Biofuels

ISSN: 1759-7269 (Print) 1759-7277 (Online) Journal homepage: http://www.tandfonline.com/loi/tbfu20

A review of production, properties and advantages

of biodiesel

Vijay Kumar Mishra & Rachna Goswami

To cite this article: Vijay Kumar Mishra & Rachna Goswami (2017): A review of production,
properties and advantages of biodiesel, Biofuels, DOI: 10.1080/17597269.2017.1336350

To link to this article: http://dx.doi.org/10.1080/17597269.2017.1336350

Published online: 07 Jul 2017.

Submit your article to this journal

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=tbfu20

Download by: [University of South Florida] Date: 08 July 2017, At: 09:36
BIOFUELS, 2017
https://doi.org/10.1080/17597269.2017.1336350

A review of production, properties and advantages of biodiesel

Vijay Kumar Mishra and Rachna Goswami
Department of Bio-Sciences, Rajiv Gandhi University of Knowledge Technologies, Nuzvid, Krishna District 521202, Andhra Pradesh, India

ABSTRACT ARTICLE HISTORY

Continuous use of fossil fuels (non-renewable natural resources) are depleting fastaly and its Received 13 March 2016
burning cousing accumulation of carbon dioxide in the environment. Renewable carbon Accepted 22 July 2016
neutral transport fuels are required for environmental and economic sustainability. Biodiesel KEYWORDS
derived from oil crops is a potential renewable carbon neutral alternative to petroleum fuels. It Biodiesel; alternate fuel;
consists of monoalkyl esters of long-chain fatty acids and is primarily produced by direct use vegetative oil;
and blending, microemulsions, thermal cracking (pyrolysis) and transesterication. The most transesterication; renewable
commonly used method for biodiesel production is transesterication of vegetable oils and
animal fats. There are several processes available for the transesterication reaction including
batch process, supercritical processes, ultrasonic methods and microwave methods. The factors
which inuence the transesterication reaction are water content of oils or fats and free fatty
acids, molar ratio of glycerides to alcohol, catalysts, reaction time and reaction temperature. In
this present review, the importance, history, properties, sources and techniques for production
of biodiesel are described.

Introduction International (International Association for Testing and

Materials) as a fuel composed of monoalkyl esters of
The demand for petroleum has been continuously
long-chain fatty acids derived from renewable vegeta-
increasing due to industrialization and modernization.
ble oils or animal fats meeting the requirements of
Economic development has led to a high demand for
ASTM D6751. Vegetable oils (edible and non-edible)
energy. The energy supplied to full the demand is
and animal fats are mainly composed of triacylglycerols
derived from fossil fuels such as petroleum, coal and
which consist of long-chain fatty acids chemically
natural gas. International Energy Agency (IEA) [1] and
bound to a glycerol (1,2,3-propanetriol) backbone. Tri-
Shahid and Jamal [2] predict that the world will need
glycerides hold promise as alternative diesel engine
50% more energy in 2030 than today, of which 45%
fuels [6,7]; [8]; [9]. Direct use of vegetable oils and/or oil
will be accounted for by China and India [3]. Climate
blends is generally considered to be unsatisfactory and
change is presently the most serious global environ-
not practical for either direct-injection or indirect-injec-
mental problem. If the average global temperature
tion diesel engines. The acid composition, high viscosity
increases by more than 2 C, nearly one million species
and free fatty acid (FFA) content of used vegetable oils
could become extinct and hundreds of millions of peo-
and/or oil blends, as well as gum formation due to oxi-
ple could lose their lives [4]. It is estimated that nearly
dation and polymerization during storage and combus-
4.1 billion metric tons of CO2 will be released into the
tion, carbon deposits, and lubricating oil thickening, are
atmosphere from 2007 to 2020. Additionally, it is
some of the more obvious problems [7,10,11]. Signi-
expected that extra 8.6 billion metric CO2 will be
cant work has gone into developing vegetable oil deriv-
released into the atmosphere from 2020 to 2035. It is
atives that approximate the properties and
estimated to be around 43% increase for the aforemen-
performance of hydrocarbon-based diesel fuels. Prob-
tioned projected period (International energy outlook
lems encountered in substituting triglycerides for diesel
2010 [5]; http://www.eia.gov/emeu/aer/inter.html). The
fuels are mostly associated with their high viscosity, low
non-renewable natural resource consumption rates and
volatility and polyunsaturated character [11]. Three
CO2 in the atmosphere increase daily, prompting many
main processes have been investigated in attempts to
researchers to look for alternative fuels friendlier to the
overcome these drawbacks and allow vegetable oils
environment than fossil fuels. Biodiesel is attractive
and oil wastes to be utilized as a viable alternative fuel:
because it is environmentally friendly (low emissions of
pyrolysis, microemulsication and transesterication [7].
carbon monoxide and particulate matters), renewable,
Among these, transesterication is the most common
highly degradable, zero toxicity and does not release
and most widely accepted.
hydrocarbons. Biodiesel is dened by ASTM

CONTACT Vijay Kumar Mishra mishravijay@rgukt.in; mishrvijay@gmail.com

Equal contribution
2017 Informa UK Limited, trading as Taylor & Francis Group
2 V. K. MISHRA AND R. GOSWAMI
The chemical process by which biodiesel is prepared
is known as the transesterication reaction. This reac-
tion involves triacylglycerols reacting with short-chain
monohydric alcohols normally in the presence of a
suitable catalyst (alkali, acid or enzyme) at elevated
temperatures to form fatty acid alkyl esters (FAAE) and
glycerol [12]. Transesterication is the easiest and most
cost-effective process to produce biodiesel.
Compared to diesel, biodiesel produces no sulphur,
no net CO2, less carbon monoxide, zero particulate
matters, no smoke and no hydrocarbons. Biodiesel pro-
duces more oxygen. More free oxygen leads to com-
plete combustion and reduced emissions [3,13,14].
Biodiesel has lubricating properties and cetane ratings
compared to low sulphur diesel fuels. Its caloric value
is about 37.27 MJ/kg which is 9% lower than regular
Number 2 petrodiesel. Variations in energy density of
biodiesel are more dependent on the used feedstock
than the production process. These variations are less
than for petrodiesel. The major feedstock for biodiesel
is fat or oil from animals and plants. There are more
than 350 oil-bearing crops identied as possible sour-
ces for biodiesel production [3]. Generally, the econ-
omy of biodiesel production depends on two crucial
factors: feedstock and catalyst (determines the number
of steps and synthesis route) [15].
Biodiesel has been utilized in Brazil, Indonesia,
Malaysia, the US, France, Germany and other European
countries [3]. Globally, annual biodiesel production is
increasing (15 thousand barrels per day in 2000; 289
thousand barrels per day in 2008) [3,14]. It is accepted
that 85% of biodiesel production comes from the
EU [3,4]. The demand for biodiesel in Europe was 10.5
billion litres in 2010 [3].
In the present review, an attempt is made to review
the importance, history, properties, sources and techni-
ques for production of biodiesel.
History of biodiesel
Rudolf Diesel designed the diesel (i.e. compression
ignition) engine to run on many fuels including coal
dust suspended in water, heavy mineral oil and vegeta-
ble oil. Diesels early engine experiments were cata-
strophic failures. In 1900 he showed his engine at the
World Exhibition in Paris, running on 100% peanut
oil [16, http://www.biodiesel.com/biodiesel/history]. In
1911, Diesel stated: The diesel engine can be fed with
vegetable oils and would help considerably in the
development of agriculture of the countries which use
it. In 1912, Diesel said: The use of vegetable oils for
engine fuels may seem insignicant today. But such
oils may become in course of time as important as
petroleum and the coal tar products of the present
time. Diesel died in 1913. His engine was later modi-
ed to run on the polluting petroleum fuel we now
know as diesel. Nevertheless, his ideas on agriculture
and his invention provided the foundation for a society
fuelled with clean, renewable, locally grown fuel [17]. In
emergency situations (in the 1930s and 1940s), vegeta-
ble oils were used as replacements for diesel fuel [10].
Today, countries are turning to using biofuels due to
its renewable sources and reduction in pollution [17].
In France, rst trials with vegetable oil methyl and
ethyl esters were carried out in 1940. At the same time,
Belgian scientists were using palm oil ethyl ester as a
fuel for buses. Research was slow until the late 1970s
and early 1980s, when concerns about high petroleum
prices motivated extensive experimentation with fats
and oils as alternative fuels [18,19]. Biodiesel, also
known as mono alkyl ester, started to be produced
widely in the early 1990s and since then production
has been increasing steadily. In the EU, biodiesel was
promoted in the 1980s as a means to prevent the
decline of rural areas while responding to increasing
levels of energy demand. However, it only began to be
widely developed in the second half of the 1990s [20].
Production of biodiesel is a current and technologi-
cal area for researchers because of the increase in
petroleum demand and the environmental advan-
tages. The most common and effective method of bio-
diesel production is the transesterication of vegetable
oils and animal fats. It is not a new process; it was pre-
sented in 1853 by Duffy and Patrick. Since that time,
many studies have been carried out using different
oils [18].
Source of biodiesel
Biodiesel can be produced from vegetative oil, waste
cooking oil and animal fats. Biodiesel can also be pro-
duced from algae, microalgae and fungi. However,
most work has been done on oil-bearing plants. The
rst step is selection of feedstock. There are more than
350 oil-bearing crops recognized as potential sources
for production of biodiesel globally [3]. The commonly
used feedstocks for production of biodiesel are shown
in Table 1. The most important factor for biodiesel pro-
duction is the availability of a wide range of feedstocks
[3,2,21,22]. The feedstock should full two main
requirements: low production costs and large-scale
production. The availability and production of biodie-
sel feedstock depends on the geographical locations,
climatic condition, local soil texture and conditions,
and agricultural practices. Biodiesel feedstocks are
divided in four categories [3,11,18,2325]:
1. Edible vegetable oils such as rapeseed, soybean,
peanut, sunower, palm and coconut oil.
2. Non-edible vegetable oils such as jatropha, kar-
anja, sea mango, algae and halophytes.
3. Waste or recycled oil.
4. Animal fats such as beef tallow, yellow grease,
chicken fat and by-products from sh oils.
 BIOFUELS 3

Table 1. Common feedstocks for biodiesel production.

