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JOURNAL OF OLEO SCIENCE

Copyright ©2006 by Japan Oil Chemists’ Society


J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
JOS
REVIEW

Biodiesel: Source, Production, Composition,


Properties and Its Benefits
Divya BAJPAI* and V.K. TYAGI
Department of Oil and Paint Technology, Harcourt Butler Technological Institute
(Kanpur-208002, INDIA)

Accepted May 29, 2006 (received for review February 6, 2006)

Abstract: Biodiesel is an eco-friendly, alternative diesel fuel prepared from domestic


renewable resources i.e. vegetable oils (edible or non-edible oil) and animal fats, that runs in
diesel engines-cars, buses, trucks, construction equipment, boats, generators, and oil home
heating units. Biodiesel has been gaining worldwide popularity as an alternative energy source
because it is non toxic, biodegradable & non flammable. Various edible and non edible oils, like
rice bran oil, coconut oil, Jatropha curcas, castor oil, cottonseed oil, mahua, karanja which are
either surplus and are nonedible type can be used for preparation of biodiesel. Biodiesel can be
used either in the pure form or as blends on conventional petrodiesel in automobiles without any
major modifications. Its biodegradability makes it eco-friendly. It may lead to a revolutionary
transformation of the current economic & energy scenario with an era of economic bloom &
prosperity for our society. This review paper describes the production, its properties, composition
and future potential of biodiesel.
Key words: degradation, employment generation, transesterification, biodiesel, biocatalyst

curcas, castor oil, cottonseed oil, mahua, karanja which


1 Introduction
are either surplus and are nonedible type, can be used
Recent petroleum crisis (1), increasing cost and for the preparation of biodiesel. (2). It is an alternative
unavailability of petroleum diesel gave impetus to the fuel derived from the conversion of agricultural lipids
scientists to work on alternative fuel, biodiesel. and a simple alcohol into fatty acid alkyl ester and glyc-
Biodiesel has been gaining worldwide popularity as an erol and is defined as “mono alkyl esters of fatty acids
alternative energy source because it is non toxic, derived from vegetable oil or animal fats”. These natu-
biodegradable & non flammable and has significantly ral oils and fats are made up mainly of triglycerides.
fewer emissions than petroleum-based diesel (petro- These triglycerides have striking similarity to petroleum
diesel) when burned.Biodiesel is an eco-friendly, alter- derived diesel so that it is known as “biodiesel”.
native diesel fuel prepared from domestic renewable Biodiesel functions in current diesel engines, and is a
resources i.e. vegetable oils (edible or non-edible ) and possible candidate to replace fossil fuels as the world’s
animal fats, that runs in diesel engines-cars, buses, primary transport energy source.
trucks, construction equipment, boats, generators, and
oil home heating units. Various edible and non edible
vegetable oils, like rice bran oil, coconut oil, Jatropha


Correspondence to: Divya BAJPAI, Department of Oil and Paint Technology, Harcourt Butler Technological Institute, Kanpur-208002, INDIA
E-mail: divyadivya_27@rediffmail.com
vinod_tyagi1960@yahoo.co.in

Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online 487
http://jos.jstage.jst.go.jp/en/
D. Bajpai and V.K. Tyagi

2 History 3 Source of Biodiesel


Transesterification of a vegetable oil was conducted Biodiesel can be produced by animal fats, cooking
as early as 1853, by scientists E. Duffy and J. Patrick, waste and vegetable oils. Biodiesel production from
many years before the first diesel engine became func- various vegetable oils in different countries is given in
tional. Rudolf Diesel’s prime model, a single 10 ft (3 Table 1(3).
m) iron cylinder with a flywheel at its base, ran on its
own power for the first time in Augsburg, Germany on
4 Production of Biodiesel
August 10, 1893. In remembrance of this event, August
10 has been declared International Biodiesel Day. Syldatk et al. (4) gave the method for biotechnical
Diesel later demonstrated his engine and received the preparation of fatty acid methyl esters (biodiesel) based
“Grand Prix” (highest prize) at the World Fair in Paris, on whey. Biodiesel is produced in a combined micro-
France in 1900. This engine stood as an example of bial/chemical process in which Cryptococcus curvatus
Diesel’s vision because it was powered by peanut oil-a in a sterile whey fraction preferably deproteinized 20%
biofuel, though not strictly biodiesel, since it was not whey concentration without further additives produces
transesterified. He believed that the utilization of a an intracellular fatty acid-rich triglyceride, “single cell
biomass fuel was the real future of his engine. In a 1912 oil”. After disruption of the cells, the oil is removed
speech, Rudolf Diesel said, “the use of vegetable oils from the culture and cell fragments and is directly
for engine fuels may seem insignificant today, but such reacted to known chemicals to produce the fatty acid
oils may become, in the course of time, as important as methyl esters.
petroleum and the coal-tar products of the present Lee et al. (5) gave a one step process for manufacture
time.” During the 1920s, diesel engine manufacturers of biodiesel and synthetic lubricating base oils from
altered their engines to utilize the lower viscosity of the animal wastes and agricultural wastes. Animal derived
fossil fuel (petrodiesel) rather than vegetable oil, a feeds, as safe nutritional ingredients as well as fatty
biomass fuel. The petroleum industries were able to acid esters as biodiesel and synthetic lubricating base
make inroads in fuel markets because their fuel was oils, were prepared from animal and plant derived agri-
much cheaper to produce than the biomass alternatives. cultural wastes without prior fat or oil extension pro-
The result was, for many years, a near elimination of
the biomass fuel production infrastructure. Only recent-
ly have environmental impact concerns and a decreas- Table 1 Production of Biodiesel in Different Countries.
ing cost differential made biomass fuels such as Country Source of biodiesel
biodiesel a growing alternative.In the 1990s, France
USA Soyabean (mustard is under study)
launched the local production of biodiesel fuel (known
locally as diester) obtained by the transesterification of Brazil Soyabean
rapeseed oil. It is mixed to the proportion of 5% into Europe Rapeseed oil (>80%) and sunflower oil
regular diesel fuel, and to the proportion of 30% into Spain Linseed and olive oil
the diesel fuel used by some captive fleets (public trans-
France Sunflower oil
portation). Renault, Peugeot, and other manufacturers
have certified truck engines for use with up to this par- Italy Sunflower oil
tial biodiesel. Experiments with 50% biodiesel are Ireland Animals fat, beef tallow
underway. From 1978 to 1996, the U.S. National Indonesia Palm oil
Renewable Energy Laboratory experimented with using
Malaysia Palm oil
algae as a biodiesel source in the “Aquatic Species Pro-
gram”. A recent paper from Michael Briggs at the UNH Australia Animals fat, beef tallow and rapeseed oil
Biodiesel Group, offers estimates for the realistic China Guang pi
replacement of all vehicular fuel with biodiesel by uti- Germany Rapeseed oil
lizing algae that has a greater than 50% natural oil con-
Canada Vegetable oil/animals fat
tent.

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
Biodiesel: Source, Production, Composition, Properties and Its Benefits

