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Current biodiesel production

technologies: A comparative review
Mohammadreza Omidkhah

Energy Conversion and Management

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 Energy Conversion and Management 63 (2012) 138–148

Contents lists available at SciVerse ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Current biodiesel production technologies: A comparative review

Ahmad Abbaszaadeh, Barat Ghobadian ⇑, Mohammad Reza Omidkhah, Gholamhassan Najafi
Tarbiat Modares University, Jalale-E-Aleahmad Highway, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Despite the high energy demand in the industrialized world and the pollution problems caused by wide-
Available online 25 August 2012 spread use of fossil fuels, the need for developing renewable energy sources with less environmental
impacts are increasing. Biodiesel production is undergoing rapid and extensive technological reforms
Keywords: in industries and academia. The major obstacle in production and biodiesel commercialization path is
Biodiesel production cost. Thus, in previous years numerous studies on the use of technologies and different meth-
Transesterification ods to evaluate optimal conditions of biodiesel production technically and economically have been car-
Catalytic transesterification
ried out. In this paper, a comparative review of the current technological methods so far used to produce
Non-catalytic transesterification
biodiesel has been investigated. Four primary approaches to make biodiesel are direct use and blending of
vegetable oils, micro-emulsions, thermal cracking (pyrolysis) and transesterification. Transesterification
reaction, the most common method in the production of biodiesel, is emphasized in this review. The two
types of transestrification process; catalytic and non-catalytic are discussed at length in the paper. Both
advantages and disadvantages of the different biodiesel production methods are also discussed.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Increased demand for energy, increasing price of crude oil, glo-
bal warming due to emission of green house gases, environmental
pollution, and fast diminishing supply of fossil fuels are the major
key factors leading to search for alternative sources of energy.
Some of the most notable alternative sources of energy capable
of replacing fossil fuels include amongst others: water, solar and
wind energy, and biofuels. Currently, 86% of the energy being con-
sumed worldwide and nearly 100% of energy desired in the trans-
portation sector is provided by non-renewable fossil fuels [1,2].
Alternative fuels for diesel engines are becoming increasingly
important due to diminishing petroleum reserves and the environ-
mental consequences of emissions from petroleum fueled engines
[3].
Biodiesel is renewable clean bioenergy as it can be produced
from vegetable oils, animal fats and micro-algal oil. The property
of biodiesel is almost similar to diesel fuel; thus it becomes a
promising alternative to diesel fuel [3]. Biodiesel has many benefits
such as it is biodegradable, non-toxic, has a low emission profile
(including potential carcinogens) and is a renewable resource
[4,5]. In addition, it does not contribute to the increase in carbon
⇑ Corresponding author. Address: Tarbiat Modares University, Jalale-E-Aleahmad
Highway, P.O. Box 14115-111, Tehran, Iran. Tel.: +98 021 445804819; fax: +98 021
44196524.
E-mail addresses: abbaszadeh62@gmail.com (A. Abbaszaadeh), ghobadib@
modares.ac.ir (B. Ghobadian), omidkhah@modares.ac.ir (M.R. Omidkhah),
nagafy_ 14@yahoo.com (G. Najafi).
dioxide levels in the atmosphere and thus minimizes the intensity
of the greenhouse effect.
Various factors contributing to the cost of biodiesel include raw
material, other reactants, nature of purification, its storage, etc.
However, the main factor determining the cost of biodiesel produc-
tion is the feedstock, which is about 80% of the total operating cost
[6]. Therefore, a great economic advantage could be achieved sim-
ply by using more economical feedstock such as waste fats and oils
[5,7]. Biodiesel production is undergoing rapid technological re-
forms in industries and academia. At present, the main drawback
for the commercialization of biodiesel is its higher cost than petro-
leum based diesel. Thus in previous years, numerous studies on the
use of technologies and different methods to evaluate optimal con-
ditions of biodiesel production technically and economically have
been carried out. A number of methods are currently available
and have been adopted for reduction of the viscosity of vegetables
oils. Four primary ways to make biodiesel are direct use and blend-
ing of vegetable oils, micro-emulsions, thermal cracking (pyrolysis)
and transesterification [8]. One of the most common methods used
to reduce oil viscosity in the biodiesel industry is called transeste-
rification which take place between a vegetable oil or animal fat
and an alcohol (methanol, ethanol, butanol) in presence of a cata-
lyst (homogeneous, heterogeneous) or without the application of
catalysts [9].
This paper reviews the technologies related to biodiesel produc-
tion starting with the direct use and blending of oils, continuing
with micro-emulsion and pyrolysis and finishing with an emphasis
on the current technology of choice, transesterification. The
purpose of this paper is to give an overview on the technological

0196-8904/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.enconman.2012.02.027
 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148 139

