Energy Conversion and Management 52 (2011) 2741–2751

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Energy Conversion and Management

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

Overview on the current trends in biodiesel production

N.N.A.N. Yusuf, S.K. Kamarudin ⇑, Z. Yaakub
Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

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

Article history: The finite nature of fossil fuels necessitates consideration of alternative fuels from renewable sources. The
Received 18 March 2010 term biofuel refers to liquid, gas and solid fuels predominantly produced from biomass. Biofuels include
Accepted 5 December 2010 bioethanol, biomethanol, biodiesel and biohydrogen. Biodiesel, defined as the monoalkyl esters of vege-
Available online 29 March 2011
table oils or animal fats, is an attractive alternative fuel because it is environmentally friendly and can be
synthesized from edible and non-edible oils. Here, we review the various methods for the production of
Keywords: biodiesel from vegetable oil, such as direct use and blending, microemulsion, pyrolysis and transesterifi-
Biodiesel
cation. The advantages and disadvantages of the different biodiesel-production methods are also dis-
Biofuel
Economy
cussed. Finally, we analyze the economics of biodiesel production using Malaysia as a case study.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction transport sector that are predominantly produced from biomass.

The world is currently facing the worst energy crisis in history.
Many countries worldwide are still heavily dependent on petro-
leum as their main source of electricity and transportation fuel,
and its price has been setting record highs in recent days. Thus,
the only possible solution to this crisis is to find a sustainable
(renewable) and economically feasible source of alternative en-
ergy. There are many alternative energy sources such as wind, so-
lar, geothermal and biomass that fulfill the first criterion
(sustainability). However, few of these can fulfill the second crite-
rion (economic feasibility). The best option, fulfilling both criteria,
is biofuel, particularly that made from readily available biomass
feedstock [1–3]. Biomass refers to all the vegetable matter that
can be obtained from photosynthesis. The great versatility of bio-
mass as a feedstock is evident from the range of materials that
can be converted into various solid, liquid and gaseous fuels using
biological and thermochemical conversion processes. Biomass en-
ergy is by far the largest renewable energy source, representing
10.4% of the world’s total primary energy supply or 77.4% of global
renewable energy supply [4].
The concept of using biofuels in diesel engines originated with
the demonstration of the first diesel engine by its inventor, Rudolf
Diesel, at the World Exhibition in Paris in 1900, using peanut oil as
the fuel. However, due to the then-abundant supply of petroleum
diesel, research and development activities on vegetable-oil fuels
were not seriously pursued. These fuels received attention only re-
cently, when it was realized that petroleum fuels were fast dwin-
dling and environmentally friendly renewable substitutes must
be identified [5,6]. Biofuels are liquid or gaseous fuels for the
⇑ Corresponding author. Tel.: +60 389216422; fax: +60 389216148.
E-mail address: ctie@eng.ukm.my (S.K. Kamarudin).
Biofuels can be produced from a variety of bio-feedstocks, they
are renewable, sustainable, biodegradable, carbon neutral for the
whole life cycle and environmentally friendly; they encourage
green industries and agriculture and are applicable as motor fuels,
without or with slight engine modifications. Several biofuels,
including bioethanol, biomethanol, biodiesel and biohydrogen, ap-
pear to be attractive options for the future of the transport sector.
The production of biofuels is expected to rise steadily in the next
few decades [7]. At present, several countries such Brazil, the Uni-
ted States, Germany, Australia, Italy and Austria are already using
biofuels such as bioethanol and biodiesel. It is expected that this
trend will continue to grow and more countries will use biofuels
[8,9].
Bioethanol is an alternative fuel based on alcohol produced by
the fermentation and distillation of raw materials with high sugars
and starch contents. Besides these raw materials, ethanol can be
obtained from lignocellulosic biomass from trees and some annual
plants. Ethanol can be produced from any organic matter of biolog-
ical origin with considerable amounts of sugars and/or materials
that can be converted into sugar such as starch or cellulose. Sugar-
cane, sugar beetroot, and sugar sorghum are examples of raw
materials with high sugar contents which thus can be used for eth-
anol production. Wheat, barley, and corn are raw materials con-
taining starch, which can easily be converted into sugar using
available technologies. A significant part of the woody part of trees
and annuals is composed of cellulose, which can also be converted
into sugar, but the process is more complicated than that required
for starch [10].
Biomethanol is another alcohol fuel produced from biomass. A
new study patented in Sweden concluded that methanol can be
produced from biomass via black-liquor gasification at a cost com-
petitive with gasoline and diesel [11]. A recent study on oil-palm

0196-8904/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.12.004
2742 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751

biomass waste showed that black liquor can be produced from the Table 1
trunk of the oil palm, but at present the black liquor is used to pro- Physical properties of biodiesel [1].

duce pulp and paper [12]. Common name Biodiesel

Biological hydrogen-generation (biohydrogen) technologies Common chemical name Fatty acid (m)ethyl ester
provide a wide range of approaches to generate hydrogen and Chemical formula range C14–C24 methyl esters or C15–25H28–
are potentially more environmentally friendly and less energy 48O2

