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Abstract - Energy demand in the world is expected to increase due to growing industrialization, urbanization and modernization,
better living standards and increasing population. The major part of the energy is derived from fossil sources such as petroleum,
coal and natural gas. However, the increasing awareness of energy security has driven the research interest for the development
of alternative fuel from plant origin and the environmental benefits of biodiesel fuel have made it more attractive in recent times.
Such fuel should be economically attractive and performance competent in order to replace the fossil fuel. There are different
potential feedstocks for biodiesel production. Biodiesel derived from plant oils, gained interest in the last two decades as an
alternative for diesel around the world. The production of biodiesel from plant oils is an effective way to overcome all the
associated problems with other feedstocks. This paper includes plant oils to be used as biodiesel feed-stocks, enhancement in
technologies of biodiesel production, characterization and engine performance.
Keywords - Biodiesel Production, Transesterification, Evaluation, Economic Feasibility
1. Introduction
Fossil fuel availability constraints, ever increasing prices, and environmental effects due to extensive use of fuel are some of the
concerns that lead to the search for alternatives sources for such petroleum products. Biodiesel from renewable resources is one
of the most attractive alternative fuels with high quality, which allows the substitution of fossil diesel oil without engine
modifications. With this perspective, considerable attention has been drawn toward the production of biodiesel as a direct
substitute or a blending option with fossil fuel to increase its performance efficiency. Biodiesel is a diesel-equivalent processed
fuel composed of mono-alkyl esters of long chain fatty acids derived from renewable sources, such as plant oils and animal fats.
Plant oils commonly used for biodiesel production are Jatropha curcas, Simarouba glauca, Sesamum indicum (Sesame), Ricinus
communis (Castor), Glycine max (Soybean) , Brassica napus (Rapeseed), Gossypium sp. (Cotton) seed oil, Oryza sativa (Rice)
bran oil, Pongamia pinnata (Karanja), Madhuca longifolia (Mahua), Elaeis guineensis (Palm) kernel oil and Brassica juncea
(Indian Mustard) oil. Biodiesel is produced by the transesterification of these lipids. Plant oils usually contain free fatty acids,
phospholipids, sterols, water, odorants and other impurities. The free fatty acids and water contents have significant negative
effects during the transesterification reaction of glycerides with alcohols using alkali or acid catalysts since they causes soap
formation, consume catalysts and reduce its effectiveness and result in a lower conversion. Recently, Shirazi et al (2013) reported
the acceleration of glycerol/biodiesel decantation through NaCl-assisted gravitational settling as an economizing strategy for
biodiesel production.
Biodiesel is biodegradable and nontoxic, and it possesses low emission profiles. It provides engine lubricity to low sulphur
diesel fuels and has a higher flash point that makes it easier to handle and store. However, few properties of biodiesel have to be
improved to make it usable in neat form (i.e. 100% biodiesel). These properties are, increase in calorific value, engine power;
reduced emission of NOx, and improvement in low temperature properties (Hoekman et al. 2010; Ozsezen et al. 2010). The
hydrocarbon emissions show a continuous reduction with increasing biodiesel blend ratios (Tan et al. 2012). One of the major
hurdles in commercialization of biodiesel is the cost in comparison to petroleum-based diesel fuel. The high cost is primarily due
to the raw material, mostly neat vegetable oil. Therefore in our previous publication (Singh et al. 2010), used cooking oil
(Mustard) was selected which is one of the economical sources for biodiesel production.
During the year 2011, the total world consumption of oil was 87.7 million barrels/day of which India consumed 3.42 million
barrels/day, which amounted to 3.9% of the global consumption, making India the fourth highest consuming nation, preceded by
US, China and Japan (OPEC, 2012). The Government of India, had launched National Biofuel Mission, in 2003, followed by
National Biofuel Policy in 2009, with approach of setting an indicative target of 20% blending of biofuel (biodiesel and
bioethanol) by 2017 ( http://mnre.gov.in/file-manager/UserFiles/biofuel_policy.pdf). Germany and France have known to be the
34 Journal of Biotechnology, Bioinformatics and Bioengineering (2014) 33-42
major producers of biodiesel along with some contribution by US. Some other mentionable biodiesel producers are Argentina,
Brazil, China, India, Indonesia and Malaysia. The expected production is projected to increase 56 percent by 2025 (OPEC,
2012).