aspects of existing transesterification methods such as feedstock
conditions, reaction conditions (temperature, pressure, mixing),
reaction time, type of catalyst, alcohol consumption and finally
economical aspects.
2. Biodiesl and its properties
Biodiesel is a renewable clean burning mono-alkyl ester (based
oxygenated) fuel made derived from natural, renewable feedstock
such as new/used vegetable oils, and animal fats. The resulting bio-
diesel is quite similar to petroleum-based diesel fuel in its main
characteristics and can be blended in any proportion with petro-
leum diesel to create a stable biodiesel blend [10]. Table 1 repre-
sents the parameters that must be met to achieve ASTM D6751-
09 quality standards. Although at present biodiesel cannot entirely
replace petroleum-based diesel fuel, this alternative fuel is becom-
ing increasingly important due to diminishing petroleum reserves
that leads to a rise in petroleum prices and the environmental con-
sequences of exhaust gases from the petroleum-fueled engines.
While biodiesel is generally considered to be a substitute for all
or part of petroleum-based diesel fuel, there are some key points
that need to be considered when examining pure biodiesel replac-
ing conventional diesel or when it is blended with conventional
diesel that are described as follow [11,12]:
1. Antifoaming: Pure biodiesel (B100) has excellent anti-foam
properties, better than petroleum diesel. This enables and
ensures fast filling of vehicles, without possible foam leaks or
overflows.
2. Cetane number: The cetane number of biodiesel is generally
varying between 45 and 70, as compared to 40 and 52 for typ-
ical petroleum diesel fuels. The Cetane number of biodiesel
depends on distribution of fatty acids in original oils or fat.
The longer fatty acids and more saturated leads to higher
Cetane number.
3. Chemical structure: Biodiesel is a combination of small range of
molecules, typically esters of fatty acids of C12, C14, C16, C18
and C22, whereas diesel is a complex mixture of a broad range
of hydrocarbons from C12 to C25, consisting of paraffins, napth-
enes and aromatics, as well as a range of nitrogen and sulfur
containing organic compounds. Biodiesels are predominantly
straight chain hydrocarbons esters, whereas diesel contains ring
structures, such as aromatic molecules.
4. Oxygen content: Biodiesel generally contains 11% oxygen, as the
ester that leads to smoother combustion, reduces energy
content and makes the biodiesel polar, through the hydroxyl
(–OH) hydrogen bond. The polarity gives it properties of sol-
vency, detergency, wet-ability (sticking to metals as a lubricant)
and conductivity. Diesel fuel does not contain oxygen.
5. Cold flow properties: For diesel fuels, each component has its
own crystallization temperature, so solidification is a gradual
process, whereas B100 biodiesel tends to be a much simpler
mixture containing relatively few components, so that one or
two components tend to dominate, and solidification is much
more rapid and difficult to control.
6. Conductivity: Pure biodiesel, due to its polarity has excellent
conductivity, greater than 500 pico S/m, and therefore reduces
the risk of static induced sparks and fires.
7. Corrosion: The water absorption coupled with the presence of
oxygen tends to contribute to increased corrosion, but this is
countered by the wet-ability that reduces oxygen transfer to
metal surfaces. The copper corrosion test focuses on sulfur com-
pounds that are aggressive to copper and yellow metals. Sulfur,
and specifically the corrosive forms thereof, are absent in bio-
diesel, and compliance to diesel specification limits is typically
easily achieved.
3. The biodiesel production procedure
There are several generally accepted technologies that have
been well established for the production of biodiesel fuel. Vegeta-
ble oils and animal fats are appropriate to be modified in order to
reduce their viscosities so that the product obtained has suitable
properties to be used as diesel engine fuels. There are many proce-
dures for this modification to produce a better quality of biodiesel
such as direct use and blending, micro-emulsions, pyrolysis of veg-
etable oil and transesterification [13–15]. In this section, an inves-
tigation was carried out to briefly review these procedures.
3.1. Direct use and blending of oils
The use of vegetable oils as alternative fuels has been around
since 1900 when the inventor of the diesel engine, Dr. Rudolph
Diesel, first tested Peanuts oil in his compression engine [16].
The direct use of vegetable oils in diesel engines is problematic
and has many inherent failings. It has only been researched exten-
sively for the past couple of decades, but has been experimented
with for near a 100 years. Crude vegetable oils can be mixed di-
rectly or diluted with diesel fuel to improve the viscosity so as to
solve the problems associated with the use of pure vegetable oils
with high viscosities in compression ignition engines [17]. Energy
consumption, with the use of pure vegetable oils, was found to

Table 1
Biodiesel (B100) Fuel Quality Standard ASTM D6751-09.

Property Method Limit Unit

Flash point (closed cup) D93 93 min °C
Water and sediment D2709 0.050 max % vol
Kinematic viscosity, 40 °C D445 1.9–6.0 mm2/s
Sulfated ash D874 0.02 max % mass
Sulfur S 15 Grade D 5453 0.0015 max (15) % mass (ppm)
Sulfur S 500 Grade D 5453 0.05 max (500) % mass (ppm)
Copper strip corrosion D130 No 3 max
Cetane number D613 47 min
Cloud point D2500 Report to Customer °C
Carbon residue D4530 0.05 max % mass
Acid number D664 0.50 max mg KOH/g
Free glycerin D6584 0.02 % mass
Total glycerin D6584 0.24 % mass
Phosphorus content D4951 10 max ppm
Vacuum distillation end point D1160 360 max °C
Acid number D 664 0.50 max mg KOH/g
Cold soak filtration Annex to D6751 360 max s
140 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148

Table 2
Performance of vegetable oils as diesel fuels.

Fuel characteristics Consequence(s)

Viscosity High viscosity interference with injection process, poor fuel atomization, high viscosity/low volatility causes poor cold engine
start-up and ignition delay. Also, caused to thickening and gelling
Cloud point, pour point, cold-filter Fuel performance compromised under cold-temperature conditions
plugging point
Cetane number Low cetane number implies long ignition delay, high auto ignition temperature and diesel knock
Combustion Inefficient mixing of oil with air leads to incomplete combustion
Flash point High flash point facilitates to lower volatility characteristics
Distillation range Presence of high-boiling components affects the degree of formation of solid combustion deposits, important to engine start-up
and warm-up
Carbon residue The limited thermal stability of partly unsaturated vegetable oils and lower volatilization characteristics lead to more deposit
formation, carbonization of injector strips, coking and trumpet formation on injectors, ring sticking and lubricating oil dilution
and degradation
Oxidative stability Oxidative and thermal polymerization cause deposition on injectors
Long-term operation Development of gumming, injector coking, ring ticking, failure of engine lubricating oil due to polymerization and serious
engine deterioration