intensive than thermochemical or electrochemical processes. Kinematic viscosity range (mm2/s, at 3.3–5.2
313 K)
There are three types of microorganisms used for hydrogen gener- Density range (kg/m3, at 288 K) 860–894
ation: cyanobacteria, anaerobic bacteria and fermentative bacteria. Boling-point range (K) >457
The cyanobacteria directly decompose water into hydrogen and Flash-point range (K) 420–450
oxygen in the presence of light energy by photosynthesis. Photo- Distillation range (K) 470–600
Vapor pressure (mm Hg, at 295 K) <5
synthetic bacteria use organic substrates such as organic acids.
Solubility in water Insoluble in water
Anaerobic bacteria use organic substances as the sole source of Physical appearance Light to dark yellow, clear liquid
electrons and energy, converting them into hydrogen. Biohydrogen Odor Light musty/soapy odor
can be generated using bacteria such as Clostridia by controlling Biodegradability More biodegradable than petroleum
temperature, pH, reactor hydraulic-retention time (HRT), and other diesel
Reactivity Stable, but avoid strong oxidizing
operating parameters of the fermentation system. Biohydrogen can
agents
be generated by direct biophotolysis, indirect biophotolysis, photo-
fermentations and dark fermentation [13].
Among all the biofuels, biodiesel has been receiving perhaps the
common. The B5 blend does not require any engine modification.
most attention, due to the similarity between biodiesel and con-
Biodiesel is perfectly miscible with, and also physically and chem-
ventional diesel in terms of chemical structure and energy content.
ically similar to, mineral diesel and so can be used in compression–
Additionally, no modification of the diesel engine is required, as
ignition engines without significant or onerous adjustments [1,10].
biodiesel is compatible with existing engine models and has been
Biodiesel can be pumped, stored and handled using the same
commercially blended with diesel as a transportation fuel in a
infrastructure, devices and procedure usually employed for con-
number of countries including Germany, Italy and Malaysia [3].
ventional diesel fuel. In fact, as biodiesel does not produce explo-
sive vapors and has a relatively high flash point (close to 150 °C),
transportation, handling and storage are safer than with conven-
2. Biodiesel
tional diesel [17].

Biodiesel is an alternative fuel for diesel engines produced by

2.1. Various raw materials used as feedstock
chemically reacting a vegetable oil or animal fat with an alcohol.
Alcohols are the most frequently used acyl acceptors, particularly
Vegetable oils are becoming a promising alternative to diesel
methanol and, to a lesser extent, ethanol. Other alcohols can also
fuel because they are renewable in nature and can be produced lo-
be used, e.g., propanol, butanol, isopropanol, tert-butanol,
cally and in environmentally friendly ways. Edible vegetable oils
branched alcohols and octanol but the cost is much higher. Regard-
such as canola [18–22] and soybean oil [23–27] in the USA, palm
ing the choice between methanol and ethanol, the former is cheap-
oil [28–33] in Malaysia, rapeseed oil [26,34–38] in Europe and corn
er, more reactive and the fatty-acid methyl esters (FAME) produced
oil [39,40] have been used for biodiesel production and found to be
are more volatile than fatty-acid ethyl esters (FAEE). However, eth-
good diesel substitutes [15]. Non-edible vegetable oils, such as
anol is less toxic and is considered more renewable because it can
Pongamia pinnata (Karanja or Honge) [41–45], Jatropha curcas
be easily produced from renewable sources by fermentation. In
(Jatropha or Ratanjyote) [43,44,46–48] and Madhuca iondica (Ma-
contrast, methanol is currently mainly produced from non-renew-
hua) [49,50] have also been found to be suitable for biodiesel
able fossil sources, such as natural gas. Regarding their character-
production.
istics as fuels, FAME and FAEE show slight differences; for
The oil yield from the crop itself is always the key factor in
example, FAEE have slightly higher viscosities and slightly lower
deciding the suitability of a feedstock for biodiesel production.
cloud and pour points than the corresponding FAME [14]. The reac-
Oil crops with higher oil yields are more preferable in the biodiesel
tion requires a catalyst, usually a strong base, such as sodium or
industry because they can reduce the production cost. Generally,
potassium hydroxide, and produces new chemical compounds
the cost of raw materials accounts for about 70–80% of the total
called methyl esters. It is these esters that have come to be known
production cost of biodiesel. Table 2 shows the oil yields in terms
as biodiesel [15,16].
of kg/ha and wt.% and also the prices for various types of edible and
The physical properties of biodiesel are given in Table 1. Biodie-
sel is a clear amber-yellow liquid with a viscosity similar to that of
petroleum diesel. Biodiesel is non-flammable and, in contrast to Table 2
Oil yields for major non-edible and edible oil sources [2].
petroleum diesel, is non-explosive, with a flash point of 423 K for
biodiesel as compared to 337 K for petroleum diesel. Unlike petro- Type of oil Oil yield Oil yield Price
leum diesel, biodiesel is biodegradable and non-toxic, and it signif- (kg oil/ha) (wt.%) (USD/ton)
icantly reduces toxic and other emissions when burned as a fuel. Non-edible oil
International practice led to the adoption of a single nomencla- Jatropha 1590 Seed: 35–40, N/A
kernel: 50–60
ture to identify the concentration of biodiesel in the blends, known
Rubber seed 80–120 40–50 N/A
as the BXX nomenclature, where XX is the percentage in volume of Castor 1188 53 N/A
the biodiesel in the diesel/biodiesel blend. For example, B2, B5, B20 Pongamia pinnata 225–2250 30–40 N/A
and B100 are fuels with a concentration of 2%, 5%, 20% and 100% Sea mango N/A 54 N/A
biodiesel, respectively. Currently, there are four main concentra- Edible oil
tions of biodiesel used in the fuel market, namely, pure (B100), Soybean 375 20 684
blends (B20–B30), additive (B5) and lubricity-additive (B2). The Palm 5000 20 478
Rapeseed 1000 37–50 683
blends in volumetric proportions between 5% and 20% are the most
 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751 2743

