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ABSTRACT: Biodiesel has been drawing a great deal of attention on account of its special environment friendly and
fuel properties. However, the cost of biodiesel production is still very high compared with that of traditional fossil
fuels. In this study, a heterogeneous super acid catalyst and inedible oil were used to reduce the cost of raw materials.
Biodiesel was obtained from cotton seed oil (CSO) and catalyzed by the super acid SO4 2− /ZrO2 , which was prepared
by impregnation and characterized by infrared spectroscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction
(XRD). Different operation parameters of the transesterification of CSO with methanol, such as methanol/oil molar
ratio, catalyst amount and loaded mass ratio, reaction time and temperature, were investigated. Under the optimum
conditions of methanol to CSO molar ratio of 9 : 1, 3.5 wt% fresh catalyst (loaded mass ratio is 0.841), 1 h reaction time
and reaction temperature of 120 ◦ C, a relatively high biodiesel yield of 98% was obtained. 2010 Curtin University
of Technology and John Wiley & Sons, Ltd.
Catalyst Preparation and Characterization rate of 15 ◦ C min−1 under a nitrogen atmosphere with
a flow rate of 15 mL min−1 .
Catalyst Preparation
Zirconia, considered as the support of the catalyst,
was prepared using the following method. A certain Transesterification
amount of zirconium (VI) oxychloride octahydrate
(ZrOCl2 ·8H2 O) was dissolved in water at the molar The transesterification reaction was carried out in an
ratio of H2 O/ZrOCl2 ·8H2 O = 8 : 1. Then the ammonia autoclave of GSH-0.5L, with electromagnetic mechan-
(25–28%) was added drop by drop to the solution to ical stirring, thermostat and on-line sampling devices.
form a precipitate and the pH kept at 9 by continuous A quantity of CSO, methanol and catalyst was placed
stirring at room temperature. After stirring for half an in the autoclave. The reaction temperature rose to the
hour, the suspension liquid was moved to an electric preset value while stirring and the very beginning heat-
thermostat and aged for 12 h at 100 ◦ C. The resulting ing was considered as time zero of this reaction. When
Zr(OH)4 was thoroughly washed with purified water the reaction was completed, the autoclave was cooled to
until there was no Cl− ion left, which was detected with room temperature and the mixture of the reaction solu-
0.5 mol L−1 AgNO3 . Then the white solid obtained by tion spilled over from the autoclave. The catalyst was
filtration was dried for 24 h at 110 ◦ C and then ground then separated from the product mixture by filtration.
to powder with a particle size of less than 100 meshes. The excess methanol was removed by vacuum distil-
The SO4 2− /ZrO2 was prepared using the impreg- lation. The latter mixture was treated with high-speed
nation method: the zirconia hydroxide powder was centrifuge and formed two phases, of which the upper
impregnated with 20 mL mol L−1 H2 SO4 solution for phase consisted of methyl esters and the lower phase
24 h at room temperature. The mixture was then dried glycerol. The upper phase was then analyzed by gas
at 110 ◦ C for 12 h and calcined in air at 600 ◦ C for 3 h chromatography with the temperature programmed.
to obtain the solid super acid catalyst. Procedure was duplicated under different reaction
conditions: reaction temperature from 100 to 180 ◦ C,
Catalyst characterization reaction time from 20 min to 3 h, catalyst mass ratio
The catalyst was characterized by infrared analy- from 0.2 to 0.841, catalyst amount from 1 to 5 wt%
sis, powder X-ray diffraction (XRD) and thermo- and molar ratio of methanol to CSO from 3 : 1 to 15: 1.
gravimetric analysis (TGA).
Infrared spectra were recorded on a NICOLET
5700 FT-IR spectrometer with a resolution of 1 cm−1 . RESULTS AND DISCUSSION
XRD measurements were performed on a Rigaku
D/max-A instrument with a Cu Kα radiation at 50 kV Catalyst Characterization
and 30 mA and a scan speed of 0.02◦ min−1 .
The catalyst was tested using an SDT Q600 simul- From the chart of infrared spectroscopy of SO4 2− /ZrO2
taneous differential scanning calorimetry DSC-TGA. that showed in Figure 3, bands at 1100 and 1030 cm−1
Samples were heated from 50 to 800 ◦ C at a scanning were typically assigned for chelating bidentate sulfate
ions coordinated to the zirconium cation. There was
also a weak band at 1380 cm−1 as a result of the
stretching vibrations of the S O bond, which proved
the presence of the SO3 species. The accurate bands
at 1660, 1640 cm−1 could be attributed to the bending
mode (δHOH) of coordinated molecular water.[24] Also,
a strong and broad band at 3000–3500 cm−1 region
assigned to physisorbed and coordinated water, as
sulfate zirconia had very strong hygroscopicity.