be similar to that of diesel fuel [5]. For short term using ratios of
1:10–2:10 oil to diesel fuel have been found to be successful [3].
But, direct use of vegetable oils and/or the use of blends of the veg-
etable oils have generally been considered to be not satisfactory
and impractical for both direct and indirect diesel engines. Table 2
represents the performance characteristics of vegetable oil as die-
sel fuels [18].
The high viscosity, acid composition, free fatty acid content, as
well as gum formation due to oxidation and polymerization during
storage and combustion, carbon deposits and lubricating oil thick-
ening are obvious problems [5]. Heating and blending of vegetable
oils may reduce the viscosity and improve volatility of vegetable
oils but its molecular structure remains unchanged, hence polyun-
saturated character remains [19]. The use of vegetable oils in diesel
engines requires significant engine modifications, including chang-
ing of piping and injector construction materials, otherwise engine
running times are decreased, maintenance costs are increased due
to higher wear, and the danger of engine failure is increased.
3.2. Micro-emulsion of oils
Micro-emulsification is the formation of microemulsions (co-
solvency) which is a potential solution for solving the problem of
high vegetable oil viscosity. A micro-emulsion is defined as a col-
loidal equilibrium dispersion of optically isotropic fluid micro-
structures with dimensions generally in the 1–150 nm range
formed spontaneously from two normally immiscible liquids and
one or more ionic or non-ionic amphiphiles [5,20]. Micro-emul-
sion-based fuels are sometimes also termed ‘‘hybrid fuels’’,
although blends of conventional diesel fuel with vegetable oils
have also been called hybrid fuels [21,22]. Microemulsions are
clear, stable isotropic fluids with three components: an oil phase,
an aqueous phase and a surfactant.
For this purpose, micro-emulsions with solvents such as meth-
anol, ethanol and 1-butanol have been studied. All micro-emul-
sions with butanol, hexanol and octanol can meet the maximum
viscosity limitation for diesel engines [23]. A microemulsion pre-
pared by blending soybean oil, methanol, 2-octanol and cetane im-
prover in the ratio of 52.7:13.3:33.3:1.0 has passed the 200 h EMA
test [24]. Micro-emulsion of vegetable oils lowered the viscosity of
the oil but resulted in irregular injector needle sticking, heavy car-
bon deposits and incomplete combustion during 200 h laboratory
screening endurance test [3].
3.3. Pyrolysis of oils
Pyrolysis is the conversion of one organic substance into an-
other by means of heat or by heat with the aid of a catalyst
[25,26]. The pyrolyzed material can be vegetable oil, animal fat,
natural fatty acids or methyl esters of fatty acids [27]. Conversion
of vegetable oils and animal fats composed mostly of triglycerides
using thermal cracking reactions represents a promising technol-

Fig. 1. The mechanism of thermal decomposition of triglycerides.

 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148
Fig. 2. Transestrification reaction of triglycerides with alcohol.
ogy for the production of biodiesel [28]. This technology is espe-
cially promising in areas where the hydro processing industry is
well established because the technology is very similar to that of
conventional petroleum refining [28]. The fuel properties of the li-
quid product fractions of the thermally decomposed vegetable oil
are likely to approach diesel fuels. Many researchers have reported
the pyrolysis of triglycerides to obtain products suitable for diesel
engines [28–31]. The research on pyrolysis of triglycerides is di-
vided into catalytic and non-catalytic processes [28]. The mecha-
nism of thermal decomposition of triglycerides is depicted in Fig
1. [32]. Mechanisms for the thermal decomposition of triglycerides
are likely to be complex, because of the many structures and mul-
tiplicity of possible reactions of mixed triglycerides.
The pyrolysis reactions of soybean, palm, and castor oils have
been studied in an investigation. The adequate choice of distilla-
tion temperature (DT) ranges made it possible to isolate fuels with
physical and chemical properties comparable to those specified for
petroleum based fuels [31]. The equipment for thermal cracking
and pyrolysis is expensive for modest throughputs. In addition,
while the products are chemically similar to petroleum-derived
gasoline and diesel fuel, the removal of oxygen during the thermal
processing also removes any environmental benefits of using an
oxygenated fuel. It produces some low value materials and, some-
times, more gasoline than diesel fuel [5].
3.4. Transesterification of oils
The most common technology of biodiesel production is transe-
sterification of oils (triglycerides) with alcohol which gives biodie-
sel (fatty acid alkyl esters, FAAE) as main product and glycerin as
by product. The basic transesterification reaction is illustrated in
Fig 2. The first step is the conversion of triglycerides to diglyce-
rides, which is followed by the conversion of diglycerides to mono-
glycerides and of monoglycerides to glycerol, yielding one methyl
ester molecule from each glyceride at each step [5]. Transesterifi-
cation, also called alcoholysis, is exchanging of alcohol from an es-
ter by another alcohol in a process similar to hydrolysis, except
that an alcohol is used instead of water [33,34].
The most relevant operating variables affecting the transestrifi-
cation process are reaction temperature, reaction time, reaction
pressure, ratio of alcohol to oil, concentration and type of catalyst,
mixing intensity and kind of feedstock [35].
4. Biodiesel production technologies: Transesterification
method
The transesterification reaction proceeds with catalyst or with-
out any catalyst by using primary or secondary monohydric ali-
phatic alcohols having 1–8 carbon atoms [36,9]. Generally,
alcohol and triglycerides (vegetable oil and animal fat) are not mis-
cible to form a single phase of mixture. Hence, the poor surface
contact between these two reactants causes transesterification
reaction to proceed relatively slow. Introduction of catalysts im-
proves the surface contact and consequently reaction rates and
141
biodiesel yield as it is able to solve the problems of two-phase nat-
ure between triglycerides and alcohol. However, without the pres-
ence of catalysts, the reaction rate is too slow for it to produce
considerable yield of biodiesel. Hence, researchers around the
world have been developing numerous alternative technologies
which can solve the problems facing catalytic reaction by using
non-catalytic processes [37,38].
4.1. Catalytic biodiesel production
Vegetable oils can be transesterified by heating them with an
alcohol and a catalyst. Catalysts used in biodiesel production are
divided in two general categories, homogenous and heterogeneous
types. If the catalyst remains in the same (liquid) phase to that of
the reactants during transesterification, it is homogeneous cata-
lytic transesterification. On the other hand, if the catalyst remains
in different phase (i.e. solid, immiscible liquid or gaseous) to that of
the reactants, the process is called heterogeneous catalytic transe-
sterification [39,40].
In catalytic methods, the suitable selection of the catalyst is an
important parameter to lower the biodiesel production cost [41].
So, commercial biodiesel is currently produced by transesterifica-
tion using a homogenous catalyst solution. Another factor affecting
the selection of catalyst type is the amount of free fatty acid (FFA)
present in the oil. For oils having lower amount of FFAs, base-cat-
alyzed reaction gives a better conversion in a relatively short time
while for higher FFAs containing oils, acid-catalyzed esterification
followed by transesterification is suitable [42]. It has been reported
that enzymatic reactions are insensitive to FFA and water content
in oil. Hence, enzymatic reactions can be used in transesterification
of used cooking oil [43–45]. Various studies have been carried out
using different oils as raw material, different alcohols (methanol,
ethanol, butanol), as well as different catalysts, including homoge-
neous ones such as sodium hydroxide, potassium hydroxide, and
sulfuric acid, and heterogeneous ones such as lipases [35], CaO
[46] and MgO [47].
4.1.1. Homogeneous catalytic transestrification
Homogenous catalysts are categorized into basic and acidic cat-
alysts. The homogenous transestrification process especially basic
type requires a high purity of raw materials and post reaction sep-
aration of catalyst, by-product, and product at the end of the reac-
tion. Both of these requirements drive up the cost of biodiesel. The
general form of homogeneous catalytic transestrification process
can be seen on a process flow diagram of Fig 3.
4.1.1.1. Homogeneous base catalytic transesterification. Currently,
biodiesel is commonly produced using homogeneous base catalyst,
such an alkaline metal alkoxides [19,48] and hydroxides [49], as
well as sodium or potassium carbonates [49]. As a catalyst in the
process of basic methanolysis, mostly sodium hydroxide or potas-
sium hydroxide have been used, both in concentration from 0.4% to
2% w/w of oil. Homogeneous base catalytic catalysts are commonly
used in the industries due to several reasons: (i) modest operation
142 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148