non-edible oils grown worldwide. It is clear that higher oil yield al- problems have been associated with the use of pure vegetable oils
ways corresponds to lower cost. Some of the costs of the non-edi- as fuels in compression–ignition engines, mainly due to the in-
ble oils were not obtained as they are not currently traded on the creased viscosity. Micro-emulsification, pyrolysis and transesterifi-
open market [2]. cation have been used as remedies to solve the problems
From Table 2, it is observed that palm oil has the highest oil encountered due to high fuel viscosity [54].
yield at 5000 kg of oil per hectare; this value is far higher than
other oils, which are only in the range of hundreds to 2000 kg of
2.2.2. Microemulsion
oil per hectare. Among the various non-edible oils shown in Table
Microemulsions are isotropic, clear or translucent, thermody-
2, jatropha has the highest yield, followed by P. pinnata and castor.
namically stable dispersions of oil, water, surfactant, and often a
However, the oil yield in P. pinnata is not constant, depending on
small amphiphilic molecule, called a cosurfactant. The droplet
many factors such as plantation type and oil-extraction technique
diameters in microemulsions range from 100 to 1000 Å. A micro-
[2].
emulsion can be made of vegetable oils with an ester and disper-
sant (cosolvent), or of vegetable oils, an alcohol and a surfactant,
2.2. The production of biodiesel
with or without diesel fuels. Because of their alcohol contents,
microemulsions have lower volumetric heating values than diesel
Considerable efforts have been made to develop vegetable-oil
fuels, but these alcohols have high latent heats of vaporization
derivatives that approximate the properties and performance of
and tend to cool the combustion chamber, which reduces nozzle
hydrocarbon-based diesel fuels. The problems with substituting
coking. A microemulsion of methanol with vegetable oils can per-
triglycerides for diesel fuels are mostly associated with their (i)
form nearly as well as diesel fuels. The use of 2-octanol as an effec-
high viscosity; (ii) low stability against oxidation (and the subse-
tive amphiphile in the micellar solubilization of methanol in
quent polymerization reactions); and (iii) low volatility, which
triolein and soybean oil has been demonstrated; the viscosity
influences the formation of a relatively high amount of ash due
was reduced to 11.2 cSt at 25 °C. The reported engine tests on a
to incomplete combustion [51]. These can be changed in at least
microemulsion consisting of soybean oil:methanol:2-octa-
four ways, as follows.
nol:cetane improver (52.7:13.3:33.3:1) indicated the accumulation
of carbon around the orifices of the injector nozzles and heavy
2.2.1. Direct use and blending
deposits on exhaust valves [55].
Vegetable oil can be mixed with diesel fuel and used directly for
Wellert et al. [56] studied the phase behavior of a microemul-
running an engine. The successful experimental blending of vege-
sion and a bi-continuous phase was identified using small-angle
table oil with diesel fuel has been done by various researchers. A
neutron scattering (SANS) and freeze-fracture electron microscopy
diesel fleet was powered with a blend of 95% filtered used cooking
(FFEM); the influence of choice of co-surfactant on the structural
oil and 5% diesel in 1982. In 1980, Caterpillar Brazil Company used
parameters was also studied. Jesus et al. [57] introduced the use
pre-combustion chamber engines with a mixture of 10% vegetable
of a microemulsion method for the determination of sodium and
oil to maintain total power without any modification to the engine.
potassium in biodiesel using a water-in-oil emulsion process for
A blend of 20% oil and 80% diesel was found to be successful [52].
biodiesel produced from different sources such as soybeans, castor,
Pramanik [53] found that a 50% blend of Jatropha oil can be
sunflower oil, animal fat and other vegetable oils.
used in diesel engines without any major operational difficulties
but further study is required to determine the long-term durability
of the engine. The direct use of vegetable oils and/or the use of oil 2.2.3. Thermal cracking (pyrolysis)
blends have generally been considered to be unsatisfactory and Pyrolysis is the conversion of one organic substance into an-
impractical for both direct and indirect diesel engines. The high other by means of heat or by heat in the presence of a catalyst.
viscosity, acid composition, free fatty-acid content, gum formation The pyrolyzed material can be vegetable oil, animal fat, natural
due to oxidation, polymerization during storage and combustion, fatty acids or methyl esters of fatty acids. The pyrolysis of fats
carbon deposits and lubricating-oil thickening are the obvious has been investigated for more than 100 years, especially in those
problems (see Table 3). areas of the world that lack deposits of petroleum. Many investiga-
It has been proven that the use of 100% vegetable oil was also tors have studied the pyrolysis of triglycerides to obtain products
possible with some minor modifications to the fuel system. Major suitable for diesel engines. Thermal decomposition of triglycerides

Table 3
Problems and potential solutions for using vegetable oils as engine fuels [53].

