SYNTHESIS OF BIO-DIESEL AND

BIO-LUBRICANT BY TRANSESTERIFICATION
OF VEGETABLE OIL WITH LOWER AND HIGHER
ALCOHOLS OVER HETEROPOLYACIDS
SUPPORTED BY CLAY (K-10)

V. V. Bokade1,2
and G. D. Yadav2

1
Catalysis Division, National Chemical Laboratory, Pune-411008, India.
2
University Institute of Chemical Technology, Mumbai-19, India.

Abstract: The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and
n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterica-
tion of vegetable oil (triglycerides) with respective alcohols also known as Bio-diesel and Bio-
lubricants was studied in detail. The reactions were carried out in a batch process. The activity
with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were com-
pared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H3PO4 . 12
WO3.xH2O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H12Mo12N3-
O40P aq] (DMAA) was used to increase the acidity and so the activity by loading on the
most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the
following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect
of different alcohols on the triglyceride conversion based on glycerol formation and selectivity
based on alkyl esters formation. The data is compared at the best-optimized identical set of oper-
ating reaction conditions: 1708C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar
ratio (oil : alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based
on the reported one.
Keywords: vegetable oil (triglyceride); alcohol; heteropolyacid; clay; ester; bio-fuel.

Correspondence to:
Dr. V.V. Bokade, Catalysis
Division, National Chemical
Laboratory, Pune-8, India.
E-mail: vv.bokade@ncl.res.in
DOI: 10.1205/psep06073
09575820/07/
$30.00 0.00
Process Safety and
Environmental Protection
Trans IChemE,
Part B, September 2007
# 2007 Institution
of Chemical Engineers
INTRODUCTION
The major part of all energy consumed world-
wide comes from fossil sources. Diesel fuels
have an essential function in the industrial
economy of a developing country. Economic
growth is always accompanied by commensu-
rate increase in the transport. Because of the
acute shortages, dramatic price increase and
high level emission of certain pollutants of con-
ventional petroleum-based fuels, there has
been a renewed interest in alternative cleaner
burning fuels. One possible alternative to pet-
roleum-based fuels is the biofuels. Biofuels
are fuels derived from renewable sources
such as naturally occurring fats and oils,
which may be obtained from variety of plants
and animals. The products such as bioethanol,
biodiesel, biogas, biomethanol, biodime-
thylether, bio-ETBE (ethyl-tertio-butyl-ether),
bio-MTBE (methyl-tertio-butyl-ether), synthetic
biofuels, biohydrogen and pure vegetable oil
are considered as biofuels. Biodiesel relates
to specic application to diesel fuel and usually
they are derived from fatty acid glycerides,
which are major components of an oil or fat.
The biodiesel nd application as either repla-
cement for, or a blending component for use
with, fossil derived diesel. Direct use or blend-
ing, microemulsions, thermal cracking and
transesterication of vegetable oils have been
explored as potential alternatives to diesel.
The transestercation process can make use
of alcohols such as methyl, ethyl, butyl and
isopropyl alcohol. Methanol, ethanol and
isopropanol are most common alcohols with
methanol having the highest demand followed
by the other two. Among these alcohols, isopro-
panol is the only one with a branched structure.
Butyl esters and isopropyl esters crystallized at
12158C and 7118C lower, respectively,
when compared to methyl esters of the same
source material. The cold ow properties of
these branched-chained esters are further
improved when blended with diesel fuel
(Demirbas and Balat, 2007; Wang, 1998).