Group Edible oils Non-edible oils Animal fats Other sources
Name of feedstocks Soybeans (Glycine max) Jatropha curcas Pork lard Bacteria
Rapeseed (Brassica napus L.) Mahua (Madhuca indica) Beef tallow Algae (Cyanobacteria)
Safower Pongamia (Pongamia pinnata) Poultry fat Microalgae (Chlorellavulgaris)
Rice bran oil (Oryza sativum) Camelina (Camelina sativa) Fish oil Tarpenes
Barley Cotton seed (Gossypium hirsutum) Chicken fat Poplar
Sesame (Sesamum indicum L.) Groundnut Karanja or honge (Pongamia Switchgrass
sorghum pinnata) Miscanthus
Wheat Cumaru Fungi
Corn Abutilon muticum Latexes
Coconut Cynara cardunculus
Canola Neem (Azadirachta indica)
Peanut Jojoba (Simmondsia chinensis)
Palm and palm kernel (Elaeis guineensis) Passion seed (Passiora edulis)
Sunower (Helianthus annuus) Moringa (Moringa oleifera)
Tobacco seed
Rubber seed tree (Hevca
brasiliensis)
Salmon oil
Tall (Carnegiea gigantea)
Coffee ground (Coffea arabica)
Nagchampa (Calophyllum
inophyllum)
Croton megalocarpus
Pachira glabra
Aleurites moluccana
Terminalia belerica
References [3,26] [3,27] [3,26,28] [29], [3];

First generation biodiesel feedstocks are those crops
which are initially used for biodiesel production. Edible
oils resources, for example soybean, palm oil, sun-
ower, safower, rapeseed, coconut and peanut, are
considered to be rst generation. Feedstock planta-
tions are well established in several countries. More
than 95% of the world total biodiesel is produced from
edible oils: rapeseed (84%), sunower oil (13%), palm
oil (1%), soybean oil and others (2%) [3,30]. However,
consumption of edible oils is increasing due to the
food versus fuel crisis. Major environmental problems
are expected, such as serious destruction of vital soil
resources, deforestation and usage of the available ara-
ble land.
Over the last 15 years, the price of crops has dramat-
ically increased: it is no longer feasible to produce bio-
diesel from edible oil sources. One possible solution is
to use non-edible oil feedstocks. The main non-edible
oils for biodiesel production are: jatropha or ratan-jyote
or seemaikattamankku (Jatropha curcas), karanja or
honge (Pongamia pinnata), Aleurites moluccana,
Pachira glabra nagchampa (Calophyllum inophyllum),
rubber seed tree (Hevca brasiliensis), Desert date (Bal-
anites aegyptiaca), Croton megalocarpus, Rice bran, Sea
mango (Cerbera odollam), Terminalia belerica, neem
(Azadirachta indica), Koroch seed oil (Pongamia glabra
vent.), mahua (Madhuca indica and M. longifolia),
Tobacco seed (Nicotiana tabacum L.), Chinese tallow,
silk cotton tree (Ceiba pentandra), jojoba (Sim-mondsia
chinensis), babassu tree and Euphorbia tirucalli. Non-
edible oils for production of biodiesel is a second gen-
eration feedstock. Animal fats used for biodiesel pro-
duction are mainly beef tallow, poultry fat and pork
lard. Waste oils and grease can also be considered as a
second generation feedstock. The use of these types of
feedstocks eliminates the costs to safely dispose of
them [3].
Janaun and Ellis [22] and Lin et al. [25] studied pro-
duction of biodiesel from genetically engineered
plants such as poplar, switchgrass, Miscanthus and big
bluestem. These genetically engineered feedstocks can
create bioenergy crops not associated with food crops.
Therefore, they represented a sustainable biodiesel
feedstock for the future. However, precautions in bio-
safety must be considered for these types of feed-
stocks. Additionally, further research is required to
identify new oil crops to meet the increasing demand
for biodiesel. A variety of tools including plant breed-
ing, molecular breeding and biotechnology are
required to increase oil production from conventional
crops and to develop new oil crops for specic regions.
Biodiesel production technologies
The second step in biodiesel production is extraction of
oil. In the oil extraction process, the oil contained in the
seeds is extracted. The main product of this process is
crude oil and the important by-products are seeds or
kernel cakes. There are three common methods for
extraction of the oil:
1. Mechanical extraction.
2. Solvent extraction.
3. Enzymatic extraction.
The mechanical method (by mechanical expellers or
presses) is the most conventional. In this method,
whole seeds, kernels or a mixture of both are used, but
4 V. K. MISHRA AND R. GOSWAMI
common practice is to use whole seeds. The extraction
yields of oil though the mechanical method is 68
80% [3]. Only kernels are used as feed for the chemical
extraction method [31]. In the solvent extraction tech-
nique, extraction of oil from seed is by use of a liquid
solvent. Several factors inuence the oil extraction rate
(such as particle size, type of liquid chosen, tempera-
ture and agitation of the solvent). Three techniques
use the solvent method for oil extraction:
1. Hot water extraction.
2. Soxhlet extraction.
3. Ultrasonication technique.
The most promising technique for oil extraction is the
enzymatic technique. In this process, appropriate
enzymes are used to extract oil from vegetable sources.
Alkaline protease gives better results in aqueous enzy-
matic oil extraction. Additionally, ultrasonication pre-
treatment is a useful step in aqueous oil extraction [3,31].
The most common problems associated with crude
vegetable oils are high viscosity, low volatility and
polyunsaturated characters. These problems can be
overcome by four methods: direct use and blending
(dilution), pyrolysis, microemulsion and transesterica-
tion [3,11,18,2325].
Direct use and blending
In 1980 it was suggested that vegetative oil could be
used as fuel [10]. The concept of using edible oil as fuel
means petroleum will be alternating fuel rather than
vegetable oil and alcohol being the alternatives and
some form of renewable energy must being to take
the place of the non-renewable resources [6]. In South
Africa, researchers studied sunower oil (during an oil
embargo). Pre-combustion chamber engines were run
with a mixture of 10% vegetable oil to maintain total
power without any alterations or adjustments to the
engine in Caterpillar, Brazil, in 1980. At that point,
substituting 100% vegetable oil for diesel fuel was not
practical, but a blend of 20% vegetable oil and 80%
diesel fuel was practical and worked [10,32]. Some
short-term experiments used a 50/50 ratio of vegeta-
tive oil and diesel.
The rst international conference on plant and vege-
table oils as fuels was organized in Fargo, North Dakota,
in August 1982. The primary concerns discussed at this
conference were: cost of the fuel; effects of vegetable
oil fuels on engine performance and durability; and fuel
preparation, specications and additives. Production of
oil, processing of oilseed and extraction of oil also were
considered at this meeting [33].
A diesel eet was powered with ltered used frying
oil or waste cooking oil [34]. Used cooking oil or waste
cooking oil and a blend of 95% used cooking oil and
5% diesel fuel were used. Blending or preheating was
used to compensate for cooler ambient temperatures.
There were no coking or carbon build-up problems.
The most important process was ltering and the only
problem reported was lubricating oil contamination
(viscosity increased due to polymerization of polyun-
saturated vegetable oils). The lubricating oil had to be
changed every 40004500 miles.
Some advantages of the use of vegetable oils as die-
sel fuel are: (1) liquid nature-portability, (2) heat content
(80% of diesel fuel), (3) ready availability and (4) renew-
ability. The disadvantages of the use of vegetable oils as
diesel fuel are: (1) higher viscosity, (2) lower volatility
and (3) unsaturated hydrocarbon chains reactivity. For
both direct and indirect diesel engines, pure vegetable
oils and/or blends have generally been unsatisfactory,
impractical and difcult [10]. It was observed that high
viscosity, acid composition, FFA content, as well as gum
formation due to oxidation and polymerization during
storage and combustion, carbon deposits and lubricat-
ing oil thickening are obvious problems.
Pyrolysis
Pyrolysis is also known as thermal cracking. Pyrolysis
refers to a chemical change due to the application of
thermal energy in the presence of a catalyst and in the
absence of air or nitrogen.
The substrates for the pyrolysis method for produc-
tion of biodiesel can be vegetable oils, animal fats, nat-
ural fatty acids or methyl esters of fatty acids. It has
been observed that the pyrolysis of triglycerides to
obtain biodiesel, it is suitable for diesel engine. The liq-
uid fractions of the temperature based conversion of
vegetable oils are likely to approach diesel fuels. This
type of decomposition of triglycerides produces alka-
nes, alkenes, alkadienes, aromatics and carboxylic
acids [3,10,11,18,23,35,36]. It has been observed that
the pyrolyzate had lower viscosity, ash point and
pour point then petroleum diesel fuel and equivalent
caloric values [3]. Singh and Singh [32] reported that
the pyrolysis process is effective, simple, zero wastage
and pollution free. The cetane number (CN) of the
pyrolyzate vegetative oil or fat was lower. Pyrolyzed
vegetable oils have an acceptable quantity of sulphur,
water and sediments and give acceptable copper cor-
rosion values but unacceptable ash, carbon residual
and pour point [37]. The pyrolysis process can be
divided into three subclasses by operating condition:
conventional pyrolysis, fast pyrolysis and ash pyroly-
sis. The mechanism of pyrolysis of triglycerides is given
by Schwab et al. [38]. The scheme of the thermal crack-
ing process is shown in Figure 1.
Microemulsication
Microemulsion formation is a potential solution for the
problem of viscosity of vegetable oil. Microemulsions