Problem Probable cause Potential solution

Short-term
1. Cold-weather starting
2. Plugging and gumming of
filters, lines and injector
3. Engine knocking
Long-term
4. Coking of injectors and
carbon deposits on
piston and head of
engine
5. Excessive engine wear
6. Failure of engine-
lubricating oil due to
polymerization
High viscosity, low cetane, and low flash point of vegetable oils
Natural gums (phosphatides) and ash in vegetable oil
Very low cetane of some oils. Improper injection timing
High viscosity of vegetable oil, incomplete combustion of fuel;
poor combustion at partial load
High viscosity, incomplete combustion of fuel, poor combustion at
partial load; possibly free fatty acids in vegetable oil; dilution of
engine-lubricating oil due to blow-by of vegetable oil
Collection of poly-unsaturated vegetable oil blow-by in crank-case
to the point where polymerization occurs
Preheat fuel prior to injection; chemically alter fuel to an ester
Partially refine the oil to remove gums; filter to 4 lm
Adjust injection timing; preheat fuel prior to injection; chemically
alter fuel to an ester
Heat fuel prior to injection; switch engine to diesel when operating
at part load; chemically alter the vegetable oil to an ester
Heat fuel prior to injection; switch engine to diesel when operating
at partial load; chemically alter the vegetable oil to an ester;
increase frequency of lubricating-oil changes; lubricating-oil
additives to inhibit oxidation
2744 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751
produces alkanes, alkenes, alkadienes, aromatics and carboxylic
acids [53,68].
2.2.4. Transesterification
Transesterification is a process of reacting a triglyceride such as
vegetable oil with an alcohol in the presence of an alkaline catalyst
to produce fatty-acid esters and glycerol. Among the alcohols,
methanol and ethanol are used commercially because of their
low cost and their physical and chemical advantages. They are eas-
ily dissolved in and react quickly with tri-glycerides and NaOH. A
catalyst is used to improve the reaction rate and yield. An alka-
line-catalyzed transesterification process is normally adopted for
biodiesel production because alkaline metal alkoxides and hydrox-
ides are more effective than acid catalysts. Sodium and potassium
methoxide are much more effective catalysts for the base-cata-
lyzed transesterification of triglycerides [58–61].
Darnoko and Cheryan [62] studied the kinetics of palm-oil
transesterification in a batch reactor. Their study illustrated that
while the overall conversion of the process did not change with
temperature, the rate of the transesterification process was in-
creased with temperature. The overall reaction kinetics is depen-
dent on the individual rate constants for the conversion of
triglycerides to diglycerides, monoglycerides and alcohol esters.
Based on the rate constants obtained, the conversion of triglycer-
ides to diglycerides was the slowest reaction in transesterification.
The time needed for the mass transfer to occur is shortened as tem-
perature is increased, leading to a higher rate of transesterification
at higher temperatures.
Figs. 1–3 represent the different transesterification reactions.
Fig. 1 shows the production of biodiesel via an alkaline catalyst.
The commonly used catalysts are sodium and potassium hydrox-
ides. These reactions are operated at 25–125 °C. Fig. 2 presents
the production of biodiesel using an acid catalyst. The reaction is
similar to the alkaline reaction but the alcohol reactants are fed
in excess in order to increase the conversion rate. This reaction is
Fig. 1. Production of biodiesel via alkaline catalysis.
operated at 55–80 °C. The other type of reaction for transesterifica-
tion is enzymatic, using lipase in hydrolysis, alcoholysis and acid-
olysis reactions. The advantage of this reaction is the ease of
product separation; however, the cost of the biocatalyst is very
expensive compared to other catalysts and so it is not yet a viable
process for commercial biodiesel production. Lastly, Fig. 3 presents
the production of biodiesel via a supercritical reaction with alco-
hol. This reaction uses methanol as alcohol and is capable of pro-
ducing high conversions in a short period of time. However the
operating temperature is very high, around 350 °C [63,64]. Table
4 summarizes the advantages and disadvantages of the different
transesterification reactions.
2.3. Advantages of biodiesel
2.3.1. Availability and renewability of biodiesel
Biodiesel is the only alternative fuel with the property that low-
concentration biofuel–petroleum fuel blends will run well in
unmodified conventional engines. It can be stored anywhere petro-
leum diesel fuel is stored. Biodiesel can be made from domestically
produced, renewable oilseed crops such as soybean, rapeseed and
sunflower. The risks of handling, transporting and storing biodiesel
are much lower than those associated with petroleum diesel. Bio-
diesel is safe to handle and transport because it is as biodegradable
as sugar and has a high flash point compared to petroleum diesel
fuel. Biodiesel can be used alone or mixed in any ratio with petro-
leum diesel fuel. The most common blend is a mix of 20% biodiesel
with 80% petroleum diesel, or B20 in recent scientific investiga-
tions; however, for future commercial applications in Europe the
current regulation foresees a maximum of 5.75% biodiesel [66].
2.3.2. Lower emissions from biodiesel
The European Transportation Policy for 2010 created by the
European White Paper Commission projects an increase in carbon
dioxide emissions from vehicles of about 50% from the years 2000
 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751 2745

Fig. 2. Production of biodiesel via acidic catalysis.

Fig. 3. Production of biodiesel via supercritical-alcohol transesterification.

Table 4
Comparison of transesterification reactions [65].