372 Vol 85 (B5) 372377

 SYNTHESIS OF BIO-DIESEL AND BIO-LUBRICANT
Although, there are many ways and procedures to convert
vegetable oil or animal fat into a diesel-like fuel, transesteri-
cation is the key and foremost important process to produce
the cleaner and environmentally safe fuel. Transesterication
signicantly reduces oil viscosity, thereby improving fuel ato-
mization and consequently fuel combustion characteristics.
Transesterication or alcoholysis is the displacement of alco-
hol from an ester by another in a process similar to hydroly-
sis, except than alcohol is used instead of water. In other
words, transesterication is the process of using an alcohol
(e.g., methanol, ethanol, propanol, butanol, pentanol, hexa-
nol, heptanol, octanol), in the presence of a catalyst to chemi-
cally break the molecule of the raw renewable oil into alkyl
esters of the renewable oil with formation of glycerol as a
by-product. Several aspects including the type of the catalyst,
alcohol/vegetable oil or animal fat molar ratio, temperature,
time, water content and free fatty acid content have an inu-
ence on the course of transesterication. Although, methanol
is commonly used in this process due to its lower cost than
other alcohols, ethanol is the preferred alcohol as it is derived
from agriculture products and it is renewable and biologically
less objectionable in the environment. Biodiesel produced by
transesterication reactions can be catalysed with alkali (e.g.,
alkaline metal alkoxides and hydroxides as well as sodium
and potassium carbonates), acid (e.g., Bronsted acids,
preferably sulfonic acid and sulfuric acid) or enzyme (e.g.,
lipase). A catalyst is usually used to improve the reaction
rate and yield.
Base catalysed transesterication reaction is the most
economical and in fact, is in practice in several countries
for bio-diesel production (Schuchardt et al., 1998; Lang,
2001; Vicente et al., 2004; Barnwal and Sharma, 2005).
Alkaline metal alkoxides (as CH3ONa for the methanolysis)
are the most active catalysts, since they give very high
yields (.98%) of fatty acid alkyl esters in short reaction
times (30 min) even if they are applied at low molar concen-
trations (0.5 mol%) (Brat and Pokorny, 2000). However, they
require high quality oil and the absence of water, which
makes them inappropriate for typical industrial processes.
Alkaline metal hydroxides (NaOH and KOH) are cheaper
than metal alkoxides but require increasing catalyst concen-
tration (12 mol%). NaOH is more superior to KOH as the
latter and other alkali hydroxides yield more soponied
products than the bio- fuel. Leclercq et al. (2001), studied
the transesterication of rapeseed oil in the presence of
Cs-exchanged NaX and commercial KW2200 hydrotalcite
catalysts. At a high methanol to oil ratio of 275 and 22 h reac-
tion time at methanol reux, the Cs-exchanged NaX gave a
conversion of 70%, whereas 34% conversion was obtained
over hydrotalcite. ETS-4 and ETS-10 catalysts gave conver-
sions of 85.7% and 52.7%, respectively at 2208C and 1.5 h
reaction time (Srinivas, 2007). Suppes et al. (2001), achieved
a conversion of 78% at 2408C and .95% at 2608C using
calcium carbonate rock as catalyst. Of late, Suppes et al.
reported the use of Na, K and Cs exchanged zeolite X,
ETS-10, NaX occluded with NaOx and sodium azide in the
transesterication of soybean oil with methanol. Furruta
et al. (2004), describe biodiesel production from soybean oil
and zirconium oxides with oil conversions over 90%. Use of
tin complexes immobilized in ionic liquids for vegetable oil
alcoholysis was reported by Abreu et al. (2004, 2005). The
transesterication process can also be catalysed by acids,
preferably by sulphonic and sulfuric acids. Acid catalytic
Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 372 377
373
transesterication of vegetable oil were reported (Schuchardt
et al., 1998) to give very high yields in alkyl esters. However,
in presence of homogeneous acid catalysts, the reactions are
slow and hence take longer time as compared to alkaline cat-
alysts. Moreover, acid-catalysed transesterication also
needs extreme temperature and pressure conditions but
soap formation and side reactions are avoided. As for the
solid catalysts, the reports on the uses of acid catalysts are
few in contrast to solid bases. Solid superacid catalysts of
sulfated tin, zirconium oxides and tungstated zirconia were
used in the transesterication of soybean oil with methanol
at 200 3008C and the esterication of n-octanioc acid with
methanol at 175 2008C. Tungstated zirconia-alumina was
reported (Furruta et al., 2004) to be a promising catalyst for
the production of biodiesel fuels from soybean oil because
of its high activity for the transesterication as well as the
esterication.
The present paper relates to a reaction for the preparation
of alkyl esters by transesterication process. It deals with the
work for producing methyl/ethyl/propyl fatty acid esters also
called as biodiesel, octyl fatty acid ester called as biolubri-
cants, which comprises contacting fatty acid glycerides/tri-
glycerides with or without free fatty acids of vegetable oil
with alcohols in the presence of a solid heteropolyacids cat-
alyst which is substantially insoluble in the reaction mixture
under reaction conditions. The present work eliminates
most of the above said drawbacks. The feedstock oil is a tri-
glyceride or a mixture of fatty acids and glycerides. The het-
eropolyacids (HPA) catalysts usually have the general
formula HnXM12O40 where X is the central metal atom and
M is the peripheral atom normally numbering 12 surrounding
the central metal atom. Since these materials are stable, they
are efcient to transform feedstocks containing fatty acids in a
single step to fatty acid alkyl esters by transesterication. The
catalyst could be separated easily by centrifugation or by
simple ltration and reused. Most importantly, the catalyst is
highly efcient and only a small amount is needed to carry
out the reaction. The process is atom-efcient and the reac-
tion conditions like temperature and pressure are only moder-
ate. Unlike the conventional base catalysts, the catalyst of
the present work is more efcient even in the presence of
water impurity in oil. Hence, there are no limitations on the
quality of oil that should be used with the catalysts presented
in this paper.
EXPERIMENTAL
Catalyst Synthesis and Characterization
The commercial grade monmorillonite clay (K-10) and acti-
vated carbon supplied by uka was used as a support without
further purication. The other supports viz; ZSM-5, TS-1 and
H-beta was prepared in the laboratory as per the procedure
(Kasture et al., 2004; Sharanappa et al., 2004). The super
acids (heteropolyacids, HPA) viz; Dodeca-Tungstophospho-
ric acid [H3PO4 . 12WO3 . xH2O] (TPA) and Dodeca-Molybdo
phosphoric acid ammonium salt hydrate [H12Mo12N3O40P
aq] (DMAA) was supplied by M/s Loba Chemie and used
as such without further purication. The HPA on support
was prepared by incipient wetness technique prepared in
our laboratory (Yadav and Bokade, 1996). Typically for
10 gm scale catalyst preparation: Take 10 gm of different
types of support viz; clay (K-10), ZSM-5 (Si/Al: 250),
374 BOKADE et al.