Fig. 3. The process flowchart of homogeneous catalytic transestrification process.

Table 3
biodiesel, glycerin and wash water that cause to more wastewater
Typical reaction conditions for biodiesel production using homogeneous base from purification [49]. Because water makes the reaction partially
catalysts [18]. change to saponification, the basic catalyst is consumed in produc-
Feedstocks Refined triglycerids (FFA<0.5 wt.%; H2O < 0.06 wt.%),
ing soap and reduces catalyst efficiency. The soap causes an in-
anhydrous short-chain alcohols (generally crease in viscosity, formation of gels which reduces ester yield
methanol) and makes the separation of glycerol difficult [53]. Therefore, side
Alcohol/oil molar ratio 3:1–9:1 (usually 6:1) reactions such as saponification and hydrolysis must be kept to a
Oil/co-solvent molar 0.2–0.4
minimum. Saponification produces soap and water as shown in
ratio
Temperature 20–75 °C (usually 60–65 °C) Fig. 4a, from excess FFA in the feedstock. Also, a second hydrolysis
Pressure 0.14–0.41 MPa reaction causes conversion of alkyl esters, using base catalysts, to
Catalyst NaOH and KOH FFA as shown in Fig. 4b.
Catalyst concentration 0.25–2 wt.%
(oil basis)
Stirring speed 300–600 rpm
4.1.1.2. Homogeneous acid catalytic transesterification. An alterna-
Reaction time 1–4 h (usually 1 h) for >98% conversion
tive way of processing triglycerides for biodiesel production is to
use an acid catalyst. Acid catalytic transestrification of biodiesel
can economically compete with base catalytic process using virgin
condition; (ii) high conversion can be achieved in a minimal time, oil, especially when the former uses low-cost feedstocks [54]. Sul-
(iii) high catalytic activity, (iv) widely available and economical furic acid, hydrochloric acid, and sulfonic acid are usually preferred
[50,51]. In general, base catalytic transesterification processes are as acid catalysts. Acid-catalyzed transesterification starts by mix-
carried out at low temperatures and pressures (333–338 K and ing the oil directly with the acidified alcohol, so that separation
1.4–4.2 bar) with low catalyst concentrations (0.5–2 wt.%) [52,21]. and transesterification occur in single step, with the alcohol acting
Typical process conditions for homogeneous base catalysis are both as a solvent and as esterification reagent [55]. The use of ex-
moderate: stoichiometeric alcohol/oil molar ratio (or slightly high- cess alcohol effects significant reductions in reaction time required
er), reaction at alcohol reflux temperature, atmospheric pressure or for the homogeneous acid catalyzed reaction. Hence, Bronsted acid
small overpressure, low reaction times (typically 1 h) and low cat- catalyzed transesterification requires high catalyst concentration
alyst concentration (Table 3). and a higher molar ratio to reduce the reaction time [53]. Miano
The limits of this process are due to the sensitivity to purity of et al. [56] investigated the various amount of molar ratio of meth-
reactants, free fatty acid content, as well as to the water concentra- anol and trifluoroacetic acid catalyst on methyl ester content and
tion of the sample. When the oils contain significant amounts of specific gravity of reaction. The optimum conversion was achieved
free fatty acids and water content, they cannot be converted into at the molar ratio of 20:1. Under this molar ratio, the methyl ester
biodiesels but to a lot of soap [49]. Free fatty acids of oil react with content and specific gravity of reaction product were 98.5%
the basic catalyst to produce soaps that inhibit the separation of and 0.878%, respectively, after 5 h of reaction time (Fig. 5). They