The present review discusses the potential of plant oils for biodiesel production and recent research related to techniques
involved in the production. The present review will be helpful for researchers to develop new technologies for biodiesel
production and to optimize and readjust biodiesel engine and its relevant systems. Several aspects related to engine performances
for biodiesel such as specific fuel consumption, brake horsepower, and thermal efficiency are introduced and summarized.
2. Biodiesel Production
The biodiesel production has seen a quantum jump in the recent past due to benefits associated with its ability to mitigate fossil
fuels. There are large numbers of commercial plants producing biodiesel by transesterification of plant oils and most widely used
industrial method is a base catalyzed transesterification process using KOH or NaOH as the homogeneous catalyst and MeOH as
the lower alcohol (Fig 1). The enhancements in biodiesel production are generally aimed at generating high quality biodiesel that
conforms to international standards such as ASTM or EN standard. There are four different methods to produce biodiesel from
bioresources blending, micro-emulsion, pyrolysis and transesterification. Direct use and blending of raw oils are among the early
approaches where plant oils are used directly or diluted with petroleum diesel to run the engine.
2.1. Feedstocks
The feed-stock must fulfill two foremost requirements: low manufacture expenses (yields profit) and large manufacture scale
(enough to substitute petro-diesel needs). In the production of biodiesel more than 95% of feed stocks come from plant oils since
they are mainly produced in many regions of the world and the properties of biodiesel produced from these oils are much suitable
to be used as diesel fuel substitute. However, use of edible oil to produce biodiesel is not feasible in view of a big gap in demand
and supply of such oils as food and they are far expensive to be used at present. Therefore, the use of non-edible vegetable oils
(non-edible oil source which are not suitable for human consumption because of the presence of some toxic components in the
oils) compared to edible oils is very significant. The cost of raw materials accounts about 60–80% of the total cost of biodiesel
production, so choosing a right feed stock is very important and properties of biodiesel produced from different feed stocks
would be quite different.
Production of biodiesel from plant oils can overcome the problems of food verse fuel as plants can also be planted on
cultivators’ field boundaries, fallow lands, and in public land such as along railways, roads and irrigation canals to solve the
economic issues related to plant oils. Table 1, enlisted the list of potential plant oils for biodiesel production. Biodiesel has been
categorised as; first generation biodiesel – pure plant oils or crop oils extracted that were also used as food or consisted of food
residues, viz., soyabean, peanut, palm, rice bran; and second generation biodiesel – non-edible plant oils, viz., Jatropha curcas,
Pongamia pinnata or waste vegetable oils. Non-edible vegetable oils can be considered as promising substitutions for traditional
edible food crops for the production of biodiesel. The use of non-edible plant oils is very significant because of the great demand
for edible oils as food source. Moreover, edible oils' feedstock costs are far expensive to be used as fuel. Therefore, biodiesel
production from non-edible oils is an effective way to overcome all the associated problems with edible oils. The appropriateness
of biodiesel produced to be used as diesel fuel substitute depends upon the properties of feedstocks.
Journal of Biotechnology, Bioinformatics and Bioengineering (2014) 33-42 35
Mustard oil Acid catalyzed Sulphuric acid as catalyst B1, B2, Prony brake Low-cost Singh et al.
esterification of the was carried out by mixing B5, internal raw 2010
FFA, followed by a mustard oil and methanol B8, B10 combustion (IC) materials.
base catalyzed and sulphuric acid in a mole diesel engine.
transesterification. ratio 1:74:1.9, at a
temperature of 70 oC
Sesame Oil Base catalyzed. 0.67% KOH and 0.34% - - - Ahmad et al.
NaOH catalyst at 60 oC 6:1 2011
molar ratio of methanol/oil.
