aghbashlo Editors
Biodiesel
From Production to Combustion
Biofuel and Biorefinery Technologies
Volume 8
Series editors
Vijai Kumar Gupta, Department of Chemistry and Biotechnology, Tallinn
University of Technology, Tallinn, Estonia
Maria G. Tuohy, School of Natural Sciences, National University of Ireland
Galway, Galway, Ireland
This book series provides detailed information on recent developments in biofuels &
bioenergy and related research. The individual volumes highlight all relevant
biofuel production technologies and integrated biorefinery methods, describing the
merits and shortcomings of each, including cost-efficiency. All volumes are written
and edited by international experts, academics and researchers in the respective
research areas.
Biofuel and Biorefinery Technologies will appeal to researchers and post-
graduates in the fields of biofuels & bioenergy technology and applications,
offering not only an overview of these specific fields of research, but also a wealth
of detailed information.
Editors
Biodiesel
From Production to Combustion
123
Editors
Meisam Tabatabaei Mortaza Aghbashlo
Biofuel Research Team (BRTeam) Department of Mechanical Engineering of
Karaj, Iran Agricultural Machinery, Faculty of
Agricultural Engineering and Technology,
and College of Agriculture and Natural
Resources
Microbial Biotechnology Department University of Tehran
Agricultural Biotechnology Research Karaj, Iran
Institute of Iran (ABRII), Agricultural
Research, Education and Extension
Organization (AREEO)
Karaj, Iran
This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface
This book is about biodiesel production presenting in-depth information on the state
of the art of global biodiesel production and investigates its impact on climate
change. Biodiesel is arguably the most commercialized type of petrodiesel alter-
native. A number of parameters including increasing energy demands and wors-
ening environmental conditions on one hand and similar physicochemical
properties of biodiesel to those of petrodiesel, on the other hand, are among the
main driving factors of the growing interest in biodiesel.
The present book, which is the eighth book in the series on Biofuel and
Biorefinery Technologies, offers a comprehensive reference guide to biodiesel
production by internationally recognized experts in the field of biodiesel production
from both academia and industry. The 10 chapters cover various aspects of bio-
diesel production technology from the basics, i.e., major principles of operation,
process control, and troubleshooting to production systems (reactor technologies) as
well as biodiesel purification and upgrading technologies. In addition, conventional
and emerging applications of biodiesel by-products with a view to further econo-
mize biodiesel production, economic risk analysis, and critical comparison of
biodiesel production systems as well as techno-economical aspects of biodiesel
plants are also comprehensively reviewed and discussed. Providing in-depth and
cutting-edge information on central developments in the field, “Biodiesel: From
Production to Combustion” also thoroughly investigates the important aspects of
biodiesel production and combustion by taking advantage of advanced sustain-
ability analysis tools including life cycle assessment (LCA) and exergy approaches.
In closing, the application of Omics technologies in biodiesel production is pre-
sented and discussed. The book is intended for all researchers, practitioners, and
students who are interested in the current trends and future prospects of biodiesel
production technologies.
It is expected that the present volume on biodiesel would assist both the sci-
entific and industrial communities in further developing this industry worldwide.
We are thankful to the authors of all the chapters for their efficient cooperation and
also for their readiness in revising the manuscripts. We also would like to extend
our appreciation to the reviewers who in spite of their busy schedule assisted us by
v
vi Preface
evaluating the manuscripts and provided their critical comments to improve the
manuscripts. We would like to sincerely thank Dr. Vijai Kumar Gupta and Dr.
Maria G. Tuohy and the team of Springer Nature, in particular, Dr. Andrea
Schlitzberger, Mr. Arumugam Deivasigamani, and Mr. Viju Falgon Jayabalan for
their cooperation and efforts in producing this book.
vii
viii Contents
M. Rouhany (&)
Strategic Carbon Management Inc., Vancouver, BC V5Z 1Z1, Canada
e-mail: mrouhany@gmail.com
H. Montgomery
Division of Medicine, Centre for Human Health and Performance, University College
London, London, UK
1.1 Introduction
Biodiesel, derived from processing biological sources such as edible and nonedible
oils, animal fats, and waste cooking oils, has similar properties to petro-diesel. It
can be used to enhance certain characteristics of petro-diesel, such as lubricity,
aiding fuel performance, and extending engine life (Traviss 2012; Pacini et al.
