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Asia-Pac. J. Chem. Eng. (2010)

Published online in Wiley Online Library
( DOI:10.1002/apj.532

Special Theme Research Article

Study on biodiesel from cotton seed oil by using
heterogeneous super acid catalyst SO42−/ZrO2
Lei Niu, Lijing Gao, Guomin Xiao* and Baosong Fu
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R. China

Received 28 November 2009; Revised 14 October 2010; Accepted 10 November 2010

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.

KEYWORDS: biodiesel; transesterification; solid super acid; autoclave

INTRODUCTION vegetable or animal oil. It is also called fatty acid methyl

ester (FAME).
With the progress of society and the resultant improve- Biodiesel has many advantages compared with tradi-
ment in living standards, people have in recent years tional fuels. It is renewable and combines high perfor-
been depending more and more on petroleum. The seri- mance with environmental benefits. It does not corrode
ous problem of air pollution caused by fossil fuel com- conventional diesel engines and can be used directly
bustion has drawn a great deal of attention thanks to the without significant modifications.[4] Moreover, its favor-
increasing consciousness about the environment. There- able lubrication performance reduces engine wear and
fore, the development of a substitute energy source has prolongs service life. Last, biodiesel is not used with
been an urgent need. dangerous goods as a result of its high assay flash point.
There are mainly two methods of replacing fossil Biodiesel can be obtained by physical methods such
fuels, of which one is to take, instead of petroleum, as dilution and emulsion or chemical methods which
coal or gas which is relatively rich in deposit reserves. consist of hit dehiscence and transesterification. Among
The gas would be used as fuel directly while the coal these methods, transesterification is considered effec-
must first be transformed into alcohol[1] or hydrocarbon tive and practical. It is a chemical process between
and then used as fuel. However, despite the rich deposit triglycerides and short-chain alcohol in the presence of
reserves, these non-renewable fuels will be exhausted a basic or acidic catalyst used to produce monoester, as
within a certain time span. The other method is to depicted in Fig. 1.This is a multi-step reaction which
develop biomass energy using the renewable capacity consists of three procedures. First, the triglycerides
of natural plants.[2] Biomass energy is a good substitute make an ester change with methanol to produce diglyc-
for petroleum, with its ability to control air pollution eride and FAME. Then the diglyceride makes a second
and alleviate the energy crisis effectively. An interesting
esterification with methanol to form another mole of
alternative is biodiesel,[3] which is produced from
FAME and monoglyceride. Finally, the monoglyceride
continues the esterification to convert into glycerol.
Short-chain alcohols such as methanol, ethanol,
*Correspondence to: Guomin Xiao, School of Chemistry and
Chemical Engineering, Southeast University, Nanjing 211189, propanol and butanol are commonly used. In our
P. R. China. E-mail: research, we used methanol because of its feasibility and
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
Curtin University is a trademark of Curtin University of Technology
L. NIU et al. Asia-Pacific Journal of Chemical Engineering

to say, it had a Bronsted acid and a Lewis acid site.