Castor Oil Dilution, Methanol as the B-20 Diesel engines Cheap Shrirame et al.
micro-emulsification, transesterification agent without any 2011
pyrolysis and compared with ethanol. modification.
transesterification.
Castor seed In-situ Ethanol and n-hexane as - - - Hincapiéet al.
oil transesterification co-solvent. 2011
(oil-bearing material
contacts with
acidified or
alkalized).
Iranian bitter Base catalyzed. Methanol to oil molar ratio - - - Atapour et al.
Almond oil (3:11 mol/mol), potassium 2011
hydroxide concentration
(0.1–1.7% w/w) and reaction
temperature (30–70 oC).
High-FFA TDSP 4.5% catalyst, 6:1 alcohol to B5, Vertical, 4-stroke, Expensive Dhar et al. 2012
Neem oil oil molar ratio, 90 min B10, single cylinder, and
reaction time at 45 oC B20, constant speed, Complex
B50 direct injection, installation
and water cooled, for biodiesel.
B100 compression
ignition engine
(Model DM-10).
Olive-pomac Acid catalyzed.. The FFA value reduced by - - - Che et al. 2012
e oil increasing the methanol/oil
ratio, by increasing the
reaction time and/or
temperature.
Mixed Base catalyzed Methanol/Oil molar ratio - - Inexpensive Qiu et al. 2011
soybean oil 5.0:1, reaction temperature feed-stock.
and rapeseed 55 oC, catalyst amount 0.8 Hence,
oil wt. % and reaction time 2.0 lower cost
hrs.
of biodiesel.
Chinese KNO3/MgO as Molar ratio of methanol/oil - - - Zhang et al.
Tallow catalyst. 8:1, reaction time 3 hrs at 50 2011
o
Kernel Oil C
Cottonseed Base catalyzed. 6:1 (v/v) methanol–oil ratio - - - Fernandes et al.
oil and 1% (wt.) NaOH at 60 oC 2013
for 1 hr.
Camelina oil Base catalyzed. Molar ratio of methanol to - Diesel engines - Wu et al. 2012
oil of 8:1, a reaction time of without
70 min at 50 oC, and a modification.
catalyst concentration of 1%
wt.
Spent Coffee Oil esterification in 1% of H2SO4 and 40 % of - Direct combustion Higher Caetano et al.
Grounds three consecutive methanol for 2 hrs. of engines. operating 2012
36 Journal of Biotechnology, Bioinformatics and Bioengineering (2014) 33-42
Rice bran oil Base catalyzed. Temperature values are - - Low cost. Boulifi et al.
below the boiling point of 2013
methanol (65 oC) molar ratio
of the methanol/oil set at 6:1,
for 60 minutes.
Plant oils are not suitable for direct combustion in standard diesel engines due to their high viscosity and thus are required to
be converted to a less viscous form with physicochemical properties similar to petro-diesel. It has been found that high viscosity,
low volatility and residual compounds are major reasons why plant oils are not used directly. These issues of plant oils can be
dealt by conversion of the lipids (usually triglycerides with some amounts of mono- and diglycerides) to fatty acid esters. This
can be carried out by a process known as transesterification. Other methods include; pyrolysis, dilution with petro-diesel oil
(blending) and micro-emulsion.
2.2. Transesterification
Transesterification has been described as a chemical reaction between triglycerides and alcohol to produce an ester and a
by-product glycerol. The purpose of transesterification process is to lower the viscosity of the oil. The process reduces the
viscosity to a value comparable to that of diesel and hence improves combustion. Depending on the fatty acid composition of the
oil, saponification number, iodine value and cetane number; it can be determined at the starting stage, whether the oil is suitable
for transesterification reaction or not. The ratio of raw material to alcohol is quite important to increase yield of Fatty acid methyl
esters (FAME) significantly. The molar ratio of alcohol, reaction temperature, catalyst amount, reaction time, water content, and
free fatty acids (FFAs) are the process variables that effect catalyzed transesterification.
