9350 Ind. Eng. Chem. Res.

2009, 48, 9350–9353

Solid Acid Catalyst for Biodiesel Production from Waste Used Cooking Oils
Cholada Komintarachat*,† and Sathaporn Chuepeng‡
Fundamental Science and Physical Education, Faculty of Resources and EnVironment, Kasetsart UniVersity,
Chonburi 20230, Thailand, and Mechanical Engineering, Faculty of Engineering at Si Racha, Kasetsart
UniVersity, Chonburi 20230, Thailand

This paper presents a study of the methanol based transesterification of waste used cooking oil (WCO, 15%
free fatty acid content) with the synthesized solid acid catalyst at different temperatures and reaction times.
The optimized conditions for fatty acid methyl ester (FAME) yield were investigated using methanol/WCO
weight ratios of 0.15-0.35 and catalyst/WCO ratios of 0.25-1.25%. The results show that the methanol/
WCO ratio of 0.3 and the catalyst/WCO ratio of 1.0% give the highest yield of 97.5% FAME at 383 K in
2 h. In addition, the capacity of porous supports for WOx synthesized catalysts, based on FAME yield was
in the following order: Al2O3 > SiO2 > SnO2 > ZnO. The WOx/Al2O3 catalyst was found to be readily
reusable and exhibited consistency in activity upon reuse for three times without loss of selectivity.

1. Introduction catalysts have recently replaced liquid acids for biodiesel

production by simultaneous esterification and transesterification
Waste used cooking oils (WCO) and fats have posed drastic of high FFA-containing oil on a supported heteropolyacid
problems related to disposal for decades. However, they have catalyst system.13
been found to be unsuitable for feeding animals as they may
The main aim of this research work is to compare activities
be harmful for animal products consumed by humans. A
of the synthesized catalysts over esterification and transesteri-
possibility for the disposal of these products is transforming
fication of WCO for biodiesel preparation. The development
them into fuels for transport or other usages. Conversion of
presented in this paper associates synthesizing solid acid catalyst
WCO and fat to esters, commonly known as biodiesel, has many
in order to enhance acidity of the catalyst support, using tungsten
environmental advantages over petroleum based diesel fuel.
solution. This has been accomplished for a retrofit of the waste
Fermentation,1 transesterification,2 and pyrolysis3 of biomass,4
used cooking oils at given FFA levels for biodiesel production.
in the forms of industrial and domestic wastes, have been
The parameters affected such as weight WCO to methanol ratio,
proposed as alternative solutions for increased energy demand
catalyst amount, reaction temperature, time, and reusability of
and environmental awareness. Among these approaches, trans-
the synthesized catalyst will also be investigated.
esterification seems to be a readily practical and efficient method
for fuel production.
2. Materials and Methods
Transesterification is the chemical process between triglyc-
erides and short-chain alcohol in the presence of basic or acidic 2.1. Preparation of the Catalysts.14,15 In the synthesis of
catalyst to produce monoester5 as depicted in Scheme 1. The the catalysts, the following reagents were used: silica (SiO2),
long- and branched-chain triglyceride molecules are transformed zinc oxide (ZnO), tin oxide (SnO2), hydrochloric acid (HCl),
to monoesters and glycerol. Commonly used short-chain alco- and dry sodium sulfate (Na2SO4) (>99%). All were supplied
hols are methanol, ethanol, propanol, and butanol.6 Methanol by Fluka. The aluminum oxide (γ-Al2O3) and ammonium
is commercially used due to its availability and cost effective- metatungstate were obtained from Sigma-Aldrich. Catalysts,
ness.7 The subsequent useful product is fatty acid methyl ester based on tungsten impregnation in dry porous support material,
(FAME) commonly known as biodiesel. were prepared by pore filling in the presence of a solution excess
WCO is considered to be advantageous in cost but it contains (wet impregnation). Simple wet impregnation was carried out
high free fatty acid (FFA) and water contents. The use of base by dissolving a certain amount of ammonium metatungstate 25%
type catalyst will cause a saponification reaction resulting in w/v in 20 mL distilled water in a round-bottomed flask, followed
unwanted soap problems on removal (see Scheme 2).8 In by the addition of the porous support material (γ-Al2O3, SiO2,
addition, the maximum content of 0.05% water in the fuel is
imposed in the FAME standard (e.g., EN 14214-2003) as it can Scheme 1. Transesterification of Triglyceride with Alkyl Alcohol
lead to engine corrosion9,10 and the hydrolysis of the esters.11
Also, FFA must be converted into their corresponding esters8
as in the reaction shown in Scheme 3. Alternatively, the
application of acid catalyst in transesterification is a two-step
process, i.e. (1) acid esterification to reduce FFA and (2) alkali
transesterification.12 To eliminate the corrosion, environmental
problems, and time saving for multiple reactions, solid acid

