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Journal of Scientific & Industrial Research

Vol. 62, January-February 2003, pp 1 24- 1 32

Conversion of Non-edible Oil into Biodiesel

Suresh Kumar, A K Gupta, S N Naik


Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi 1 1 00 1 6, India
-

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.

1 Introduction brilliant i n ventor named Rudolph Diesel designed the

/ . / Need and Historical Development


original Diesel Engine to run on vegetable oi l . He
2
used peanut oil to fuel one of his engines at the Paris
Recent petroleum crises, rapidly i ncreasing Exposi tion of 1 900. Transesterification is also not a
prices and uncertamtles concerning petroleum new process as E Duffy and J Partrick did it in 1 85 3 .
avail ability let the scientists work on alternative fuel One o f the first uses o f transesterified vegetable oil
sources, so vegetable oil as fuel becomes current was powering heavy-duty vehicle in the South Africa
studies among various investigations. Biodiesel is a before World War II. The name biodiesel has been
liquid; ester-based oxygenated fuel, similar to given to transesterified vegetable oil to describe its
petroleum based diesel fuel but made from vegetable use as a diesel fuel .
products; either plant oils or animal fats. Although vegetable oils may be used d i rectly as
B iodiesel produces favorable effects on the fuel in diesel engines without refining, but they
environment, such as decrease in acid rain and present several problems mainly related to viscosity.
emission of CO2, SOx and unburned hydrocarbons Vegetable oils have very h i gh viscosity and therefore
during the combustion process. Due to these factors very difficult to bum in the internal combustion ( IC)
and to its easy biodegradabi l i ty, production of engines. Chemical conversion of oil with short chain
biodiesel is considered an advantage over that of alcohols; such as methanol or ethanol, to its
fossil fuels. The processing of biodiesel has a positive corresponding fatty ester appeared to be the most
energy balance of roughly 2 . 5 : I , no appreciable promising solution to the high viscosity problem2 .
difference between biodiesel and diesel - in engine Transeslerified vegetable oils or animal fat proved to
durabil ity or in carbon deposits - have been be the alternative with the best results ' .
demonstrated in most l aboratory studies ' . The US
2 Use of Vegetable Oil
Department of Energy estimated that up to 50 per
cent of the total diesel fuels consumption could be
2 2. 1 Direct Use of Vegetable Oil
replaced with biodiesel .
Beginning in 1 980, there was considerable
The idea of using vegetable oils as fuel for discussion regarding use of vegetable oils as a fuel.
diesel engines is not new. More than 1 00 y ago, a The concept of using food for fuel , indicating that
petroleum should be "alternative" fuel rather than
* Corresponding author 4
vegetable oils and alcohol • The most advanced work
KUMAR et al. : CONVERSION OF NON-EDIBLE OIL IN BIODIESEL 1 25

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

2 . 2 Dilution of Diesel Oil with Vegetable Oils


that may be obtained from the reactions that occur.
The pyrolyzed material can be vegetable oils, animal
fats, natural fatty acids and methyl esters of fatty
B lumberg and Ford, made short and long term
acids. The pyrolysis of fats has been investigated for
(200 h) engine performance and emission tests using
more than 1 00 y, especially in those areas of the
eight different ratios of cottonseed oil to 2D diesel oil
world that lack deposits of petroleum4 .
(v/v): 0: 1 00, 30:70, 50:50, 65:35, 80:20, and ratio of
transesterified cottonseed oil to 2D diesel fuel, viz, The first pyrolysis of vegetable oil was
50:50, 1 00:0, and 50:50 mix of cottonseed oil and conducted in an attempt to synthesize petroleum from
transesterified cottonseed oil S . They reported that vegetable oi l . In 1 947 a l arge scale of thermal
short-term results were more desirable than the long­ cracking of tung oil calcium soaps was reported4 .
term results. Long-term tests showed carbon deposit, Soyabean oil was thermally decomposed and disti l led
ash and wear in the combustion chamber and sticky in air and nitrogen sparged in standard ASTM
gum content in fuel-line elements. Engine disti llation apparatus used safflower oil as a high
performance tests for 200 h using 25:75 blend (v/v) of oleic oil control . The total identified hydrocarbons
soybean and sunflower oil fuel with diesel fuel ; obtained from distil lation of soybean and h igh oleic
showed that engine torque values with mixtures were safflower oi Is were 73-77 and 80-88 per cent
greater than that with pure diesel operation s . respectivel / .

