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Biodiesel has become more attractive since one decade because of limited fossil resources and increasing demand for
diesel. Biodiesel derived from vegetable oils/animal fats triglycerides is a worthy replacement for the hydrocarbon based
diesel fuels, because of its multiple benefits, and it can be used in diesel engines without any modit1cation in the existing
engines. Transesterification is the most commonly used method for the production of biodiesr;1 from vegetable oils and
animal fats in presence of catalytic NaOHlH2S04 at 70 "c. The transesterification of these oils is affected by the mode of the
reaction, molar ratio of the glycerides to alcohol, type and quantity of catalyst, reaction temperature, reaction time and purity
of oil and fats. Cost of biodiesel thus obtained is the main obstacle in its commercialization. Efforts are under way in many
countries to search options to reduce cost of biodiesel production. Other methods for the preparation of biodiesel with
different combination of oils and catalysts have also been summarized. Biodiesel standards provided by different countries
are given.
with sunflower o i l occurred in South Africa because long-term use in a direct-injection engine. The
-A.
of oil embargo. Rapeseed oil was used as a fuel and viscosity of a 25:75 (v/v) high safflower oil and diesel
concluded that, the physical and chemical properties blend was 4.92 cSt at 40 °C. A mixture of 50:50 (v/v)
of rapeseed oil as a fuel was very similar to those of soybean oil and S toddard solvent (48 per cent
diesel fuel, and on a long term basis it can be used in paraffins and 52 per cent naphthens) from Union Oil
diesel engines ) . Co had a viscosit/ of 5 . 1 2 cSt at 38 °C. B oth blends
Two severe problems associated with the use of of safflower and soybean oil passed the 200 h EMA
vegetable oils as fuel were oil deterioration and (Engine Manufacturers' Association) test.
incomplete combustion4 . Polyunsaturated fatty acids
2.3 Pyrolysis of Vegetable Oils
were very susceptible to polymerization, and gum
formation caused by oxidation during storage or by
Pyrolysis strictly defined; is the conversion of
complex oxidative and thermal polymerization at the
one substance into another by means of heat or by
higher temperature and pressure of combustion. The
heat with the aid of a catalyst. It involves heating in
gum did not combust completely, resulting in carbon
absence of air or oxygen and cleavage of chemical
deposits and lubricating oil thickening. One more big
bonds to yield small molecules. Pyrolytic chemistry is
problem is high viscosity of the vegetable oil ; around
difficult to characterize because of variety of the
1 0- 1 5-times more than the diesel fuels4 .
reaction paths and variety of the reaction products
Mixtures of degummed soybean oil and No. 2 Catalytic cracking of copra and palm oils at 450
diesel fuel in the ratios of 1 :2 and I : I were tested for °C using Si021AI 20, as catalysts to produce biofuel
engine performance and crankcase lubricant viscosity have been studied. Rapeseed oil was pyrolyzed to
produce a mixture of methyl esters in a tubular
reactor at 500-850 °c and in nitrogen" . A mechanism
in a John Deere 6-cylinder, 6.6 L displacement,
direct-injection, turbocharged engine for a total of 4
600 h. The lubricating oil thickening and potential of thermal decomposition of triglycerides is gi yen
gell ing existed with the I : I mix, but it did not occur below in Figure I .
with the 1 : 2 mix. The results indicated that 1 : 2 mix The l iquid fractions of thermal decomposed
should be suitable as a fuel for agricultural equipment vegetable oils are l ikely to approach diesel fuels6 . The
during periods of diesel fuel shortage or allocation4 . pyrolyzed soyabean oil contained 79 per cent carbon
and 1 1 .88 per cent hydrogen. It has low viscosity and
Sunflower oil and diesel fuel blend (25 :75, v/v) a high cetane number compared to the pure vegetable
shoed viscosity of 4.88 cSt at 40 °C, exceeding the oil. The cetane number of pyrolyzed soyabean oil was
maximum allowable value of 4.0 cSt as per the enhanced to 43 from 37.9 and the viscosity reduced to
ASTM standard. It was considered not suitable for 1 0.2 cSt from 32.6 at 3 8 °C.
1 26 J SCI IND RES VOL 62 JANUARY-FEBRUARY 2003
• CH2(CH2)SCO - OH
CHa(CH2)3CH2 • ! H
HI
CH3(CH2)SCO - OH
l-COz
yH,- -R
CH -o-co-R
J 3
HN/C�C Ha_�. 3
I
+ 'CH:zCH3 +
CH2-O-C-R
b
Diethylarbine Amides Glycerol
Triglyceride
Scheme I
sent to a rectifying column for purification and this way, the reaction can be driven to completion.
recycled. When 1 00 per cent excess methanol is used, the
reaction rate is at i ts highest. A mol ar ratio of 6: I is
4. 2 Effect of Diffe rent Parameters on the Production
normal ly used in industrial processes to obtain methyl
of Biodiesel
ester yields greater than 98 per cent on weight basis.