2014). Compared to petro-diesel, it has a higher cetane number (and thus better
ignition quality) but a lower heating value, higher density, and higher viscosity
(Taher and Al-Zuhair 2017) and is thus less suitable for colder climates due to
gelling, clouding, and overall reduced cold weather performance (Traviss 2012).
Biodiesel can be blended in all ratios and many jurisdictions use these, from farm
level to industrial scale, in preference to pure biodiesel. The quality of biodiesel is
determined by the quality of feedstock oil, the processing technology used, and the
process parameters (Knothe et al. 2010; Rathore et al. 2016). Biodiesel and ethanol
make up the majority of the renewable share of the world road and marine trans-
portation sector’s energy demand (REN21 2016). Biodiesel is also utilized in sta-
tionary machinery and in some jurisdictions for heat and electricity generation
(Rathore et al. 2016).
The net environmental benefit of biodiesel is a topic of continuing debate.
Biodiesel is biodegradable. Whether used pure or as a petro-diesel blend, it can
provide air quality benefits namely lower loads of carbon monoxide, sulfur oxides,
and volatile organic compounds (Pacini et al. 2014). In many cases, net greenhouse
gas emissions are reduced. The majority of criticism targets the negative impacts
that biodiesel sourced from agriculture-based biomass feedstock farming have on
forests and grasslands, food and animal feed prices, loss of biodiversity due to
mono-cropped fields, water resource management, food security, and air quality. To
date, edible oilseeds such as soybean and rapeseed have been the dominant bio-
diesel feedstocks. Biofuels developed from food or animal feed crops are referred to
as “first generation” or conventional biofuels. Developing biodiesel from crops that
can be grown on land that is not suitable for growing food, from biomass sources
that are less dependant on the availability of land, or from nonedible feedstocks or
by-products, can alleviate many of the sustainability concerns. Biofuels that are
developed from nonedible biomass except algae are known as “second generation”
or advanced biofuels. Biodiesel produced from microalgae would be considered a
“third generation” biofuel. Algae, municipal and industrial organic waste, sugar
cane bagasse, corn stover, perennial grasses, cereal straw, as well as forestry and
agricultural waste are examples of more sustainable feedstock. These sources, while
not yet produced at commercial scale, are receiving considerable attention due to
their smaller environmental footprint (Rathore et al. 2016; Anuar and Abdullah
2016; Royal Academy of Engineering 2017).
Important challenges for the biodiesel industry come from low petro-diesel
prices, fuel–food competition resulting in reciprocal price increases and destabi-
lization of the feedstock market, as well as negative socio-environmental impacts of
the feedstock oilseeds (Anuar and Abdullah 2016). The implementation of biofuel
1 Global Biodiesel Production: The State of the Art … 3
The first known transesterification of a vegetable oil was conducted by E. Duffy and
J. Patrick in 1853. This was four decades before Rudolf Diesel’s engine first ran
independently in Augsburg Germany on August 10, 1893 (Abdalla and Oshaik
2013). The diesel engine, since its inception, could run on a variety of fuels
including vegetable oils. One of the first publicly demonstrated uses of biodiesel in
a diesel engine was in the year 1900 when, during the Paris exposition, the French
company Otto operated a small diesel engine on peanut oil. According to Rudolf
Diesel’s papers, published in 1912 and 1913, in addition to research by the French
on peanut oil, experiments were being conducted in St. Petersburg using castor oil
and train-oil (oil obtained from the blubber of marine animals) with excellent
results. France, Belgium, Germany, Italy, and the UK had varying interests in fuels
from vegetable oils during the first half of the twentieth century (Knothe et al.
2010). Triglycerides from easily available oil-rich feedstocks were contenders for
being the main fuel source for the diesel engine in its early years. However, natural
oils are viscose with relatively low cetane numbers compared to petro-diesel, which
resulted in them gradually being replaced by petroleum oil (Taher and Al-Zuhair
2017).
The petroleum industry has commonly dominated the global fuel market with its
cheaper production and price. Generally, when petroleum fuel supplies are plentiful
and inexpensive, interest in bio-sourced oils has been low. Disruption of petroleum
fuel supplies during World War II drove countries like Argentina, Brazil, India, and
China to use vegetable oil as fuel (Van Gerpen et al. 2007).