* To whom correspondence should be addressed. E-mail: k-cholada@ Scheme 2. Esterification of Free Fatty Acid
src.ku.ac.th. Tel.: +6638 354587 ext. 2754. Fax: +6638 354587.
†
Fundamental Science and Physical Education, Faculty of Resources
and Environment, Kasetsart University.
‡
Mechanical Engineering, Faculty of Engineering at Si Racha,
Kasetsart University.

10.1021/ie901175d CCC: $40.75  2009 American Chemical Society

Published on Web 09/18/2009

Scheme 3. Saponification of Free Fatty Acid Alkyl Ester
Table 1. Properties of Porous Materials
entry porous support pore volume (cm3/g) surface area (m2/g)
1 Al2O3 0.95 260
2 SiO2 0.75 250
3 ZnO 0.2 40
4 SnO2 0.3 112
ZnO, and SnO2). Characteristics of porous support materials
such as surface area and pore volume are presented in Table 1.
The pH value of the contents was maintained at 2 by HCl
addition. The resulting porous support materials were filtered,
and the catalyst samples were dried in ambient air at 393 K
overnight and treated in ambient air at 723 K for 4 h.
2.2. Pretreatment of the Waste Used Cooking Oil. WCO
were collected from the author’s university canteen. The sampled
WCO, comprised of free water and other impurities, were
prepared by heating at 378 K to remove water and dried over
Na2SO4. The subsequent solution was filtered under vacuum to
remove traces of any suspended matter and Na2SO4 crystals.
Its FFA content was determined by a standard titrimetry method
instead of gas chromatography analysis.16 The treated WCO
presented an FFA level of 15% w/w.
2.3. Procedure for the Biodiesel Synthesis. To synthesis
biodiesel through the transesterification: the treated WCO,
methanol (chromatographic grade, 99.5%), and the catalyst were
mixed together in a two-necked round-bottom flask equipped
with a magnetic stirrer and a thermometer. The mixture was
heated to the desired temperature for a certain period. Upon
completion, the excess methanol was distilled under vacuum.
After the mixture was centrifuged, it formed three phases, i.e.
FAME in the upper layer, glycerol in the middle layer, and traces
of catalyst and glycerol in the lower layer. The catalyst entrained
in the lower layer can be recovered by filtering and washing
with petroleum ether and drying at 333 K for 4 h.
2.4. Purification of the FAME Phase. The glycerol-rich
phase was separated from the FAME layer in a separating
funnel. The latter phase was washed with warm water three
times and with water to provide a purified FAME, then it was
dried over Na2SO4 and filtered under vacuum. The quantitative
analysis of the FAME was carried out using a temperature
programmed JASCO (GC, polyethylene glycol) gas chromato-
graph. One microliter of the upper oil layer was dissolved in
10-mL n-hexane and 1-µL internal standard solution (heptade-
canoic acid methyl ester) for GC analysis. On each run, the
1-µL sample was injected into the GC at the temperature of
140 °C. After holding for 5 min, the GC’s oven was heated at
10 °C/min rate to 250 °C. Helium was a carrier gas at 10 bar of
pressure and a 20 mL/min flow rate. The injector and the flame
ionization detector (FID) were set up to the operating temper-
ature of 250 °C. The GC determined the mass concentration of
the FAME, and the FAME yield was calculated by the following
expression.17
mactual CesternVester
FAME yield ) × 100 ≈ × 100
mtheoretical moil
(1)
where mactual and mtheoretical are the actual and theoretical masses
of FAME in grams; moil is the mass of WCO in grams; Cester in
Ind. Eng. Chem. Res., Vol. 48, No. 20, 2009 9351
Table 2. Effect of Porous Supporters of Catalyst
entry catalyst FAME yields (wt %)a acid value (1/mg KOH)b
1 WOx/Al2O3 (WAl) 98 4.7
2 WOx/SiO2 (WS) 92 5.6
3 WOx/ZnO (WZn) 84 4.4
4 WOx/SnO2 (WSn) 91 5.8
a