Figure 1. Thermal cracking process and procedure for biodiesel production.
are transparent, thermodynamically stable colloidal
dispersion. Microemulsions are a colloidal equilibrium
dispersion of optically isotropic uid having micro-
structure (with dimensions generally 1150 nm)
formed spontaneously from two normally immiscible
liquids and one or more ionic amphiphiles. Microemul-
sions can be formed by use of solvents such as metha-
nol, ethanol, hexanol, butanol and 1-butanol.
Microemulsions with these solvents meet the maxi-
mum viscosity requirements for diesel fuel. The range

of droplet diameter in microemulsions are 1001000 A.
Microemulsions can be developed from vegetable oils
with an ester and dispersant (co-solvent), or vegetable
oil, alcohol, surfactant and cetane improver, with or
without diesel fuel. All microemulsions developed with
butanol, hexanol and octanol met the maximum vis-
cosity requirement for diesel fuel. The 2-octanol was
found to be an effective amphiphile in the micellar sol-
ubilization of methanol in triolein and soybean
oil [10,39]. Schwab et al. [39] used the ternary phase
equilibrium diagram and the plot of viscosity versus
solvent fraction to determine the formation of emulsi-
ed fuel. All microemulsions with butanol, hexanol and
octanol met the maximum viscosity requirement for
No. 2 diesel. The 2-octanol was an effective amphiphile
Figure 2. Transesterication reaction.
BIOFUELS 5
in the micellar solubilization of methanol in triolein
and soybean oil. Methanol was often used due to its
economic benet over ethanol. Short-term perfor-
mance of both ionic and non-ionic microemulsions of
aqueous ethanol in soybean oil are nearly as good as
No. 2 diesel fuel [3,10,23,32,35].
Transesterication
For synthesis of biodiesel, triglycerides are reacted with
alcohol (methanol) in a reaction known as transesteri-
cation or alcoholysis. Transesterication produces
methyl esters of fatty acids that are biodiesel and glyc-
erol (Figure 2). The transesterication reaction under-
takes three steps. First step is triglycerides convert to
diglycerides, second step is diglycerides convert to
monoglycerides, and third step is monoglycerides
nally convert to glycerol (Figure 3) [30]. This process
requires 3 mole of alcohol for 1 mole of triglyceride to
produce 1 mole of glycerol and 3 mole of fatty acid
esters, i.e. biodiesel (Figure 2). The reaction is equilib-
rium. Industrial processes use 6 mole of methanol for
each mole of triglyceride [7]. This surplus amount of
methanol conrms that the reaction is driven in the
direction of methyl esters, i.e. towards biodiesel. Yield
6 V. K. MISHRA AND R. GOSWAMI
Figure 3. Steps involved in the transesterication process.
of methyl esters exceeds 98% on a weight basis [7].
Transesterication is catalysed by different catalysts,
i.e. acids, alkalis [7,30,40,41] and lipase enzymes
[42]; [30]). Transesterication catalysed by an alkali cat-
alyst is about 4000 times faster than an acid-catalysed
reaction [7,40]. Subsequently, alkalis such as sodium
and potassium hydroxide are generally used as com-
mercial catalysts at a concentration of about 1% by
weight of oil. Alkoxides, for example sodium methox-
ide, are even better catalysts than sodium hydroxide
and are being increasingly used. Use of lipases enzyme
offers important advantages, but is not currently feasi-
ble because of the relatively high cost of the cata-
lyst [7,40]. The alkali-catalysed transesterication
process is carried out at approximately 60 C and atmo-
spheric pressure, as methanol boils off at 65 C and
atmospheric pressure. At 60 C and atmospheric pres-
sure conditions, the reaction takes about 90 min to
complete. A higher temperature can be used in combi-
nation with a higher pressure, but this is very
expensive.
Both ethanol and methanol can be used to alcohol-
ize the transesterication reaction of biodiesel produc-
tion. The low cost, chemical (shortest chain of alcohol)
and physical (polar) properties of methanol make it the
rst preference in chemical reactions. Methanol and oil
are immiscible; hence the reaction mixture contains
two liquid phases.
To prevent yield loss due to saponication (i.e. soap
formation), the oil and alcohol should be dry and the
oil should have a minimum FFA. Biodiesel is recovered
by repeated washing with water to remove glycerol
and methanol. Biodiesel production by the transesteri-
cation method is by two types: catalytic and non-
catalytic.
Catalytic transesterication
The catalysts for the transesterication of triglycerides
are classied as alkali, acid, enzyme or heterogeneous.
Alkali catalysts such as sodium hydroxide, sodium
methoxide, potassium hydroxide and potassium meth-
oxide are more effective [41]. The preferred acid cata-
lysts are sulfuric, hydrochloric and sulfonic. Biodiesel
also can be synthesized by the use of heterogeneous
catalysts. Heterogenous catalysts include enzymes, tita-
nium-silicates, alkaline-earth metal compounds, anion
exchange resins and guanidines heterogenized on
organic polymers [43]. Catalytic transesterication of
vegetable oils/animal fats with methanol is an impor-
tant industrial method used in biodiesel synthesis. Also
known as methanolysis, this reaction is well studied
and established using acids or alkalis, such as sulfuric
acid or sodium hydroxide, as catalysts. However, these
catalytic systems are less active or completely inactive
for long-chain alcohols. Usually, industries use sodium
or potassium hydroxide or sodium or potassium meth-
oxide as catalyst, since they are relatively less expen-
sive and quite active for this reaction [18,44]. The
different catalysts used in transesterication are shown
in Table 2.
Alkali-catalysed transesterication. The transesteri-
cation reaction is catalysed by alkaline metal alkox-
ides [39,53], hydroxides [41,54,55] and sodium or
Table 2. An overview of use of different catalysts in transesterication for biodiesel production.
Type of catalyst Used feedstock
Homogeneous alkali catalysts Pretreated/rened vegetable oils
(NaOH, KOH)
Heterogeneous alkali catalysts Pretreated/rened
(CaO, ZnO, mixed oxides) vegetable oils
Homogeneous acid catalysts Waste and crude vegetable oils
(H2SO4, HCl) containing large amount of FFA
Heterogonous acid Suitable for waste and crude
catalysts (AC vegetable
supported-SO3H, SBA-15, HPA, oils containing large amount of FFA
etc.)
Enzyme (lipase) Suitable for pretreated/rened
vegetable oils as well as waste and
crude vegetable oils containing
large
amount of FFA
Ionic liquids Depends on the nature of IL used; for
acidic, waste and crude oils or and
for
basic, rened or pretreated oils
Carbon based Depends on the nature of the catalyst; <90
catalysts for acidic, waste and crude oils or
and
for basic, rened or pretreated oils
% Yield Benet of using homogeneous catalyst
9698  Reaction rate is very fast
 Mild condition required for reaction
 Low cast and widely available (NaOH, KOH)
<90  Comparatively faster reaction
 Reactions are low energy intensive
 Occur at mild conditions
 Separation of product is very easy by ltration
Up to  Free from FFA and water content in the oil
99  Esterication and transesterication reactions can
simultaneously catalyse
 This catalyst system preferable for low grade
feedstock oil with very
high FFA content (e.g., waste cooking oil, crude
non-edible oils)
 Saponication reaction not taking place
<90  Free from FFA and water content in the oil
 Esterication and transesterication reactions can
simultaneously catalyse
 Easy separation of catalyst from product and
reusability
 Saponication reaction not taking place
 Non-corrosive to reactor and reactor parts
99  Free from FFA and water content in the oil
 Purication steps are simple
 Mild reaction conditions required
 Low alcohol/oil ratio required
 Ionic liquid can act as both solvents and catalyst
 Separation of products is easy
 Depending upon its chemical properties, can act as
both acid or base catalyst
 This catalyst system can be reused
 Synthesis route is simple
 Inexpensive
 High thermal stability of catalyst
 Large surface area and uniform distribution of
active particles
Drawback of using homogeneous catalyst References
 Pre-treatment required for vegetable oils as feedstock (FFAso1 wt%) which will [45,46]
increase the production cost of biodiesel.
 Sensitive to water and FFA can cause soap formation if high amount of catalyst
is used.
 Recyclability of catalyst is very difcult
 Pre-treatment required for vegetable oils as feedstock (FFAso1 wt%) which will [15,47];
increase the production cost of biodiesel.
 Sensitive to water and FFA can cause soap formation if high amount of catalyst
is used.
 Catalyst leaching may result in product contamination
 Rate of reaction are very slow [24,48]
 Corrosive nature of acids like H2SO4, HCl
 Problem of corrosion on reactor and pipelines
 Catalyst recovery is not easy
 High concentration of catalyst can increase the acid value of biodiesel, requiring
extensive washings which generate huge amount of wastewater
 Requires high alcohol/oil ratio
 Rates of reaction are very slow compared to alkali catalysts [49,50]
 In some cases it is a complicated and expensive synthesis route
 Energy demanding, requires high alcohol/oil ratio
 Catalyst leaching may result in product contamination
 Reaction rate are slower, even slower than acid-catalysed transesterication [51,52]
 Highly expensive
 It is sensitive to alcohol, typically methanol that can deactivate the enzyme
 High cost [15]
 Slow reaction rate compared to the conventional catalytic systems even for basic
ionic liquids
 Separation of ionic liquids and glycerine is difcult
 Reaction rates are slow [15,47].
 Leaching
 High methanol to oil molar ratio used
BIOFUELS
7
8 V. K. MISHRA AND R. GOSWAMI
potassium carbonates [18,56,57]. Alkaline catalyst-
based transesterications show high conversions for
obtaining vegetable oils with high quality, but the oils
contain signicant amounts of FFA which do not con-
vert into biodiesels but into soap [58]. These FFA react
with the alkaline catalyst to produce soaps which hin-
der the separation of biodiesel, glycerine and wash
water [59]. Triglycerides are readily transesteried
batchwise in the presence of an alkaline catalyst at
atmospheric pressure and 6070 C temperature with
an excess amount of methanol [11]. The alkali (NaOH
or KOH) catalytic transesterication reaction is a more
time-consuming process. In addition, removal of these
catalysts is technically difcult and brings extra costs
to the nal product [60,61]. Alkoxides of alkaline group
element (as CH3ONa for the methanolysis) are the
highly active catalysts, since they give very high yields
(>98%) in short reaction times (30 min) even if they
are applied at low molar concentrations (0.5 mole %).
Hydroxides of alkaline elements (KOH and NaOH) are
cheaper than metal alkoxides but comparatively less
active. However, these are a good alternative since
they can give the same high conversions of vegetable
oils just by increasing the catalyst concentration to 1
2 mole % [62]. The most economic thing about this
transesterication process is that some of the metha-
nol can be recovered and that glycerine (used in phar-
maceuticals and other applications) is produced as a
by-product. In this process, the glycerin needs to be
removed continuously otherwise it will convert to
formaldehyde or acetaldehyde when burned; both are
health hazards [18].
Acid-catalysed transesterication. The transesteri-
cation process is catalysed by sulphuric [63,64], hydro-
chloric [64,65] or organic sulphuric acids [18]. The
reaction was conducted at four different catalyst con-
centrations, 0.5, 1.0, 1.5 and 2.25 M HCl in the presence
of 100% excess alcohol and the result was compared
with 2.25 M H2SO4 and the decrease in viscosity was
observed [66]. H2SO4 has superior catalytic activity in
the range of 1.52.25 M concentration. In general, acid-
catalysed reactions are performed at high alcohol-to-
oil molar ratios, low-to-moderate temperatures and
pressures, and high concentration of acid catalyst.
Acid-catalysed reactions for biodiesel production
require high alcohol-to-oil molar ratios to obtain good
product yields in practical reaction times. However,
biodiesel yields do not proportionally increase with
molar ratio. For example, for soybean methanolysis
using sulphuric acid as catalyst, ester formation signi-
cantly improved from 77% using a methanol-to-oil
ratio of 3.3:1 to 87.8% with a ratio of 6:1. Higher molar
ratios gave only moderate improvement until reaching
a maximum value at 30:1 ratio (98.4%) [67]. Even with
its insensitivity to FFA in the feedstock, acid-catalysed
transesterication has been largely ignored mainly
because of its relatively slower reaction rate [68].
Enzyme-catalysed transesterication. Transesterica-
tion can also be catalysed by enzymes. The most com-
monly used enzyme for transesterication is lipase.
Lipase of different organisms are reported such as Can-
dida antarctica [69,70], Candida rugasa [71], Pseudomo-
nas cepacia [72,73], immobilized lipase (Lipozyme
RMIM) [74,75], Pseudomonas sp. [76] and Rhizomucor
miehei [76,77]. The enzymatic transesterication of soy-
bean oil with methanol and ethanol was investigated
using a commercial, immobilized lipase (Lipozyme
RMIM) [74]. In this investigation, the best conditions
were observed in a solvent-free system with ethanol/
oil molar ratio of 3.0, temperature of 50 C, and enzyme
concentration of 7.0% (w/w). They obtained a yield of
60% and reaction duration was 1 h. Shah and
Gupta [73] obtained a 98% yield by using P. cepacia
lipase immobilized enzyme on celite material at 50 C
in the presence of 45% (w/w) water and duration was
8 h. As for the enzyme-catalysed system, the transes-
terication reaction is more time consuming than the
other two catalytic methods of transesterication [68].
The lipase of both extracellular and intracellular will
catalyse the transesterication of triglycerides in either
aqueous or non-aqueous systems effectively. Enzy-
matic catalysed transesterication methods can over-
come the problems mentioned above either by alkali-
or acid-catalysed transesterication [7].
The disadvantage of the lipase-catalysed process is
the high cost of the lipases used as catalyst [69]. The
enzyme reactions are very specic and chemically
clean. Due to the alcohol acting as inhibitory to the
enzyme, a specic strategy is to feed the alcohol into
the reactor in three steps of 1:1 mole ratio each. The
reaction rate is very slow, with a three-step sequence
requiring 440 h, or more. The reaction conditions are
modest, from 3545 C [78].
Non-catalytic supercritical methanol
transesterication
The transesterication of triglycerides for production of
biodiesel by supercritical alcohol such as supercritical
methanol (SCM), ethanol, propanol and butanol has
proved to be a most promising process [79]. The critical
temperatures and critical pressures varies with alco-
hol [18]. Saka and Kusdiana [80] developed a catalyst-
free method for biodiesel production by employing
supercritical methanol. The supercritical treatment at
350 C, 43 MPa and 240 s with a molar ratio of 42 in
methanol is the optimum condition for transesterica-
tion of rapeseed oil to biodiesel fuel. Demirbas [60]
observed the changes in percentage yield of methyl
esters (biodiesel) with supercritical methanol method
with a molar ratio of 41. The critical temperature and
the critical pressure of methanol were 512.4 K and