The petroleum oil embargo of the 1970s led to a renewed interest by the United
States, Austria, and South Africa in vegetable oils and their direct use in diesel
engines as fuel. Since the 1920s, diesel engine manufacturers had altered their
designs to match the lower viscosity of petroleum diesels (Van Gerpen et al. 2007;
Abdalla and Oshaik 2013). Thermal cracking, pyrolysis, transesterification, the
formation of microemulsions, and dilution of oils with solvent were, thus, experi-
mented with to address the viscosity limitations of vegetable oils. With the emer-
gence of suitable catalysts, the transesterification with short-chain alcohols, such as
methanol and ethanol, became the preferred and most commonly used method to
convert bio-oils to biodiesel (Taher and Al-Zuhair 2017). The term biodiesel was
most likely first used around 1984. The commercial production of biodiesel started
in the early 1990s and the first standard for biodiesel was published in 2001, the
ASTM D6751.
4 M. Rouhany and H. Montgomery
The world’s market share of diesel in transportation fuels has been increasing in
comparison to gasoline and this share is expected to continue to grow globally at
varied rates mainly driven by non-OECD countries. Biodiesel production growth
has been following this trend and is increasing faster than that of ethanol.
International trade in biodiesel has also been considerably higher than the trade in
ethanol and, despite its small share compared to production, the international
biodiesel trade has been paramount in the development of the biodiesel industry in
developing economies. Pro-biodiesel policies in the EU and USA have driven the
development and expansion of biodiesel industries for export in agricultural
countries with established oilseed industries, namely palm-based biodiesel in
Indonesia and Argentina’s soy-based biodiesel (Naylor and Higgins 2017). Global
fuel demand in conjunction with domestic policies and trade interactions are the
main drivers for the global biodiesel sector.
Between 2005 and 2015, global biodiesel production expanded by more than
20% per year, which resulted in a sevenfold expansion in a single decade. This
occurred parallel to a rise in petro-diesel prices during the same period. Diesel and
oil prices have been in decline since mid-2014 and lower petroleum prices stimulate
petro-diesel use. However, despite the downward pressure from recent low oil
prices and policy uncertainty in some markets, biofuel production and demand
continued to increase in 2016, and ethanol and biodiesel still comprised the
majority of the renewable share of global energy demand for transportation with
roughly 4% of the world road transport fuel (REN21 2017; Naylor and Higgins
2017).
According to the Organization for Economic Cooperation and Development and
the UN’s Food and Agriculture Organization 2016 Agricultural Outlook, global
biodiesel use is expected to gradually increase over the next 10 years. The largest
demand increase will be from developing countries, mainly Indonesia, Brazil, and
Argentina, with an estimated 68% increase in 2025 compared to 2015 (OECD/FAO
2016).
The European Union and the United States are, together, the largest influencers
of biofuel demand. Implementation of biofuel mandates has led to an increase in
biofuel use in the United States. The current maize-based ethanol mandate is
expected to decline after 2018 and be replaced by an increase in the advanced
mandate covering biofuels from sources other than maize. This would result in
lower ethanol use and an increase in biodiesel use in the United States. In the
European Union, the Renewable Energy Directive target has to be met by 2020
which is expected to sustain an expansion of ethanol and biodiesel fuel use until
then. Thereafter, a decrease is expected in line with lower gasoline and diesel use
prospects. Palm oil is expected to decline as a feedstock in European biodiesel.
In developing countries, biodiesel use is also expected to expand steadily with
Indonesia, Brazil, and Argentina leading the way due to their domestic mandates.
Biofuel demand is expected to remain low in Central Asia and Eastern Europe as
1 Global Biodiesel Production: The State of the Art … 5
these regions are either oil and gas producers or lack biofuel incentive policies for
producers or blending mandates for consumers (OECD-FAO 2015). Global bio-
diesel supply grew from 3.9 billion liters in 2005 to 30.8 billion liters in 2016 and is
expected to reach 41.4 billion liters in 2025, a 34% increase over 2016 levels
(Onguglo et al. 2016; REN21 2016; OECD/FAO 2016). An estimated 72% of
biofuel production (in energy terms) was fuel ethanol, 23% was biodiesel, and 4%
was hydrotreated vegetable oil (REN21 2017). More than 80% of the world’s
biodiesel production is from vegetable oils, with the majority produced from
European canola and soybeans from the United States, Brazil, and Argentina.
Indonesian palm oil and other sources such as jatropha and coconut make up a
small share of vegetable-based biodiesel. Waste-based biodiesel accounted for 8%
of the global supply in 2015 (OECD/FAO 2016; REN21 2016). In 2015, biodiesel
was responsible for 162,600 direct and indirect jobs in Brazil while in the same year
the U.S. biodiesel sector provided 49,486 direct and indirect jobs (REN21 2016).