Technique Biodiesel (%) Advantage Disadvantage

Acidic-catalyst 99% after 4 h of High production of biodiesel Acidic catalyst
transesterification reaction
Alkaline-catalyst 99% after 2 h of High and rapid production of biodiesel in a short Formation of calcium foam at initial stage of
transesterification reaction period of time transesterification
Lipase-catalyst 95% after 105 h of Can be operated at room temperature Slow reaction
transesterification reaction
2746 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751
to 2010. The White Paper states that the only way around this
problem is to develop clean alternative fuels so that the green-
house effects can be decreased [67]. The best potential future en-
ergy source in the transportation sector is biodiesel.
Biodiesel mainly emits carbon monoxide, carbon dioxide, oxi-
des of nitrogen, sulfur oxides and smoke. Combustion of biodiesel
alone provides over a 90% reduction in total unburned hydrocar-
bons (HC) and a 75–90% reduction in polycyclic aromatic hydrocar-
bons (PAHs). Biodiesel further provides significant reductions in
particulates and carbon monoxide over petroleum diesel fuel. Bio-
diesel provides a slight increase or decrease in nitrogen oxides
depending on engine family and testing procedures [66].
Currently, global warming caused by CO2 is the main climatic
problem in the world. Therefore, environmental protection is
important for the future of the world. Because biodiesel is made
from renewable sources, it presents a convenient way to provide
fuel while protecting the environment from unwanted emissions.
Biodiesel is an ecological and non-hazardous fuel with low emis-
sion values, and therefore it is environmentally useful. Using bio-
diesel as an alternative fuel is a way to minimize global air
pollution and in particular reduce the emission levels of potential
or probable carcinogens [68].
Carraretto et al. [69] investigated the emission of unburned
hydrocarbons, carbon dioxide, carbon monoxide, sulfates, polycy-
clic aromatic hydrocarbons, nitrated polycyclic aromatic hydrocar-
bons and particulate matter from biodiesel; the net emission of
CO2 was considerably lower than that of diesel oil. Kegl [70]
stressed the importance of fuel-injection system to reduce engine
emissions as well as fuel consumption. The author suggested that
pressure squareness (ratio of mean to maximum injection pres-
sure) should be at a maximum, and fuelling in the first part of
the injection should be reduced to reduce NOx emission. Simulta-
neously, the fuelling in the last part of the injection should be low-
ered to reduce smoke emissions.
Pradeep and Sharma [71] studied the use of hot-exhaust-gas
recirculation for the control oxides of nitrogen in a compression–
ignition engine fuelled with biodiesel from Jatropha oil. Exhaust-
gas recirculation was shown to be an effective method for NOx con-
trol. The exhaust gases mainly consist of inert carbon dioxide and
nitrogen and possess a high specific heat. When recirculated to the
engine inlet, they reduce oxygen concentration and act as a heat
sink. This process reduces oxygen concentration and peak combus-
tion temperature, which results in reduced NOx. Exhaust-gas recir-
culation is not free from demerits. It can significantly increase
smoke and fuel consumption and reduce thermal efficiency unless
suitably optimized.
2.3.3. Biodegradability of biodiesel
The biodegradability of biodiesel has been proposed as a solu-
tion for the waste problem. Biodegradable fuels such as biodiesels
have an expanding range of potential applications and are environ-
mentally friendly. Therefore, there is growing interest in degrad-
able diesel fuels that degrade more rapidly than conventional
petroleum fuels. Biodiesel is non-toxic and degrades about four
times faster than petroleum diesel. Its oxygen content improves
the biodegradation process, leading to an increased level of quick
biodegradation [72].
Vegetable-oil methyl esters are reported to be non-toxic and
easily biodegradable in an aquatic environment. It was determined
that during a 21-day period, 98% of pure rapeseed oil methyl ester
(RME) was biologically decomposed, while only 60% of pure fossil
diesel fuel decomposed. This means that RME fully meets the main
requirements of international standards for biological degradation
(more than 90% degraded within 21 days for biofuels) [73]. Pasqua-
lino et al. [74] reported more than 98% degradation of pure biodie-
sel after 28 days in comparison to 50% and 56% for diesel fuel and
gasoline respectively. Also, the time taken to reach 50% biodegra-
dation was reduced from 28 to 22 days in 5% biodiesel mixture
and from 28 to 16 days in the case of a 20% biodiesel mixture at
room temperature. The biodegradability of the mixture was re-
ported to increase with the addition of biodiesel.
2.3.4. Higher lubricity
Biodiesel has good lubricant properties compared to petroleum
diesel oil, in particular very-low-sulfur diesel. This is very impor-
tant to reduce wear in the engine and the injection system [69].
Demirbas [68] stated that the oxygen content of biodiesel im-
proves the combustion process and decreases its oxidation poten-
tial. The structural oxygen content of a fuel improves combustion
efficiency due to the increase of the homogeneity of oxygen with
the fuel during combustion. Due to this, the combustion efficiency
of biodiesel is higher than petroleum diesel, and the combustion
efficiency of methanol/ethanol is higher than that of gasoline. A vi-
sual inspection of the injector types would indicate no difference
between the biodiesel fuels when tested on petroleum diesel.
The overall injector coking is considerably low. Biodiesel contains
11% oxygen by weight and contains no sulfur. The use of biodiesel
can extend the life of diesel engines because it is more lubricating
than petroleum diesel fuel.
The higher heating values (HHVs) of biodiesels are relatively
high. The HHVs of biodiesels (39–41 MJ/kg) are slightly lower than
that of gasoline (46 MJ/kg), petroleum diesel (43 MJ/kg) or petro-
leum (42 MJ/kg), but higher than coal (32–37 MJ/kg). Table 5
shows a comparison of the chemical properties and HHVs of bio-
diesel and petroleum–diesel fuels.
2.3.5. Engine-performance evaluation using biodiesel
Cetane number (CN) is widely used as a diesel–fuel quality
parameter. It is related to the ignition-delay time and combustion
quality; a higher cetane number indicates better ignition proper-
ties [16]. CN is measured by the ISO 5156 test method. This test
method is recommended for diesel and biodiesel and the passing
limits are 46 and 51, respectively. However, there are reports of
the theoretical estimation of cetane numbers without running
extensive engine tests. The cetane number of biodiesel from vari-
ous sources has been estimated to vary from 48 (grape biodiesel)
to 61 (palm biodiesel) [75]. The CN of biodiesel is generally higher
than for conventional diesel. The longer the fatty-acid carbon
chains and the more saturated the molecules are, the higher the
CN is. The CN of biodiesel from animal fats is higher than those
of vegetable oils [76].
Altın et al. [77] studied a single-cylinder engine fueled with var-
ious types of vegetable oils. The results obtained gave a very good
comparison of engine performance when various vegetable oils are
used as fuel. The engine was operated at 1300 rpm and a torque of
35 Nm. Petroleum diesel–fuel performance was used as a refer-
ence. The observed maximum torque differences between the ref-
erence value and peak values of the vegetable-oil fuels were about
10% with raw sunflower oil, raw soybean oil and opium-poppy oil
fuels. The maximum power differences between the reference
Table 5
Comparison of chemical properties and higher heating values (HHVs) of biodiesel and
petroleum–diesel fuels [63].
Chemical property Biodiesel (methyl ester) Diesel
Ash (wt.%) 0.002–0.036 0.006–0.010
Sulfur (wt.%) 0.006–0.020 0.020–0.050
Nitrogen (wt.%) 0.002–0.007 0.0001–0.003
Aromatics (vol.%) 0 28–38
Iodine number 65–156 0
HHV (MJ/kg) 39.2–40.6 45.1–45.6
 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751 2747

value and peak values of the vegetable-oil fuels were about 18% Table 6
with raw cottonseed oil and raw soybean oil. The minimum torque ASTM standards of biodiesel and petroleum–diesel fuels.