8.0 MPa, respectively. He concluded that increasing the
reaction temperature, especially supercritical tempera-
tures, had a favourable inuence on ester conversion.
For ethanol, the critical temperature and the critical
pressure were 516.2 K and 6.4 MPa, respectively. The
non-catalyst options are designed to overcome the
reaction initiation lag time due to the extremely low
solubility of the alcohol in the triglyceride phase.
Another method which is phasing to commercializa-
tion is the use of a co-solvent. Tetrahydrofuran (THF)
acts as a co-solvent which solubilizes the methanol.
With this technique, reaction duration decreases, i.e. 5
10 min, and there are no catalyst residues in either the
ester or the glycerol phase. THF as a co-solvent is
chosen, in part, because its boiling point is very
close to methanol. This method requires a temperature
of 30 C. A non-catalytic approach is the use of a
high (42:1) alcohol to oil ratio, with supercritical
conditions (350400 C and more than 80 atm or
1200 psi). The reaction duration is about 4 min [78].
The reaction by supercritical methanol has some
advantages [81]:
1. Glycerides and free fatty acids are reacted with
equivalent rates.
2. Diffusion problems are eliminated by the homo-
geneous phase.
3. The process tolerates water in the feedstock; the
catalytic process requires the periodical removal
of water in the feedstock or in the intermediate
stage to prevent catalyst deactivation.
4. The catalyst removal step is eliminated.
5. If high methanol:oil ratios are used, total conver-
sion of the oil can be achieved in a few minutes.
Some disadvantages of the one-stage supercritical
method are:
1. Very high operational pressures (2540 MPa)
required.
2. The high temperatures required so heating and
cooling costs are very high.
3. High methanol:oil ratios (usually set at 42)
involve high costs for evaporation of the
unreacted methanol.
4. The process does not explain how to reduce free
glycerol to less than 0.02%.
Effect of reaction parameters on conversion
yield of transesterication
Effect of free fatty acid and moisture
In the transesterication process the FFA and moisture
content are key parameters for determining the viabil-
ity of the vegetable oil [41]. In this process, FFA and
water always cause a negative effect. The presence of
BIOFUELS 9
FFA and water causes soap formation. This process
consumes catalyst and reduces catalyst effectiveness,
both of which result in a low conversion to biodie-
sel [82]. Available water has negative effects on the
yields of methyl esters in catalysed transesterication
methods [79]. In acid-catalysed transesterication, fatty
acids can be formed by the reaction of carbocation II in
the presence of water in the reaction mixture [83].
FFA reacts with the alkaline catalyst to produce
soap. Soap production in alkali-catalysed transesteri-
cations creates difculty in separation of the biodiesel,
glycerin and wash water [59]. For continuous reaction
by the base catalyst to completion, a FFA value lower
than 3% is needed [41].
The presence of water has been more negative
effect on trans esterication than that of the FFAs. Ma
et al. [28] reported the transesterication of beef tallow
catalysed by sodium hydroxide (NaOH) in the presence
of FFA and water. The water and FFA content of the
beef tallow had to be maintained below 0.06 wt% and
0.5 wt%, respectively. Using NaOH catalysed transester-
ication, methyl esters can usually be prepared in high
yields for low FFA oils, being nearly quantitative for the
palm oils containing <1% FFA. For example, the yield
of methyl esters from RBD (rened, bleached, deodor-
ized) palm oil with about 0.05% FFA was 98% [83].
The effect of molar ratio and type of alcohol
One of the most important factors that affect the yield
of ester from the transesterication reaction is the
molar ratio of alcohol to triglyceride. Although the stoi-
chiometric molar ratio of methanol to triglyceride for
transesterication is 3:1, higher molar ratios are used
to enhance the solubility and to increase the contact
between the triglyceride and alcohol molecules [84].
Higher molar ratios result in greater ester conversion in
a shorter duration. In the transesterication of peanut
oil with ethanol, a 6:1 molar ratio liberated signicantly
more glycerine than a ratio of 3:1 [85].
The effects of molar ratio on the transesterication
of sunower oil with methanol were investigated by
Freedman et al. [53]. They obtained the results for sun-
ower oil transesterication, in which the molar ratio
varied from 6:1 to 1:1 and concluded that 98% conver-
sion to ester was obtained at a molar ratio of 6:1. The
transesterication of Rice bran oil with methanol was
studied at molar ratios of 4:1, 5:1 and 6:1. At molar
ratios of 4:1 and 5:1, there was signicant increase in
yield when the reaction time was increased from 4 to
6 h. Among the three molar ratios studied, ratio 6:1
gave the best results. Noureddini et al. [84] reported
that at all mixing levels the molar ratio of 8:1 results in
signicantly higher conversions than 6:1. The molar
ratio is much more effective than the catalyst on the
transesterication reaction [86]. The molar ratio is asso-
ciated with the type of catalyst used. Acid-catalysed
10 V. K. MISHRA AND R. GOSWAMI
transesterication reactions require the use of high
alcohol-to-oil molar ratios to obtain good product
yields in practical reaction times. However, the yield of
ester does not proportionally increase with molar ratio.
For example, for soybean methanolysis using sulphuric
acid, ester formation signicantly improved from 77%
using a methanol-to-oil ratio of 3.3:1 to 87.8% with a
ratio of 6:1. Higher molar ratios of methanol-to-oil
showed only moderate improvement until reaching a
maximum value at a 30:1 ratio (98.4%) [67]. The effect
of molar ratio of dibutyltin oxide to dimethyl carbonate
(DMC) on the transesterication of DMC with phenol
was in the presence of triic acid (Bu2SnO/CF3SO3H =
1/1) at 180 C transesterication studies. The yields of
methyl phenyl carbonate (MPC) and diphenyl carbon-
ate (DPC) increased rapidly with increasing molar ratio
of dibutyltin oxide/DMC = 0.02. Above 0.02, however,
the yields of MPC and DPC remained unchanged [87].
Canakci and Gerpen [88] reported the effects of differ-
ent alcohol types on acid-catalysed transesterication
of pure soybean oil. They obtained yields of 87.8 and
to 95.8% after 48 and 96 h of reaction.
Catalyst effect
Catalysts used for the transesterication of triglycerides
are alkali, acid or enzyme. Alkali-catalysed transesteri-
cation is much faster than acid-catalysed transesteri-
cation and is most often used commercially [10].
May [83] investigated the effect of different catalysts
on methanolysis of RBD palm oil with a low FFA con-
tent of <0.1%. In that study, it was found that Na,
NaOH and KOH were the most effective catalysts. The
authors investigated the effect of different catalyst
concentrations on base catalysed transesterication
during biodiesel production from vegetable oil by
means of ultrasonic energy [55]. The best yields of
ester were obtained when the catalyst was used in
small concentration, i.e. 0.5% wt/wt of oil. Meneghetti
et al. [89] investigated the effect of different types of
catalyst at variable temperatures during the produc-
tion of free and bound ethyl ester (FAEE) from castor
oil. Results from the different studies showed that
hydrochloric acid is much more effective than sodium
hydroxide at higher reaction temperatures. The results
of different catalyst studies are shown in Table 2.
The effect of temperature and time
Transesterication can occur at different temperatures
depending on the type of vegetable oil or fat
used [10,41]. Few reports are available for the transes-
terication reaction at room temperature [9092]. Enci-
nar et al. [90] studied the transesterication reaction
with ethanol of Cynara cardunculus L. oils using alkali
catalyst sodium and potassium hydroxides and
reported 91.6% conversion at room temperature. For
palm oil transesterication with methanol (6:1) and 1%
KOH, the reaction was examined at different tempera-
tures [93]. After 4 min, ester yields were 73 and 82% for
50 and 65 C, respectively. The effect of reaction tem-
perature on production of propyl oleate was examined
at 4070 C with free immobilized P. uorescens
lipase [94]. The conversion ratio to propyl oleate was
observed to be highest at 60 C, whereas the activity
decreased at 70 C.
Scientists have employed a microwave system to
heat the chemical reactions on both laboratory and
industrial scales. Transesterication can be imple-
mented in both batch and continuous-ow systems, of
which batch is the most common process due to its
simplicity. In comparison with conventional heating, a
microwave heating system is an effective instrument
to speed up the transesterication [30].
Properties and qualities of biodiesel
Biodiesel quality advancements are being developed
globally. When biodiesel is produced from different
scale plants of varying origins, property and qualities, it
is necessary to have a standardization of biodiesel
quality to ensure engine performance without any dif-
culties [3,23,25]. Austria was the rst country to dene
and approve standards for rapeseed oil methyl esters
as a diesel fuel. The standard properties and qualities
of biodiesel have been dened in France, Germany,
Italy, the Czech Republic and the US [3,41]. The proper-
ties and qualities of biodiesel must hold with interna-
tional biodiesel standard specications. These
specications take account of the American Standards
for Testing Materials (ASTM 6751-3) or the EU (EN 14
214) Standards for biodiesel fuel [21]. There are also
standards from Germany (DIN 51 606), Austria (ON)
and the Czech Republic (CSN) [25]. The properties or
quality of biodiesel are characterized through physico-
chemical properties. Some of these properties are CN,
caloric value (MJ/kg), density (kg/m3), viscosity (mm2/
s), cloud and pour points ( C), ash point ( C), acid
value (mg KOH/g-oil), ash content (%), water content
and sediment, copper corrosion, distillation range, car-
bon residue, sulphur content, glycerine presence (%
m/m), phosphorus (mg/kg) and oxidation stability. The
chemical and physical properties of biodiesel depend
on the type of raw material (i.e. feedstock) and their
composition of fatty acids [3,21,25,95].
Viscosity
Viscosity describes the ability of a fuel to ow. This
characteristic plays an important role in the operation
of fuel injection equipment and spray atomization,
mostly at low temperatures when the increase in vis-
cosity affects the uidity of the fuel. The viscosity of
biodiesel is 1015 times greater than that of diesel