Fig. 4. Side reaction in biodiesel production including (a) saponification to create soaps and (b) FFA formation from hydrolysis [49].
 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148 143

compared C1–C4 linear alcohols for the acid catalytic (0.1%

H2SO4) transesterification of waste frying oil at reflux tempera-
tures. Reaction rates varied as follows: BuOH > n-PrOH > EtOH > -
MeOH. The reverse was true for the base catalytic process.
Apparently, the initial reagent phase miscibility is more critical
in homogeneous acid catalyzed transesterification than base cata-
lytic [57].
One advantage of homogeneous acid catalytic over homoge-
neous base catalytic transesterification is their low susceptibility
to the presence of FFA in the feedstock. However, homogeneous
acid catalytic transesterification is especially sensitive to water
concentration. It was reported that as little as 0.1 (wt.%) water in
the reaction mixture was able to affect ester yields in transesteri-
fication of vegetable oil with methanol, with the reaction almost
completely inhibited at 5 (wt.%) water concentration [55]. Table 5
shows that higher water concentration in soybean oil in homoge-
Fig. 5. The methyl ester content (D) and specific gravity (N) of reaction product
with different molar ratio of methanol to oil. Reaction conditions: 120 °C, 2.5 M neous acid catalytic methanolysis after 2 h of reaction, result in sig-
catalyst, 5 h of reaction time [56]. nificantly lower FAME yields, probably due to the water inducing a
second phase (at higher conversions, methanol alone would not in-
duce this phase) that extracted methanol and catalyst from the oil
reached the maximum amount of the methyl ester content (98.4%) [18,58].
and the lower specific gravity (0.878) after 5 h of reaction time in Another disadvantages of homogeneous acid catalytic transe-
2.0 M concentration of trifluoroacetic acid catalyst. There was no sterification are equipment corrosion, more waste from neutraliza-
significantly improvement of the methyl ester content and the spe- tion, difficult to recycle, formation of secondary products, higher
cific gravity with the concentration of catalyst higher than 2.0 M reaction temperature, long reaction times, relatively slow reaction
(Fig. 6). rate, weak catalytic activity and elaborate process engineering
Table 4 shows the typical conditions in homogeneous acid cat- [58,59].
alyzed transesterification processes [18]. The elevated boiling
points of higher alcohols enable the liquid reaction system to be
4.1.2. Heterogeneous catalytic transestrification
operated at higher temperatures whiles maintaining moderate
In comparison with homogeneous catalysts that act in the same
pressures. This is important for homogeneous acid catalyzed
phase as the reaction mixture, heterogeneous catalysts act in a dif-
transesterification since higher reaction temperatures are often re-
ferent phase from the reaction mixture. Being in a different phase,
quired here to achieve faster reaction conditions. Nye et al. [57]
heterogeneous catalysts have the advantage of easy separation and
reuse. The high consumption of energy and costly separation of the
homogeneous catalyst from the reaction mixture, however, have
called for development of heterogeneous catalyst. The use of heter-
ogeneous catalyst does not yield soap [60]. The use of heteroge-
neous catalytic systems in transestrification of triglycerides
implies the elimination of several steps of washing/recovery of bio-
diesel/catalyst, ensuring thereby higher efficiency and profitability
of the process as well as lowering its production costs. There is also
the possibility of being implemented in a continues way by using a
fixed bed reactor. A typical schematic diagram for heterogeneous
catalytic transesterification process is shown in Fig. 7.
Compared to homogenous catalytic transesterification process,
the heterogeneous catalytic transesterification process can tolerate
extreme reaction conditions. The temperature could go from 70 °C
to as high as 200 °C to achieve more than 95% of yield using MgO,
CaO, and TiO2 catalysts [61]. Kiss et al. [62] carried out a compar-
ative assessment of cost and environmental aspects of the homo-
Fig. 6. The influence of catalyst concentration on the methyl ester content (D) and geneous and heterogeneous catalytic transesterification process
specific gravity (N) of reaction product. Reaction conditions: 120 °C, 20:1 M ratio of in large scale biodiesel production plants. The economic assess-
methanol to oil, 5 h of reaction time [56].
ment of heterogeneous and homogeneous processes in large scale
biodiesel production plants revealed the advantages of the hetero-
geneous process in terms of higher yield of biodiesel and higher
Table 4
Typical reaction conditions for biodiesel production using homogeneous acid purity of glycerin, as well as lower cost of catalyst and mainte-
catalysts. nance. This would result in estimated US$59 reduction in operating
Feedstocks Triglycerides mixture with high FFA content, alcohols
(usually methanol) Table 5
Alcohol/oil molar 30:1–50:1 Effect of water concentration on the homogeneous acid catalytic methanolysis [58].
ratio
Temperature 50–150 °C Catalyst Water concentration
Pressure 0.4 MPa
<0.1 wt.% 1 wt.%
Catalyst H2SO4
Catalyst load 1.3:1 (molar ratio H2SO4/oil) 0.1 wt.% H2SO4 40% 21%
Conversion 97% after 4 h 0.5 wt.% H2SO4 >90% 66%
144 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148

Fig. 7. The schematic flow diagram of heterogeneous catalytic transestrification process.

cost per mt of biodiesel, relative to the homogeneous process. The

energy consumption and associated costs are higher in the case of
heterogeneous catalyst. The analysis showed that at current mar-
ket value of glycerin, prices of auxiliary material and assuming
equal capital cost of heterogeneous and homogeneous production
plants, the heterogeneous process would be economically compet-
itive if the utility costs were lower than US$85 per mt of biodiesel,
or in other words, not more than threefold of the utility cost of the
homogeneous catalytic transesterification process. Regarding envi-
ronmental aspects, the application of the heterogeneous process
would result in reduced risk associated with spillage or leakage
of hazardous and flammable chemicals. Additional environmental
benefits can be expected from the absence of energy intensive
and waste generating glycerin purification step.