Reaction condition: WCO 10 g, 0.3 methanol/WCO weight ratio,
catalyst 1.0% w/w, 383 K, 2 h. b Tritration the FAME at the end of 2 h,
reaction time with 0.02 N of KOH.
Figure 1. Effect of methanol amount on the reaction at the following
conditions: WCO 10 g, WAl 1.0% w/w, 383 K, and 2 h.
grams per milliliter is the FAME concentration acquired by GC;
n is the dilution multiplication of FAME; and Vester is the volume
of the FAME layer in milliliters.
3. Results and Discussion
3.1. Effect of Different Porous Supports of the Catalyst.
The prepared catalysts were investigated for synthesizing
biodiesel from the WCO under reaction conditions of 383 K
temperature, 100 rpm stirring speed, 0.3 methanol/WCO weight
ratio, and 1.0% w/w catalyst for WCO. On the basis of the yield
of FAME and the acid value at the end of 2 h of reaction time,
the best catalyst was WOx/Al2O3 (WAl) and the rest were in
the following order: SiO2 > SnO2 > ZnO; the results are shown
in Table 2. This is due to the fact that the γ-Al2O3 used as a
porous support had a higher surface area (260 m2/g) and greater
volume (0.95 cm3/g) compared to the others in Table 1. Large
pores can easily accommodate a bulky triglyceride molecule,18
giving WAl large active sites and surface area, resulting in the
highest activities (esterification and transesterification). The
advantages of the pore filling method are mainly a short
impregnation time and a smaller volume of impregnating
solutions.14,19 Therefore, the WAl was selected to further study
the effect of various reaction parameters on FAME yield.
3.2. Effect of Methanol to WCO Weight Ratio. The
methanol to oil weight ratio is one of the important parameters
that affect the yield of FAME. Theoretically, the transesterifi-
cation of vegetable oil requires 3 mol of methanol per mole of
triglyceride.16 Since transesterification of triglyceride is a
reversible reaction, the excess methanol shifts the equilibrium
toward the direction of ester formation.20 In the present work,
with preoptimized reaction parameters, the methanol to WCO
weight ratio was varied in the range of 0.15-0.35 and its
influence on the FAME yield was investigated. Figure 1 shows
the effect of the methanol to oil weight ratio on the FAME yield
at the end of 2 h of reaction time at 383 K. It can be clearly
seen from the activity profile that, when the weight ratio
9352 Ind. Eng. Chem. Res., Vol. 48, No. 20, 2009
Figure 2. Effect of catalyst amount. Reaction conditions: WCO 10 g, WAl
as catalyst, 0.3 methanol/WCO weight ratio, 383 K, and 2 h.
Figure 3. Effect of Reaction time. Reaction conditions: WCO 10 g, WAl
1.0% w/w, 0.3 methanol/WCO weight ratio, and 383 K.
increased from 0.15 to 0.35, the FAME yield was found to
increase from 88% to 97.5%. The highest conversion of 97.5%
was registered at the weight ratio of 0.3. Further increase in
the methanol amount has not shown any significant improvement
in the FAME yield.
3.3. Effect of Catalyst Amount. The catalyst amount is also
important for the reaction that needs to be optimized in order
increase the FAME yield. The effect of the WAl amount
(0.25-1.25% w/w of WCO) on the reaction was studied, and
the results are shown in Figure 2. At low catalyst amounts, there
were not enough active sites for the reaction while the reverse
reaction may take place when excess catalyst was employed.
The optimal amount of the catalyst was found to be 1.0% w/w.
3.4. Effect of Reaction Time. The effect of reaction time
on the yield was investigated, and the results are shown in Figure
3. Increasing the reaction time up to 2 h enhanced the FAME
yield. Further increase in the reaction time did not show any
increase in the FAME yield. This may be due to catalyst
deactivation from the reaction in longer time that the change in