derived from fossil fuels. This is due to its large molecu-
lar mass and large chemical structure [3]. At low tem-
peratures, biodiesel becomes highly viscous or may
even solidify. The higher viscosity of biodiesel can
affect the volume ow and injection spray characteris-
tics in the engine. At low temperatures, it may even
compromise the mechanical integrity of the injection
pump drive systems. The maximum acceptable limit of
viscosity according to ASTM D445 ranges are 1.96.0
mm2/s and 3.55.0 mm2/s in EN ISO 3104 [3,23,9598].
Fuel density and relative density
Weight per unit volume denes the density of a fuel.
Oils are denser having more energy [3]. The density of
biodiesel can measured according to EN ISO 3675/12
185 and ASTM D1298 standard. With this reference
standard, density should be tested at the temperature
reference of 15 or 20 C [99]. Relative density is the den-
sity of the fuel compared to the density of water. The
relative density of biodiesel is required to make mass
to volume conversions, calculate ow and viscosity
properties, and is used to determine the homogeneity
of biodiesel tanks [3].
Flash point
Flash point is the temperature at which the fuel will
ignite when exposed to a ame. Fuel volatility varies
inversely with ash point. The ash point of biodiesel is
higher than the prescribed limit of petroleum diesel,
which is safe for transport, handling and storage pur-
pose [21,41,95]. Biodiesel has a ash point greater than
150 C, while conventional diesel fuel has a ash point
of 5566 C. Demirbas [100] stated that the ash point
values of fatty acid methyl esters are signicantly lower
than those of vegetable oils. The limit of ash point in

ASTM D93 is 93 C and in EN ISO 3679 is
120 C [3,97,101].
Cloud point, pour point and cold lter plugging
point (CFPP)
The characteristics of biodiesel at low temperatures is
an important quality criterion. Partial or full solidica-
tion of the fuel may cause blockage of the fuel lines
and lters, leading to fuel starvation, problems of start-
ing, driving and engine damage due to inadequate
lubrication. The cloud point of biodiesel is the temper-
ature at which wax crystals rst become visible when
the fuel is chilled. Pour point is the specic tempera-
ture at which the total wax out of solution is sufcient
to gel the fuel. Pour point is the lowest temperature at
which the fuel can ow. For the measurement of pour
point, ASTM D2500, EN ISO 23 015 and D97 procedures
are used. Biodiesel has higher cloud point and pour
point compared to conventional diesel [3,97,102]. Cold
BIOFUELS 11
lter plugging point (CFPP) is the temperature at which
the test lter starts to plug because fuel constituents
have started to crystallize or gel. CFPP is used as indica-
tor of low temperature operability of fuels and reects
their winter weather performance. At low operational
temperature, fuel may thicken and might not ow
properly which affects the performance of fuel lines,
fuel pumps and injectors. CFPP denes the fuels lter-
ability limit, having a better correlation than cloud
point for biodiesel as well as diesel. CFPP is measured
using ASTM D6371 [3,41,95].
Cetane number
The sign of ignition characteristics or ability to auto
ignite quickly after being injected is known as the CN
of fuel. Better ignition quality is always associated with
higher CN value [3]. For using as biodiesel, CN is one of
the most important parameters considered during the
methyl esters selection procedure [41,95,97,103]. CN
increases with increasing fatty acid chain length and
increasing saturation. A higher CN represents the
shorter time between the ignition and the initiation of
fuel injection into the combustion chamber of the
engine [104,105]. Biodiesel has higher CN than conven-
tional petroleum diesel fuel, which indicates higher
combustion efciency. CN of diesel specied by ASTM
D613 is 47 min and EN ISO 5165 is 51.0 min [105].
Titre
The temperature at solidied oil change to liquid oil is
known as titre [3]. The titre property of fuel is impor-
tant because the transesterication process for biodie-
sel production is fundamentally a liquid process, and
oils with high titre may require heating, which
increases the energy requirements and production
costs for a biodiesel plant [104].
Oxidation stability of fuel
The oxidation property of fuel is one of the valuable
factors that helps assess the quality of biodiesel. Oxida-
tion stability is an indication of the measure of oxida-
tion, potential reactivity with air, and the need for
antioxidants [3]. Oxidation takes place because of the
unsaturated fatty acid chains presence and the double
bond in a molecule, which react immediately with the
air oxygen after exposure [21]. The chemical composi-
tion of biodiesel fuels makes it more susceptible to oxi-
dative degradation than fossil diesel fuel. The
Rancimat method (EN ISO 14 112) is the oxidative sta-
bility specication in ASTM D6751 and EN 14 214. A
minimum IP (110 C) of 3 h is required for ASTM D6751,
whereas a more stringent limit of 6 h or more is speci-
ed in EN 14 214 [106].
12 V. K. MISHRA AND R. GOSWAMI
Lubrication properties of fuel
Atadashi et al. [21] proposed that the lubrication prop-
erties of biodiesel are more than diesel. The lubrication
properties of a fuel can help to increase the engine
life [3]. Lapuerta et al. [105] stated that FAAE (biodiesel)
have better lubrication properties, but can contribute
to the formation of deposits (plugging of lters)
depending on degradability, glycerol (and other impu-
rities) content, and cold ow properties. Biodiesel pro-
vides signicant lubricity improvement over diesel
fuel [24]. A high value of lubricant property of biodie-
sel might result in reduced friction loss and thus
improve brake effective power [107].
Acid value of fuel
Acid number is also known as neutralization number. It
is a determination of FFA contained in a fresh fuel sam-
ple. FFA are the saturated or unsaturated monocarbox-
ylic acids that occur naturally in fats, oils or greases but
are not attached to glycerol backbones [3]. Fatty acid
varies with carbon chain length and in the number of
unsaturated bonds (double bonds). Higher acid value
indicates a higher amount of FFA. Acid value is
expressed as mg KOH required for neutralizing 1 g of
FAME. The effect of higher acid content causes severe
corrosion in the fuel supply system of an engine. Acid
value is determined using ASTM D664 and EN 14 104.
Both standards approved a maximum acid value for
biodiesel of 0.50 mg KOH/g [108]; [97,109].
Free glycerin
Free glycerol refers to the amount of glycerol remain-
ing in the nished biodiesel. The amount of free glyc-
erol in biodiesel is dependent on the process of
production. The availability of glycerol in biodiesel may
be due to insufcient separation during washing of the
ester product. Glycerol is insoluble in biodiesel so
almost all of the glycerol is easily removed by settling
or centrifugation. Free glycerol can cause injector cok-
ing and damage to the fuel injection. ASTM specica-
tion requires that the total glycerol should be less than
0.24% of the nal biodiesel product. It is measured by
using a gas chromatographic method described in
ASTM D6584 and EN 14 105/14 106. This property has
limit maximum of 0.02% [97,110].
Total glycerol
Total glycerin is calculation of how much triglyceride
leftovers into methyl esters. Total glycerin is the sum of
free glycerin, monoglycerides, diglycerides and trigly-
cerides [111]. Each transesterication reaction step pro-
duces a molecule of a methyl ester of a fatty acid. If the
reaction is incomplete, then there will be triglycerides,
diglycerides and monoglycerides left in the reaction
mixture. Each of these compounds still contains a glyc-
erol molecule that has not been released. The glycerol
portion of these compounds is referred to as bound
glycerol. When the bound glycerol is added to the free
glycerol, the sum is called total glycerol. According to
ASTM specication, total glycerol must be less than
0.24% of the nal biodiesel product as measured using
the gas chromatographic method described in ASTM D
6584 and 0.25% in EN 14 105 [3].
Available water and sediment in fuel
Water and sediment contamination in biodiesel are
housekeeping issues. The presence of water can be in
two modes: dissolved water or suspended water drop-
lets. While biodiesel is normally considered to be insol-
uble in water, it takes up considerably more water than
diesel fuel. Biodiesel can contain as much as 1500 ppm
of dissolved water while diesel fuel usually contains
50 ppm. Sediment may be suspended rust and dirt par-
ticles or it may originate from the fuel as insoluble
compounds formed during fuel oxidation [97,112].
Water in the fuel generally causes corrosion of engine
fuel system components. The most direct form of cor-
rosion is rust, but water can become acidic with time
and the resulting acid corrosion can attack fuel storage
tanks. Water contamination can lead to microbial
growth. Yeast, fungi and bacteria can grow at the inter-
face between the fuel and water at the bottom of a
storage tank. These organisms produce sludges and
slimes that can cause lter plugging. Some of the
organisms can convert the sulphur in to the sulphuric
acid which can corrode metal fuel tanks. The standard
of water content and sediment for biodiesel in ASTM
D2709 and EN ISO 12 937 specications is 0.05 (vol %)
max [97,110].
Ash of sulphate
Ash content describes the amounts of inorganic con-
taminants such as abrasive solids, residue of catalyst
and soluble metal soaps contained in the fuel. The bio-
diesel is ignited and burned and then treated with sul-
phuric acid to determine the percentage of sulphated
ash present. ASTM D874 standard mentions that the
samples can have a maximum 0.02% of sulphated
ash [97].
Carbon residue
Carbon residue of the fuel expresses the carbon
depositing property of fuel after combustion. Carbon
residue shows a high correlation with presence of FFA,
higher unsaturated fatty acids, soaps, glycerides, poly-
mers and inorganic impurities. Although it is not only
composed of carbon, the term carbon residue is found