This kind of catalyst, insensitive to the acid-value and
water content of raw oil and more suitable for catalyz-
ing this kind of oil, was welcomed. Martino Di Serio
Figure 1. Transesterification of triglycerides with methanol.
used Pb(Ac)2 to catalyze soybean oil with methanol to
produce biodiesel and got a 57% FAME yield (the initial
free fatty acid concentrate of soybean was 20.5%) and
92% FAME yield (soybean oil with non-free fatty acid)
under the reaction conditions of methanol/oil molar
ratio of 12 : 1, 1 h reaction time, 5.38 × 10−5 mol cata-
lyst and 180 ◦ C reaction temperature.[15] Lou Wen-Yong
used a carbohydrate-derived solid acid catalyst to pro-
Figure 2. Saponification of free fatty acid. duce biodiesel with high free fatty acid-containing waste
oils and methanol. Under the optimum conditions, the
FAME yield reached 93%.[16] As a matter of fact, the
economic efficiency. Also, methanol with only one car- acid heterogeneous catalyst could be separated more
bon atom and a relatively high polarity made the trans- easily from reaction products with reaction conditions
esterification easy to perform. This reaction could be less drastic compared to the basic heterogeneous cat-
catalyzed by acid, base or enzyme. Although the trans- alyst when catalyzing the oil with a certain amount
esterification rate of base catalyst[5,6] was faster, the use of free fatty acid. Also, the acid-catalyzed procedure,
of alkali-catalyst for biodiesel synthesis had the prereq- being a one-step process, was more economical than the
uisite of low content of water and fatty acids, which alkali-catalyzed process, which required an extra step to
largely limited the raw materials. Various kinds of vir- convert free fatty acids to methyl esters, thus avoiding
gin oils with higher fatty acid content prevented a large soap formation.[17 – 19]
amount of homogeneous basic catalysts. It could be Nowadays, cotton seed oil (CSO) is mainly used
explained that in the alkaline-metal-hydroxide-catalyzed in industries to produce soap and glycol lubricants
transesterification, some bases might lose their activities besides being used as edible oil. Therefore, compared
in the neutralization of fatty acid; moreover, the water to soybean oil,[20] palm oil[21,22] and colza oil, CSO
and the fatty acids would form soap, as depicted in is an appropriate raw material of biodiesel because of
Fig. 2, which complicates the separation progress.[7] its advantages in origin and uses. In this work, a kind
In the past, liquid acids and bases were used to cat- of solid super catalyst sulfated zirconia was prepared,
alyze the transesterification but they had many disad- and its performance in transesterification of CSO with
vantages. For example, concentrated sulfuric acid was methanol was investigated. An autoclave[23] was used
always used as the homogeneous catalyst for transester- as a reactor to provide high temperature and pressure
ification because of its low cost and preferable catalysis. in order to improve the yield of biodiesel. We aimed
As a result of the etherification and adduction accom- to debase the reaction temperature and time to play
panying the reaction, which would increase the load of down the energy consumption to get a high yield of
after treatment, the liquid acid catalyst was fading out FAME. Ultimately, under the optimum conditions of
the stage of catalysis in the etherifying reaction. Oth- methanol to CSO molar ratio of 9 : 1, 3.5 wt% fresh
erwise, the after treatment such as alkali neutralization catalyst, 1 h reaction time, and reaction temperature of
and water washing, which produce a large amount of 120 ◦ C, a FAME yield of 98% was obtained.
waste, made the recycling of the catalyst impossible.
Furthermore, the liquid acid catalyst had a strong cor-
rosive, which added to the requirement for instruments
and input cost. Therefore, the heterogeneous solid acid EXPERIMENTAL
or base catalyst had drawn considerable research. Many
heterogeneous catalysts which were based on acidic[8] Materials
and basic[9,10] solids have been reported in the literature.
Heterogeneous catalysts had the advantages of long ser- In the synthesis of the catalyst, the following reagents
vice life and large specific surface area. A solid base were used: zirconium (VI) oxychloride octahydrate
catalyst (such as KF/γ -Al2 O3 [11] or KF/hydrotalcite[12] ) (ZrOCl2 ·8H2 O), sulfuric acid (98.0%), deionized water,
showed good performance during the transesterification silver nitrate solution (0.5 mol L−1 ), ammonia (25–
process, with a biodiesel product of high purity and 28%) and methanol (99.5%). They were purchased
yield in a relatively short time,[13,14] but it had a certain from Sinopharm Chemical Reagent Co., Ltd., Shanghai
requirement for water content and acid-value of raw oil Ying Xiang Biology Technology Co., Ltd., Nanjing
as a result of neutralization and saponification. A solid Chemical Reagent Co., Ltd. and Nanjing Chemical
acid would give out a proton and electron pair, that is Industry Corporation Chemical Plant, respectively.
 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