4.1.2.1. Heterogeneous solid-base catalytic transesterification. Most

of heterogeneous solid catalysts are base or basic oxides coated
over large surface area. Solid-base catalysts are more active than
solid-acid catalyst. The most common solid-base catalysts are Basic
zeolites, alkaline earth metal oxides and hydrotalcites. Solid base
can leads to the heterogeneous catalytic process, which promises
the cost reasonable biodiesel production. Using the solid base cat-
alyst in form of fixed-bed reactor system causes easier separation
of catalyst from transesterified product. Also, the solid base cata-
lyst is active in the transesterification at the temperature around
the methanol boiling point [63]. Similar to their homogeneous
counterparts, solid basic catalysts are more active than solid acid
catalysts [64,65]. Oxides of group 2 metals are basic and have lim-
ited solubility in polar media. These metal oxides, particularly CaO
and MgO are cheap and readily available, so if found to be active
and stable, would be desirable catalysts for industrial biodiesel
production. CaO and MgO are inexpensive materials, and their
activities are relatively high. However, CaO does leach into the
reaction mixture, so metal ions would still have to be removed
from the biodiesel by water washing, thus the advantage of using
a heterogeneous catalyst would be lost. CaO is widely used as a so-
lid basic catalyst possesses and has many advantages such as long
catalyst lifetimes, higher activity, lower solubility in methanol and
requires only moderate reaction conditions. The reaction rate,
however, was slow in producing biodiesel [66].
Viola et al. [67] investigated the effects of powder and granules
size of CaO catalyst on catalytic activity in the transesterification
process. It was observed that powder or granules size of CaO cata-
lyst have a similar catalytic activity in the process (Fig. 8). The tri-
als with granules are affected by the slow formation of powder
Fig. 8. Comparison between powder and granules catalytic size performance in
transesterification reaction; other reaction conditions: T 65 °C, molar ratio meth-
anol/oil 6:1, catalyst concentration 5 wt.% [67].
during the reaction and powder was become visible after 40–
60 min from the reaction start, but the most of granules persisted
until the end.
4.1.2.2. Heterogeneous solid-acid catalytic transesterification. Despite
lower activity, heterogeneous solid acid catalysts have been used
in many industrial processes because they contain a variety of acid
sites with different strength of Bronsted or Lewis acidity, compared
to the homogenous acid catalysts. Using solid acid catalysts have
following advantages: insensitive to FFA content, simultaneous
esterification and transesterification [68], elimination of purifica-
tion step of biodiesel [69], easy separation of the catalyst from
the reaction products and reduction of the corrosion problem, even
with the presence of acid species [14].
Heterogeneous Solid acid catalysts, such as Nafion-NR50, sul-
fated zirconia and tungstated zirconia have been chosen to cata-
lyze biodiesel forming transesterification due to the presence of
sufficient acid site strength. Among the solid catalysts, Nafion
demonstrated higher selectivity towards the production of methyl
ester and glycerol due to its acid strength [55,61,65]. However,
Nafion has disadvantages of high cost and lower activity compared
to liquid acids [70].
 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148 145