Gas Chromatography HP 5890 series II, using column

Suplco, SPB-5M with nitrogen as a carrier gas and program-
mable temperature range of 200 2758C. The product
samples were conrmed by GC-Mass Spectrometry. The
conversion of oil based on glycerol formation and selectivity
based on alkyl ester formation was estimated for different
supports, different HPA and its percent loading, various veg-
etable (edible and non-edible) oils and alcohols. Quanti-
cation of various products was accomplished using
response factors of typical standard mixtures and the liquid
mass balance was of the order of 98%.

RESULTS AND DISCUSSION

Powder X-ray Diffraction
Figure 1. Powder XRD pattern for all prepared HPA/clay samples.
From several synthesis runs, samples were selected on
the basis of supports, different heteropolyacids (HPA), and
its percent loading. Figure 1, shows the phase crystallinity
H-beta and TS-1. Weigh 0.5 g, 1 g and 2 g of HPA (wt/wt),
for the only most prominent samples as far as activity is con-
which corresponds to 5%, 10% and 20% HPA loading with
cerned. The increase in phase crystallinity with loading of
respect to support, respectively. The measured HPA was dis-
HPA and increase in percent HPA loading was observed.
solved in methanol, which formed a homogeneous solution.
There are some most intense peaks are observed at 2u of
The methanaolic HPA solution was added slowly on the
28, 30, 37, 56 and 65 by loading HPA and its percent on
measured quantity of supports viz; clay, with constant stirring
plane clay. The 10% TPA/clay is found to be well crystalline
with the help of glass rod. Initially, support was in powdered
as compared to 10% DMAA/clay. The 20% TPA/Clay has
form but upon subsequent addition of methanolic HPA sol-
shown more crystalline sample as far as XRD is concerned.
ution on them form a paste or wet cake. The formed wet cat-
There is a chance of extra layer formation by increase in HPA
alyst sample was dried on a water bath for 1.5 h at 1008C.
loading.
The sample was further dried in an oven for 2 h at 1008C,
in order to complete removal of methanol and then the
dried catalyst sample was kept in a sealed bottle. Prior to
use, sample was dried is an oven for 1 h at 1008C, to Nitrogen Adsorption
remove the moisture. The XRD patterns for all the prepared Table 1 shows the micropore surface area obtained from
samples are shown as Figure 1. The all the prepared low temperature nitrogen adsorption data was found to
samples were observed to be well crystalline in nature. The decrease by loading HPA on clay and also decrease by
nitrogen adsorptions were done for all the prepared samples increase in percent loading of HPA. Among the support
and the results are tabulated as Table 1. used, the clay (K-10) was found to be the lowest surface
area compared to other studied support viz; activated
carbon, ZSM-5, H-beta and TS-1.
Catalyst Performance
The typical reaction, for the synthesis of fatty acid methyl
ester from sunower oil with methanol was carried out in a The Catalytic Behaviour of Supported
batch reactor (100 ml volume) with 5% catalyst loading with Heteropolyacids (HPA) Catalyst with Its Different
respect to oil. The reaction was carried out using optimized Percent Loading
identical reaction conditions: molar ratio (oil to methanol:
The trans-esterication of vegetable oil (triglycerides) with
1:15), reaction temperature (1708C), 170 rpm, time on
alcohol to fatty acid alkyl ester is known (Suppes et al.,
stream of 8 h. The collected product was analysed by using
2004) to proceed through owing three consecutive steps:

Triglyceride alcohol , diglyceride alkyl ester (1)

Table 1. Nitrogen adsorption for the prepared samples.
Diglyceride alcohol , monoglyceride alkyl ester (2)
Catalyst Surface area (m2 g21) Monoglyceride alcohol , glycerol alkyl ester (3)
Clay (K-10) 223
Activated carbon 300 Overall reaction:
ZSM-5 350
H-beta 550 Triglyceride (1 mol) alcohol (3 mol)
TS-1 400
5% TPA/clay 217 , glycerol (1 mol) alkyl ester (3 mol)
10% TPA/clay 195
20% TPA/clay 190 The formation of glycerol is 10% by weight of the oil used
5% DMAA/clay 221 and theoretically equivalent to 100% oil conversion based on
10% DMAA/clay 219
20% DMAA/clay 186 glycerol formation. There is a chance that glycerol may
further react with alcohol and can get ether. Due to the

Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 372 377
 SYNTHESIS OF BIO-DIESEL AND BIO-LUBRICANT 375

Table 2. Catalyst support comparison for transesterication of Table 3. Effect of heteropolyacids and its percent loading on clay (K-
sunower oil with methanol. 10), for transesterication of sunower oil with methanol.

Clay Activated Catalyst A B C D E F G

Catalyst (K-10) carbon ZSM-5 H-beta TS-1
%Oil (triglycerides) 46 52 73 75 61 84 86
% Oil (triglycerides) 46 30 25 18 15 conversion based on
conversion based ester formation
on ester formation %Selectivity of mono and 91 72 58 55 65 34 33
% Selectivity of 91 95 98 100 100 diglycerides
mono and % Selectivity of fatty acid 9 28 42 45 35 66 67
diglycerides methyl ester (C16 19)
% Selectivity of fatty 9 5 2
acid methyl ester Reaction conditions used: Temperature: 1708C, Molar ratio
(C16 19) (methanol : oil): 15, Catalyst loaded (%w/w reaction mixture): 5, Time
on stream (TOS): 8 h. A: Clay (K-10), B: 5%DMAA/K-10, C:
Reaction conditions used: Temperature: 1708C, Molar ratio (oil:alco- 10%DMAA/K-10, D: 20%DMAA/K-10, E: 5%TPA/K-10, F: 10%TPA/
hol):1:15, Catalyst loading: 5% w/w of reaction mixture, RPM: 170, K-10, G: 20%TPA/K-10. % oil (triglycerides) conversion [oil (triglycer-
Time on stream: 8 h. ides) converted to ester / Initial triglycerides in the oil]
100.
% oil (triglycerides) conversion [oil (triglycerides) converted to
ester/initial triglycerides in the oil]
100.