cesses that involved deactivation, fat hydrolysis and acceptors. In noncontinuous batch operation, the opti-
esterification, transesterification and separation process- mal oil/alcohol ratio and temperature were 1:4 and 40-
es. 50℃; however, during continuous batch operation, the
Vicenta et al. (6) discussed the properties, combus- optimal oil/alcohol ratio and temperature were 1:1 and
tion characteristics, advantages and production tech- 30℃. 95% of enzymatic activity remained after 10
nologies involved in the use of methyl esters of sun- batches when iso-propanol was adopted to remove
flower oil fatty acids as an alternative to diesel fuel. The byproduct glycerol during repeated use of lipase.
oil is extracted from the seeds, refined and subjected to Komers et al. (10) studied the biodiesel fuel obtained
transesterification. The combustion properties of the from rapeseed oil, methanol and KOH and presented a
biodiesel are compared to those of diesel fuels, exhaust review paper on analytical methods in research and pro-
emissions show reduced level of CO, SO2, particulates, duction of biodiesel. In this review the enumeration of
aromatic hydrocarbons and increased levels of alde- the analytical methods used in the production of
hydes. biodiesel were published till 1997. Some of the original
Encinar et al. (7) described the preparation and prop- methods for individual or simultaneous determination
erties of biodiesel obtained from Cyanara cardunculus of the main components in the reaction mixture were
oil. In this method of transesterification of Cyanara described. All these methods can be also used to ana-
cardunculus oil by means of methanol, using sodium lyze the non equilibrium complex and heterogenous
hydroxide, potassium hydroxide and sodium methoxide mixtures.
as catalysts. The objective of work was to characterize Hillion et al. (11) gave a method of producing
the methyl esters for use as biodiesels in internal com- biodiesel by a continuous process using a heterogenous
bustion motors. The operation variables used were catalyst. This catalyst consists of a mixed oxide of zinc
methanol concentration (5-21 wt%), catalyst concentra- and aluminium which promotes the transesterification
tion (0.1-1 wt%) and temperature (25-60℃).The evolu- reaction without catalyst loss. In this heterogenous pro-
tion of the process was followed by gas chromatogra- cess the catalyst was stable with no metal leaching, no
phy, for determining the concentration of the methyl formation of either glycerate salts or metal soaps.
esters at different reaction times. The biodiesel was
characterized by determining its density, high heating
5 General Method of Production of
value, cetane number, cloud and pour points, rams bot-
Biodiesel
tom carbon residue, flash and combustion points
according to ISO norms. The biodiesel with the best 5・1 Basic Technology
properties was obtained using 15% methanol, sodium 5・1・1 Chemical reaction
methoxide as catalyst (1%) and 60℃ temperature. This The feed stock is degummed, clarified and dried. The
biodiesel has very similar properties to those of two step process involves the esterification of fatty
petroleum diesel. acids with an acid catalyst followed by transesterifica-
Shah et al. (8) gave a method of production of tion of triglycerides by an alkaline catalyst (12). Trans-
biodiesel by lipase catalyzed transesterification of Jat- esterification (13-15) is also called alcoholysis. It is dis-
ropha oil. In the process of enzymatic transesterification placement of alcohol from an ester by another alcohol
of Jatropha oil, three different lipases (Chromobacteri- in a process similar to hydrolysis except that an alcohol
um viscosum, Candida rugosa and Porcina pancreas) is used instead of water. The reaction can be represent-
were screened and only lipase from Chromobacterium ed as shown below:
viscosum was found to give appreciable yield. It was
seen that immobilization of lipases and optimization of Equation 1 Chemical Reaction of Synthesis of Biodiesel.
transesterification conditions resulted in adequate yield
CH2-COO-R1 R1-COO-R’ CH2OH
of biodiesel in the case of enzyme based process. │ │
Du et al. (9) studied the effects of temperature, oil/ CH-COO-R2 + 3R’OH ./ R2-COO-R’ + CHOH
│ │
alcohol molar ratio and byproduct glycerol during CH2-COO-R3 R3-COO-R’ CH2OH
lipoenzyme TLIM-catalyzed continuous batch opera-
tion when short chain alcohols were used as the acyl Agro fat Alcohol Fatty acid esters Glycerol

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

This reaction is associated with several other side tions, but plants tend to be bulky &labor intensive.
reactions, which if uncontrolled can severely 5・1・4・2 CSTR
hamper the product yield & quality. Since reactions are slow, CSTR is likely to low con-
Some of the factors that affect the reaction kinetics are: version for a given reactor volume.
・ Concentration of the catalyst. 5・1・4・3 Continuous reactor without recycle
・ Presence of water and the subsequent soap forma- Presents flow regime problems owing to low flows
tion. (however, literature reports that some success has been
・ Presence of free fatty acids. achieved with reaction columns oscillators).
・ Separation of glycerol phase. 5・1・5 Key unit operations
Therefore, the key to a successful process technology 5・1・5・1 Liquid liquid operations
is to have the above factors under control to get maxi- It can be handled by combination of gravity setters,
mum yield & product purity. coalescers or centrifuges depending on capacity and
5・1・2 Thermodynamics (16) constraints.
In the esterification reaction same type of bonds are 5・1・5・2 Solvent recovery by distillation
broken and remade on either sides, so heat effects are Conventional, however, if ethanol is used then an
bound to be low. Since both reactants and products are azeotrophic separation is required for obtaining recti-
liquids, entropy change would be near zero. Hence, fied spirit
equilibrium constant (of order exp (-dG/RT)) is low. 5・1・5・3 Oil degumming
However equilibrium can be shifted, say by glycerol Combination of hot water and acid degumming may
removal. be required depending on type of feed stock & route
5・1・3 Reaction kinetics (16) selected.
In chemical reaction, the effect of intermediate prod- 5・1・6 General method of manufacturing
ucts such as mono & di-glycerides has to be considered. Triglycerides are readily transesterified batch wise in
In the initial stages of reaction, production of methyl the presence of alkaline catalyst at atmospheric pressure
ester is rapid then diminishes & finally reaches equilib- and at 60-70℃ with an excess of methanol. The mix-
rium. The decrease in reaction rates is believed to be ture at the end of reaction is allowed to settle. The
due to formation of glycerol as a second phase, which lower glycerin layer is drawn off, while the upper
leads to a loss of methanol and catalyst. It is difficult to methyl ester is washed to remove entrained glycerin
make general predictions, but the best kinetic model and then processed further. The excess methanol is
appears to be a pseudo-second order for the initial recovered in the condenser, sent to the rectifying col-
stages of reaction. umn for purification and recycled.
Komers et al. (17) studied the kinetics and mecha- 5・1・7 Effect of different parameters on the produc-
nism of KOH catalyzed methanolysis of rapeseed oil tion of biodiesel
for biodiesel production. The reaction of rapeseed oil 5・1・7・1 Impurities
with MeOH, catalyzed by KOH, consists of two Impurities present in oils also effect conversion level.
sequences. The first sequence expressed the methanoly- For alkali catalyzed transesterification, the glycerides
sis of rapeseed oil to methyl esters (biodiesel) whereas and alcohol must be substantially anhydrous as water
the second sequence described the always present side causes a partial saponification which produces
reaction separation of glycerides and methyl esters by soap(18), that consumes the catalyst, reduces the cat-
KOH. The proposed chemical model was described by alytic efficiency, as well as causing an increase in vis-
a system of differential kinetic equations, which were cosity, the formation of gels, and difficulty in achieving
solved numerically by two independent computing separation of glycerol.
methods. Kinetic and equilibrium results were com- 5・1・7・2 Alcohol type
pared numerically and/or graphically with the experi- Methanol and ethanol are most commonly used for
mental parameters. transesterification of vegetable oils and fats but other
5・1・4 Reactor types alcohols can also be used. It is reported that yield of
5・1・4・1 Batch reactor alcohol esters was the highest with methanol, as
Batch routes are traditionally selected for slow reac- methanol is the shortest chain alcohol and is more reac-

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
Biodiesel: Source, Production, Composition, Properties and Its Benefits

