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Bioresource Technology 101 (2010) S59–S61

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Esterification of used vegetable oils using the heterogeneous WO3/ZrO2 catalyst


for production of biodiesel
Young-Moo Park a, Joon Yeob Lee a, Sang-Ho Chung a, In Seon Park a, Seung-Yeon Lee a,
Deog-Keun Kim b, Jin-Suk Lee b, Kwan-Young Lee a,*
a
Department of Chemical and Biological Engineering, Korea University, 5-1, Anam-dong, Sungbuk-ku, Seoul 136-701, Republic of Korea
b
Biomass Research Center, Korea Institute of Energy Research, Yuseong 305-600, Taejeon, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Tungsten oxide zirconia, sulfated zirconia and Amberlyst-15 were examined as a catalyst for a conversion
Received 17 December 2008 of used vegetable oils (VOs) to fatty acid methyl esters (FAMEs). Among them, tungsten oxide zirconia
Received in revised form 4 April 2009 was a promising heterogeneous catalyst for the production of biodiesel fuels from used VOs because of
Accepted 10 April 2009
high activity in the conversion over 93% and no leaching WO3 in the esterification reaction. The reaction
Available online 9 May 2009
conditions were optimized. A study for optimizing the reaction parameters such as the reaction temper-
ature, stirring speed, WO3 loading over ZrO2 and reaction time, was carried out. The catalyst was charac-
Keywords:
terized by BET, XRD, FT-IR, and NH3-TPD. With increasing WO3 loading over ZrO2, the triclinic phase of
Biodiesel
Esterification
WO3 increased and the tetragonal phase of zirconia was clearly generated. The highest acid strength of
Tungsten oxide zirconia 20 wt% tungsten oxide zirconia catalyst was confirmed by NH3-TPD analysis and the result was correlated
Heterogeneous catalyst to the highest catalytic activity of the esterification reaction.
Free fatty acid Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction ally mild process for production of biodiesel from VOs using heter-
ogeneous base catalysts was developed in our previous study (Kim
Recently, many countries have reported rapid progress in et al., 2004).
renewable fuels, with biodiesel being the most well known. Biodie- Despite the environmental advantage of the biodiesel, produc-
sel fuel obtained from vegetable oils (VOs) has attracted consider- tion cost of biodiesel is pretty high compared to conventional die-
able attention over recent decades as a renewable, biodegradable, sel fuel. In order to reduce the production cost, used VOs has been
eco-friendly and non-toxic fuel, and several processes have been suggested as feedstock. However, the free fatty acids (FFAs) in used
developed for its production. Biodiesel is gaining prominence as VOs are known to cause severe problems for the transesterification
a substitute for petroleum-based diesel due to environmental con- catalyzed by base catalyst. FFA can react with the base catalyst
siderations and the depletion of vital resources, such as petroleum (neutralization reaction), which brings a loss of catalyst and a pro-
and coal. The possible uses of renewable resources are fuels and duction of soap as by-product which accelerates the deactivation
major feedstocks for the chemical industry. Petroleum is a rapidly of the base catalyst (Park et al., 2008). Consequently, FFA contained
depleting natural resource, making an alternative renewable route in used VOs should be removed or converted to inert material. In
to petroleum a necessity. Furthermore, biodiesel is a clean burning this work, we tried to convert FFA to fatty acid methyl esters
fuel with no sulfur emissions and no efficiency loss despite its heat (FAMEs) using heterogeneous acid catalysts (Eq. (1)), which are
of combustion being slightly lower than that of petro-diesel (Sri- the components of biodiesel themselves. The catalytic esterifica-
vastava and Prasad, 2000), and no engine adjustments are neces- tion activity of SO2
4 /ZrO2, WO3/ZrO2, and Amberlyst-15 was con-
sary. In addition, it is non-corrosive and can be produced under firmed and compared. WO3/ZrO2 was finally chosen on account
low pressure and temperature conditions. of its high activity and stability. A series of experiments were per-
Biodiesel is commonly derived from triglycerides (VOs) and formed using WO3/ZrO2 with temperature, WO3 loading, amount
methanol through transesterification using homogeneous cata- of catalyst (g/ml (oil)) and reaction time as parameters to deter-
lysts, such as alkali hydroxides (NaOH and KOH), carbonates, and mine the optimal reaction conditions. The WO3/ZrO2 catalyst was
sodium and potassium alkoxides (Canakci and Van Gerpen, 2001, characterized by BET, X-ray diffraction (XRD), Fourier transform
2003; Dorado et al., 2002; Ghadge and Raheman, 2005). A gener- infrared (FT-IR) spectroscopy, NH3-temperature programmed
desorption (TPD).
Free fatty acids ðFFAsÞ þ methanol
* Corresponding author. Tel.: +82 2 3290 3299; fax: +82 2 926 6102.
! Fatty acid methyl esters ðFAMEsÞ þ water ð1Þ
E-mail address: kylee@korea.ac.kr (K.-Y. Lee).