Whilst spread across many countries, biodiesel production is dominated by only
a few In 2016, the EU was the largest producer (with a 26% share of global
production), and 76% of the world’s fatty acid methyl ester (FAME) biodiesel was
produced by the EU, United States, Brazil, Argentina, and Indonesia. No other
country outside of this group had a share larger than 5% (REN21 2016, 2017)
(Fig. 1.1).
The domestic policy incentives in the United States, Argentina, Brazil, and
Indonesia and, to a lesser extent, the fulfillment of the Renewable Energy Directive
(RED) target in the European Union, are the main drivers for global biodiesel
production (OECD/FAO 2016).
The EU is experiencing a decline in investment in new biodiesel capacity mainly
due to a continuing decrease in policy and public support for first-generation
Brazil, 12.3%
EU-28, 26.0%
Argentina, 9.7%
Thailand, 4.5%
Indonesia, 9.7%
6000
5000
Imports, and Consumption
4000
3000
2000
1000
0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015
Production Exports Consumption Imports
Fig. 1.2 U.S. biodiesel 10-year production, consumption, imports, and exports from 2001 to 2015
(U.S. EIA 2017)
1 Global Biodiesel Production: The State of the Art … 7
35,000.00
MILLIONS OF LITRES BIODIESEL
30,000.00
25,000.00
20,000.00
15,000.00
10,000.00
5,000.00
0.00
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Fig. 1.3 Global biodiesel production, consumption, and exports 10-year overview (OECD/FAO
2016)
8 M. Rouhany and H. Montgomery
$4.50
$4.00
$3.50
$3.00
$2.50
$2.00
$1.50
$1.00
B99/B100 Diesel
$0.50
$0.00
Fig. 1.4 Average U.S. diesel and B99/B100 biodiesel 10-year price overview (USDoE 2017)
The impressive growth of the global biodiesel market and industry during the last
decade at rates exceeding 20% per year despite downward pressure from low fossil
fuel prices is primarily driven by policies enhancing production and demand at the
national and regional level. Blending mandates, tax exemptions, subsidies, fuel
quality standards, import tariffs, and investment backings are examples of such
supportive regulations. Such policies are, in turn, driven and influenced by a
combination of factors, such as a desire for increased energy security, environ-
mental concerns and climate-related targets, lobby groups, feedstock availability,
effective use of co-products, enhancing rural development, and increasing the
demand and price for vegetable oils (REN21 2016; Cadham 2015; Naylor and
Higgins 2017).
Examples where biodiesel production has been profitable in the absence of
additional financial incentives are very few. Studies show that this has only been
achieved with palm oil as the feedstock and during times when feedstock prices
were low and oil prices were high. To improve the overall financial and opportunity
costs, governments often accompany quantitative targets with other policies such as
blending mandates, subsidies, and tax credits (Naylor and Higgins 2017).
The policy instrument that is most commonly used across various countries and
regions is the blend mandate. A blend mandate specifies a share or volume of
biodiesel to be blended with petro-diesel. Blending mandates lead to consistency in
demand which is instrumental in protecting biodiesel markets from the effects of
1 Global Biodiesel Production: The State of the Art … 9
low global petro-diesel prices. By the end of 2015, biodiesel blend mandates were
in place at the national level in 18 countries (REN21 2016).
The majority of mandates are in place in the EU, where its Renewable Energy
Directive requires a 10% renewable content in fuel by 2020. RED establishes
sustainability requirements for liquid biofuels, including greenhouse gas
(GHG) reductions, land use changes, and other environmental, social and economic
criteria. A 7% limit on the share of food-crop-based transportation biofuels to the
EU’s 10% renewable mandate and the exclusion of biofuels grown on land with
peat or high carbon stocks was introduced in the amendments to RED. Adoption of
second-generation biofuels is further incentivised through a 0.5% voluntary target
and by allowing the contribution of nonfood crop-based biofuels to be
double-counted toward meeting the overall EU target (Naylor and Higgins 2017;
Araújo et al. 2017).
Agricultural support and the expansion of renewable fuels and climate mitigation
have been the main motivations driving biodiesel policies in the EU. Recently, a
stronger focus on sustainability and reducing GHG emissions has resulted in
changes in EU policies regarding feedstock sourcing. The current regulations
require that all biofuels from existing plants must result in a 50% reduction in
lifecycle greenhouse gas emissions in comparison to fossil fuels, beginning in 2018.