tive to oil with the added advantage of alkali catalysts was observed after 1 min for soybean and sunflower
being easily soluble in methanol. oils at methanol to oil ratio of 6:1, 5percent of sodium
5・1・7・3 Reactants ratio methoxide catalyst at 60℃. After 1 hr. the conversions
The stoichiometry of the transesterification reaction were almost the same (93-98 percent). The effect of
requires 3 mol of alcohol per mol of triglyceride to reaction time for palm oil at 40:1 methanol: oil (mol/
yield 3 mol. of fatty esters and 1 mol. of glycerol. The mol) with 5 percent H2SO4 (v/w) at 950C for 9 hr., gave
reaction is reversible so it is necessary to use either a maximum esters yield (20) of 97 percent.
large excess of alcohol or to remove one of the products 5・1・7・6 Reaction temperature
from the reaction mixture to favorably shift reaction to The rate of reaction is strongly influenced by reac-
the product side. tion temperature. However, given enough time, the
5・1・7・4 Catalysts used in transesterification reaction will proceed to near completion even at room
Three type of catalysts are used in the production of temperature. Generally the reaction is conducted close
biodiesel. These are: to boiling point of methanol, 60-70℃, at atmospheric
5・1・7・4・1 Basic catalyst pressure. These mild reaction conditions, however,
Alkali catalyzed transesterification is much faster require the removal of free fatty acids from the oil. The
than other type of the catalysts. Alkalis included sodi- pretreatment is not required if the reaction is carried out
um hydroxide, sodium methoxide, sodium hydride, under high pressure (9000 kPa) and temperature
potassium hydroxide, potassium hydride etc. (240℃). Under these conditions, simultaneous esterifi-
5・1・7・4・2 Acid catalyst cation and transesterification take place. The maximum
However, if glyceride has a higher level of FFA and yield of esters occurs at 60-80℃, with molar ratio of
more water then acid catalyzed transesterification suit- alcohol to oil of 6:1. Further increase in temperature
able, that can be sulphuric, phosphoric, hydrochloric or has negative effect on the conversion.
organic sulfonic acid. Acid catalyzed methylation is 5・1・7・7 Stirring effect
energy sensitive because it is usually conducted at high In the transesterification reaction, the reactants ini-
temperature. Palm oil with 3% H2SO4 gives highest tially form a two phase liquid system. The reaction is
yield of 78% of methyl esters (19) at 23:1 ratio. diffusion controlled and poor diffusion between the
5・1・7・4・3 Biocatalyst phases results in a slow rate. As methyl esters formed,
Recovery of acid and alkali catalysts in the produc- they act as a mutual solvent for the reactants and a sin-
tion of biodeisel is very difficult. it can effect the pro- gle phase system is formed. The mixing effect is most
cess economically as well as ecologically. Several significant during the slow rate region of reaction, as
reports describe enzymatic alcoholysis of vegetable the single phase is established, mixing becomes
oils. When EtOH, iso-propanol, butanol and long chain insignificant. Conversion of soybean oil as a function of
alcohols were used as substrates, the oil were efficiently time and stirring (21) after optimization of the reaction
converted to their fatty acid esters. The efficiency of conditions-methanol: oil ratio of 7.5:1 at 60℃ with 1%
conversion was low with methanol (21). Lipase cat- sodium methoxide at 600 rpm-90% conversion was
alyzed alcoholysis in the absence of solvent is impor- noted after 30 minutes.
tant in industrial application. In an earlier study, the
crude lipase from the yeast, Cryptococcus spp. was
6 Fatty Acid Composition of Biodiesel
shown to possess considerable stability in solvents and
it could be used for the hydrolysis of vegetable oils Many Scientists have studied the Fatty acid composi-
(20). tion of biodiesel obtained from different sources, some
5・1・7・5 Reaction time of those are given in Table 2.
The conversion rate increases with time. On transes-
terification of beef tallow, the reaction time was deter-
7 Properties of Biodiesel
mined. The reaction was very slow during the first
minute due to the mixing and dispersion of methanol Biodiesel is an alternative source of energy that is
into beef tallow; from one to five minute reaction pro- replacing the use of gasoline & diesel. The emergence
ceeded very fast. An approximate yield of 80 percent of biodiesel fuel substitutes has led to several studies on

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

their properties. Which are: the resulting monoesters have viscosities that are closer
to petroleum based diesel fuel (28-30).
7・1 Surface Tension, Viscosity and Cloud Noureddini et al. (31) investigated a system and pro-
Point cess for producing biodiesel fuel with reduced viscosity
The ASTMD-445 specification for viscosity at 40℃ and cloud point. In this process triglycerides were react-
of 4 centistokes is generally met by biodiesel and ed in a liquid phase reaction with a homogenous basic
biodiesel blends. However, the viscosity of biodiesel catalyst and alcohols such as ethanol and methanol. The
and its blends is higher than diesel. Soy methyl ester is reaction yields a separated two phase result with an
reported to have a viscosity ranging from 3.8 to 4.1 cen- upper located non polar phase consisting principally of
tistokes at 40℃. Glycerine contamination will cause transesterified triglycerides and/or glycerol phase. Each
biodiesel viscosity to increase, among other problems. separation was passed through strong cationic ions
Estimates of the surface tension of biodiesel suggest exchanger to remove anions, resulting in neutral prod-
that it may be two to three times as great as that for uct(s). The crude glycerol was then flashed to remove
diesel. Higher viscosity and cloud point is a major alcohols and was reacted with an etherifying agent such
problem of using biodiesel in diesel engines. High vis- as isobutylene and iso-amylene, in the presence of a
cosity of vegetables oils and animal fats tends to cause strong acid catalyst to produce glycerol ethers. The
problems when directly used in diesel engines (24-27). glycerol ethers were then added back to the transesteri-
These properties affect the fuel droplet size during fied triglycerides to provide and improved biodiesel
injection. Biodiesel has both larger viscosity and sur- with lower viscosity and cloud point.
face tension, resulting in larger droplets, one of a num-
ber of contributing factors that have been identified as 7・2 Storage Stability/Oxidative Stability
possible causes for higher NOx emissions. If the oils Oxidative stability is a major industry issue for diesel
and fats are transesterified using short chain alcohols, and biodiesel fuels. Oxidative stability is measured by

Table 2 Composition of Biodiesel Obtained from Different Sources (22, 23).


Fatty acid composition (wt.%)
Oil or Fat
12:0 14:0 16:0 18:0 18:1 18:2 18:3 22:1
Babassu 44-45 15-17 5.8-9 2.5-5.5 12-16 1.4-3
Canola 4-5 1-2 55-63 20-31 9-10 1-2
Coconut 44-51 13-18.5 7.7-10.5 1-3 5-8.2 1.0-2.6
Corn 7-13 2.5-3 30.5-43 39-52 1
Cottonseed 0.8-1.5 22-24 2.6-5 19 50-52.5
Linseed 6 3.2-4 13-37 5-23 26-60
Olive 1.3 7-18.3 1.4-3.3 55.5-84.5 4-19
Palm 0.6-2.4 32-46.3 4-6.3 37-53 6-12
Peanut 0.5 6-12.5 2.5-6 37-61 13-41 1
Rapeseed 1.5 1-4.7 1-3.5 13-38 9.5-22 1-10 40-64
Safflower 6.4-7.0 2.4-29 9.7-13.8 75.3-80.5
Safflower (high oleic) 4-8 2.3-8 73.6-79 11-19
Sesame 7.2-9.2 5.8-7.7 35-46 35-48
Soybean 2.3-11 2.4-6 22-30.8 49-53 2-10.5
Sunflower 3.5-6.5 1.3-5.6 14-43 44-68.7
Tallow (beef) 3-6 25-37 14-29 26-50 1-2.5

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
Biodiesel: Source, Production, Composition, Properties and Its Benefits