In the available literature, two approaches for the production of low-cost biodiesel fuel have been cited. The first approach is
a two-step process, which requires an initial acid catalyzed esterification of the FFAs, followed by a base-catalyzed
transesterification of triglycerides. The second approach dealt with a one-step process that uses an acid catalyst that
simultaneously promoted both esterification and transesterification reactions.
Most commonly used methods for transesterification reaction are catalytic and non-catalytic transesterification and other
methods such as supercritical processes, microwave and ultrasound systems. The catalyst is used to increases the esterification
reaction rate and enhances the solubility of alcohol. Acid-catalyzed reactions (i.e.H2SO4, H3PO4) are used to convert FFAs to
esters, and are characterized by slow reaction rate and high ratio of alcohol. Base-catalyzed (i.e. NaOH, KOH, and NaMeO,
CH3ONa) process is considered to be better than the acid catalysis, since the reaction is faster (barely 30 min. compared to 1–8 hr)
and have roughly the same yield. However, base catalysed reaction is affected by water content and FFAs of oils or fats. FFAs
can react with base catalysts to form soap and water. Moreover, acidic catalyst is corrosive and destructive to the reactor and
other supporting equipment involved in the process.
Transesterification reaction can be catalyzed by both homogeneous (basics and acids) and heterogeneous catalysts.
Homogeneous catalysts show greater performance toward transesterification to obtain biodiesel when the free fattya cid content
is less than 1%. Homogeneous catalysts have certain disadvantages such as expensive separation of the homogeneous catalyst
Journal of Biotechnology, Bioinformatics and Bioengineering (2014) 33-42 37
from the reaction mixture, generation of large amount of waste water during separation and cleaning of catalyst and the products,
formation of unwanted by-product (i.e. soap) by reaction of the FFA. However, uses of heterogeneous catalysts overcome
problems when free fatty acid content is more than 1% and catalyst can be separated more easily from reaction products. Use of
heterogeneous catalysts avoid the undesired saponification reactions, and also facilitate the transesterification of plant oils. The
use of heterogeneous catalysts considered more environmental friendly and therefore researchers focus on that more as compared
to homogeneous. Heterogeneous catalyzed production of biodiesel has emerged as a preferred route as it is environmentally
benign needs no water washing and product separation is much easier. Some of the commonly used heterogeneous base catalyst
are K/γ-Al2O3 catalyst , HTiO2 hydrotalcite catalyst, Ca and Zn mixed oxide , Al2O3 supported CaO and MgO catalysts , alkaline
earth metal oxides , KF/Ca–Al , basic zeolites, alkali metal loaded alumina. Leung et al (2010) studied materials such as, acid
solids, base solids, and bi-functional solids (acid–base character) for transesterification reaction (Leung et al. 2010). Dias et al.
(2012) studied transesterification of soybean oil using magnesia supported SrO heterogeneous catalyst transesterification. They
prepared it by combining commercial MgO with aqueous solutions of strontium nitrate and reported that catalysts with atomic
ratios Sr/Mg higher than 0.10, showed analogous catalytic behaviours giving 94% higher FAME contents with no soap formation.
Similarly, Zhang et al. (2010) observed high FFA using ferric sulfate-catalyzed esterification followed by transesterification
using calcium oxide (CaO) as an alkaline catalyst. Ho et al (2012) reported biodiesel production from crude palm oil using
catalysts from calcium oxide (CaO)/calcined calcium carbonate (CaCO 3).
In view of the fact that both homogeneous acid and base catalysts have certain limitations, a combination of both the catalysts
(sequentially) called transesterification double step process (TDSP) are used that have high yield of FAME especially in the
feed-stocks having high FFAs content like Neem oil. In the first step, the acid catalyst is used to transesterify the FFAs to ester
which drops FFAs to less than 0.5 wt%. In the second step transesterification of low FFAs oil is carried out with needs the base
catalyst. Therefore, TDSP helps to eliminate the limitations of the basic or acid catalytic methods and resulting in an efficient and
easier biodiesel production. Guzatto et al. (2011) carried out production by TDSP having high conversion indexes (97% for
waste cooking oil and soybean oil and 98% for linseed oil) and high yields (waste cooking: 87±5%, soybean: 92±3% and linseed:
93±3%) and the produced biodiesel met ASTM, ENISO and ABNT standards.