and power difference was about 3% between the reference value Property Test ASTM D975 ASTM D6751
and the oils. These results may be due to the higher viscosity and method (petroleum diesel) (biodiesel, B100)
lower heating values of vegetable oils. The specific fuel consump- Flash point D 93 325 K min 403 K
tion of petroleum diesel was very low in comparison with all veg- Water and sediment D 2709 0.05 max vol.% 0.05 max vol.%
etable oils and their esters. Specific fuel-consumption values of Kinematic viscosity D 445 1.3–4.1 mm2/s 1.9–6.0 mm2/s
(at 313 K)
methyl esters were generally less than those of the raw oil fuels. Sulfated ash D 874 – 0.02 max wt.%
The higher specific fuel-consumption values of vegetable oils are Ash D 482 0.01 max wt.% –
due to their lower energy contents. Relatively low CO emissions Sulfur D 5453 0.05 max wt.% –
were obtained with the esters in comparison with raw vegetable Sulfur D – 0.05 max wt.%
2622/
oils. Maximum CO2 emissions were about 10.5% with petroleum
129
diesel fuel and slightly lower with vegetable oil. This was due to Copper-strip corrosion D 130 No. 3 max No. 3 max
the better spraying qualities and more uniform mixture prepara- Cetane number D 613 40 min 47 min
tion of these esters. NOx emissions with vegetable-oil fuels were Aromaticity D 1319 35 max vol.% –
lower than those with petroleum diesel fuel and the NOx values Carbon residue D 4530 – 0.05 max mass%
Carbon residue D 524 0.35 max mass% –
of the methyl esters were higher than those of the raw fuels. NOx
Distillation temp. (90% D 1160 555 K min– –
formation is related to maximum combustion temperature. As volume recycle) 611 K max
the injected particle size of the vegetable oils was greater than
with petroleum diesel fuel, the combustion efficiency and maxi-
mum combustion temperatures with each of the vegetable oils
were lower and NOx emissions were reduced. Smoke-opacity per-
centages during each of the vegetable-oil operations were greater
than that with petroleum diesel fuel. The opacity values of methyl
esters were between those of diesel fuel and raw vegetable-oil
fuels. The greater smoke-opacity percentages of the vegetable-oil
fuels were mainly due to the contents of heavier hydrocarbon mol-
ecules. Acceleration tests indicated that maximum engine-power
output depended on the biodiesel content in the fuel and de-
creased as the biodiesel concentration increased.
It was observed that with pure biodiesel the acceleration time
increased by approximately 8% compared to the baseline petro-
leum diesel fuel, while B50 led to an increase of 4.1%. These differ-
ences were expected due to the lower energy content of the blends.
Poorer atomization may also explain reductions in maximum en- Fig. 4. Global vegetable-oil blending stock and biodiesel production [2].
gine-power output [78].
imbalance in the food supply-and-demand market. Recently, envi-
2.4. Disadvantages of biodiesel ronmentalists have cited the negative impact on the planet of bio-
diesel production from edible oils, especially deforestation and the
The main problem associated with the use of biodiesel, espe- destruction of ecosystems. EEB, claimed that the expansion of oil-
cially that prepared from palm oil, is its poor low-temperature flow crop plantations for biodiesel production on a large scale has
properties, measured in terms of cloud point, pour point and CFPP. caused deforestation in countries such as Malaysia, Indonesia and
The low-temperature properties are very critical for the use of bio- Brazil because more and more forest has been cleared for planta-
fuels in aviation applications. The low-temperature properties can tion purposes. Furthermore, the line between food and fuel econo-
be improved by blending with biodiesel from unsaturated feed- mies is blurred as both of the fields are competing for the same oil
stocks [79]. resources. In other words, biodiesel is competing with the food
Other major disadvantages of biodiesel are its higher viscosity, industry for limited land availability for the plantation of oil crops.
lower energy content, higher nitrogen-oxides (NOx) emissions, Arable land that would otherwise have been used to grow food
lower engine speed and power, injector coking, engine compatibil- would instead be used to grow fuel [80].
ity, high price and higher engine wear. Table 6 shows the ASTM There has been significant expansion in the plantation of oil
fuel standards for biodiesel and petroleum-diesel fuels. Important crops for biodiesel in the past few years in order to fulfill the con-
operating disadvantages of biodiesel in comparison with petro- tinuously increasing demand for biodiesel. Fig. 4 shows the trend
leum diesel include cold-start problems, the lower energy content, in global vegetable-oil blending stocks due to the production of
higher copper-strip corrosion and fuel-pumping difficulty due to biodiesel in the years 1991–2010 [2]. Although there is continuous
the higher viscosity. This increases fuel consumption when biodie- increase in the production of vegetable oil, the blending stocks of
sel is used, in comparison with pure petroleum diesel and in vegetable oils are continuously decreasing due to increasing pro-
blends, in direct proportion to the share of the biodiesel content. duction of biodiesel. Eventually, with the implementation of bio-
Taking into account the higher production costs of biodiesel com- diesel as a substitute fuel for petroleum-derived diesel oil, this
pared to petroleum diesel, this increase in fuel consumption com- may lead to the depletion of edible-oil supply worldwide.
pounds the overall increased cost of application of biodiesel as an
alternative to petroleum diesel [63].
As more than 95% of biodiesel is made from edible oil, there 3. Current trends in biodiesel
have been many claims that this may give rise to further economic
problems. By converting edible oils into biodiesel, food resources The international biofuel market is still at an early and very
are being used as automotive fuels. It is believed that large-scale dynamic stage. Future conditions for an international biofuel mar-
production of biodiesel from edible oils may bring about a global ket in Europe will largely be decided by the European Union (EU)
2748 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751