in all standards. The range of limit of carbon residue
standard ASTM D4530 is max. 0.050% (m/m) and EN
ISO10370 is max. 0.30% (m/m) [95,97].
Corrosion of copper strip
The copper corrosion test evaluates the corrosion pro-
pensity of fuel when used with copper, brass or bronze
parts. A copper strip is warmed to 50 C in a fuel bath
for 3 h followed by comparison with a standard strip to
determine the degree of corrosion. Corrosion resulting
from biodiesel might be induced by some sulphur
compounds by acids; thus, this parameter is correlated
with acid number. ASTM D130 standard mentions that
the samples can have class 3 and EN ISO 2160 has class
1 [97].
Cold soak ltration
Cold soak ltration is the newest property of biodiesel
in ASTM D6751. The cold soak ltration test is done to
determine if crystals form at low temperatures and do
not re-dissolve when the biodiesel goes back to a
higher temperature. ASTM D6751 procedure involves
chilling 300 mL of biodiesel fuel for 16 h at 4.44 C, and
then allowing the sample to warm to room tempera-
ture. When the sample has warmed to 2022 C, it is l-
tered through a 0.7 mm pore size lter paper. The time
for all 300 mL to pass through the paper is reported in
seconds. The maximum permissible test result for cold
soak ltration is 360 s [3].
Visual inspection
The visual inspection test of biodiesel is used to nd
the presence of water and particulates. The haze value
is found by placing a chart behind a clear jar of biodie-
sel and referencing how the lines compare to six differ-
ent pictures with haze ratings from 1 to 6, with 1 being
the least amount of particulates and 6 being the high-
est. A haze rating of 1 is the clearest, i.e. no water and
particulate matter; while a haze rating of 6 means that
the biodiesel is very cloudy, i.e. water and particulate
matter. Visual inspection of biodiesel is usually deter-
mined by ASTM D4176, Standard Test. Method for Free
Water and Particulate Contamination in Distillate Fuels
(Visual Inspection Procedures), Procedure 2 [3].
Presence of phosphorous, calcium and magnesium
According to ASTM D6751, phosphorous content in
biodiesel must be less than 10 ppm, and calcium and
magnesium combined must be less than 5 ppm. Pres-
ence of phosphorous is determined by using ASTM
D4951. Calcium and magnesium are determined using
EN Standard 14 538 [3].
BIOFUELS 13
Advantages and disadvantages of biodiesel
Several advantages are associated with biodiesel. Bio-
diesel fuel has 1011% oxygen. This makes a fuel with
high combustion characteristics [21,23,103,113115].
Burning of biodiesel produces 78% less CO2 on a life-
cycle basis when compared to conventional diesel fuel.
It also produces less smoke due to free soot [113]. It is
renewable, non-toxic, non-ammable, portable, readily
available, biodegradable, sustainable, eco-friendly and
free from sulphur and aromatic content. This property
makes biodiesel an ideal fuel for heavily polluted cities
and urban areas. Biodiesel also produces less particular
matter in the ambient air and hence reduces air toxic-
ity; therefore, it provides a 90% reduction in cancer
risks and neonatal defects due to its less polluting com-
bustion [2,23,98,113]. Biodiesel production facilitates
rural development to recycle degraded lands. In addi-
tion, biodiesel has good potential for rural employment
and economic gain [114]. Biodiesel is climate neutral,
an important element of energy use and develop-
ment [23,113,114]. The CN of biodiesel (6065 depend-
ing on the vegetable oil) is higher than petroleum
diesel [103] thus it reduces ignition delay [2,23,98,115].
Biodiesel production can be increased easily. Produc-
tion of biodiesel requires less time compared to petro-
leum diesel because there is no need for drilling,
transportation or rening. Each country can produce
biodiesel locally. There is no requirement to pay tariffs
or similar taxes to the countries from which oil and
petroleum diesel is imported [115]. Biodiesel has good
lubricity properties which improves lubrication in fuel
pump and injector units. Increased lubrication
decreases engine wear and increases engine ef-
ciency [23,98]. Biodiesel is very safe for transportation,
handling, distribution, utilization and storage due to its
higher ash point (100170 C) than petroleum diesel
(6080 C) [2]. Biodiesel deceases the environmental
effects of waste products and can be made from used
cooking oils and lards [115]. Biodiesel may not require
engine modication up to B20, however higher blends
may need some minor modications [35].
Disadvantages are also associated with biodiesel. It
has 12% lower energy content than petroleum diesel,
leading to an increased fuel consumption of 210%.
Biodiesel has higher cloud point, pour point, and nitro-
gen oxide emissions than diesel. Biodiesel has lower
volatilities that cause the formation of deposits in
engines because of incomplete combustion character-
istics [2,3,23,98]. It causes unnecessary carbon deposi-
tion and gum formation (polymerization) in engines
and the oil gets contaminated and suffers from ow
problem. Biodiesel has comparatively high viscosity
(1118 times petroleum diesel) and lower volatility
than petroleum diesel and thus needs higher injector
pressure [115]. Biodiesel stability of oxidation is lower
than petroleum diesel. Biodiesel can be oxidized into
14 V. K. MISHRA AND R. GOSWAMI
fatty acids in the presence of air and causes corrosion
of fuel tanks, pipes and injectors [95,115]. Biodiesel has
a high oxygen content, thus it produces relatively
higher NOx levels than diesel in the range of 1014%
during combustion [3,95]. Biodiesel can cause corro-
sion in vehicle materials (cooper and brass) such as
fuel system blockages, seal failures, lter clogging and
deposits at injection pumps [95]. Most biodiesels
(more than 95%) are derived from edible oil. Many
reports claim that this may give rise to further eco-
nomic problems. By converting edible oils into biodie-
sel, food resources are being used as automotive fuels.
Large-scale production of biodiesel from edible oils
may create global imbalance in the food supply-and-
demand market [98]. Low engine speed and power,
high price, high engine wear and engine incompatibil-
ity are the main disadvantages [98]. If the transesteri-
cation process is not economic then the cost of the
fuel increases. These oils require expensive fatty acid
separation or expensive acid catalysts [3,95]. Transes-
terication has environmental effects such as waste
disposal and water requirement for washing and soap
formation. [3,95].
Conclusion
Energy is a primary requirement to preserve economic
growth and maintain standards of human growth
index. The transportation sector is the second largest
energy demanding sector after the industrial sector
and accounts for 30% of total delivered energy. Nearly
all fossil fuel energy consumption in the transportation
sector is from oil (97.6%). However, the expected
decrease of fossil fuels and the environmental prob-
lems associated with burning them has encouraged
many researchers to investigate the possibility of using
alternative fuels. Biodiesel is a very promising resource.
The two key reactions in biodiesel production are
esterication and transesterication. These reactions
are inuenced mainly by the type of feedstock oil, reac-
tion conditions, catalyst used, and alcohol to oil molar
ratio. The wide range of available feedstocks for biodie-
sel production represents one of the most important
advantages of the production of biodiesel. Selecting
the best feedstock is vital to ensure the low production
cost of biodiesel. Extraction of the oil is the second
step in biodiesel production. There are three popular
methods that have been identied for extraction of
the oil: mechanical, solvent and enzymatic oil extrac-
tion. There are two aspects to the production costs of
biodiesel: by-product recovery and the transesterica-
tion process. A continuous transesterication process
is the best choice to lower the production costs of bio-
diesel. Biodiesel properties must hold with the interna-
tional biodiesel standard specications such as the
American Standards for Testing Materials (ASTM 6751-
3) or the EU (EN 14 214). The recovery of glycerol is
another way to reduce the production costs. Because
water is present in the system, the biodiesel glycerol is
more concentrated. Biodiesel properties are character-
ized by physicochemical properties including CN, den-
sity, viscosity, cloud and pour points, ash point, acid
value, copper corrosion, glycerine and oxidation
stability.
Future prospects for biodiesel
Acceptance of the Kyoto protocol and clean develop-
ment mechanism (CDM) will lead to more biodiesel
production around the world. Production of biodiesel
is expanding rapidly, driven by energy security and
other environmental concerns. Given geographic dis-
parities between demand and supply potential and
supply cost, expanded trade in biodiesel makes sense.
The global potential for biodiesel production is not
clear, but it could supply a substantial percentage of
transport fuel demand. With the increase in global
human population, more agricultural land will be
needed to produce food for human consumption.
Thus, the insufcient lands could increase the produc-
tion cost of biodiesel feedstock. These problems are
already being experienced in Asia where vegetable oil
prices are relatively high. The same trend will eventu-
ally occur in the rest of the world. Therefore, non-edi-
ble oil, genetically engineered plants and microalgae
feedstock are possible solutions to this problem and
can ensure the sustainability of biodiesel production in
the future. Supporting policies are important to pro-
mote biodiesel research and make their prices compet-
itive with other conventional sources of energy.
Further developments in the use of by-products will
enhance the economic viability of the biodiesel pro-
duction process overall.
Disclosure statement
No potential conict of interest was reported by the authors.
References
[1] International Energy Agency (IEA). World energy out-
look 2007. OECD/IEA, Paris 2007. Available from: http://
www.worldenergyoutlook.org/media/weowebsite/
2008-1994/WEO_2007.pdf.
[2] Shahid EM, Jamal J. Production of biodiesel: a technical
review. Renew Sustain Energy Rev. 2011;15(9):4732
4745.
[3] Atabani AE, Silitongac AS, Badruddin IA, et al. A com-
prehensive review on biodiesel as an alternative
energy resource and its characteristics. Renew Sustain
Energy Rev. 2012;16:20702093.
[4] Ahmad AL, Mat Yasin NH, Derek CJC, et al. Microalgae
as a sustainable energy source for biodiesel produc-
tion: a review. Renew Sustain Energy Rev. 2011;15
(1):584593.