Enzyme catalyzed transesterification include lipases that have immense specificity, activity and stability and ability to
catalyse reactions even in non-aqueous mediums. The microorganisms commonly used for lipases production are Mucor miehei,
Rhizopus oryzae, Candida antarctica and Pseudomonas cepacia. Most of the studies on lipases for biodiesel production have
principally focused on screening of lipases and on investigating the factors that influence the reaction (Sonare et al. 2010). Aria et
al (2010) catalysed soyabean oil transesterification using four types of whole-cell lipases; wildtype R. oryzae producing
triacylglycerol lipase, recombinant A. oryzae expressing Fusarium heterosporum lipase, Candida antarctica lipase B, and mono-
and diacylglycerol lipase from A.oryzae.
In the fact of above view on biodiesel production some common problems involved are–(i) the immiscible nature of the
reactants (alcohol and vegetable oil) coupled with the difference in their densities can lead to poor contact between the reactants
(ii) low mass transfer rate results loading to low reaction rate and increased reaction time (iii) due to the lag in the film between
two immiscible fluids the reaction between them is analogous to the heterogeneous transport phenomena (heat, mass and fluid).
Therefore a number of alternative approaches have been investigated to overcome problems faced in biodiesel production
process and each of its have own benefits and limitations.
production proved the potential of the technology to achieve superior results over conventional techniques. Short reaction time,
cleaner reaction products, and reduced separation-purification times are the key observations reported by many researchers. The
required wavelength and frequency range of microwave irradiation for transesterification of oil is 0.01 to 1 m and frequency
range of 0.3 to 300 GHz, respectively.
Non-catalyzed production of biodiesel includes two processes -supercritical and Biox processes. Supercritical alcohol
transesterification reaction takes place under extremely high temperature and pressure. A supercritical fluid (SCF) is a compound,
mixture, or element above its critical pressure and critical temperature, but below the pressure required to condense into a solid
(Goembira et al. 2013). Under such conditions, the densities of both liquid and gas phases become identical, and the distinction
between them become disappears. The properties of supercritical alcohol are lie in-between those of a gas and a liquid (Ilham et
al. 2010). Supercritical method is expected to be not affected by FFAs and no soap generation is involved and therefore, the
quality of biodiesel and glycerin is better than catalyzed reaction with significantly low reaction time. Goembira and Saka (2013)
reported highest yields of FAME (96.7 wt. %) and triacetin (8.8 wt. %) with supercritical methyl acetate method. The main
limitations of this method are that it depends on critical conditions of alcohol which demands high pressure (4.9–8.1MPa) and
temperature (239–290 oC). Modification of supercritical process involve two-step for high yield of FAME consisting of
hydrolysis of oils in sub-critical water and subsequent supercritical dimethyl carbonate esterification. Sawangkeaw et al (2011)
reported enhancement in fuel up to 4.7% and 12.9% using supercritical methanol and supercritical ethanol process, respectively.
Ionic liquids (ILs) uses as both solvents and catalysts have attracted significant attention for their use in biofuel production. ILs
are organic salts with melting points around or below the ambient temperature. ILs are composed of organic cations and either
organic or inorganic anions. The most common ILs are divided into four groups according to their cations: quaternary
ammonium ILs, N-alkyl-pyridinium ILs, N-alkyl-isoquinolinium ILs, and 1-alkyl-3-methyl-imidazolium ILs.