policies on renewable energy and their interplay with national en-
ergy policies. So far, the Commission has indicated that biomass
will play an important role in the future. In that context, the biofuel
trade seems to be a plausible scenario for Europe. It is likely that
novel trade flows will appear and disappear as this new fuel mar-
ket evolves [81].
European research and testing indicate that, when used as a die-
sel fuel substitute, biodiesel can replace petroleum diesel. Fig. 5
shows the world biodiesel capacity between 1991 and 2010. In
the EU, biodiesel is by far the biggest biofuel and represents 82%
of the biofuel production.
Biodiesel has become more attractive recently because of its
environmental benefits. The cost of biodiesel, however, is the main
obstacle to commercialization of the product. Biodiesel reduces
carbon dioxide, carbon monoxide, PAH and nitrated PAH emis-
sions. The use of biodiesel decreases the solid-carbon fraction of
PM and reduces the sulfate fraction, while the soluble, or HC, frac-
tion stays the same or increases. Emissions of nitrogen oxides in-
crease with the concentration of biodiesel in the fuel. Some
biodiesel produces more nitrogen oxides than others, and some
additives have shown promise in moderating the increases. Ger-
many produced 1.9 billion liters or more than half the world total.
Other countries with significant biodiesel markets in 2005 in-
cluded France, the United States, Italy and Brazil. All other coun-
tries combined accounted for only 11% of world biodiesel
consumption in 2005. In Germany biodiesel is also sold at a lower
Fig. 5. World biodiesel capacity, 1991–2010 [82].
price than fossil diesel fuel. Biodiesel is treated like any other vehi-
cle fuel in the UK. In February 2006, the European Union set the
goal of fulfilling 5.75% of transportation-fuel needs with biofuels
in all member states by 2010. Many countries have adopted vari-
ous policy initiatives. Specific legislation to promote and regulate
the use of biodiesel is in force in Germany, Italy, France, Austria
and Sweden [68]. By 2010, the United States is expected to become
the world’s largest single biodiesel market, accounting for roughly
18% of world biodiesel consumption, followed by Germany. New
and large single markets for biodiesel are expected to emerge in
China, India and Brazil [83].
Demand for energy is increasing every day due to the rapid
growth of population and urbanization. As the major conventional
energy resources such as coal, petroleum and natural gas are at the
verge of becoming extinct; biomass can be considered as one of the
promising environmentally friendly renewable energy options
[13]. The biomass-intensive future energy-supply scenario in-
cludes 385 million hectares of biomass-energy plantations globally
in 2050, with three quarters of this area established in developing
countries [84].
Based on a study conducted by the 9th National Plan of Malay-
sia, the demand for fossil fuel is increasing continuously. In the
term of the 8th National plan of Malaysia, which ranged from
2000 to 2005, the demand for energy in the commercial sector in-
creased from 1244 PJ to 1632 PJ. The energy intensity increased
from 5.9 GJ in the year 2000 to 6.2 GJ in the year 2005. Petroleum
is the main source of energy, and, as shown in Table 7a, the per-
centage from other energy sources is very low (4–6%). The increas-
ing demand for natural gas (7–9%) parallels the policy of fuel-
source diversity. From Table 7b, it can also be observed that the
transportation sector is the primary energy consumer in Malaysia,
accounting for 40.5% of the total energy demand in the commercial
sector in the 2005. The industrial sector comprises 38% of the total
demand while domestic and other sources account for about 13.1%.
Based on these figures, Malaysia is predicted to become a net im-
porter of fossil fuels by the year 2015. However, the introduction
of alternative fuels such as hydrogen, ethanol and biodiesel, will
reduce the dependence on imported fuel sources. Malaysia is capa-
ble of generating its own alternative fuels, as mentioned previ-
ously, using domestic renewable resources [65]. The potential
future use of biodiesel in the transportation sector necessitates a
shift in the current energy supply from petroleum products such
as gasoline and diesel, to biodiesel.

Table 7a
Final demand of commercial energy by source, 2000–2010 [65].

Source Petajoules Percentage of the total Average annual growth rate (%)
2000 2005 2010 2000 2005 2010 RMKe-8 RMKe-9
Petroleum products 820.0 1023.1 1372.9 65.9 62.7 61.9 4.5 6.1
Natural gas 161.8 246.6 350.0 13.0 15.1 15.8 8.8 7.3
Electricity 220.4 310.0 420.0 17.7 19.0 18.9 7.1 6.3
Coal 41.5 52.0 75.0 3.4 3.2 3.4 4.6 7.6
Total 1243.7 1631.7 2217.9 100.0 100.0 100.0 5.6 6.3

Table 7b
Final demand of commercial energy by sector, 2000–2010 [65].

Source Petajoules Percentage of the total Average annual growth rate (%)
2000 2005 2010 2000 2005 2010 RMKe-8 RMKe-9
Industrial 477.6 630.7 859.9 38.4 38.6 38.8 5.7 6.4
Transportation 505.5 661.3 911.7 40.6 43.5 41.1 5.5 6.6
Residential and commercial 162.0 213.0 284.9 13.0 13.1 12.8 5.6 6.0
Agricultural 4.4 8.0 16.7 0.4 0.5 0.8 12.9 15.9
Total 1243.7 2217.9 1631.7 100.0 100.0 100.0 5.6 6.3
 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751 2749