ASTM D2274. It is reported that when compared to was stored at room temperature. Secondary oxidation
diesel, biodiesel fuels were far more prone to oxidation. products were formed in greater amounts in the pres-
The degree of saturation of the fatty acid chains tends to ence of iron (from the primary peroxides) while in glass
be correlated with its stability. Stability of fatty com- the concentration of primary oxidation products is high-
pounds is influenced by factors such as presence of air, er. Acidity values were also monitored in this work.
heat, traces of metal, peroxides, light, or structural fea- Even for samples stored at 40℃, the increase in free
tures of the compounds themselves, mainly the pres- acids was within the limits of technical specifications.
ence of double bonds. The more conjugated or meth- The free acids need to be controlled because they are
ylene-interrupted double bonds in a fatty molecule, the mainly responsible for corrosion.
more susceptible the material is to oxidation and degra-
dation. 7・3 Crystallization Temperature
Early storage tests gave the following decreasing Biodiesel has low crystallization temperature as com-
order of stability for different refinement grades of vari- pared to petrodiesel. To reduce the tendency of
ous vegetable oils (32) soybean oil ≫ degummed soy- biodiesel to crystallize at low temperatures, branched
bean oil > refined soybean oil = refined sunflower oil chain alcohols were used to esterify various fats and
> degummed sunflower oil = crude sunflower oil. oils.
The stability of the crude and degummed oils was sig- Dittmar et al. (35) investigated the production of
nificantly improved by the addition of diesel fuel (in 1:1 biodiesel and studied the cold flow stability of fatty
mixtures) but this did not improve the stability of acids alkyl esters. According to this article, the cold
refined oils. The storage stability of 1:1 mixtures were resistance of biodiesel at low temperature arises many
in the decreasing order of crude soybean oil = crude problems due to insufficient fuel supply. This phe-
sunflower oil > degummed soybean oil > degummed nomenon was investigated with regard to the fatty acid
sunflower oil ≫ refined soybean oil > refined sun- profile and structure of the alkyl groups of the fatty acid
flower oil. A degummed oil/diesel blend with better sta- alkyl esters. In order to improve the cold resistance of
bility characteristics than that of a refined oil/diesel biodiesel branched chain fatty acid alkyl esters were
blend could be prepared. Additionally, the purity of the synthesized using different feedstock. The CFPP values
degummed oils was sufficiently improved by the addi- were measured for the individual esters. The derived
tion of diesel fuel to meet the required fuel specifica- math-statistical dependence between the CFPP value
tion. and composition of biodiesel (determined by GC) were
A study on the stability of the methyl and ethyl esters discussed.
of sunflower oil reports that ester fuels (biodiesel) Lee et al. (36) reduced the crystallization tempera-
should be stored in airtight containers, the storage tem- ture of biodiesel by winterizing methyl soyate. The use
perature should be < 30℃, that mild steel (rust-free) of biodiesel fuels based on blends of methyl soyate and
containers could be used, and that tert.-butylhydro- diesel fuel (soy diesel), is limited in spite of their envi-
quinone (TBHQ), an oxidation inhibitor, has a benefi- ronmental benefits (37-41). Problems with soy diesel
cial effect on oxidation stability (33). Methyl esters often developed from plugged fuel lines and filters
were slightly more stable than ethyl esters. Light caused caused by crystallization of high melting saturated
only a small increase in the oxidation parameters of methyl esters at cold operating temperatures. The crys-
esters stored at the high temperature level. The changes tallization properties of biodiesel fuel traditionally
in the samples were reflected by increasing acid and methyl or ethyl esters of vegetable oils or animal fats
peroxide values in storage at 50℃ and increases in can be improved by replacing the straight chain methyl
ultraviolet (UV) absorption. or ethyl moieties with branched chain alcohol moieties,
Two parameters, namely temperature and the nature such as isopropyl or 2-butyl (42). Another alternative is
of the storage container, were claimed to have the great- to remove saturated methyl esters by inducing crystal-
est influence on the storage stability (34). Samples lization with cooling, and separating the high melting
stored in the presence of iron behaved differently than components by filtration, a process known as winteriza-
those stored in glass. Higher temperature favored degra- tion. Winterization is commonly used in producing
dation of the hydroperoxide at a faster rate than when it refrigerator-stable salad oils by removing components

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

that are responsible for turbidity in certain vegetable and conventional 2 diesel fuel is a nearly linear function
oils (43-45). In this study, winterization was assessed as equal to the average of the cetane numbers for the fuels.
a process for reducing the crystallization temperature of This implies that the neat cetane numbers for diesel and
biodiesel fuels, based on the methyl esters of typical biodiesel can be used to estimate the cetane number
and low palmitate soybean oil. over the entire range of mixtures of biodiesel with
diesel fuel.
7・4 Cetane Number Knothe et al. (46) studied the cetane number of
Cetane number is widely used diesel fuel quality branched and straight fatty esters determined in an igni-
parameter related to the ignition delay time and com- tion quality tester. In this work, the cetane numbers of
bustion quality. The higher cetane no of biodiesel com- 29 samples of straight chain and branched chain C1-C4
pared to petro-diesel indicates potential for higher esters as well 2-ethyl-hexyl-ester of various common
engine tests have shown that bio diesel has similar or fatty acids were determined. The cetane numbers of
better fuel consumption, horse power and torque and these esters are not significantly affected branching in
haulage rates as conventional diesel. the alcoholic moiety. Therefore, branched esters, which
The cetane number of the fuel, specified by ASTMD- improved the cold flow properties of biodiesel, can be
613, is a measure of its ignition quality. The cetane employed without greatly influencing ignition proper-
number of biodiesel exceeds that of conventional diesel, ties compared to the more common methyl esters.
which implies that biodiesel may provide cetane Unsaturation in the fatty acid chain was again the most
enhancement when used neat or in blends, and may significant factor causing lower cetane numbers.
provide emission benefits that have been correlated to Wong et al. (47) gave a green approach for the pro-
cetane number. Higher cetane numbers (as high as 55 to duction of bio-cetane enhancer for diesel fuels. Catalyt-
60) generally improve diesel emissions, but above that ic hydro-treatment of vegetable oils and fats had been
level little improvement is demonstrated. The cetane tested on a pilot scale to convert many types of biomass
index is a calculated property that correlates well with oil into a 60-90 cetane number middle distillate. This
cetane number for natural petroleum stocks, and is bio-cetane product can be used as a neat diesel fuel or
defined by ASTMD-976. Cetane index is also a meas- as a blending agent for ordinary diesel fuel.
ure of fuel aromaticity. It is not relevant to biodiesel.
The cetane number of biodiesel depends on the oil or 7・5 Flash Point
fat feedstock. Fatty acids consist of long chains of car- Flash point, as defined by ASTMD-93, is a measure
bon atoms attached to carbonyl groups. Fats and oils of the temperature to which a fuel must be heated such
contain a distribution of carbon chains of varying that a mixture of the vapor and air above the fuel can be
lengths, typically ranging from 10 to 18 carbons ignited. All conventional diesel fuels have high flash
(referred to as C10 to C18 chains). Some carbon chains points (54℃, minimum; 71℃, typical). The flash point
contain 0, 1, 2, or more double bonds between the car- of neat biodiesel is typically greater than 93℃. The
bons, and have carbonyl groups in different locations. U.S. Department of Transportation considers a material
Cetane number increases with chain length, decreases with a flash point of 93℃ or higher to be non haz-
with number and location of double bonds, and changes ardous. From the perspective of storage and fire hazard,
with various locations of the carbonyl group. As bonds biodiesel is much safer than diesel. In blends, the diesel
or carbonyl move toward the center of the chain, the flash point will prevail. The Engine Manufacturers’
cetane number decreases. Cetane numbers increases Association expressed concern that the oxidative insta-
from 47.9 to 75.6 when the number of carbons in the bility of some types of biodiesel may result in fuels that
fatty acids in biodiesel increases. When the number of have unacceptably low flash points after storage. Some
carbons in the fatty acid chains exceeds C12, the cetane biodiesels have excellent storage histories; others have
number exceeds 60. For soy methyl ester, reported tended to oxidize rapidly. An ASTM test method on
cetane numbers range from 45.8 to 56.9. The variation oxidative stability of biodiesel is under development to
is due to the distribution of carbon chain lengths in each help researchers test biodiesel and determine its storage
fuel tested. The average of the available data is 51.3. characteristics. The number and location of the double
Generally, the cetane number for a blend of biodiesel bonds have been identified as possibly contributing to

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
Biodiesel: Source, Production, Composition, Properties and Its Benefits