New plants should demonstrate a 60% reduction in GHG emissions in their biofuel
product considering emissions from cultivation, processing, and transport. A 2015
amendment to RED requires that calculations of indirect land use change (iLUC)
emissions associated with biodiesel feedstock be incorporated in GHG emission
calculations by fuel suppliers. iLUC emissions do not officially count in the GHG
reduction targets. As the majority of current biodiesel feedstocks will not meet the
50% reduction in GHG emissions target, EU member states are increasingly con-
sidering alternative feedstocks such as waste oils which provide significant GHG
emission reductions compared to fossil fuels and do not have land-use change
impacts. It is expected that the legislation that will replace the RED after it expires
in 2020 will have more stringent sustainability criteria, namely further limits on
GHG emissions, on the use of food crop feedstocks, and on land-use change
impacts. A reduction in the food crop share from the current 7 to 3.8% in 2030 and
raising the minimum greenhouse gas savings over fossil fuel alternatives to 70% by
2021 was proposed in the European commission in late 2016 (Naylor and Higgins
2017).
In the EU, petro-diesel is the primary fuel used for road transportation which
accounted for roughly 75% of the energy used in transportation in the EU in 2016.
The share of diesel fuel in the EU’s road transport grew from 52% in 2000 to 70%
in 2014. Historically, the European biodiesel industry was developed in order to
provide a substitute for petro-diesel. The EU introduced the Renewable Energy
Directive in 2009, which required 10% of all transportation energy to come from
renewable resources by 2020. RED allows member states flexibility in selecting
their own policies for meeting the target. Between 2005 and 2015, the EU’s bio-
diesel production tripled, and its production capacity expanded more than fivefold.
10 M. Rouhany and H. Montgomery
In 2016, 80% of the EU biofuels market was composed by biodiesel and ethanol
held the remaining 20% (EEA 2016; Naylor and Higgins 2017).
The EU has implemented a 3.5% import duty on biodiesel blends of B30 (30%
biodiesel content) and under, and a 6.5% import duty on B30–B100 (pure biodiesel
with no blending) fuels to protect its domestic rapeseed and biodiesel production.
Other EU trade policies include anti-dumping tariffs on biodiesel imports from the
USA, Canada, Argentina, and Indonesia. In September 2016, the EU terminated its
anti-dumping duties against Argentina and Indonesia (Naylor and Higgins 2017).
In the United States under the Renewable Fuel Standard, the Environmental
Protection Agency releases annual biomass-based diesel volume requirements. By
the end of 2015, biodiesel blend mandates were in place in 27 jurisdictions (REN21
2016). For 2017, the volume requirement for biomass-based diesel was 7.6 billion
liters (2.0 billion gallons). The RFS places a cap on the share of corn-starch ethanol
and a minimum requirement for the share of cellulosic biofuels. A $1-per-gallon
biodiesel blending tax credit was implemented in 2005, which expired at the end of
2016. Furthermore, the American Renewable Fuel and Job Creation Act of 2017
was introduced in the US Senate on April 26, 2017 to replace the Biodiesel
blending credit. The bill modifies and extends the income tax credit for biodiesel
and renewable diesel used as fuel, and the excise tax credit for biodiesel fuel
mixtures. The Act proposes a $1-per-gallon production credit for biodiesel pro-
duced in the United States from December 2016 until December 2020 and an
additional 10 cent-per-gallon credit for small US biodiesel producers (under 15
million gallons/year). The small producer credit would be available to biodiesel
produced from all feedstocks (Library of Congress 2017).
The political context within each nation forms its policy priorities, goals,
instruments, and methods. While national biodiesel policy implementation in major
producing countries seems to address a wide range of interests across several
objectives, in reality, the support of specific sectors and interests, such as farm
lobbies and energy groups, often determines policy design and implementation.
Large agricultural economies often install policies that indirectly support local
agriculture by enhancing the use of domestic oil crops for biodiesel feedstock to
support farm revenues throughout their agricultural supply chain. Consequently, all
large biodiesel producing nations are using their domestic agricultural products as
the main feedstock for biodiesel production, resulting in a complex interaction of
energy and agricultural interests. These interests provide the drive for governments
to maintain and even enhance their support for the biodiesel sector during the
current era of low crude oil prices (Naylor and Higgins 2017). In addition, there are
national and international interests in reducing fossil fuel use so as to reduce GHG
emissions and meet climate targets. Fossil fuel lobbies and political forces working
to expand fossil fuel use, as is currently seen in play in the US, are opposing and
complicating factors. This creates a state of affairs in which uncertainties exist that
could significantly change the projections for biofuel markets over the next decade.