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.04.025
S60 Y.-M. Park et al. / Bioresource Technology 101 (2010) S59–S61

2. Methods

The SO2
4 /ZrO2 catalyst was prepared by the dehydration of
H2SO4 and Zr(OH)4. WO3/ZrO2 was synthesized by impregnating
on Zr(OH)4 with an ammonium metatungstate (Aldrich) solution.
A series of catalysts with different WO3 loadings ranging from 10
to 30 wt% were prepared and calcined at 800 °C. The Amberlyst-
15 was purchased from Rohm and Haas. The esterification reaction
of soybean oil contained 4 wt% oleic acid to simulate the used VOs
was carried out in a 100 ml autoclave batch reactor. Generally used
oil contains FFA of 1–3.7 wt% depending on the sources. The load-
ing ratio of used oil and methanol added in excess was 1:9. The
reactions were carried out with different stirring speeds, WO3
loadings, temperature, amount of catalyst and reaction time. The
conversion of oleic acid (FFA) to the methyl ester was confirmed
by a titration method reported elsewhere (Park et al., 2008). The Fig. 1. TPD results of the WO3/ZrO2 catalyst.
XRD patterns of the catalysts were obtained using a Rigaku
D/max 2000 ultima plus diffractometer (monochromatic nickel
filter, Cu Ka radiation). An FT-IR spectrometer (Perkin–Elmer perature but also some improvement of the mass transfer limita-
Spectrum GX1) was used to acquire the transmission spectra. The tions between the reactant and catalyst. Generally soybean oil
BET surface area and pore volume of the prepared catalysts were (contained 4 wt% oleic acid) was known as viscous material, and
measured using an ASAP 2100 BET surface analyzer. The acidity it showed a tendency to be attached on the catalyst during the
of the catalysts was measured using the temperature programmed reaction. As the reaction temperature increased, the viscosity de-
desorption of NH3 (NH3-TPD) in a 3/8 in. stainless steel. reactor creased and the miscibility of the oil and methanol also increased,
equipped with an on-line gas chromatograph (Agilent 6890 N) resulting in an increase in FFA conversion.
and a mass spectrometer detector (Agilent 5975). In order to investigate how pure FFA affects the catalytic activ-
ity, the reactions were carried out with oleic acid and methanol
only. The test was carried out at temperatures ranging from 75
3. Results to 200 °C using 100 wt% FFA (oleic acid) under the same reaction
conditions. The FFA conversion increased from 80% to 94% with
3.1. Reaction of heterogeneous acid catalyst for biodiesel increasing reaction temperature from 75 to 200 °C. The catalytic
activity decreased in high FFA content, but the activity was re-
The WO3/ZrO2, SO2 4 /ZrO2 and Amberlyst-15 catalysts were stored as elevating reaction temperature. As the result, WO3/ZrO2
used for the esterification of 4 wt% oleic acid in soybean oil with catalyst was found that it was possible to apply to the high temper-
methanol. The experiments were carried out under the following ature reaction.
conditions: temperature of 75 °C, reaction time of 2 h, vegetable
oil:methanol molar ratio of 1:9, 0.29 g of catalyst per ml of oil 3.3. Catalyst characterization
and a stirring speed of 800 rpm. All catalysts were confirmed to
show approximately 93% FFA conversion. Amberlyst-15 is a poly- XRD analysis of the catalysts with different WO3 loading was
meric catalyst and should not be used at temperature over performed to certify structural property. Crystalline WO3 and
180 °C because heat can cause collapse of the catalyst structure. ZrO2 peaks were confirmed in the XRD patterns. The formation of
The concern with the SO2 4 /ZrO2 catalyst is the possible leaching a triclinic phase WO3 with increasing WO3 loading was identified
of SO2 4 from the catalyst into the liquid phase reaction (Park by three peaks in the range of 2h = 23–25°. A tetragonal phase of
et al., 2008). Therefore, it makes sulfur content elevate in biodiesel zirconia which could not be present in pure ZrO2 appeared in the
fuel. The WO3/ZrO2 catalyst reveals as high activity as others and WO3/ZrO2 catalyst. With increasing WO3 loading over ZrO2, the tri-
leaching or loss of WO3 has not been reported but if so, it is not clinic phase of WO3 increased and the tetragonal phase of zirconia
harmful. WO3/ZrO2 was chosen as the catalyst in this paper after was clearly generated. Thus, the structures mentioned here are
considering its relative stability. thought to affect an enhancement in catalytic activity.
BET analysis was carried out to determine the surface area and
3.2. Effect of reaction conditions pore volume of the catalyst. The pure zirconium hydroxide de-
gassed at 200 °C showed a surface area and pore volume of
The effect of the WO3 loading in the catalyst on the esterifica- 137.2 m2/g and 0.07 cm3/g, respectively. After calcination at
tion of FFA was examined using WO3 loadings of 10–30 wt%. 800 °C, the surface area and pore volume of ZrO2 decreased to
A 10 wt% WO3/ZrO2 showed the lowest FFA conversion of 78%. 18.1 m2/g and 0.019 cm3/g, respectively. However, the addition of
The conversion increased gradually with increasing WO3 loading: WO3 to ZrO2 resulted in an increase in surface area to 55.1 m2/g
20 wt% WO3/ZrO2 catalyst was confirmed to have the highest FFA at a 30 wt% WO3 loading, which means that the added WO3 could
conversion of 93%. But 30 wt% WO3/ZrO2 showed lower FFA con- reduce the sintering of ZrO2 (Iglesia et al., 1993). With increasing
version of 89%. The increase of FFA conversion correlated to in- crystallization in the XRD, the pores became narrow or closed,
crease of WO3 loading until 20 wt% WO3/ZrO2. On the other hand and the specific surface area decreased. Hence, the surface area is
this correlation was not maintained over the 20 wt% WO3 loading. dependent on the WO3 loading.
Therefore, the optimal WO3 loading was concluded to be in 20 wt%. FT-IR is an important tool for analyzing the nature of the surface
The effect of the reaction temperature was examined from 75 to tungsten oxide species on zirconia. The FT-IR spectrum of the WO3/
200 °C using the 20 wt% WO3/ZrO2 catalyst. The FFA conversion in- ZrO2 catalyst shows one distinct absorption band centered at
creased with increasing temperature. At 75 °C, FFA conversion was approximately 791 cm1, which was assigned to a W–O vibration
93%, which increased to 98% at 200 °C. The increased conversion band from crystalline and non-crystalline species as reported pre-
might be due to not only the increase of reaction rate by high tem- viously (Boyse and Ko, 1997). Consequently, the enhanced crystal-
Y.-M. Park et al. / Bioresource Technology 101 (2010) S59–S61 S61