the instability of biodiesel fuels. Fatty acid chains can 7・9 Flow Properties (cold temperature
be saturated (adding hydrogen or alcohol) to reduce the sensitivity)
number of double bonds, and it may be possible to The key flow properties for winter fuel specification
remove the fatty acids with excessive double bonds if are cloud and pour point. These are static tests that indi-
indeed, these characteristics are confirmed as sources of cate first wax and non-flow temperatures for the fuel.
the problem. In addition, soy oil contains natural Cloud point, as defined by ASTMD-2500, is a measure
antioxidants, which can be added back to the fuel if of the temperature at which the first wax crystals form,
removed during processing. The current minimum and is related to the warmest temperature at which these
cetane number of 40 is intended to regulate the aromat- will form in the fuel. Wax crystals cause fuel filter plug-
ic content in diesel fuel antioxidants have been identi- ging. Pour point is a measure of the fuel gelling temper-
fied that significantly reduce the amount of oxidation ature, at which point the fuel can no longer be pumped.
that occurs during storage. Research is continuing is The pour point, as defined by ASTMD-97, is always
this area. lower than the cloud point. Additives called flow
improvers do not generally affect the cloud point of
7・6 Distillation conventional diesel fuel; however, they do reduce the
Biodiesel fuels have a narrow range of boiling points size of the wax crystallites that form when the fuel
from 327℃ to 346℃. Some B20 blends have met the cools. Additives tend to allow the fuel filters to operate
ASTMT-90 distillation specification, using ASTMD- at lower temperatures. Diesel and kerosene are common
86. However, others have reported that intake valve pour point additives that reduce the fuel gelling temper-
deposit formation is a problem with soy methyl esters at ature significantly when mixed with diesel. Refiners
light load, which may be related to the large percentage and marketers vary fuel cloud and pour points to meet
of olefinic content in the B20 mixtures. Excess glycer- local climatic conditions, and ASTM provides recom-
ine and glycerides in the fuel have also been associated mended fuel characteristics by season and be degree of
with deposits. Quality control on biodiesel fuel stand- latitude. The cloud point of soy methyl ester, used in
ards was not evident before 1997 and remains an indus- this study, can be 30℃ higher than that for diesel. The
try problem today; off spec fuel may also contribute to difference in pour points may be 10℃ higher for soy
some of the fuel problems identified in past studies. methyl ester. The relevant structural properties of
biodiesel that affect freezing point are degree of unsatu-
7・7 Specific Gravity ration, chain length, and degree of branching. Fully sat-
Specific gravity is determined by ASTMD- urated fatty acid chains tend to become solids at rela-
287. Diesel exhibits a specific gravity of 0.85. Biodiesel tively high temperatures (tallow, hydrogenated soy oil,
specific gravity is reported to vary between 0.86 and palm oil). Rape and canola methyl esters have lower
0.90 depending on the feedstock used. The average cloud and pour points than soy methyl ester. Tallow
gravity reported for soy methyl esters is 0.885. The spe- methyl ester has a cloud point of 16℃ and a pour point
cific gravities of biodiesel and diesel are very similar. of 10℃. Producing biodiesel with ethanol instead of
methanol tends to reduce the cloud and pour points by a
7・8 Energy Content few degrees. Rape ethyl esters have cloud points of
Generally, fuel consumption is proportional to the 10℃ and a pour point of 15℃. Isopropyl alcohol has
volumetric energy density of the fuel based on the been used to make a biodiesel with a pour point 90℃
lower or net heating value. Petroleum diesel contains lower than methanol-based biodiesel; pour point tem-
about 131,295 Btu/gal while biodiesel contains approxi- perature was reduced by 30℃. Other solutions, such as
mately 117,093 Btu/gal. If biodiesel has no impact on customizing the fatty acid profiles of the fuel, remain
engine efficiency, volumetric fuel economy would be possible but unexplored. Traditionally, cloud and pour
approximately 10% lower for biodiesel compared to points of biodiesel blends have been modified by
petroleum diesel. However, fuel efficiency and fuel changing the amount of biodiesel in the blends. Blends
economy of biodiesel tend to be only 2%-3% less than of more than 35% biodiesel demonstrate significant
that of diesel. The reasons behind this unexpected dif- winter problems in the Midwest. In Europe, cold weath-
ference have not been established. er additives have been identified for use with rape

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

methyl esters, but they are not effective with soy methyl ties of vegetable oil biodiesels and standard specifica-
esters. Several studies have shown that a number of tions of diesel oil are given in Table 4 (49-54).
diesel flow improvers do not work for biodiesel blends. Development in many developing countries increases
The biodiesel industry continues to fund research in this the energy demand. The demand for liquid fuels will
critical area. Currently, solutions are limited to recom- increase by transportation, industry & generation of
mending lower blends of biodiesel in the winter com- electricity. In addition, urgent protection of the remain-
pared to summer, blending with diesel or kerosene, and ing areas requires the substitution of firewood by liquid
using heated storage tanks andin-line fuel heating sys- gas, which leads to increase imports. Most of the devel-
tems in vehicles. oping countries including India are large petroleum
There were two field demonstrations in the winter importers & there dependence on external energy
(1997-1998) using biodiesel blends of 20% to 35% in sources from highly unstable regions would increase to
heavy-duty, on-road vehicles but the precautions dis- uncomfortable levels. India is sale of economic devel-
cussed earlier have been taken. An approach being con- opment is the need to import about 70 percent of its
sidered by the industry is marketing specific types of petroleum demand. The petroleum import bill is cur-
biodiesel to meet cold temperature by altering the types rently about 13 billion dollar (about 30 percent of the
of alcohol and oil feed stocks used. By customizing total import bill) compared to the current trade deficit
seasonal fuel compositions, similar to diesel producers, of about USD 11 billion. The current yearly consump-
more acceptances in cold weather could be established. tion of diesel fuel in India is approximately 40 percent
Additives may still be necessary. A lot of research of the total petroleum product consumption. The ongo-
remains to be done in this area. ing economic expansion would increase the demand for
transportation fuel at high rates. India produces only
7・10 Sulfur, Aromatic, Ash, Sediments, 22% of its diesel requirement and 78% is imported at a
Water, Methanol, Glycerine, and huge cost in foreign currency and our expenditure and
Glyceride Content outlay for the import of Petroleum fuel is second to our
These contaminates, if they exist at all, are limited Defence budget. Using biodiesel keeps our fuel buying
less than 2% in the biodiesel, in total. The ester content dollars at home instead of sending it to foreign coun-
of a fuel-grade biodiesel generally exceeds 98%. tries. This reduces our trade deficit and creates jobs so
Biodiesel is non aromatic and does not contain sulfur. with the introduction of compulsory use of 10-20%
Sodium and potassium containing ash may be present biodiesel in UK, USA, France, Germany, Japan and
because of contamination from catalysts used in trans- other countries who specify a 40-50% mix by 2010. In
esterification. Phosphorous may be present from inferi- India the import of liquid fuels creates approximately
or oil refining (poor gum removal). Water and sedi- 850 jobs in saffination storage, distribution and admin-
ments may be by-products of long-term storage. Glyc- istration. Because of tight economic situation the one
erine and methanol in the biodiesel may scavenge and the only way to replace imported petroleum from
water. Glycerine, glycerides, and excess alcohol are the market is the production of alternative. According to
major fuel contamination problems, and newly devel- an economic survey conducted by Government of India,
oped industry standards have taken aim at controlling the cultivable land area about 175 mha has been classi-
these contaminants. Sediment may result from oxida- fied as waste or degraded land which is suitable for cul-
tion of esters and reactive glycerides in the fuel. Algae tivation of some of the plant like Jatropha curcas. It is
growth may also produce sediment. significant to point out that the non edible vegetable oil
of Jatropha curcas has the requisite potential of provid-
ing a promising and commercially viable alternative to
8 Benefits of Biodiesel
diesel as it has the desirable physicochemical and per-
8・1 Similar to Diesel Fuel formance characteristics comparable to diesel to facili-
Biodiesel is similar to petroleum diesel fuel in many tate necessitating much change in design. Indian Rail-
chemical and physical properties. Engine performance ways have already completed a trial run on Amritsar-
& the fuel consumption were favorable that make it bet- shatabdi express. The Chief Minister of Chattisgarh
ter substitute to diesel fuel. The comparison of proper- runs his official vehicle on biodiesel, Haryana state

496
J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
Biodiesel: Source, Production, Composition, Properties and Its Benefits

Table 3 Biodiesel Standard DIN V51606 (Germany) (48).