phase of powder XRD, TPD measurement, reduction in sur-

presence of such products (diglycerides, monoglycerides)
formed by these three consecutive steps, the yield of desired
product drops considerably, depending upon the reaction
conditions and characteristics of the catalysts.
Catalyst Support Screening
The inuence of different types of catalyst support on the
product distribution in the transalkylation of vegetable (trigly-
ceride) oil with alcohol was investigated under an identical
set of reaction conditions. The results after 8 h time on
stream are summarized in Table 2. All the reaction shows
98100% liquid mass balance. The activity trend follows:
Clay (K-10) . activated carbon . ZSM-5 . H-beta . TS-1.
The study includes all types of probable supports of
medium to large pore size and surface area, in order to see
its effect on the activity. The clay having lowest surface
area (223 m2 g21), as compared to other studied support
has shown better oil conversion of 46% than other. The pre-
sence of higher surface area having medium to large pore
size increases rate of adsorption of reactants (vegetable oil
and alcohol) but decreases surface reaction of adsorbed oil
and alcohol, which reduces the mass transfer between the
two reactants resulting in lowering of oil conversion. In
order to increase the oil conversion, the best support clay
(K-10) was modied by loading HPA on it.
face area by deposition of HPA on clay. The TPA observed to
be the best heteropolyacids among the studied HPA. This is
due to the more acidity, well deposition of HPA on the clay as
can be seen in the reduction of surface area and powder
XRD. The percent loading of TPA (HPA) shows, the increas-
ing trend with increase in TPA loading up to 10%. Above 10%
TPA (HPA) loading, there is marginal increase in oil
conversion was observed. The optimum HPA loading
seems to be 10%. Prompted by the above observations,
the inuence of yet another parameter such as effect of differ-
ent oils on the transesterication with methanol under the
identical set of operating conditions.
Effect of Different Oils on Transesterifcation with
Methanol over 10% TPA/K-10
One of the typical ways of monitoring the catalyst stability
in presence of free fatty acid is to vary the oil content or
use different oils and check the conversion and selectivity.
The inuence of different edible and non-edible vegetable
oil on oil conversion and ester selectivity was investigated
under the identical set of operating conditions and the results
are tabulated as Table 4. The rened sunower and soya-
bean oil has shown the similar oil conversion of 8486%.
The selectivity of methyl ester (66 69%) is more than the
selectivity of mono and diglycerides (34 31%). The crude

Supported Catalyst Screening

The different heteropolyacids (HPA) viz; Dodeca- Table 4. Effect of different oil on transesterication with methanol over
10%TPA/K-10.
Tungstophosphoric acid [H3PO4.12WO3.xH2O] (TPA) and
Dodeca-Molybdo phosphoric acid ammonium salt hydrate Oil used I II III IV V
[H12Mo12N3O40P aq] (DMAA) were loaded on the best
% Oil (triglycerides) conversion 84 86 78 81 75
support clay (K-10), among the studied supports. The results based on ester formation
of different HPA and its percent loading on clay for the trans- % Selectivity of mono and 34 31 42 38 45
alkylation of oil with alcohol at the identical set of operating diglycerides
conditions are summarized in Table 3. The activity trend % Selectivity of fatty acid methyl 66 69 58 62 55
ester (C16 19)
based on the oil conversion is as follows: 20%TPA/K-10
(86%) . 10% TPA/K-10 (84%) . 20%DMAA/K-10 (75%) . Reaction conditions used: Temperature: 1708C, Catalyst loading
10%DMAA/K-10 (73%) . 5%TPA/K-10 (61%) . 5%DMAA/ (wt%, of reaction mixture): 5, Mole ratio of oil to methanol: 1:15,
K-10 (52%) Time on stream (TOS): 8 h. Reactor used: Batch reactor, Oil used:
I: Rened sunower, II: Rened soyabean, III: Crude sunower, IV:
. Clay (K-10) (46%). This result clears that the modication Rened sunower (cooked), V: Karanja. % oil (triglycerides)
by loading HPA on clay improved the oil conversion by conversion [oil (triglycerides) converted to ester/Initial triglycerides
increasing the active acid sites as can be seen in crystalline in the oil]
100.

Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 372 377
376 BOKADE et al.