US and EU policies on climate mitigation, feedstock sourcing, blending mandates,
and trade barriers together with fuel prices and the biodiesel sector’s ability to
1 Global Biodiesel Production: The State of the Art … 11
In one of the most extensive studies to date, the UK’s Royal Academy of
Engineering conducted an assessment of over 250 separate studies on the GHG
emission reductions of biofuels versus fossil fuels (Naylor and Higgins 2017).
In the UK study, the GHG emissions per unit of energy generated for
first-generation biodiesels produced from common feedstocks displayed a large
variation ranging from 4 to 505 grams of CO2 equivalent-per-Mega Joule (gCO2e/
MJ) across different LCA studies. As a point of comparison, it should be noted that
the carbon intensity of EU petro-diesel is around 84 gCO2e/MJ. However, the
average biodiesel GHG emissions from all the feedstocks considered were lower
than emissions from fossil diesel if no land use change (LUC) was involved. The
only type of first-generation biodiesel that would meet the EU RED requirement for
50% less GHG emissions compared to conventional diesel was palm oil biodiesel
without LUC (Naylor and Higgins 2017).
Where land-use change-related carbon emissions are included in the calcula-
tions, all varieties of first-generation biodiesels considered in the study had a higher
average carbon footprint than petro-diesel. Soybeans had the largest negative GHG
emission impact, which could be due to soybean cultivation in South and Central
America actuating both direct and indirect land use change (iLUC). Biodiesel
produced from palm oil harvested from peat and forest lands in Indonesia and
Malaysia demonstrated 3–40 times higher GHG emissions per unit of energy
compared to petro-diesel. A large variability was observed in results of the assessed
studies including LUC-related GHG emissions. This is due to the differences in
LUC GHG estimation methods and emission factors and the fact that some studies
included either direct or indirect LUC-related emissions and others included both
(Naylor and Higgins 2017).
The average GHG emissions per unit of energy for second-generation biodiesels
from nonedible feedstocks are considerably lower than petro-diesel, with the values
ranging from −88 to 80 gCO2e/MJ. Negative values are a result of credits for
co-products. The three feedstocks evaluated were Jatropha, Camelina and used
cooking oil/tallow. The average carbon intensity of Jatropha, used cooling oil/
tallow, and Camelina are, respectively, 26, 27, and 33 gCO2e/MJ. Similar to
first-generation biodiesels, the range of these results varied broadly due to regional
differences in yield and different estimation methods particularly in regard to
co-product allocation. In most of the studies assessed by the Royal Academy of
Engineering biodiesel from tallow and used cooking oil showed 60–90% lower
carbon intensity than petro-diesel. The average GHG intensity value for
third-generation microalgae biodiesel was 3.5 times higher than conventional diesel
also with a large variation in the individual results. Due to costly and
energy-intensive production, biodiesel produced from algae at its current phase of
development results in more GHG emissions than its petroleum counterpart and is
not yet a viable choice (Naylor and Higgins 2017).
Agriculture phase LUC is the major contributor to biodiesel GHG emissions
followed by the transesterification process. The EU is intent on a continuous
reduction in the share of first-generation biofuels in transport fuel and increasing the
share of climate-friendly advanced biofuels (REN21 2017). As crude oil becomes
1 Global Biodiesel Production: The State of the Art … 13
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Chapter 2
Biodiesel Production Systems: Reactor
Technologies
Abstract The dwindling of fossil resources has prompted producers of fuels, fine
chemicals, and polymers to switch from fossil carbon sources and search for
renewable feedstock. Biomass holds one of the keys to this transition to a circular
economy. In this context, biodiesel obtained by transesterification of natural oils
with alcohols is gaining importance in the fuel sector. Various reactor concepts
have been developed for the transesterification reaction. Depending on the scale of
the biodiesel production plant, reactors with varying designs are operated in the
batch, semi-batch mode, or continuously. In this chapter, the optimal reactor
technologies are analyzed with respect to the stages the chemical conversion runs
through. The initial reaction mixture of natural oil and methanol, the most common
alcohol in biodiesel production, is characterized by a liquid–liquid two-phase
system. The high polarity difference of natural oil and methanol leads to a mixa-
bility gap and formation of a natural oil-rich phase and a methanol-rich phase. The
mass transfer of the reagents across the phase boundary is slow relative to the
chemical reaction, thereby resulting in diffusion limitations. Various mixing tech-
nologies, such as sonication, and the use of microreactors are explored to overcome
these diffusion limitations. Once the reaction is 15–20% complete, the reaction
mixture becomes homogeneous, reducing the need for intensive mixing. As the
reaction continues and higher conversions are obtained, the fatty acid methyl ester
separates from glycerin. The two phases are separated and purified. Recent tech-
nologies for process intensification aim at enhancing mass and heat transfer at all
stages of the reaction.