Limits Max.
Property
Min.
Density at 15℃, g/mL 0.875 0.90
Kinetic viscosity at 40℃, mm2/s 3.500 5.00
Flash point (Pensky-Martens), ℃ 100
Cold filter plugging point, ℃ 15Apr-30 Sep 1 Oct-15 0.00 -10.00 -20.00
Nov 16 Nov-28 Feb 1 Mar-14 April -10.00
Sulphur, percent (w/w) 0.01
Carbon residue, percent (w/w), 10 percent distillation 0.30
Cetane number 49.0
Ash, percent (w/w) 0.01
Water, mg/kg 300
Total dirt, mg/kg 20.0
Copper corrosion for 3 h. at 50℃ 1.00
Neutralization no. mg KOH/g 0.50
Methanol, percent (w/w) 0.30
Monoglycerides, percent (w/w) 0.80
Diglycerides, percent (w/w) 0.10
Triglycerides, percent (w/w) 0.10
Free glycerol, percent (w/w) 0.02
Iodine no. g Iodine/100 g 115.0
Phosphorus, mg/kg 10

Table 4 Properties of Vegetable Oil Biodiesel and Diesel Fuel 8.2 Economic Studies.
kinematic
cetane flash point lower heating cloud point pour point
vegetable oil viscosity at density (kg/l)
number (℃) (℃) value (MJ/kg) (℃) (℃)
38℃ (mm2/s)
peanut 4.9 564 176 33.6 5 0.883 −
soyabean 4.5 45 178 33.5 1 0.885 –7
sunflower 3.6 63 127 31.8 4 0.875 −
palm 5.7 62 164 33.5 13 0.880 −
babassu 4.6 49 183 33.5 1 0.860 −
tallow − − 96 − 12 9
diesel 3.06 50 76 43.8 − 0.855 –16
20% biodiesel
3.2 51 128 43.2 − 0.859 –16
blend

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

transport buses have been run from Kharagpur and all so the use of biodiesel may directly displace this
lands by the side of Railway tracks in India will be amount of CO2 when used in engines. The combustion
planted with Jatropha and Indian oil and other agencies of biodiesel has been reported to emit lesser pollutants
in possession of a Biodiesel Processing units will even- compared to diesel. The emission of SO2, soot, CO,
tually process the Jatropha oil into Biodiesel for Indian hydrocarbons (HC, polyaromatic hydrocarbons (PAH),
Railways and for the national needs. and aromatics is given in Fig. 1 (59), which indicates
In earlier studies of biodiesel production, the main that the engine exhaust contains no SO2, and shows
economic criteria were capital cost, manufacturing cost decreasing emissions of PAH, soot, CO, HC and aro-
and biodiesel break even price. Results of three recent matics. The NOx emissions are reported to be in the
studies are given in Table 5 (55) evaluated from eco- range between G 10% as compared to diesel depending
nomic feasibility of a plant producing approximately on engine’s combustion characteristics.
10,000 tonne/year of biodiesel. Environmental problem that might crop up from
increased fuel consumption also need taken into
8・3 Sustainability & Non-Toxicity account. India has a huge requirement by 2010 to meet
Biodiesel is 100% renewable. Being plant based it the world norms and emission standards and a national
does not emit sulphur/CO on burning and is non pollut- policy has already been given a green signal by the GOI
ing, biodegradable and environmentally safe. Bunger et in the year 2003. A Harvard University study has come
al. (56) studied the cytotoxic and mutagenic effects of out with the dramatic figure of death per hour in
diesel engine emissions using biodiesel and petroleum Delhi(INDIA) caused by air pollution. Increased green
diesel as fuel. In this study the particulates associated house gases and resultant climatic change has dramati-
emissions from the DEP of biodiesel and common cally increased the number of natural disasters
petroleum diesel fuel and their vitro cytogenic and .Increased consumption of energy results in the increase
mutagenic effects were compared and the results release of green house gases into the atmosphere, main-
showed the lower mutagenic potency of biodiesel as ly transport related pollutant emission causes air pollu-
compared to diesel fuel. tion. Biodiesel is nearly carbon-neutral, meaning it con-
tributes almost zero emissions to global warming.
8・4 Environmental and Health Effects of Biodiesel also dramatically reduces other emissions
Biodiesel fairly dramatically. For example the characteristics of
In view of environmental considerations (57), Jatropha oil biodiesel are comparable to European spec-
biodiesel is considered ‘carbon neutral’ because all the ifications. The analysis of exhaust gases suggests that
carbon dioxide released during consumption had been Jatropha oil biodiesel will be environmentally safer
sequestered from the atmosphere for the growth of veg- fuel. Tests conducted the USEPA have shown that the
etable oil crops. Studies have shown that the combus- use of biodiesel almost completely eliminates life cycle
tion of 1 1 of diesel fuel leads to the emission of about of CO2 emissions.
2.6 kg of CO2 against 1 kg of CO2/kg of biodiesel (58), Makareviciene et al. (60) studied the environmental

Table 5 Recent Studies on Capital Cost, Manufacturing and Break Even Price of Biodiesel (55).
Nelson et al. Noordam and Withers et al. Bender et al.
Plant capacity 100,000 tonne/year 7800 tonne/year 10,560 tonne/year
Process type Alkali catalyzed continuous process Alkali catalyzed batch process Alkali catalyzed batch process
Raw material Beef tallow Canola oilseed Animal fat
Total capital cost $12 million Not reported $3.12 million
Total manufacturing cost $34 million $5.95 million Not reported
Biodiesel break-even price $340/tonne $760/tonne $420/tonne
Glycerine credit $6 million $0.9 million $1.2 million

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Biodiesel: Source, Production, Composition, Properties and Its Benefits

plete combustion.
Ball et al. (62) studied the fuel lubricity from blends
of di-ethanol-amine derivatives and biodiesel. The
investigation relates to the use of blends of di-ethanol-
amine derivatives and biodiesel as an additive for
improving lubricity in low-S fuels (e.g. diesel fuel, jet
fuel, kerosene, gasoline, gasoline alcohols blends) and
to fuels and additives concentrations comprising the
lubricity additives. Typically the additive can eliminate
failure of a fuel injection pump caused by inadequate
Fig. 1 Lower emissions of biodiesel compared with fuel lubricity.
petrodiesel. Karonis et al. (63) studied the effect of the addition
of biodiesels on the lubricity of Greek road diesel. In
effect of the rapeseed oil ethyl esters. Exhaust emis- this study, a series of representative fuels of the Greek
sions tests were conducted on rapeseed methyl esters, fuel market were tested. In some of them, the lubricity
rapeseed oil ethyl esters and fossil fuels as well as on was measured three times, during a period of three
their mixtures. Results showed that when considering months from the day of each sample was produced. In
emissions of nitrogen oxides (NOx), carbon-mono- all cases a decrease of the wear scar diameter (WSD)
oxide and smoke, rapeseed ethyl esters had less nega- was measured; this behaviour can be attributed to the
tive effect on the environment in comparison with that oxidation reactions that take place during the storage
of rapeseed oil methyl esters. period. In order to monitor the effect of the addition of
Zhang et al. (61) studied the biodegradability of biodiesel on the lubricity of road diesel, biodiesel pro-
biodiesel in the aquatic environment. The biodegrad- duced from sunflower oil and olive oil were used. The
ability of various biodiesel fuels were examined by the use of rapeseed oil biodiesel as a diesel fuel substitute
CO2 evolution method (EPA 560/682003), BOD (EPA was a common event in central Europe; in the United
405.1), COD (EPA 410) and gas chromatography (GC) States the soybean oil biodiesel has been examined in
analysis in aquatic system. The fuel examined included detail. However, biodiesels prepared from other starting
the methyl and ethyl esters of rapeseed oil and soy- materials, such as sunflower oil and olive oil had not
abean oil, neat rapeseed oil, neat soyabean oil and been examined extensively, although the above types of
phillips 2-D low sulphur, refined petroleum diesel. vegetable oil comprise interesting candidates for
Blends of biodiesel/petroleum diesel at different volu- biodiesel production in Southern Europe. The methyl
metric ratios, including 80/20, 50/50, 20/80 were also esters of sunflower oil and olive oil were added in the
examined. The results demonstrated that all the diesel fuels in concentrations varying from 0.25 % to
biodiesel fuels are readily biodegradable. In the pres- 10 % volume. In all cases noticeable decrease in WSD
ence of rapeseed ethyl ester, the degradation rate of was observed, which eventually approached asymptoti-
petroleum diesel increased to twice that of petroleum cally a constant value.
diesel fuel alone. The pattern of biodegradation in the
blends and reason why biodiesel is more readily 8・6 Drivability
degradable than petroleum were discussed. The We have yet to meet anyone who doesn’t notice an
biodegradation monitoring results from both, the CO2 immediate smoothing of the engine with biodiesel. It
evolution and GC methods were compared. just runs quieter, and produces less smoke. Biodiesel
can be used 10%, 20% or in any proportion doping the
8・5 Good Lubricity and Long Engine Life petro-diesel and it can be very safely used as 100%
The super or lubricating properties of biodiesel replacement of petro-diesel in all kinds of diesel
increases functional engine efficiency. The biodiesel engines without any modification of the currently avail-
molecules are simple hydrocarbon chains having no able diesel engines.
sulphur or aromatic substances. They use higher Serdari et al. (64) studied the impact of using biodiesel
amount of O2 (up to 10 percent) that ensures more com- of different origin and additives on the perform-