catalyst structure and state occurs. These lead to the loss of
active sites on the catalyst’s surface, resulting in the reduction
of catalyst activity. Therefore, the 2-h reaction time was chosen
for the optimum for the WAl catalyst.
3.5. Effect of Reaction Temperature. The rate of reaction
is strongly influenced by reaction temperature. The effect of
temperature on FAME production from WCO using WAl was
experimentally studied at different temperatures, e.g. 363, 373,
383, and 393 K with initial WCO of 10 g, WAl concentration
of 1.0% w/w, 0.3 methanol/WCO weight ratio, and 2-h reaction
time. The FAME yields obtained from specified temperatures
are shown in Figure 4. The maximum FAME yield of 97.5%
Figure 4. Effect of reaction temperature on the FAME yield. Conditions:
WCO 10 g, WAl 1.0% w/w, 0.3 methanol/WCO weight ratio, and 2 h.
Figure 5. Reusability of WAl in FAME yield. Conditions: WCO 10 g,
WAl 1.0% w/w, 0.3 methanol/WCO weight ratio, 383 K, and 2 h.
Table 3. Catalyst Comparison
entry catalyst FAME yields (wt %)a
1 WAl 97.5
2 K2CO3 91.5
3 H2SO4 95.0
4 KOH 97.5
a
Reaction conditions: WCO 10 g, WAl 1.0% w/w, 0.3 methanol/
WCO weight ratio, 383 K, and 2 h.
was obtained at 383 K. The results show that during the course
of transesterification, the FAME yield continuously increased
up to 383 K while stabilizing afterward.
3.6. Catalyst Stability and Reusability. Reusability of the
catalyst was also investigated as the cost of the process can be
reduced. After the reaction completion, the solid acid catalyst
was recovered by filtering, washing with petroleum ether, and
drying at 333 K (petroleum ether’s boiling point) for 4 h. The
stability studies were carried out at a reaction temperature of
383 K, 10 g WCO, 0.3 methanol/WCO weight ratio, and 1.0%
w/w catalyst. The results shown in Figure 5 reveal that the
FAME yield decreased was subtle even at the third reuse.
However, significant losses in activity were observed at the
fourth reuse and onward.
3.7. Catalyst Comparison. Catalytic activities of conventional
catalysts, i.e. potassium hydroxide (KOH), potassium carbonate
(K2CO3), and sulfuric acid (H2SO4), were compared with the WAl
catalyst under the same condition; the data are shown in Table 3.
It can be seen that the WAl and KOH catalysts show highest
activity compared to the rest by yielding the maximum FAME.
However, the base KOH catalyst leads to promoting soap formation

8
which generates separating problems. Therefore, the WAl catalyst
can be considered to be one of the best choices as being
economically convenient, user- and environmentally friendly, and
advantageous for industrial investment.
4. Conclusion
A study of solid acid catalysts for biodiesel production based
on methanol transesterification is presented in this paper. The
synthesized tungsten on alumina supported catalyst (WAl) has
been found to be suitable for the synthesis of biodiesel from
waste used cooking oil with high FFA (15% w/w). Such
operating parameters, i.e. methanol to WCO weight ratio,
catalyst amount, reaction time, and temperature, were investi-
gated as they are found to be affected the FAME yields. The
catalyst was very efficient for the reaction with the maximum
FAME yield of 97.5%. The catalyst stability was found to be
reusable with consistency in activity up to three times. This
catalyst can be applied in the academic and industrial scale
production of biodiesel.
Acknowledgment
The authors acknowledge Kasetsart University for financial
support and thank the technical staff in the Laboratory of
Organic Chemistry of the Faculty of Resources and Environment
for their experimental assistance.
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ReceiVed for reView July 23, 2009
ReVised manuscript receiVed September 11, 2009
Accepted September 13, 2009
IE901175D