4.1.3. Biocatalytic transesterification
Biocatalysts have been becoming increasingly important in the
discussion of biodiesel production recently. It is even hypothesized
that these catalysts will eventually have the ability to outperform
chemical catalysts [71]. Biocatalysts are naturally occurring lipases
which have been identified as having the ability to perform the
transesterification reactions that are essential to biodiesel produc-
tion. These lipases have been isolated from a number of bacterial
species: Pseudomonas fluorescens, Pseudomonas cepacia, Rhizomucor
miehei, Rhizopus oryzae, Candida rugosa, Thermomyces lanuginosus,
and Candida antarctica [72]. There are two major classification of
enzymatic biocatalyst: (1) extracellular lipases (i.e. the enzyme
has previously been recovered from the live-producing microorgan-
ism broth and then purified) which the major producer microorgan-
isms are Mucor miehei, R. oryzae, C. Antarctica, P. cepacia; and (2)
intracellular lipase which remains either inside or in the cell-pro-
ducing walls which in both cases the enzyme is immobilized. The
advantage of immobilization in this system is frequent utilization
due to its easy recovery from the reaction mixture [73]. There are
several methods for lipase immobilization, including adsorption,
covalent bonding, entrapment, encapsulation, and cross-linking.
These immobilization methods have been employed to improve li-
pase stability for biodiesel production in recent years. Adsorption is
still the most widely employed method for lipase immobilization
[74]. Several researchers have reported that the commercially avail-
able C. antarctica lipase immobilized on acrylic resin (Novozym 435)
was the most effective lipase between any of the extracellular li-
pases tested for transesterification reaction of vegetable oils where
methanol is used as acyl acceptor [75–77]. Although immobiliza-
tion of extracellular enzyme seemed to be a common method for
enzymatic alcoholysis, it needs complicated methods for separa-
tion, purification and stabilization of lipases which in turn increase
the process cost in industrial scale [78]. In recent years, there has
been considerable interest in the direct use of intracellular lipase
as a whole cell biocatalyst (indirect immobilization of the enzyme)
for biodiesel production. Utilizing whole cell overproducing intra-
cellular lipase in which the purification and stabilization of the en-
zyme are not necessary instead of conventional immobilized lipase
for biodiesel production is a potential way to reduce the biocatalyst
cost, because immobilization can be carried out spontaneously dur-
ing the process of cell cultivation [79].
For transestrification synthesis, at least stoichiometric amount
of methanol is required for the complete conversion of triacylgly-
cerols to their corresponding fatty acid methyl esters. However,
methanolysis is decreased significantly by adding 1/2 M equivalent
of methanol at the beginning of the biocatalytic transestrification.
This reduction in activity caused by the polar short chain alcohols
was the major obstacle for the enzymatic biodiesel production
[80]. In order to solve this problem, researchers use the following
three options, methanol stepwise addition, acyl acceptor altera-
tions (methyl acetate, acetate ethyl) and solvent engineering (with
t-butanol, 1,4-dioxane, ionic liquid as solvents) [81–83]. During the
transesterification of triglycerides via biocatalysts, glycerol is pro-
duced. The presence of glycerol can then inhibit the reaction by
binding to the biocatalyst instead of the triglyceride molecule. To
overcome this, an acyl acceptor molecule can be used to bind the
glycerol, forming a triglyceride molecule that can no longer bind
to the active site of the biocatalyst. When an acyl acceptor is intro-
duced to the reaction, the biocatalyst can exhibit a higher rate of
turnover, proving more usefulness. It has also been shown that
the triacetylglycerol molecule does not diminish the properties of
biodiesel when used as a fuel [72].
Biocatalytic transesterification process has many advantages
over the chemical-catalyzed transesterification process such as
generation of zero by-product, no difficulty in product removal, re-
quires moderate process conditions (temperature, 35–45 °C), and
recycling of the catalysts. Enzymatic reactions can successfully be
used for the transesterification of used cooking oil because; enzy-
matic reactions are insensitive to free fatty acid and water content
of the feedstock [83,84]. A brief comparison between the transes-
trification process based on homogeneous base and acid catalysts
and biocatalyst is shown in Table 6.
Biocatalysts such as lipases break down the triglycerides into
FFA and glycerin that exhibits maximum activity at oil–water
interface. Under low-water conditions, the hydrolysis reaction is
reversible, i.e., the ester bond is synthesized rather than hydro-
lyzed. Scientists are interested in the development of lipase appli-
cations to the interesterification reactions of vegetable oils for
production of biodiesel. These advantages prove that biocatalytic
biodiesel production has high potential to be an eco-friendly pro-
cess and a promising alternative to the chemical process. However,
it still has its fair share of constraints especially when imple-
mented in industrial scale such as high cost of enzyme, slow reac-
tion rate and enzyme deactivation [85]. New immobilization
techniques with higher activity and stability at low cost still need
to be explored and developed. If the cost of the catalyst lipase is re-
duced, the industrial production of biodiesel using enzymatic
methods will soon have a bright future. Generally speaking, there
are two approaches to reduce the lipase cost. One is to reduce
the production cost of the lipase, which can be realized through
new lipase development, fermentation, optimization, and down
stream processing improvement. Another approach is to im-
prove/extend the operational life of the lipase, and this can be
achieved through enzyme immobilization, alcoholysis reaction
optimization, etc. There are extensive reports associated with the
aforementioned research fields, and some big progresses have been
achieved, for example, the operation al life of the lipase could be
prolonged greatly in some special reaction systems, and such

Table 6
Comparison of biodiesel production by homogeneous base and acid catalytic and biocatalytic process.

Homogeneous base catalytic Homogeneous acid catalytic process Biocatalytic process

process
Reaction temperature 40–60 °C Need high temperature (60–100 °C) Low temperature (30–40 °C)
Free fatty acids in Saponified products (soap No influence (Alkyl esters production) No influence (Alkyl esters production)
feedstock formation)
Water in raw Inhibition of the reaction rate Under low water content reaction is Under low water condition, lipase show maximum activity at
materials not hindered oil–water interface
Yield of product Normal High Depends on different type of enzymes
Recovery of glycerol Difficult Comparatively easy Easy
Purification of Repeated water washing (soap Easy to water washing for product None
Biodiesel emulsifier) separation
Catalyst cost Cheap Cheap Expensive
Rate of reaction Faster comparatively Slower than base catalytic process Relatively lower than base and acid catalytic process
146 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148