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

Figure 4. DSC-TGA curves for SO4 2− /ZrO2 . This figure is

available in colour online at Figure 5. XRD spectrum of SO4 2− /ZrO2 and ZrO2 calined
at 600 ◦ C. A: SO4 2− /ZrO2 calcined at 600 ◦ C and B: ZrO2
calcined at 600 ◦ C. This figure is available in colour online at
be caused by the oxidation of the catalyst. The increase
in weight up to 750 ◦ C might also be due to the same
Figure 5 shows the XRD patterns of SO4 2− /ZrO2 and
ZrO2 calcined at 600 ◦ C. Sample B, the ZrO2 without
the load of SO4 2− , had a mixed crystal phase which
contained both monoclinic and tetragonal phases. After
being loaded with sulfuric acid, in XRD pattern A, both
the typical crystal phases disappeared, accompanied
by four clear observations of characteristic diffraction
which were signed as peaks a, b, c, d in the figure.
This could be explained by the destruction of ZrO2 and
the formation of a new structure of SO4 2− /ZrO2 during
the loaded and calcined processes. The four new peaks
might stand at the active centers of the catalyst and
could explain the catalytic activity.
Figure 6 shows the XRD patterns of SO4 2− /ZrO2
samples with different calcined temperatures. All the
samples showed the sulfate zirconia peaks during band
7–22◦ in XRD patterns of A, B and C. After being
calcined at 400 ◦ C, the typical peaks of ZrO2 disap-
peared and the new peaks of SO4 2− /ZrO2 were almost Figure 6. XRD spectrum of SO4 2− /ZrO2 with different
calcination temperatures. A: SO4 2− /ZrO2 calcined at 400 ◦ C;
not formed. This could be explained by the prelim- B: SO4 2− /ZrO2 calcined at 500 ◦ C; and C: SO4 2− /ZrO2
inary binding of SO4 2− and ZrO2 at low tempera- calcined at 600 ◦ C. This figure is available in colour online at
ture. Therefore, sample A was almost amorphous and
merely showed a weak typical peak of SO4 2− /ZrO2 .
As the calcination temperature increased, typical peaks
of SO4 2− /ZrO2 appeared and were then followed by be seen from the figure, compared with XRD pat-
more peaks at 500 ◦ C. When sample C was calcined at tern A, sample B had no obvious crystal phases after
600 ◦ C, obvious typical peaks of SO4 2− /ZrO2 resulted. being used three times. Considering the transesterifi-
Higher temperature might cause the changes in the cation results that the FAME yield obtained the third
crystal phase. Therefore, SO4 2− /ZrO2 at 600 ◦ C gave a time using the catalyst was less than 50%, it can be
stronger acidity, followed by a better catalyzing perfor- concluded that the new crystal phases that existed in
mance which has been verified in the experiment below. the SO4 2− /ZrO2 , which were shown as peaks a, b,
Figure 7 shows the XRD patterns of newly produced c, d in XRD pattern A, were the active centers of
SO4 2− /ZrO2 and SO4 2− /ZrO2 used three times. As can the catalyst. However, these active centers were lost
 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

kind of super acid catalyst which had a much stronger

acidity compared to the traditional strong acid. This
characteristic made it possess higher activity in the
transesterification, which was proved in the following
experiments. From the figure, it can be concluded that
higher yield can be obtained with a higher SO4 2− mass
ratio. However, the higher the ratio of SO4 2− , the more
easily it deliquated, and of course, the more difficult
it was to conserve. Beyond the SO4 2− load of 0.51
ratio, the FAME yield did not rise much accompanied
by the SO4 2− load increase. Therefore, we chose the
catalyst that has a loaded mass ratio of SO4 2− to ZrO2
as 0.841, which was the largest mass ratio we could get
without much difficulty, as the optimum catalyst in the
following study.
Reaction condition: reaction temperature = 120 ◦ C;
catalyst amount = 3.5 wt%; reaction time = 1 h; molar
ratio of methanol to CSO = 9 : 1
Figure 7. XRD spectrum of newly produced SO4 2− /ZrO2 The temperature effect on FAME yield at 100, 120,
and SO4 2− /ZrO2 used three times. A: SO4 2− /ZrO2 calcined at 140, 160 and 180 ◦ C was investigated, as shown in
600 ◦ C; and B: SO4 2− /ZrO2 calcined at 600 ◦ C and used in Fig. 9. From this figure, when the reaction temperature
reaction three times. This figure is available in colour online
at rose from 100 to 120 ◦ C, the FAME yield increased
sharply from 80.23% to 97.99%. When the temperature
continued increasing, as the FAME yield was nearly
100%, its increase was not remarkable. Temperature
rise could shift the balance to production and at
120 ◦ C this balance was at a critical point. When the
temperature exceeded 120 ◦ C, this balance might have
come to a threshold of thermodynamics and kinetics.
Meanwhile, because transesterification was a reaction
with less thermal effects, the higher temperature did
not impact the balance point of the reaction very much.
Considering the energy cost, 120 ◦ C should be the
optimum reaction temperature.
Reaction condition: molar ratio of methanol to CSO
= 9 : 1; reaction time = 1 h; catalyst amount = 3.5
wt%; catalyst mass ratio = 0.841.

Figure 8. Influence of catalyst mass ratio on the yield of


slowly during the reaction, and after being used three

times or more, they would be completely lost without


The SO4 2− load ratio effect on the FAME yield of

0.205, 0.361, 0.51, 0.663 and 0.841 was investigated,
as can be seen from Fig. 8. As the SO4 2− mass ratio
increased, the FAME yield increased sharply at first.
When the mass ratio reached 0.51, the increasing speed
of the FAME yield slowed. The SO4 2− /ZrO2 was a Figure 9. Influence of temperature on the yield of FAME.
 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

Figure 10. Influence of reaction time on the yield of FAME. Figure 11. Influence of catalyst amount on the yield of

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
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 2010 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2010)
DOI: 10.1002/apj