The large-scale use of biomass energy in the EU would be facil- Table 8

itated by a European market for biofuels. Regions rich in biomass Comparison of estimated costs for producing biodiesel from palm, rapeseed and
soybean oils.
resources could become net exporters of biofuels to regions with
fewer opportunities for biofuel production, which would increase Cost component (US$/ ton) Palm oil Rapeseed Soybean
the Union’s total use of biomass energy. Inter-regional and interna- from oil from the oil from
Malaysia EU the US
tional biofuel trade is also a likely consequence of the growing use
of biomass energy. At the moment, there is a mounting interest in Feedstock (FOB at producing country) 547 800 601
Biodiesel production cost:
the biofuel trade in Europe [81]. Solvents, acids and chemicals 47 – –
Kartha and Larson [84] reported that various scenarios have Other costs 35 – –
been proposed in estimating the yields of biofuels from biomass Adjustment for energy parity with 55 – –
sources in the future energy system. The availability of resources petroleum diesel (based on 90%
of kJ/kg of energy of petrol–diesel)
is an important factor in cogenerative use of biofuel in the electric-
Total 137 196 150
ity, heat or liquid-fuel market. There are currently two global bio- Cost of biodiesel 684 996 751
mass-based liquid transportation fuels that might replace gasoline Estimated freight and insurance cost 70 – 50
and diesel fuel, bioethanol and biodiesel. Transport is one of the to Rotterdam
main energy-consuming sectors. It is assumed that biodiesel will Total cost in EU 754 996 801
Local distribution (approximation) 30–50 30–50 30–50
be used as a fossil diesel replacement and that bioethanol used
Total cost at petrol kiosk in EU 784–804 1029–1046 831–851
as a gasoline replacement. Biomass-based energy sources for heat, Price of retail biodiesel (Germany)a 1322
electricity and transportation fuels are potentially carbon dioxide
Assuming production plant with capacity > 100,000 ton/annum; other figures based
neutral and recycle the same carbon atoms. Due to the widespread
on pricing as of March 2007.
availability of biomass resources, opportunities for biomass-based a
FO Licht based on UFOP Marktinformation (three-month average retail prices
fuel technology will potentially employ more people than current from November 2006 to January 2007).
fossil-fuel based technology.
About 60% of current world ethanol production is from sugar-
relatively small quantities (in comparison to petroleum products
crop feedstocks. Ethanol is a well-established biofuel for transport
and ethanol). The competitiveness of biodiesel versus petroleum
and industry sectors in several countries, notably in Brazil. The
diesel depends greatly on fuel-taxation approaches and levels.
United States has used ethanol produced from maize (corn) in fuel
Generally, the production costs of biodiesel remain much higher
blends since the 1980s. The United States ethanol production, with
than for petroleum diesel. Therefore, biodiesel is not competitive
corn as the primary feedstock, totaled 2821 million gallons in 2003
to petroleum diesel under current economic conditions. The com-
and is projected to increase to 4544 million gallons in 2025. In
petitiveness of biodiesel relies on the prices of biomass feedstock
2004, 3.4 billion gallons of fuel ethanol were produced from over
and costs as well as the conversion technology [63].
10% of the corn crop. Ethanol demand is expected to more than
The price of the feedstock will become a more important factor
double in the next ten years. For the supply to be available to meet
as it represents 80% of the cost of biodiesel production. Even at cur-
this demand, new technologies must be moved from the laboratory
rent vegetable oil prices this is an advantage for palm oil which
to commercial reality [82].
trades at a considerable discount compared to rapeseed oil and
soybean oil.
Rabobank [85] estimates that the price of palm biodiesel in the
4. Economic analysis
EU – if produced in Malaysia – will be about US$784–804/ton (Ta-
ble 8). The estimated theoretical production cost for rapeseed bio-
One of the main limiting factors for the market diffusion of bio-
diesel is US$1035/tonne and US$840 for soybean biodiesel. These
diesel is the high economic cost of production compared to petro-
figures are based on the average prices of each vegetable oil,
leum diesel oil. Currently, the cost of biodiesel is competitive only
including an approximately 20% cost of production, international
when excise tax is not applied. Nevertheless, the promotion of bio-
freight and domestic distribution charges. The reported consumer
diesel is justified by the fact that the global emission of CO2 is
biodiesel price in Germany, based on a three-month average up
greatly reduced and that the net energy yield is positive. In addi-
to January, was US$1332/ton. Palm biodiesel from Malaysia is still
tion, the use of biodiesel involves an appreciable reduction of some
competitively priced although this estimate does not consider any
emitted pollutants. This could be a key solution to reduce urban
potential excise nor import duty that could be imposed by the EU
pollution [69].
member-states on palm methyl ester.
The major economic factor to consider for the input costs of bio-
diesel production is the feedstock, which is about 80% of the total
operating cost. Other important costs are labor, methanol and cat- 5. Conclusions
alyst. In some countries, filling stations sell biodiesel more cheaply
than conventional diesel. The cost of biodiesel fuels varies depend- The term biofuel refers to liquid or gaseous fuels for the trans-
ing on the base stock, geographic area, variability in crop produc- port sector that are predominantly produced from biomass. Biofu-
tion from season to season, the price of crude petroleum and els including bioethanol, biomethanol, biodiesel and biohydrogen
other factors. Biodiesel has sold for over twice the price of petro- appear to be attractive options for the future transport sector. Bio-
leum diesel. The high price of biodiesel is in large part due to the diesel is better than diesel fuel in terms of sulfur content, flash
high price of the feedstock. Biodiesel is becoming of interest to point, aromatic content and biodegradability.
companies for commercial-scale production as well as the more Biodiesel, defined as the monoalkyl esters of fatty acids derived
usual ‘‘home-brew’’ biodiesel user and the user of straight vegeta- from vegetable oil or animal fat, has demonstrated a number of
ble oil or waste vegetable oil in diesel engines. Biodiesel is com- promising characteristics in applications as an extender for com-
mercially available in most oilseed-producing countries. Biodiesel bustion in compression–ignition engines (CIEs), including a reduc-
is a technologically feasible alternative to petroleum diesel, but tion of exhaust emissions. Biodiesel is much less polluting than
currently biodiesel cost is 1.5–3 times higher than the fossil diesel petroleum diesel, resulting in much lower emissions of almost
cost in developed countries. Biodiesel is more expensive than every pollutant: carbon dioxide, sulfur oxide, particulates, carbon
petroleum diesel, although it is still commonly produced in monoxide, air toxics and unburned hydrocarbons. Biodiesel does,
2750 N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 2741–2751

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