T. E. Müller (&)
Chemical and Process Engineering, Rheinische Fachhochschule Köln,
Schaevenstraße 1 a-b, Köln 50676, NRW, Germany
e-mail: thomas.mueller@rfh-koeln.de
2.1 Introduction
The dwindling of fossil resources has spurred the need to switch the production of
fuels, chemicals, and polymers from fossil carbon sources to renewable feedstock.
Biomass holds one of the keys to the transition of a fossil-based unidirectional to a
circular economy. It is a renewable and widely available resource. In the fuel sector,
biodiesel has been on the market for some time and is gaining further in importance.
It is an environmentally benign, biodegradable, nontoxic fuel associated with
comparably low emissions (Chuah et al. 2017; Kumar et al. 2013). Currently, two
main types of biodiesel fuels are produced on a large scale—fatty acid methyl esters
and hydroprocessed esters and fatty acids (Dimian and Rothenberg 2016). The term
biodiesel refers primarily to fatty acid methyl esters. For biodiesel production,
natural oils, i.e., the glycerol ester of fatty acids are used as raw material. The
primary feedstock can be vegetable oil crops derived from rapeseed, sunflower, soy
or palm (Dimian and Rothenberg 2016). Moreover, residual lipid materials and
nonedible vegetable oils derived from jatropha, camelina, and ricinus are suitable
(Dimian and Rothenberg 2016; Bhuiya et al. 2016; Demirbas et al. 2016). Future
raw material (Perego and Ricci 2012) may include algae biomass with a certain oil
contents (Brennan and Owende 2010) or lipids obtained by the conversion of
carbohydrates with special yeasts (Arous et al. 2016). The fatty acid moieties
comprise alkyl chains differing in the number of carbon atoms (R′, R″, R‴ = C14H29
to C20H41) (Feasibility report small-scale biodiesel production 2006). Besides sat-
urated alkyl chains, unsaturated chains are also present to a smaller extent. For
biodiesel production, natural oil is reacted with alcohol to the corresponding fatty
acid ester and glycerol in an equilibrium reaction (Eq. 2.1). The fatty acid ester is
then purified to yield biodiesel within the legal specifications (International A
2013).
O
O
O R' OH
RO R'
O [Cat.]
3 R OH + O R''
RO
O
R''
+ OH ð2:1Þ
O
O
O R''' OH
RO R'''
the sequence of physical and chemical steps. When diffusion limitations are present,
the overall reaction rate is reduced. To counter this effect the interphase area is
increased by technical means, and various mixing technologies, such as mechanical
stirring, static mixers, sonication, or microreactors, have been explored. A larger
interphase area leads to a higher flux of reagents across the phase boundary and helps
overcome the diffusion limitations. More recent technologies for process intensifi-
cation are aimed at overlaying chemical reaction with physical separation of products
and excess reagents.
Diverse reactor concepts have been developed for the transesterification of
natural oils with alcohols to biodiesel (Dimian and Bildea 2008). Depending on the
scale of the biodiesel production plant, the reactor designs comprise batch,
semi-batch, or continuous operation (He and Gerpen 2016).
Biodiesel production plants based on batch reactors require a vessel that is filled
with the reagents natural oil, methanol and catalyst as well as equipment for
work-up. This results in comparably small initial capital and infrastructure invest-
ment. The operation of batch reactors is flexible and allows accommodating vari-
ations in feedstock type, composition, and quantity. Even so, the major drawbacks
of biodiesel batch processes include low productivity due to the time needed to
charge and empty the reactor, a certain variation in product quality as every batch is
unique, and more intensive labor and energy requirements compared to continuous
operation.
Biodiesel processes based on reactors operated in the semi-batch mode are
similar to the batch process. The production commences with a smaller volume of
the reaction mixture than the vessel will hold. Reactants are then added until the
vessel is filled. This process, however, is relatively labor-intensive and rarely used.