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J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

ance of a stationary diesel engine. With the exception of and Constraints In Developing Countries Like India, Chemical
Industry Digest, April, p. 77 (2004).
rapeseed oil which is the principal raw material for
4. C. SYLDADATK, M. REUSS, A. DANIEL and R. OTTO,
biodiesel production, sunflower oil, corn oil and olive
Methods for Biiotechnical Preparations of Fatty Acid Methyl
oil, which are the abundant in the southern Europe, Esters (Biodiesel) Based on Whey, Ger. Offen. DE 19 838 011
along with the some wastes such as used frying oils, (1999).
appear to be attractive candidates for biodiesel produc- 5. J.H. LEE, U. S. Patent 22 929, (2004).
tion. In this study, the fuel consumption and exhaust 6. G. VICENTE, M. MARTINEZ and J. ARACIL, Methyl Esters
emissions measurement from a single cylinder, station- of Sunflower Oil as Fuels: Alternative to Petroleum-Derived
ary diesel engine were described. The engine was Diesel Fuel, Ing. Quim., Vol. 31, 153-159 (1999).
7. J.M. ENCINAR, J.F. GONZALEZ, F. JAUN, E. SABIO and
fueled with fuel blends containing four different types
J.M. RAMIRO, Preparation and Properties of Biodiesel from
of biodiesel at proportions up to 100%; the further
Cyanara cardunculus, Ind. Eng. Chem. Res., Vol. 38, 2927-2931
impact of the usage of two specific additives was also (1999).
investigated. The four types of biodiesel were appeared 8. S. SHAH, S. SWETA and M.N. GUPTA, Biodiesel Preparation
to have equal performance, their addition to the tradi- by Lipase Catalyzed Transesterification of Jatropha Oil, India
tional diesel. Energy & Fuels, Vol. 18, 154-159 (2004).
9. W. DU, Y. XU and D. LIU, Lipase Catalyzed Transesterification
of Soyabean Oil for Biodiesel Production during Continuous
9 Conclusion Batch Operation, Biotech. & appli. Biochem., Vol. 38, 103106
(2003).
Biodiesel is a better fuel than petrodiesel and meets 10. K. KOMERS, R. STLOUKAL, J. MACHEK, FRANTISEK and
most of the chemical/physical standards of Petrodiesel. A. KOMERSOVA, Biodiesel Fuel from Rapessed Oil, Methanol
Biodiesel can be considered as the best option and has and Koh-Analytical Method in Research and Production, Fats &
the largest potential, which meets the requirements and Lipids, Vol. 100, 507-512 (1998).
could ensure fuel supply in the future. Plant oils, 11. G. HILLION, B. DELFORT, L. BOURNAG, P. LE,
biodiesel, biogas and ethanol have been successfully DOMINIQUE and A.J. CHODORGE, Biodiesel Production by a
Continuous Process using a Heterogenous Catalyst, Computer
introduced and are already in use. Fuels derive from
optical disk, Vol. 48, 636-638 (2003).
biomass are not only potentially renewable but also suf-
12. O.P. NAMBIAR, Energy Resources of the Future-Oil Wells in
ficiently similar in origin to the fossil fuels to derived our Backyard, Saarc Oil & Fats Today, Sep, p. 47 (2003).
direct substitute. They can be converted into a wide 13. M. BENDER, Economy Feasibility Review for Community
variety of energy carriers (biogas, biodiesel, ethanol, Scale Farmers Co-operative for Biodiesel, Biosour. Technol, Vol.
methanol, DME, diesel, gasoline, hydrogen) as of 70, 81 (1999).
recent fossil fuel through conversion technologies & 14. M.A. FANGRUI, A. MILFORD and HANNA, Biodiesel Pro-
duction-A Review, Biosour Technol, Vol. 70 (1999).
thus have the potential to be significant new sources of
15. A. SRIVASTAVA and R. PRASAD, Triglyceride Based Diesel
energy into the 21st century. In future, alternative fuels
Fuels, Renew. sustain. energy Rev., Vol. 4, 111 (2000).
should offer the possibilities to be used as the current 16. Infocus, Simon India’s Continuous Process for Biodiesel Pro-
fuels within existing infrastructure, to contribute in duction, Chemical Industry Digest, March-April, pp. 39-41
reduction of green house gases, to promote the develop- (2003).
ment of new technologies of the recent combustion sys- 17. F. KOMERS, F. SKOPAL, R. STLOUKAL and MACHEK,
tems and energy generetics (i.e. fuel cells), to be afford- Kinetics and Mechanism of the KOH Catalyzed Methanolysis of
able, sustainable and should be renewable. Rapeseed Oil for Biodiesel Production, Journal of Lipid Science
and Technology, Vol. 104, 728-737 (2000).
18. R. ALTIN, S. CENTINKAYA and H.S. YUCESN, The Potential
References of Vegetable Oil Fuels as Fuel for Diesel Engines, Ener Converv
Manag., Vol. 4, 529 (2001).
1. Based Biodiesel-Opportunities and Contents in Developing 19. O.E. IKWAGUAGWU, I.C. ONONOGBU and O.U. NJOKU,
Countries like India, Chemical Industries News, April, p. 79 Production of Biodiesel Using Rubber [Hevea brasiliensis
(2004). (Kunth. Muell)] Seed Oil, Ind Crops Prod, Vol. 12, 57 (2000).
2. R.K. MALHOTRA and L.M. DAS, Biofuels as Blending Com- 20. N.R. KAMINI and H. LEFUGI, Lipase Catalysed Methanolysis
ponents for Motor Gasoline and Diesel Fuels, Journal of Scien- of Vegetable Oil in Aqueous Medium by cryptococus spp. S-2,
tific and Industrial Research, Vol. 61, 91 (1999). Process Biotechnol., Vol. 37, 405 (2001).
3. N.S. VENKATARAMAN, Agro Based Biodiesel-Opportunities

500
J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
Biodiesel: Source, Production, Composition, Properties and Its Benefits