achievements definitely will make biocatalytic transesterification Therefore, the ability of supercritical transesterification methods in
have great potential in the future. using low value feedstocks could probably reduced the share of
feedstock cost in biodiesel production cost.
4.2. Non-catalytic biodiesel production
4.2.2. BIOX co-solvent transesterification
In a catalytic reaction to produce biodiesel through tranestrifi- Due to low solubility of methanol in oil, the rate of conversion
cation, several processes, such as purification of the esters, separa- of oil into ester is very slow. Another approach to overcome these
tion and recovery of unreacted reactants and catalysts, are problems that is now commercialized is the use of co-solvent
involved. These process render production of biodiesel through a which is soluble in both methanol and oil. The result is a fast reac-
conventional transesterification system complicated, thus giving tion, on the order of 5–10 min, and no catalyst residues exist in
a reason to investigate the production of biodiesel from triglycer- either of the ester or the glycerol phase. One of such co-solvents
ides via non-catalytic reactions. Beside catalytic methods, there is tetrahydrofuran, chosen in part, because it has a boiling point
are two non-catalytic transesterification processes. These are the very close to that of methanol and the system requires a rather
supercritical alcohol process and BIOX process. low operating temperature of 30 °C. The Biox (co-solvent) process
is a new Canadian process developed originally by Professor David
Boocock of the University of Toronto that has attracted consider-
4.2.1. Supercritical alcohol transesterification
able attention. In patented Biox production processes, both triglyc-
Supercritical alcohol methods is a non-catalytic method for bio-
erides and free fatty acids are converted in a two-step, single
diesel production in which instead of using catalysts, high pressure
phase, continuous process at atmospheric pressures and near
and temperature are used to carry out the transesterification reac-
ambient temperatures, all in less than 90 min [91]. Co-solvent op-
tion [38]. The reaction is fast and conversion raises 50–95% for the
tions are available to overcome slow reaction rate caused by the
first 10 min but it requires temperature range of 250–400 °C. The
extremely low solubility of the alcohol in the triglyceride phase.
transesterfication of triglycerides by supercritical methanol, etha-
Demirbas [92] used tetrahydrofuran (THF) as a co-solvent and
nol, propanol and butanol has proved to be the most promising
methanol to make mixture one phase. After the completion of
process. The vegetable oils were transesterified 1:6–1:40 vegetable
the reaction, the biodiesel-glycerol phase separation was clean
oil-alcohol molar ratios in supercritical alcohol conditions [50].
and both the excess alcohol and the tetrahydrofuran co-solvent
Table 7 shows the critical temperatures, critical pressures and
could be recovered in a single step. However, because of the possi-
reaction conditions for esterification and transesterification of the
ble hazard and toxicity of the co-solvents, they must be completely
various alcohols where percent conversion to fatty acid esters were
removed from the glycerol phase as well as the biodiesel phase and
shown for comparison at 10 min and 30 min reaction times at
the final products should be water-free [93]. The use of a co-sol-
300 °C [86].
vent such as tetrahydrofuran or methyl tertiary butyl ether speeds
The disadvantages of the supercritical methods mostly are high
up methanolysis considerably. However, like one-phase butanoly-
pressure and temperature requirement [87], high methanol to oil
sis, one-phase methanolysis initially exhibits a rapid formation of
ratios (usually 42) that renders the production expensive. Kusudi-
ester, but then slows drastically [93]. Fig. 9 depicted the phases
ana and Saka [37,88,89] studied a non-catalyst process in which
vegetable oil was transesterified with supercritical methanol and
found that the amount of water in the reaction does not affect
the conversion of oil into biodiesel. Conversely, the presence of cer-
tain amount of water increases the formation of methyl esters and
esterification of free fatty acids takes place simultaneously in one
stage. Their results showed that the reaction took only 4 min. to
convert rapeseed oil into biodiesel, even though the high temper-
ature (250–400 °C) and high pressure (35–60 MPa) were required
for making methanol reach the supercritical state. Iijima et al.
[90] have proposed a supercritical conditions (reaction parame-
ters: T = 643–773 K; p = 20–60 MPa and residence time =
4–12 min) for producing an unconventional biodiesel fuel (mainly
FAME, mono- and diacylglycerol) without yielding glycerin as a by-
product. Supercritical transesterification methods at high temper-
ature and pressure conditions provide improved phase solubility,
decrease mass transfer limitations, provide higher reaction rates
and make easier separation and purification steps. Besides, the
supercritical transesterification method is more tolerant to the
presence of water and FFAs than the homogeneous base catalyst
method, and hence more tolerant to various types of feedstocks.
Regarding many researches that have been reported, the cost of
biodiesel could certainly be lowered by using low value feedstocks. Fig. 9. Mixture of oil and alcohol with the use and without the use of co-solvent.

Table 7
Critical states for various alcohol and yeilds of fatty acid esters of after 10 min esterification and 30 min transesterification.

Alcohol Critical temperature (°C) Critical pressure (Mpa) Esterification yeild (10 min)% Transesterification yeild (30 min)%
Methanol 239.2 8.09 98 98
Ethanol 243.2 6.38 79 88
1-Propanol 264.2 5.06 81 85
1-Botanol 287.2 4.9 80 75
1-Octanol 385 2.86 – –
 A. Abbaszaadeh et al. / Energy Conversion and Management 63 (2012) 138–148
distribution of oil and alcohol with the use of co-solvent and with-
out the use of co-solvent.
The research showed that the recovery of excess alcohol is dif-
ficult when using Biox co-solvent process because the boiling point
of the THF co-solvent is very close to that of methanol [94]. The
outstanding advantage of the Biox co-solvent process is that it uses
inert, recoverable co-solvents in a single pass reaction that takes
only seconds at ambient temperature and pressure, and no catalyst
residues appear in either the biodiesel phase or the glycerol phase
[94]. This process can carry out not only crude vegetable oils but
also waste cooking oils and animal fats.
5. Conclusion
The objective of this paper was to review the current technolo-
gies in conversation of triglycerides into biodiesel. The following
specific conclusions are based on the review from this paper:
1. Fundamentally, high viscosity appears to be a property at the
root of many problems associated with direct use of vegetable
oils as diesel engine fuel.
2. The transesterfication of triglycerides by methanol, ethanol,
propanol, and butanol has proved that it is currently the
method of choice.
3. Selection of a transesterification process depends on the
amount of free fatty acid and water content of the feedstock.
4. Among all current transesterification methods, the homoge-
neous base catalyst based reaction, is still a common and com-
mercial method. The main reason is due to the fact that it is
kinetically much faster than heterogeneously catalyzed transe-
sterification and is economically viable. The high consumption
of energy and costly separation of the homogeneous catalyst
from the reaction mixture, however, have called for develop-
ment of heterogeneous catalyst. From the review of aforemen-
tioned research and environmental consideration it seems
that the heterogeneous and biocatalysts would be the method
of choice in the future.
5. The use of lipase is a great viable method for production of ester
from different sources of oil or grease. The low solubility of
glycerin in biodiesel also poses a challenge in enzymatic transe-
sterification because it reduces the enzymes activity. Research
on this topic is still in progress due to the enzyme flexibility
and adaptability to new process but it seems that new immobi-
lization techniques with higher activity and stability at low cost
still need to be explored and developed.
6. From a scientific perspective, much remains unknown about
non-catalytic synthesis of biodiesel. The mechanism and
detailed kinetics have not yet been resolved. In non-catalytic
methods, where supercritical alcohol was used, it was demon-
strated that one gets a higher reaction rate for esterification
than for transesterification. Another advantage of this process
is that the free fatty acid changes completely into esters.
7. A new technology called Biox process, has been developed in
order to overcome the problem of low solubility of methanol
in oils. This process uses a co-solvent to stabilize the alcohol.
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