linity of WO3 with increase of WO3 loading over ZrO2 was con- catalysts with WO3 loading amount from 10 to 30 wt%, 20 wt%
firmed by the high intensity of the band for W–O vibration. WO3/ZrO2 showed the highest catalytic activity. TPD analysis indi-
The acidic properties of the WO3/ZrO2 catalyst were examined cated that the 20 wt% WO3/ZrO2 catalyst had higher acidity than
by NH3-TPD analysis. Fig. 1 shows the NH3-TPD profiles of the cat- the other samples, as evidenced by the existence of a high temper-
alysts. The TPD profiles showed that in all samples, the acid ature desorption peak at 750 °C. Therefore, it can be concluded that
strength was broadly distributed over the temperature range with the strong acidity of the catalyst is thought to be one of the reason
the highest peaks of the 25 and 30 wt% WO3/ZrO2 catalysts ob- for the highest catalytic activity of the 20 wt% WO3/ZrO2 catalyst.
served at approximately 250 °C. Over all temperature regions, the
TPD profiles of 10, 15, 25 and 30 wt% WO3/ZrO2 catalysts were sim- Acknowledgement
ilar with a single desorption peak. However, the profile of the
20 wt% WO3/ZrO2 catalyst was distinguished from the others, The authors wish to acknowledge the support by the Resource
showing two desorption peaks; the first at 250 °C and the second Recycling R&D Center, 21C Frontier R&D Program.
at 750 °C. This second desorption shoulder showed that the acid
site had a stronger interaction with the adsorbed NH3, indicating References
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