21. R. ALCANTARA, J. AMORES, L. CANAIRA, E. FIDALGO, Resources (J.S. CUNDIFF, ed.), American Society of Agricul-
M.J. FRANCO and A. NAVARRO, Catalytic Production of tural Engineers, St. Joseph, pp. 79-88 (1992).
Biodiesel from Soybean Oil, Using Frying Oil and Tallow, 39. T. MURAYAMA, Evaluating Vegetables Oils as a Diesel Fuel,
Biomass Bioener., Vol. 80, 515 (2000). INFORM, Vol. 5, 1138-1145 (1993).
22. T.H. APPLEWHITE, in Kirk-Othmer, Encyclopedia of Chemical 40. R.O. DUNN, M.W. SHOCKLEY and M.O. BAGBY, Improving
Technology, 3rd edn, John-Wiley & Sons, New York, NY, Vol. 9, Low Temperature Flow Performance of Biodiesel Fuels and
795-811 (1980). Blends, INFORM, Vol. 5, 529 (1994).
23. F.D. GUNSTONE, J.L. HARWOOD and F.B. PADLEY, Lipid 41. Fosseen Manufacturing and Development, Ltd., Evaluation of
Handbook, 2nd edn., Chapman & Hall, London (1994). Methyl Soyate/Diesel Blend in a DDC 6V-92TA Engine,
24. T.W. RYAN, T.J. CALLAHAN and L.G. DODGE, Characteriza- ORTECH Final Report No. 93-E14-21/93-E14-36, ORTECH
tion of Vegetable Oils for Use as Fuels in Diesel Engines, Veg- Mississauga, Ontario (1993).
etable Oil Fuels-Proceedings of the International Conference on 42. I. LEE, L.A. JOHNSON and E.G. HAMMOND, Use of
Plant and Vegetable Oils as Fuels, August, 70-81 (1982). Branched Chain Esters to Reduce the Crystallization Tempera-
25. E.F. FORT and P.N. BLUMBERG, Performance and Durability ture of Biodiesel, J. Am. Oil Chem. Soc., Vol. 72, 1155-1160
of a Turbocharged Diesel Fueled with Cottonseed Oil Blends, (1995).
Vegetable Oil Fuels-Proceedings of the International Confer- 43. G.R. LIST and T.L. MOUNTS, Partially Hydrogenated-Winter-
ence on Plant and Vegetable Oils as Fuels, August, 374-382 ized Soybean Oil, Handbook of Soy Oil Processing and Utiliza-
(1982). tion (D.R. ERICKSON, E.H. PRYDE, O.L. BREKKE, T.L.
26. J.P. WALTER and J. DERRY, The 1981 “Flower Power” Field MOUNTS and R.A. FALB, ed.), American Oil Chemists’ Soci-
Testing Program, Vegetable Oil Fuels-Proceedings of the Inter- ety, Champaign, pp. 193-214 (1980).
national Conference on Plant and Vegetable Oils as Fuels, 44. T.J. WEISS, Salad Oil Manufacture and Control, J. Am. Oil
August, 384-393 (1982). Chem. Soc., Vol. 44, 146A, 148A, 186A and 197A (1967).
27. R.A. BARANESCU and J.J. LUSCO, Performance, Durability 45. G.M. NEUMUNZ, Old and New in Winterizing, J. Am. Oil
and Low Temperature Evaluation of Sunflower Oil as a Diesel Chem. Soc.,Vol. 55, 397A-398A (1978).
Fuel Extender, Vegetable Oil Fuels-Proceedings of the Interna- 46. G.H. KNOTHE, A.C. MATHEAUS and T.W. RYAN, Cetane
tional Conference on Plant and Vegetable Oils as Fuels, August, Number of Branched and Straight Chain Fatty Esters Deter-
312-328 (1982). mined in an Ignition Quality Tester, Fuel, Vol. 82, 971-975
28. M.S. GRABOSKI and R.L. MCCORMICK, Combustion of Fat (2003).
and Vegetable Oil Derived Fuels in Diesel Engines, Prog. Energ 47. A. WONG and E. HOGAN, A Green Approach for the Produc-
Combust. Sci.,Vol. 24, 125-164 (1998). tion of Biocetane Enhancer for Diesel Fuels, Biomass Conf. Am.,
29. H. NOUREDDINI, B.C. TEOH and D.L. CLEMENTS, Viscosi- Vol. 1, 837-841 (1999). Biodiesel Report; National Biodiesel
ties of Vegetable Oils and Fatty Acids, J. Am. Oil Chem. Soc., Board: Jefferson City, MO, March 1996.
Vol. 69, 1189-1191 (1992). 48. Biodiesel Report; National Biodiesel Board: Jefferson City, MO,
30. T.H. GOUW, J.C. VLUGTER and C.J.A. ROELANDS, Physical March 1996.
Properties of Fatty Acid Methyl Esters .VI, J. Am. Oil Chem. 49. Y. ALI, M.A. HANNA and S.L. CUPPETT, Fuel Properties of
Soc., Vol. 43, 433-436 (1966). Tallow and Soyabean Oil Esters, J. Am. Oil Chem. Soc., Vol. 72,
31. H. NOUREDDINI, U. S. Patent., 174 501, (1997). 1557-1564 (1995).
32. DU PLESSIS, L.M. CHEMSA, 8, 150-154 (1982). 50. S. RAO and K.V. GOPALAKRISHNAN, Vegetable Oils and
33. L.M. DU PLESSIS, J.B.M. DE VILLIERS and W.H. VAN DER their Methylesters as Fuels for Diesel Engines, Indian J.
WALT, J. Am. Oil Chem. Soc., Vol. 62, 748-752 (1985). Technol., Vol. 29, 292-297 (1991).
34. P. BONDIOLI, A. GASPAROLI, A. LANZANI, E. FEDELI, S. 51. O. FEUGE and A.T. GROS, Modifications of Vegetable Oils.
VERONESE and M. SALA, J. Am. Oil Chem. Soc., Vol. 72, VII Alkali Catalyzed Interesterification of Peanut Oil with
699-702 (1995). Ethanol, J. Am. Oil Chem. Soc., Vol. 26, 97 (1949).
35. T. DITTMAR, B. ONDRUSCHKA, P.T. HA, J. HAUPT and M. 52. O. DUNN and M.O. BAGBY, Low Temperature Properties of
LAUTERBACH, Erdoel, Erdgas, Kohle, Vol. 119, 356-362 Triglyceride-Based Diesel Fuels: Transesterified Methyl Esters
(2003). and Petroleum Middle Distillate/Esters Blends, J. Am. Oil Chem.
36. I. LEE, A.J. LAWRENCE and G.H. EARL, Reducing the Crys- Soc., Vol. 72, 895-904 (1995).
tallization Temperature of Biodiesel by Winterizing Methyl Soy- 53. D.Y.Z. CHANG, J.H. VANGERPEN, I. LEE, L.A. JOHNSON,
ate, J. Am. Oil Chem. Soc., Vol. 73, 631-636 (1996). E.G. HAMMOND and S.J. MARLEY, Fuel Properties and
37. National Soy Diesel Development Board, Biodiesel Alert, Vol. 1, Emissions of Soybean Oil Esters as Diesel Fuel, J. Am. Oil
9 (1993). Chem. Soc., Vol. 73, 1549 (1996).
38. C.R. ENGLER, W.A. LEPORI, L.A. JOHNSON and C.M. 54. N.J. NYE and P.H. SOUTHWELL, Esters from Rapeseed Oil as
YARBROUGH, Processing Requirements for Plant Oils as Diesel Fuel: Proceedings of Vegetable Oil as Diesel Fuel, Semi-
Alternative Diesel Fuels, Liquid Fuels from Renewable nar III, I. L. PEORIA, (1983).

501
J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)
D. Bajpai and V.K. Tyagi

55. Y. ZHANG, M.A. DUBE, D.D. MCLEAN and M. KATES, 2395-2403 (2003).
Biodiesel Production from Waste Cooking Oil: 2, Economic 61. X. ZHANG, C. PETERSON, D. REECE, R. HAWS and G.
Assessment and Sensitivity Analysis, Bioresource Technology, MOLTER, Biodegradability of Biodiesel in the Aquatic Environ-
Vol. 90, 229-240 (2003). ment, Trans ASAE, Vol. 41, 1423-1430 (1998).
56. J. BUNGER, J. KRAHL, K. BAUM, O. SHRODER, M. 62. K.F. BALL, J.G. BOSTICK and T.J. BRENANN, U. S. Patent 5
MULLER, G. WESTPHAL and P. RAHNAU, Cytogenic and 891 203, (1999).
Mutagenic Effects, Particle Size and Concentrations: Analysis of 63. D. KARONIS, G. ANASTOPOULOS, E. LOIS, S. STOUR-
of Diesel Engine Emissions Using Biodiesel and Petrodiesel as NAS, F. ZANNIKOS and A. SERDARI, Assessment of the
fuel, Arch. Toxicol., Vol. 74, 490-498 (2001). Lubricity of Greek Road Diesel and the Effect of the Addition of
57. B.K. BARNWAL and M.P. SHARMA, Renewable and Sustain- Specific Types of Biodiesel, Soc. Automot. Eng. [Spec. Publ.],
able Energy Reviews, Vol. 9, 363-378 (2005). (1999).
58. J. TICKELL, The fryer to the fuel tank, 2nd edn, Sarasota, FL: 64. SERDARI, K. FRAGIOUDAKIS, S. KALLIGEROS, S.
GreenTeach Publishing (1999). STOURNAS and E. LOIS, Impact of Using Biodiesel of Differ-
59. L.J. ROSENBLUM, Feasibility of biodiesel for rural electrifica- ent Origin and Additives on the Performance of a Stationary
tion in India [Draft], June (2000). Diesel Engine, J. Eng. Gas Turbines Power, Vol. 122, 624-631
60. V. MAKAREVICIENE and P. JANULIS, Environmental Effect (2000).
of the Rapeseed Oil Ethyl Esters, Renewable Energy, Vol. 28,

502
J. Oleo Sci., Vol. 55, No. 10, 487-502 (2006)

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