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

Figure I -Thermal decomposition mechanism of vegetable oils

Microemulsion An emulsion of alkali-refined and winterized


To solve the problem of high viscosity of sunflower oil, 1 90-proof ethanol and I -butanol (53,
vegetable oil, micro-emulsions with solvents such as 1 3.3, 3 3 .4 per cent, v/v) was prepared. This nonionic
methanol, ethanol and I -butanol have been studied. emulsion was characterized by a viscosity of 6.3 1 cSt
Microemu lsions are isotropic, clear, or translucent at 40 °C, cetane number of 25 and less than 0.0 I per
thermodynamical ly stable dispersion of oil, cent an ash content. Lower viscosities and better
water, surfactant, and often a smal l amphiphi l ic spray patterns (more even) were observed with an
molecule, cal led co-surfactant. The droplet increase of I -butanol ratio. In a 200 h laboratory
diameters in microemulsions ranged from 1 - 1 50 nm. screening endurance test, no significant deteriorations
A microemulsion can b� made of vegetable oils with in performance were observed, but i rregul ar injector
an ester and dispersant (co-solvent), or of vegetable needle sticking, heavy carbon deposits, incomplete
oils, an alcohol and a surfactant, with or without combustion and an increase of lubricating oil
diesel fuels. Microemulsions because of their alcohol viscosity were however reported4 .
content have lower volumetric heating values than
3 Vegetable Oil Based Fuels in I.e Engines
diesel fuels, but the alcohols have high latent heat of
vaporization and tend to cool the combustion 3. 1 Amidation
chamber, which would reduce nozzle coking.
It has been reported that diethyl amides of fatty
A micro emulsion of methanol with vegetable acids show higher cetane numbers than the fatty
oils can perform nearly as well as diesel fuels because alcohols or fatty methyl or ethyl esters? Moreover,
of lower viscosity than the parent vegetable oil . The the chemical transformation of mixtures of
use of 2-octanol as an effective amphiphile in the triglycerides (oils/fats) to diethyl amides can be easily
micell ar solubilization of methanol in triolein and accompl i shed in a single chemical process. Thus,
soyabean oil has been demonstrated6 . The viscosity amide biodiesel would make a good candidate to
reduced to 1 1 .2 cSt at 25 °C. The reported engine incorporate the 5 per cent of biofuels to
tests on a microemulsion consisting of soyabean oil : petrochemical diesel that the European Union plans to
methanol : 2-octanol : cetane i mprover (52.7 : 1 3 .3 : achieve for the year 2005 . The amidation reaction of
33.3 : I , v/v) indicated accumulation of carbon fats and oils with diethyl amine was carried out taking
around the orifices of injector nozzles and heavy into account different experimental procedures, and is
deposits on exhaust valves. summarized in the scheme I (ref. 7):
KUMAR el al. : CONVERSION OF NON-EDIBLE OIL I N B IODIESEL 1 27

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

3. 2 Transesterification reaction scientists developed methods for alcoholysis


4 of oils without catalysts. A fundamental study of
Transesterification 1 , , 6, also called alcoholysis,
biodiesel production in supercritical methanol has
is the displacement of alcohol from an ester by
been carried out) ' 8 , It has been demonstrated that
another alcohol in a process similar to hydrolysis,
preheating oil to 350 °C and treatment for 240 s in
except than an alcohol is used insteaJ of water. This
supercritical methanol is sufficient to convert
process has been widely used to reduce viscosity of
rapeseed oil to its methyl esters, Moreover, while
triglycerides, The general transesterification reaction
methyl esters produced were basically the same as
is represented by the equation:
those obtained in the conventional method with a
Cat,l yst basic catalyst, its yield was higher in the supercritical
RCOOR+R" OH ( ) RCOOR'+R' OH ... ( I )
methanol method, Transesterification of six vegetable
If methanol is used in the above reaction, it is oils (cottonseed, hazelnut kernel, poppyseed,
termed methanolysis and fatty acid methyl esters are rapeseed, safflowerseed and sunflowerseed) in
generated, which are called biodiesel. supercritical methanol w ithout using any catalyst was
2
Three consecutive and reversible reactions are carried out , A kinetic study in free catalyst
believed to occur in the transesterification which are transesterification of rapeseed oil was made in sub­
given below: and super-critical methanol under different
9
temperatures and reaction times . Runs were made in
ClItlllr." �
Triglyceride + ROH ( Di g lyco'ide + R' COOR a bath-type reaction vessel ranging from 200 °C at
. . ( 2)
.
subcritical state to 500 °C at supercritical state with
Diglyceride + ROH
( ClIta/lst
) Monoglyceride + R" COOR different molar ratios of methanol to rapeseed oil to
. . . (3) determine rate constants a simple method, The
conversion rate of rapeseed oil to its methyl esters
Monog lyceride + ROH ) G lycero l + R'" COOR
( COtO/lst
increased dramatical ly in the supercritical state, and
. (4)
. .
reaction at 350 "c was considered as the best, with
the molar ratio of methanol in rapeseed oil being 42.
The first step is the conversion of trig!ycerides
to diglycerides, followed by the conversion of 4 Biodiesel Production -Transesterification of
diglycerides to monoglycerides, and final ly Vegetable Oil
monoglycerides to glycerol, yielding one methyl ester
4
molecule from each glyceride at each step , 6 when 4. J General Method of Manufacturing
methanol is used in the esterification A catalyst and Triglycerides are readily transesterified batch­
excess alcohol are used to increase rate of reaction wise in the presence of alkaline catalyst at
and to shift the equ i li brium to the product side, atmospheric pressure and at 60-70 nC with an excess
. I y4 .
respective of methanol . The mixture at the end of reaction is
3.3 Supercritical Methanol for Transesterification
allowed to settle. The lower glycerin layer is drawn
off, while the upper methyl ester l ayer is washed to
Separation of catalysts from the reaction remove entrained glyceri n and then processed further.
mixture is very difficult. To avoid catalysts in the The excess methanol is recovered in the condenser,
1 28 J SCI IND RES VOL 62 JANUARY-FEBRUARY 2003

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.