[5] U.S. Energy Information Administration. International
energy outlook 2010. 2010. Available from: http://
www.eia.doe.gov/oiaf/ieo/pdf/0484%282010%29.pdf;
[cited 22.02.11].
[6] Bartholomew D. Vegetable oil fuel. J Am Oil Chem Sot.
1981;58:286A288A.
[7] Fukuda H, Konda A, Noda N. Biodiesel fuel production
by transestirication of oils. J Biosci Bioeng. 2001;92:
405416.
[8] Shay EG. Diesel fuel from vegetable oils: status and
opportunities. Biomass Bioenerg. 1993;4:227242.
[9] Strayer RC, Blake JA, Craig WK. Canola and high erucic
rapeseed oil as substitutes for diesel fuel: preliminary
tests. J Am Oil Chem Sot. 1983;60:15871592.
[10] Ma F, Hanna MA. Biodiesel production: a review. Biore-
sour Technol. 1999;70:115.
[11] Srivastava A, Prasad R. Triglycerides-based diesel fuels.
Renew Sust Energ Rev. 2000;4:111133.
[12] Moser BR. Biodiesel Production, Properties, and Feed-
stocks. Vitro Cell.Dev BiolPlant. 2009;45:229266.
[13] Fazal MA, Haseeb ASMA, Masjuki HH. Biodiesel feasibil-
ity study: an evalua-tion of material compatibility; per-
formance; emission and engine durability. Renew
Sustain Energy Rev. 2011;15(2):13141324.
[14] Silitonga AS, Atabani AE, Mahlia TMI, et al. A review on
prospect of Jatropha curcas for biodiesel in Indonesia.
Renew Sustain Energy Rev. 2011;15:37333756.
[15] Konwar LJ, Boro J, Deka D. Review on latest develop-
ments in biodiesel production using carbon-based cat-
alysts. Renew Sustain Energ Rev. 2014;29:546564.
[16] Pacic biodiesel. 2017. Available from: http://www.bio
diesel.com/biodiesel/history.
[17] Owolabi RU, Adejumo AL, Aderibigbe AF. Biodiesel:
Fuel for the Future (A Brief Review). Int J Energ Eng.
2012;2(5):223231.
[18] Balat M, Balat H. A critical review of biodiesel as a
vehicular fuel. Energ Convers Manage. 2008;49:2727
2741.
[19] Friedrich MS. A worlwide review of the commercial
production of biodiesel a technological, economic
and ecological investigation based on case studies.
Department of Technology and Sustainable Product
Management (ITNP), Wien, August 26, 2004.
[20] Dufey A. Biofuels production, trade and sustainable
development: emerging issues. Environment Report.
London, UK: International Institute for Environment
and Development (IIED); 2006. Available from: www.
iied.org/pubs.
[21] Atadashi IM, Aroua MK, Abdul Aziz A. High quality bio-
diesel and its diesel engine application: a review.
Renew Sustain Energy Rev. 2010;14(7):19992008.
[22] Janaun J, Ellis N. Perspectives on biodiesel as a sustain-
able fuel. Renew Sustain Energy Rev. 2010;14(4):1312
1320.
[23] Balat M, Balat H. Progress in biodiesel processing. Appl
Energy. 2010;87(6):18151835.
[24] Demirbas A. Biodiesel a realistic fuel alternative for
diesel engines. Springer- Verlag London Limited; 2008,
DOI: 10.1007/978-1-84628-995-8.
[25] Lin L, Cunshan Z, Vittayapadung S, Xiangqian S, et al.
Opportunities and challenges for biodiesel fuel. Appl
Energy. 2011;88(4):10201031.
[26] Bajpai D, Tyagi VK, Biodiesel: Source, Production, Com-
position Properties and its benets. J Oleo Sci. 2006;55
(10):487502.
[27] Seenuvasan M, Selvi PK, Anil KM, et al. Standardization
of non-edible Pongamia pinnata oil methyl ester
BIOFUELS 15
conversion using hydroxyl content and GCMS analy-
sis. J Taiwan Inst Chem Eng. 2014;45(4):14851489.
[28] Ma F, Clements L D, Hanna MA. Biodiesel Fuel from
Animal Fat. Ancillary Studies on Transesterication of
Beef Tallow. Ind. Eng. Chem. Res. 1998, 37(9):3768
3771. DOI: 10.1021/ie980162s.
[29] Li Q, Du W, Liu D. Perspectives of microbial oils for
biodiesel production. Appl Microbiol Biotechnol.
2008;80:749756.
[30] Soltani S, Rashid U, Yunus R, et al. Synthesis of Biodie-
sel through Catalytic Transesterication of Various
Feedstocks using Fast Solvothermal Technology: A
Critical Review. Catal Rev Sci Eng. 2015;00:129.
[31] Achten WMJ, Verchit L, Mathijs Franken YJ, et al. Jatro-
pha biodiesel production and use. Biomass Bioenergy.
2008;32(12):10631084.
[32] Singh SP, Singh D. Biodiesel production through the
use of different sources and characterization of oils
and their esters as the substitute of diesel: a review.
Renew Sustain Energy Rev. 2010;14(1):200216.
[33] ASAE. Vegetable oil fuels. Proceedings of the Interna-
tional Conference on Plant and Vegetable Oils as Fuels.
Backers Leslie, editor. St Joseph, MI: ASAE; 1982.
[34] Anon. Filtered used frying fat powers diesel eet.
JAOCS. 1982;59:780A781A.
[35] Jain S, Sharma MP. Prospects of biodiesel from Jatro-
pha in India: a review. Renew Sustain Energy Rev.
2010;14(2):763771.
[36] Parawira W. Biodiesel production from Jatropha curcas:
a review. Sci Res Essays. 2010;5(14):17961808.
[37] Sharma YC, Singh B, Upadhyay SN. Advancements in
development and char-acterization of biodiesel: a
review. Fuel. 2008;87(12):23552373.
[38] Schwab AW, Dykstra GJ, Selke E, et al. Diesel fuel from
thermal decomposition of soybean oil. JAOCS.
1988;65:17811786.
[39] Schwab AW, Bagby MO, Freedman B. Preparation and
properties of diesel fuels from vegetable oils. Fuel.
1987;66:13721378.
[40] Chisti Y. Biodiesel from microalgae. Biotechnol Adv.
2007;25(3):294306.
[41] Meher LC, Vidya Sagar D, Naik SN. Technical aspects of
biodiesel production by transesterication a review.
Renew Sustain Energy Rev. 2006;10(3):248268.
[42] Xiao MA, Mathew S, Obbard JP. Biodiesel fuel produc-
tion via transesterication of oils using lipase biocata-
lyst. Gcb Bioenergy. 2009;1(2):11525.
[43] Vicente G, Martnez M, Aracil J. Integrated biodiesel
production: a comparison of different homogeneous
catalysts systems. Bioresour Technol. 2004;92:297305.
[44] Macedo CCS, Abreu FR, Tavares AP, et al. New heteroge-
neous metal-oxides based catalyst for vegetable oil
transesterication. J Braz Chem Soc. 2006;17:12911296.
[45] Naik M, Meher LC, Naik SN, et al. Production of biodie-
sel from high free fatty acid Karanja (Pongamia pin-
nata) oil. Biomass Bioenerg. 2008;32:354357.
[46] Meng X, Chen G, Wang Y. Biodiesel production from
waste cooking oil via alkali catalyst and its engine test.
Fuel Process Technol. 2008;89:851857.
[47] Zu Y, Liu G, Wang Z, et al. CaO supported on porous
carbon as highly efcient heterogeneous catalysts for
transesterication of triacetin with methanol. Energ
Fuel. 2010;24:38103816.
[48] Zhang J, Jiang L. Acid-catalyzed esterication of
Zanthoxylum bungeanum seed oil with high free fatty
acids for biodiesel production. Bioresour Technol.
2008;99:89958998.
16 V. K. MISHRA AND R. GOSWAMI
[49] Ji J, Zhang G, Chen H, Wang S, Zhang G, Zhang F, Fan
X. Sulfonated graphene as water-tolerant solid acid
catalyst. Chemical Science. 2011;2(3):4847.
[50] Peng F, Zhang L, Wang H, et al. Sulfonated carbon
nanotubes as a strong protonic acid catalyst. Carbon.
2005;43:24052841.
[51] Naranjoa JC, Co
rdobaa A, Giraldob L, et al. Lipase sup-
ported on granular activated carbon and activated car-
bon cloth as a catalyst in the synthesis of biodiesel
fuel. J Molec Catal B Enzym. 2010;66:166171.
[52] Giraldoa L, Moreno-Piraj
an JC. Lipase supported on
mesoporous materials as a catalyst in the synthesis of
biodiesel from Persea americana mill oil. J Molec Catal
B Enzym. 2012;77:3238.
[53] Freedman B, Buttereld RO, Pryde EH. Transesterica-
tion kinetics of soybean oil. J Am Oil Chem Soc.
1986;63:13751380.
[54] Dmytryshyn SL, Dalai AK, Chaudhari ST, et al. Synthesis
and characterization of vegetable oil derived esters:
evaluation for their diesel additive properties. Biore-
sour Technol. 2004;92:5564.
[55] Stavarache C, Vinatoru M, Nishimura R, et al. Fatty acids
methyl esters from vegetable oil by means of ultra-
sonic energy. Ultrason Sonochem. 2005;12:367372.
[56] Korytkowska A, Barszczewska-Rybarek I, Gibas M. Side-
reactions in the transesterication of oligoethylene
glycols by methacrylates. Des Monom Polym.
2001;4:2737.
[57] Varghaa V, Truterb P. Biodegradable polymers by reac-
tive blending transesterication of thermoplastic
starch with poly(vinyl acetate) and poly(vinyl acetate-
co-butyl acrylate. Eur Polymer J. 2005;41:715726.
[58] Furuta S, Matsuhasbi H, Arata K. Biodiesel fuel produc-
tion with solid superacid catalysis in xed bed reactor
under atmospheric pressure. Catal Commun.
2004;5:721723.
[59] Canakci M, Gerpen JV. A pilot plant to produce biodie-
sel from high free fatty acid feedstocks. Trans ASAE.
2003;46:945955.
[60] Demirbas A. Biodiesel from vegetable oils via transes-
terication in supercritical methanol. Energ Conv
Mgmt. 2002;43:23492356.
[61] Demirbas A. Biodiesel fuels from vegetable oils via cat-
alytic and non-catalytic supercritical alcohol transester-
ications and other methods: a survey. Energy Conv
Mgmt. 2003;44:20932109.
[62] Schuchardta U, Serchelia R, Vargas RM. Transesterica-
tion of vegetable oils: a review. J Braz Chem Soc.
1998;9:199210.
[63] Goff MJ, Bauer NS, Lopes S, et al. Acid-catalyzed alco-
holysis of soybean oil. J Am Oil Chem Soc.
2004;81:415420.
[64] Liu Y, Lotero E, Goodwin Jr JG. Effect of water on sulfu-
ric acid catalyzed esterication. J Molec Catal A Chem.
2006;245:132140.
[65] Lee Y, Park SH, Lim IT, et al. Preparation of alkyl (R)-(2)-
3-hydroxybutyrate by acidic alcoholysis of poly-(R)-(2)-
3-hydroxybutyrate. Enzyme Microb Technol.
2000;27:3336.
[66] Mohamad IAW, Ali OA. Evaluation of the transesteri-
cation of waste palm oil into biodiesel. Bioresour Tech-
nol. 2002;85:25256.
[67] Lotero E, Goodwin JG, Bruce DA, et al. The catalysis of
biodiesel synthesis. Catalysis. 2006;19:4183.
[68] Zhang Y, Dube MA, McLean DD, et al. Biodiesel produc-
tion from waste cooking oil: 1. Process design and
technological assessment. Bioresour Technol.
2003;89:116.
[69] Royon D, Daz M, Ellenrieder G, et al. Enzymatic produc-
tion of biodiesel from cotton seed oil using t-butanol
as a solvent. Bioresour Technol. 2007;98:648653.
[70] Watanabe Y, Shimada Y, Sugihara A, et al. Conversion
of degummed soybean oil to biodiesel fuel with immo-
bilized Candida antarctica lipase. J Mol Catal B Enzym.
2002;17:151155.
[71] Linko YY, Lamsa M, Wu X, et al. Biodegradable prod-
ucts by lipase biocatalysis. J Biotechnol. 1998;66:4150.
[72] Ghanem A. The utility of cyclodextrins in lipase-cata-
lyzed transesterication in organic solvents: enhanced
reaction rate and enantioselectivity. Organic & biomo-
lecular chemistry. 2003;1:128291.
[73] Shah S, Gupta MN. Lipase catalyzed preparation of bio-
diesel from Jatropha oil in a solvent free system. Pro-
cess Biochem. 2007;42:409414.
[74] Bernardes OL, Bevilaqua JV, Leal MCMR, et al. Biodiesel
fuel production by the transesterication reaction of
soybean oil using immobilized lipase. Appl Biochem
Biotechnol. 2007;137140:105114.
[75] De A, Vieira AP, Da Silva MAP, et al. Biodiesel produc-
tion via esterication reactions catalyzed by lipase. Lat
Am Appl Res. 2006;36:283288.
[76] Lai OM, Ghazali HM, Chong CL. Use of enzymatic trans-
esteried palm stearin sunower oil blends in the
preparation of table margarine formulation. Food
Chem. 1999;64:8388.
[77] Skagerlind P, Jansson M, Bergenstahl B, et al. Binding
of Rhizomucor miehei lipase to emulsion interfaces and
its interference with surfactants. Colloids Surf B Bioint.
1995;4:129135.
[78] Van Gerpen J, Shanks B, Pruszko R, et al. Biodiesel ana-
lytical methods: August 2002January 2004. Colorado:
National Renewable Energy Laboratory (NREL); 2004
[NREL/SR-510-36240].
[79] Demirbas A. Biodiesel production via non-catalytic SCF
method and biodiesel fuel characteristics. Energy Conv
Mgmt. 2006;47:22712282.
[80] Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as
prepared in supercritical methanol. Fuel. 2001;80:225
231.
[81] Vera CR, DIppolito SA, Pieck CL, et al. Production of
biodiesel by a twostep supercritical reaction process
with adsorption rening. In: 2nd Mercosur congress on
chemical engineering and 4th Mercosur congress on
process systems engineering (ENPROMER-2005), Rio
de Brasil. August 1418, 2005.
[82] Demirbas D, Karsloglu S. Biodiesel production facilities
from vegetable oils and animal fats. Energy Sour A.
2007;29:133141.
[83] May CY. Transesterication of palm oil: effect of reac-
tion parameters. J. Oil Palm Res. 2004;16:111.
[84] Noureddini H, Harkey D, Medikonduru V. A continuous
process for the conversion of vegetable oils into
methyl esters of fatty acids. JAOCS. 1998;75:1775
1783.
[85] Feuge RO, Grose T. Modication of vegetable oils. VII.
Alkali catalyzed interesterication of peanut oil with
ethanol. JAOCS. 1949;26:97102.
[86] Tomasevic AV, Siler-Marinkovic SS. Methanolysis of
used frying oil. Fuel Proc Tech. 2002;80:16.
[87] Lee H, Kim SJ, Ahn BS, et al. Role of sulfonic acids in the
Sncatalyzed transesterication of dimethyl carbonate
with phenol. Catal Today. 2003;87:139144.