From the curve of the DSC-TGA of SO4 2− /ZrO2 that
showed in Figure 4, the weight losses were concentrated
to two ranges: 80–200 ◦ C and up to 700 ◦ C, the former
was mostly attributed to the removal of water and
the latter was mainly caused by the decomposition of
sulfate. Compared with the heat flow, below 700 ◦ C,
there were no obvious heat changes, whereas up to
700 ◦ C the decomposition of sulfate let out a great deal
of heat that made the curve move straight down. And
Figure 3. Infrared spectroscopy of SO4 2− /ZrO2 . between 200 and 700 ◦ C, the weight fluctuation might
2010 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2010)
DOI: 10.1002/apj
L. NIU et al. Asia-Pacific Journal of Chemical Engineering
Transesterification
Figure 10. Influence of reaction time on the yield of FAME. Figure 11. Influence of catalyst amount on the yield of
FAME.
The effect of the reaction time on FAME yield at Therefore, 3.5 wt% was considered as the optimum cat-
20 min, 40 min, 1 h, 2 h and 3 h was investigated, alyst amount with the FAME yield of 97.5%.
as shown in Fig. 10. FAME yield increased with the Reaction condition: molar ratio of methanol to CSO
increasing reaction time. Usually, the transesterification = 9 : 1; reaction time = 1 h; reaction temperature =
reaction catalyzed by acid needs a long reaction time 120 ◦ C; catalyst mass ratio = 0.841.
to obtain a high conversion under relatively low tem- The effect of the molar ratio of methanol to CSO
perature, but from this figure, however, over 97% of on a FAME yield of 3 : 1, 6 : 1, 9 : 1, 12 : 1, 15 : 1 was
the FAME yield was obtained after only 1 h reaction at investigated, as shown in Fig. 12. The methanol/CSO
120 ◦ C. This indicates that the high temperature accel- molar ratio was one of the most important variables
erated the reaction rate and the increase in temperature that influenced the FAME yield. Theoretically, the
could speed up the process of transesterification. As the transesterification of vegetable oil required 3 mol of
FAME yield did not increase dramatically after 1 h, we methanol per mole of triglyceride according to the
chose the reaction time 1 h as the optimum condition. transesterification mechanism, as shown in Fig. 1.
Reaction condition: molar ratio of methanol to CSO As the molar ratio of methanol/CSO increased, the
= 9 : 1; reaction temperature = 120 ◦ C; catalyst amount FAME yield increased; it could be explained that the
= 3.5 wt%; catalyst mass ratio = 0.841.
The effect of the catalyst amount on a FAME yield
of 1, 2, 3, 4 and 5 wt% was investigated, as shown
in Fig. 11. The FAME yield increased when more
catalyst amount was added, as the catalyst could provide
active centers which would reduce the reaction time and
improve the reaction rate.
As this reaction was a multiphase one, the increase
in catalyst amount could decrease the reaction activa-
tion energy and accordingly accelerate the reaction rate.
Therefore, the increase in the catalyst amount could
improve the yield of the product in the same reaction
time. However, the catalyst could not alter the equi-
librium position; when the reaction reached its balance
point, the yield of the product no longer increased. In a
1-hour reaction, for example, when it came to equilib-
rium point after the 1-h benefit from the increase in the
catalyst amount, the FAME yield no longer increased
even if more catalyst was used. The increase in yield
was fast as the catalyst amount went up from 1 to 3 Figure 12. Influence of methanol/CSO molar ratio on the
wt%, while the increase was less dramatic after 3 wt%. yield of FAME.
2010 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2010)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering STUDY ON BIODIESEL FROM COTTON SEED OIL
transesterification was an equilibrium reaction, and the mass ratio is 0.841). However, after being used three
excess methanol would push the reaction forward to times, the FAME yield decreased to 50%. Therefore,
increase the FAME yield. When the molar ratio came to improving the reusability and stability of the catalyst is
9 : 1–12 : 1, the FAME yield reached the highest point. worth addressing.
However, after 12 : 1 molar ratio, the yield decreased; it
could be explained that the excess of methanol dilutes
CSO, which decreases the reaction rate and affects the Acknowledgements
yield. Considering the economic factor, we selected 9 : 1
molar ratio of methanol/CSO as the optimum condition. The authors are grateful to the National High Technol-
Reaction condition: reaction time = 1 h; reaction ogy Research and Development Program of China (No.
temperature = 120 ◦ C; catalyst amount = 3.5 wt%; 2009AA03Z222 and No. 2009AA05Z437), National
catalyst mass ratio = 0.841. Natural Science Foundation of China (No. 20906013
Of course, all the catalysts used in the transterification and No. 21076044/B6) and ‘Six Talents Pinnacle Pro-
experiment were fresh. After being used three times, gram’ (No. 2008028) of Jiangsu Province of China for
the yield of biodiesel decreased from 98% to less than financial support.
50%; this might have been caused by the loss of sulfur,
which is the main problem with SO4 2− /ZrO2 that has
not yet been resolved. Therefore, how to make this
catalyst more stable would be the key to putting this
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2010 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2010)
DOI: 10.1002/apj