Biodiesel processes based on continuous-flow reactors are preferred over batch
processes in large-capacity commercial production. The most common type of
continuous-flow reactor is the continuous stirred-tank reactor. Yet mixing of the two
phases present at the initial stage of the reaction can be a challenge. Conventionally,
mechanical stirrers ensure macro-mixing of the reaction mixture. The use of static
mixers can enhance the mixing. Micro-mixing can be improved by ultrasound or by
operation at supercritical conditions. Fixed bed tubular reactors have been intro-
duced to overcome intrinsic limitations in conversion caused by the use of
back-mixed reactors. Even though reactive distillation has been explored to intensify
the process, it has not yet been used to produce biodiesel on a commercial scale.
Compared to biodiesel production in batch processes, continuous operation
results in a more constant product quality. In addition, lower operating costs are
obtained per unit of product. Certain capital investment, however, is needed to build
the plant. In general, continuous-flow processes require intricate process controls
and online monitoring of product quality. Pumps for natural oil and methanol and
the dosing system for the catalyst are operated continuously. Moreover, the pumps
used for product removal and the equipment in downstream processing are operated
continuously. Feedback loops of process analytics to the operation parameters
conform to the principles of Green Chemistry (Gupta et al. 2010; Jessop et al. 2009;
Anastas and Eghbali 2010). Within certain constraints, the production capacity can
18 T. E. Müller
be adjusted to the availability of natural oil by adjusting the feed rate. Since the
vessel size is usually fixed, such changes in the feed rate lead to a different resi-
dence time of the reaction mixture in the vessel. Adjusting the ratio of
methanol-to-natural oil as well as the catalyst concentration helps to compensate for
the resulting changes in conversion.
In biodiesel production, natural oil and methanol form a two-phase system. The
limited mutual solubility of natural oil and methanol results in diffusion limitations
across the phase boundary restricting the overall rate of reaction (Gerpen et al.
2005). The difference in solubility is particularly relevant at the onset of the
reaction. Creating a large interphase between the natural oil-rich phase and the
alcohol-rich phase enhances mass transfer across the phase boundary. Thus, good
reaction engineering is required in biodiesel production. If the interphase area is too
small, the chemical reaction rate is slowed down by the limited availability of one
of the reactants. The reaction rate over conventional catalysts depends on the
concentration of natural oil and methanol (Wei et al. 2014), and the highest reaction
rates are observed when the concentrations of both reagents are approximately
equal. This holds for homogeneous catalysts, such as sodium or potassium
hydroxide. With potassium hydroxide, the conversion of triglyceride to diglyceride
is the rate-determining step with an activation energy of 30.2 kJ/mol and 26.8 kJ/
mol for palm oil and mustard oil, respectively (Issariyakul and Dalai 2012). In the
case of heterogeneous catalysts, the concentration of methanol and natural oil on the
surface of the catalyst ought to be similar (Ilgen and Akin 2012).
The batch reactor is typically a vessel that is equipped with some type of agitation.
The main characteristics of a batch reactor are that the vessel is first filled with
unreacted material, the reaction then proceeds, and the reaction mixture is removed
sometime later on. Consequently, the vessel holds a reaction mixture with different
compositions depending on which time one happens to look at it. For biodiesel
production, the tank is filled with the reactants, i.e., natural oil, alcohol, and cata-
lyst. The reaction mixture is then heated and agitated for a certain period. After the
required time has elapsed, the contents of the vessel are drained out, fatty acid ester
and glycerol are separated, and the two products are further processed. Batch
reactors are generally used in small biodiesel production plants, but they are rela-
tively inflexible in terms of productivity. To increase production, it may be nec-
essary to reduce the cycle time, set up further vessels or replace the vessel with a
larger vessel.
2 Biodiesel Production Systems: Reactor Technologies 19
400
comparison to the size of a
batch reactor to achieve a
certain conversion (adopted 100
from Emig and Klemm 2005).
The analysis assumes a 40
first-order reaction A ! B
10
1
99.9 99.6 99 96 90 60 0
Conversion [%]
20 T. E. Müller
Dried oil
Methanol
Catalyst
Biodiesel
Phase Phase
separaƟon separaƟon
Glycerol
First reactor Second reactor
Fig. 2.2 Biodiesel production in a process with a cascade of two continuous stirred-tank reactors
(adopted from He and Gerpen 2016)