In Biox processes, co-solvent is primarily used to overcome low solubility of methanol in oil. The process took place at a low
temperature of 30oC and convert oil with high percentage of FFA (more than10%) into biodiesel. The process involve two steps
where in the first step, the conversion of FFA was achieved and in the second step conversion of triglyceride take place. The
addition of the co-solvent is required in each step. The most commonly used co-solvent is tetrahydrofuran due to its close boiling
point to that of methanol. Fig. 2 shows the procedure where the reactor stage refers to individual stage involved while the
separation of methanol and co-solvent is achieved in the lower separation process. The co-solvent is recycled and reused through
the continuous process. In the separation process, both excess methanol and the co-solvent are recovered from the products. The
main advantages to use this process its ability to handle feeds with high FFA, the reaction time is short and it can be carried out
under ambient temperature and pressure. The limitation of this method include complete removal of co-solvent is required due to
its hazardous and toxicity natures and further the separation of methanol and the co-solvent is difficult due to the very close
boiling point of them.
High % of FFA + MeOH+ Co-solvent
Refining
Separation Separation
Glycerine Biodiesel
Fig. 2. Flow diagram of the Biox process
Journal of Biotechnology, Bioinformatics and Bioengineering (2014) 33-42 39
Alcohol + Catalyst
Mixing
Oil Reactor
Phase separation
Biodiesel Separation
Alcohol Glycerine
Fig. 3. Basic scheme for ultrasonic batch biodiesel production
Two methods batch and continuous are generally adopted for biodiesel production. Early attempts on the study batch process
under ultrasonic field were made using transesterification of plant oils. Investigation on a batch process to use ultrasonic
irradiation instead of mechanical stirring has been made using ultrasonic horn or probe that is immersed in the reaction media.
The ultrasonic probe provides the reactor with ultrasonic energy followed by phase separation stage. Fig. 3 shows a schematic
diagram of ultrasonic-assisted batch reactor system for biodiesel production. Limitations of batch process include the
requirement of larger reactor, low efficiency due to its start up and shut down requirements and high labour costs will affect the
process economics. Therefore researchers have tried to study continuous systems provided with ultrasonic irradiation to tackle
these problems and to find suitable procedure that can satisfy various needs in biodiesel production. Thanh et al (2010) has
attempted the design of a pilot plant for continuous production of high quality biodiesel and this pilot scale plant was designated
to perform the transesterification in a circulation process in the presence of low frequency ultrasound. The flow diagram that
describes the circulation process is shown in Fig. 4. The oil and methanol containing the dissolved catalyst were fed into the
ultrasound reactor using liquid pumps that further passed to circulation-separation unit. Later on, feeding valves were closed and
circulation valves were opened to circulate reaction mixture through the reactor. Finally, the reaction mixture was left to undergo
phase separation in the circulation separation unit for 4 h.
F = [(Mt+Mi)-(Mt+Mf)]/t
Where, F - fuel mass flow (kg/s), Mt- storage tank mass (kg), Mi - initial fuel mass (kg), Mf - final fuel mass (kg), t - test time
(sec)
Brake horsepower
It is the amount of power generated by a motor without taking into consideration any of the various auxiliary components like
gear, friction, transmission etc. that may slowdown the real speed of the motor. It is also known as “crank horsepower”. It is
given by: BHP = (2π NT)/ 60
Where, T - torque (Nm), N - Rotational speed (revolutions/minute)
Thermal efficiency
Brake thermal efficiency is the percentage of energy taken from the combustion which is actually converted into mechanical
work.
The following equation represents thermal efficiency of the engine:
η = [(3600/ (LHV) (SFC)] 100
Where, η - set efficiency (%), SFC- specific fuel consumption (g/kW/h), LHV - lower heating value (MJ/kg) – It is the
effective energy released per unit of fuel mass and also the work generated.
4.4. Effect of Engine type and its operating conditions on biodiesel engine power
Engine type and its operating conditions, such as engine load, engine speed, injection timing and injection pressure, etc., have
significant effects on biodiesel engine power. The engine power and torque can be increased by the application of the low heat
rejection engine, due to the increased exhaust gas temperatures before the turbine inlet in LHR engine. Comparison on naturally
aspirated (NA) conditions to the turbocharged (TU) conditions on a 4-stroke, DI diesel engine showed mean increase in torque
for biodiesel with the TU conditions.
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