[88] Canakci M, Gerpen JV. Biodiesel production via acid
catalysis. Trans ASAE. 1999;42:12031210.
[89] Meneghetti PSM, Meneghetti MR, Wolf CR, et al. Etha-
nolysis of castor and cottonseed oil: a systematic study
using classical catalysts. JAOCS. 2006;83:819822.
[90] Encinar JM, Gonzalez JF, Rodriguez JJ, et al. Biodiesel
fuels from vegetable oils: transesterication of Cynara
cardunculus L. oils with ethanol. Energy Fuel.
2002;16:443450.
[91] Marinetti GV. Hydrolysis of lecithin with sodium meth-
oxide. Biochem. 1962;1:350353.
[92] Marinetti GV. Low temperature partial alcoholysis of tri-
glycerides. J Lipid Res. 1966;7:786788.
[93] Darnoko1 D, Cheryan M. Kinetics of palm oil transester-
ication in a batch reactor. JAOCS. 2000;77:12631267.
[94] Iso M, Chen B, Eguchi M, et al. Production of biodiesel
fuel from triglycerides and alcohol using immobilized
lipase. J Molec Catal B Enzym. 2001;16:5358.
[95] Murugesan A, Umarani C, Chinnusamy TR, et al. Pro-
duction and analysis of biodiesel from non-edible
oils a review. Renew Sustain Energy Rev. 2009;13
(4):825834.
[96] Demirbas AH, Demirbas I. Importance of rural bioen-
ergy for developing countries. Energy Convers Man-
age. 2007;48(8):23862398.
[97] Fernando S, Karra P, Hernandez R, et al. Effect of
incompletely converted soybean oil on biodiesel qual-
ity. Energy. 2007;32(5):844851.
[98] Yusuf NNAN, Kamarudin SK, Yaakub Z. Overview on
the current trends in biodiesel production. Energy
Convers Manage. 2011;52(7):27412751.
[99] Torres-Jimenez E, Jerman MS, Gregorc A, et al. Physical
and chemical properties of ethanoldiesel fuel blends.
Fuel. 2011;90(2):795802.
[100] Demirbas A. Progress and recent trends in biodiesel
fuels. Energy Convers Manage. 2009;50(1):1434.
[101] Antol
n G, Tinaut FV, Brice~no Y, et al. Optimisation of
biodiesel production by sunower oil transesterica-
tion. Bioresour Technol. 2002;83(2):111114.
[102] Demirbas A. Biodiesel production from vegetable oils
by supercritical methanol. J Sci Ind Res. 2005;64:858865.
BIOFUELS 17
[103] Balat M. Potential alternatives to edible oils for biodie-
sel production a review of current work. Energy
Convers Manage. 2011;52(2):14791492.
[104] Karmakar A, Karmakar S, Mukherjee S. Properties of
various plants and animals feedstocks for biodiesel
production. Bioresour Technol. 2010;101(19):7201
7210.
[105] Lapuerta M, Armas O, Rodr
guez-Fern
andez J. Effect of
biodiesel fuels on diesel engine emissions. Prog Energy
Combust Sci. 2008;34(2):198223.
[106] Moser BR, Vaughn SF. Coriander seed oil methyl esters as
biodiesel fuel: unique fatty acid composition and excel-
lent oxidative stability. Biomass Bioenerg. 2010;34(4):550
558.
[107] Xue J, Grift TE, Hansen AC. Effect of biodiesel on engine
performances and emissions. Renew Sustain Energy
Rev. 2011;15(2):1098116.
[108] Agarwal AK. Biofuels (alcohols and biodiesel) applica-
tions as fuels for internal combustion engines. Prog
Energy Combust Sci. 2007;33(3):233271.
[109] Rashid U, Anwar F, Knothe G. Evaluation of biodiesel
obtained from cottonseed oil. Fuel Process Technol.
2009;90(9):11571163.
[110] Van Gerpen JH, Hammond EG, Johnson LA, et al. Bio-
diesel processing and production. Fuel Process Tech-
nol. 2005;86(10):10971107.
[111] Maceiras R, Rodrguez M, Cancela A, et al. Macroalgae:
raw material for biodiesel production. Appl Energy.
2011;88(10):33183323.
[112] Li Z, Deng L, Lu J, Guo X, Yang Z, Tan T. Enzymatic syn-
thesis of fatty acid methyl esters from crude rice bran
oil with immobilized candida. Chin J Chem Eng.
2010;18(5):870875.
[113] Chincholkar SP, Srivastava S, Rehman A, et al. Biodiesel
as an alternative fuel for pollution control in diesel
engine. Asian J Exp Sci. 2005;19(2):1322.
[114] Knothe G. Biodiesel and renewable diesel: a compari-
son. Prog Energy Combust Sci. 2010;36(3):364373.
[115] Li S, Wang Y, Dong S, et al. Biodiesel production from
Eruca Sativa Gars vegetable oil and motor: emissions
properties. Renew Energy. 2009;34(7):18711876.