Table 5. Effect of different alcohol on transesterication of sunower
oil over 10%TPA/K-10.
Alcohol used Methanol Ethanol n-Propanol n-Octanol
% Oil (triglycerides) 84 80 76 72
conversion based on
ester formation
% Selectivity of mono 34 35 38 40
and diglycerides
% Selectivity of fatty acid 66 68 72 78
alkyl ester (C16 19)
Reaction conditions used: Temperature: 1708C, Catalyst loading
(wt%, of reaction mixture): 5, Mole ratio of oil to methanol: 1:15,
Time on stream (TOS): 8 h, Reactor used: Batch reactor. % oil (trigly-
cerides) conversion [oil (triglycerides) converted to ester/Initial
triglycerides in the oil]
100.
sunower oil contained 56% free fatty acid has shown
marginal decrease in oil conversion of 78%. This may be
due to the presence of free fatty acid which hindrance the
activity by deactivating some of the active sites. The
cooked rened sunower oil has also shown comparable oil
conversion of 81% as against rened sunower oil (84%).
The presence of more than 56% free fatty acid further
lower down the oil conversion to 75% (karanja oil), as can
be seen from Table 4. In overall, the present catalyst was
observed to be tolerable for the free fatty acid contained in
the vegetable oil. The above observations prompted us to
check, the inuence of yet another parameter such as
effect of alcohol on the transesterication with vegetable oil
(rened sunower oil), under the identical set of operating
conditions.
Effect of Different Alcohols on Transesterification
with Refined Sunflower Oil Over 10% TPA/K-10
One of the typical ways of monitoring oil conversion and
ester selectivity is to vary the alcohol from lower (methanol)
to higher (n-octanol). The inuence of alcohol on oil conver-
sion and ester selectivity was investigated by varying the
alcohol from lower carbon number (methanol) to higher
(n-octanol). The results are summarized in Table 5. The
present catalyst has shown the following activity trend with
alcohol: methanol (84%) . ethanol (80%) . n-propanol
(76%) . n-octanol (72%). The decreasing trends of oil
conversion and ester selectivity with increase in carbon
number in the alcohol (higher alcohol), may be due to the
reduction in the rate of reaction with increase in carbon
number of alcohol.
The activity based on methyl ester formation is compared
with the reported (Suppes et al., 2004) and the comparative
data is summarized as Table 6. The present catalyst has
shown good activity compared to other reported catalyst.
CONCLUSIONS
Catalyst support of different surface area and pore size
were prepared, characterized and their potentiality was
investigated for the transesterifcation of vegetable oil (trigly-
cerides) with alcohol. The best support (clay, K-10) among
studied was modied by loading different heteropolyacids
(HPA) by wetness incipient technique. The different percent
of the HPA was loaded and compared the oil conversion
and ester selectivity for the reaction, under the identical set
of optimized reaction operating conditions. The optimized
HPA (dodecatungestophosphoric acid, TPA) and its loading
(10%) on clay (K-10) was observed to be best as far as oil
conversion (84%) and ester selectivity (66%), are concerned.
The best catalyst (10%TPA/Clay) was further investigated for
the different rened, crude, cooked vegetable oil (edible and
non-edible) having 5 6% or even more free fatty acid. The
effect of free fatty acid on the activity, stability of the catalyst
was evaluated. The present catalyst of 10%TPA/Clay was
observed to be tolerable with 56% free fatty acid with mar-
ginal compromise of oil conversion and ester selectivity. The
catalyst was also evaluated for the presence of lower (metha-
nol) and higher alcohol (n-octanol). The marginal decrease in
oil conversion and ester selectivity with increase in carbon
number of alcohol was observed. Overall, the studied opti-
mized heteropolyacids (10%TPA) supported on clay a solid
heterogeneous catalyst was observed to be the best,
stable, free fatty acid tolerable catalyst for the transesterica-
tion of edible and non-edible oil with lower and higher alcohol
to get biodiesel and biolubricants.

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ACKNOWLEDGEMENT
V VB thanks Director NCL, Pune and Director, UICT,
Mumbai for allowing to carry out research in NCL and provid-
ing facilities. He also thanks as a student of UICT. GDY
acknowledge the Darbari Seth Endowment for Professor
Chair.
The manuscript was received 20 December 2006 and accepted for
publication after revision 14 February 2007.