4.2.1 Impurities Transmethylated palm oil at 70 DC in toluene with
Impurities present in oils also affect conversion sodium methoxide as catalyst resulted in the
level. For alkali catalyzed transesterification, the conversion that increased with molar ratio of
6
glycerides and alcohol must be substantial ly methanol . A molar ratio of 6: I was used for
anhydrous as water causes a partial reaction change to transesterification of beef tallow with methanol 4 .
saponification, which produces soaps . The soap Zhang reported 80 per cent recovery of esters by
consumes the catalyst, reduces the catalytic tal low weight in laboratory. Methanol present in
efficiency, as well as causing an increase in viscosity, amounts above 1 .75 equi valents tended to prevent
the formation of gels, and difficulty in achieving gravity separation of glycerol, thus adding more costs
separation of glycerol . Under the same conditions 67- to the process4 .
84 per cent conversion of crude vegetable oils into 4.2.4 Catalyst Used in Transesterification
esters can be obtained compared with 94-97 per cent There are three types of catalyst used in
when refined oils are used. The free fatty acids in biodiesel production depending upon the nature of
native oils interfere with the catalyst. However, under oi l. The reaction rate increased with catalyst
conditions of high temperature and pressure this 6
tremendously, about 4000-ti mes than without it .
problem can be overcome. The effect of free fatty Specific instances of the different type of catalysts
acids and water on transesterification of beef tal low used are given below:
with methanol was investigated. The results showed
that the water content of beef tal low should be kept 4. 2.4. 1 Basic Catalyst Catalysts are c lassified
-
below 0.06 per cent (w/w) and free fatty acid be kept as alkali, acid, or enzyme. Alkali-catalyzed
below 0.5 per cent (w/w) in order to get the best transesterification is much faster than other type of
conversion. Water content was a more critical factor the catalysts4 . Alkal i s include sodium hydroxide,
in the transesterification process than were the free sodium methoxide, potassium hydroxide, potassium
fatty acids. The maximum content of free fatty acids methoxide, sodium amide, sodium hydride, potassium
4 amide, and potassium hydride. Sodium hydroxide
confirmed the results of earlier work .
was also chosen to catalyze the transesterification as
4.2.2 Alcohol Type it is cheaper. Ester conversions at the 6: I ratio for I
Methanol and ethanol are most commonly used per cent NaOH and 0.5 per cent NaOCH, were almost
for transesterification of vegetable oils and fats but the same after 60 min4 . NaOH and NaOCH, reached
other alcohols can also be u sed. It has been reported their maximum activities at 0.3 and 0.5 per cent (w/w,
that yield of alcohol esters was the highest for beef tallow basis), respectively.
methanol, as methanol is the shortest-chain alcohol 4. 2.4. 2 Acid Catalyst -However, if a glyceride
and more reactive to oil with the added advantage of has a higher level of free fatty acids (FFA) content
alkali catalysts being eas i ly soluble in it. and more water, then acid-catalyzed
6
4.2.3 Reactants Ratio transesterification is suitable [4. J • The acid could be
sulfuric, phosphoric, hydrochloric or organic sulfonic
Very i mportant factor affecting the yield of ester acid. Acid catalyzed methylation is energy sensitive
is the molar ratio of alcohol to vegetable oil. The because it i s usuall y conducted at h i gh temperature.
stoichiometry of the transesterification reaction Palm oil with 3 per cent H 2 S04 gives highest yield of
78 per cent methyl esters O at 2 3 : I mollmol .
requires 3 mol of alcohol per mole of triglyceride to l
yield 3 mol of fatty esters and I mol of glycerol . The
reaction being reversible in nature, it is necessary to 4.2. 4.3 Bio Catalyst -A s described above that
use either a large excess of alcohol or to remove one the catalysts used in the biodiesel production are
of the products from the reaction mixture to alkali and acid, but the recovery of catalysts are very
favourably shift reaction to the product side. The difficult. It can affect the process economically as
second option is preferred wherever feasi ble, since in well as ecologically. Several reports describe enzymic
KUMAR et at.: CONVERSION OF NON-EDIBLE OIL IN BIODIESEL 1 29
alcoholysis of vegetable oils. When ethanol, conditions, however, require the removal of free fatty
isopropanol, butanol and long-chain alcohols were acids from the oil by refining or pre-esterification .
used as substrates, the oils were efficiently converted Therefore, the degummed and de-acidified feedstock
to their fatty acid esters. The efficiency of conversion is used at these conditions. The pretreatment is not
was low with methanol J J . Lipase catalyzed required if the reaction is carried out under h igh
alcoholysis in the absence of solvent is important in pressure (9000 kPa) and temperature (240 °C). Under
industrial applications. Studies on methyl ester these conditions, simultaneous esterification and
synthesis in aqueous medium have been reported with transesterification take place6 . The maximum yield of
lipases from Geotrichum candidum and Candida esters occurs at 60-80 DC, with molar ratio of alcohol
deformans. However, yields of the reaction were 62 to oil of 6: I . Further increase in temperature is
and 58 per cent, respectively, with oleic acid and reported to have a negative effect on the conversion.
triolein as substrates. A three-step reaction for the The butanolysis and methanolysis of soyabean oil
methanolysis of a mixture of soybean and rapeseed were studied at different temperatures in the presence
oil has been proposed. The Candida antarctica lipase of acidic and alkaline catalysts. These studies
was inactivated in reaction mixture containing more indicated that transesterification can proceed
than 1 .5 Meq of methanol and showed a methyl ester . satisfactorily at ambient temperature in the case of
yield of over 95 per cent. Therefore, it is necessary to alkaline catalysts6 .
find a lipase that efficiently catalyses methanolysis 4.2.7 Stirring effect
reaction in aqueous medium and in a single step
without an additional organic solvent. In an earlier In the transesterification reaction, the reactants
study, the crude lipase from the yeast, Cryptococcus initially form a two-phase liquid system. The reaction
spp. S-2 (strain CS2) was shown to possess is diffusion-controlled and poor diffusion between the
considerable stabil ity in solvents and it could be used phases results in a slow rate. As methyl esters are
for the hydrolysis of vegetable oi Is J J . formed, they act as a mutual solvent for the reactants
and a single-phase system is formed. The mixing
4.2.5 Reaction Time effect is most significant during the slow rate region
The conversion rate increases with reaction of the reaction. As the single phase is established,
time. The effect of reaction time on transesterification mixing becomes insign ificant. The understanding of
of beef tallow with methanol was determined. The the mIXIng effects on the kinetics of the
reaction was very slow during the first minute due to transesterification process is a valuable tool in the
the mixing and dispersion of methanol into beef process scale-up and design. Conversion of soybean
tallow. From one to five min, the reaction proceeded 7
oil as a function of time and stirring , after
very fast. The apparent yield of beef tallow methyl optimization of the reaction conditions-methanol :oil
esters surged from I to 38. The production of beef ratio of 7.5 : I , at 60 °C ; with I per cent sodium
tallow esters then slowed down and reached the methoxide, at 600 rpm - 90 per cent conversion was
maximum value at about 1 5 min. An approximate noted after 30 min, while at 360 rpm, only 20 per cent
yield of 80 per cent was observed after I min for conversion was obtained after 8 h.
soybean and sunflower oils at methanol to oil ratio of
6: I , 5 per cent sodium methoxide catalyst at 60 °C. 5 Biodiesel Standards
After I h, the conversions were almost the same for
B iodiesel is produced in quite differently scaled
al l four oi ls4 (93-98 per cent). The effect of reaction
ti me for palm oil at 40: I methanol :oil (mol/mol) with
plants from vegetable oils of varying origin and
quality. Therefore, it was necessary to install a
5 per cent H2S04 (v/w) at 95 °C for 9 h, gave a
standardization of fuel quality to guarantee engine
maximum esters yield J J of 97 per cent.
performance. Therefore, in 1 992, Austria was the
4.2.6 Reaction Temperature first country in the world to define and approve the
The rate of reaction is strongly influenced by the standards for the rapeseed oil methyl esters as diesel
reaction temperature. However, given enough time, fuel (O-NORM, 1 992). As standardization is
the reaction will proceed to near completion even at prerequisite for the successful market introduction
room temperature. Generally, the reaction is and penetration of biod iesel, standards or gUidelines
conducted close to the boi ling point of methanol, 60- for defining the quality of biodiesel have also been
70 °C, at atmospheric pressure. These mild reaction defined in other countries, l ike Germany (DIN V
1 32 J SCI I N D RES VOL 62 JANUARY-FEBRUARY 2003
Prof Ashok Kumar Gupta, bom 011 28 March 1 945, obtained his B Tech in 1966 from LIT, Nagpur, and M
Tech in / 968 and PhD ill 1 9 73 in Chemical Engineering from I1T, Kanpur. He had a stint as II Post-Doctoral
Fellow at Imperial College, London from 1 9 73 to 1 975. He has been teaching ill /ITs (Kanpur and Delhi) ever since
his return from London in 1 975. At present he is associated as Professor in I1T, Delhi. He has supervised more than
80 undergraduate projects, about 30 Graduate theses and projects and 7 PhD theses. He has puhlished 30 papers ill
national and illtemational journals. His research interests are adsO/ptioll and iOIl exchange, and processing of
plant lllateiais.
Dr S N Naik obtained his M Tech ill oil technology from LIT, Nagpur and PhD from liT, Delhi in
extraction of natural plant products /Ising super critical fluid gases. He also worked at the University of Siegen,
Gerlllany under Indo-Germall projects. He has several years of industry experience apart from the teaching in
which he is engaged ill for the past several years. A t present he is associated as A ssociate Professor ill tile Centre
for Rural Development & Technology at Indian Institute of Technology, Delhi.