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Biodiesel Synthesis Catalyzed by the

KF/Ca−Mg−Al Hydrotalcite Base Catalyst
Lijing Gao, Guangyuan Teng, Jianhua Lv and Guomin Xiao*
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People’s
Republic of China
Energy Fuels, 2010, 24 (1), pp 646–651
DOI: 10.1021/ef900800d
Publication Date (Web): November 17, 2009
Copyright © 2009 American Chemical Society
*To whom correspondence should be addressed. Telephone: +86-25-52090612. Fax: +86-25-
52090612. E-mail: xiaogm@seu.edu.cn.

Abstract
A series of solid base catalysts, KF/Ca−Mg−Al hydrotalcite (KF mass ratio of 100%) with
different cation ratios, were prepared and studied in this research. Effects of the cation ratio of
the Ca−Mg−Al hydrotalcite and the methanol/oil molar ratios on the fatty acid methanol ester
(FAME) yield of the transesterification of palm oil with methanol were investigated. The results
of the transesterification reactions showed that all of these kinds of catalysts had a very high
activity for the biodiesel yields, obtaining 90% or more with 10 min of reaction under the
conditions of 338 K, 12:1 methanol/oil molar ratio, and 5% (wt/wt oil) catalyst amount. In
addition, the FAME yield could reach 99.6% in 10 min catalyzed by the optimal catalyst
KF/Ca−Mg−Al hydrotalcite (2.2:0.8:1 Ca/Mg/Al; KF mass ratio of 100%), under the same
reaction conditions as above.

1 Introduction
Biodiesel, whose main content is fatty acid methanol esters (FAMEs), is one of the most
potential substituted energy resources(1) and is mainly produced by the transesterification
reaction of vegetable oil or fat with methanol catalyzed by base, acid, and enzyme.
To solve the problems caused by the homogeneous catalyst, which was widely used in industrial
production, such as in a huge amount of waster water, product-separating problems, and limits of
raw materials, heterogeneous catalysts, such as solid base, acid,(2-5) and immobilized
enzyme,(6-8) were studied to replace the homogeneous catalyst. Among them, solid base was
given more attention. For acid, even super-acid required a greater methanol/oil molar ratio(9)
and more reaction time, and the enzyme was much more expensive.
Recently, studies had reported some solid bases as biodiesel synthesis catalysts, for example,
metal oxides, such as MgO, CaO, or BaO,(10-14) modified metal oxides, such as Li-doped
CaO(15) and La-modified CaO,(16) anionic ion-exchange resin,(17) and supported ones, such as
Na/NaOH/γ-Al2O3(18) and KF/γ-Al2O3.(19, 20) In particular, layered double hydroxides (LDHs)
or so-called hydrotalcite (HT) could also be used as catalysts for the transesterification reaction
directly or as catalyst supports.
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LDH, whose chemical composition can be represented by the general formula

[M(1−x)2+Mx3+(OH)2]x+(An−)x/n·yH2O, had also been reported as a catalyst or catalyst carrier for the
transesterification reaction. Corma et al.(21, 22) had reported that calcined Li−Al and Mg−Al
LDHs were able to catalyze the glycerolysis of fatty acid methyl esters to monoglycerides (the
reverse of biodiesel synthesis). Shumaker et al.(23, 24) used calcined Li−Al LDHs to catalyze
soybean oil with methanol. Liu et al.(25) used calcined Mg−Al HT to catalyze poultry fat with
methanol. Broito et al.(26) showed that Mg−Al LDH could catalyze the transesterification
reaction of waste oil with methanol. All of these studies showed that LDHs, except the Li−Al
LDHs, performed low activities at lower temperatures and, when the reactions were performed in
an autoclave at high temperatures, the conversion of soybean oil or acid cottonseed oil could
reach 90%.(26-28) While on the basis of the HT properties, loading an active substance could
improve the activity of the HT. Sun et al.(29) had reported that KNO3/HT showed stronger
alkality and more activity in the methylation of cyclopentadiene than KNO3/Al2O3. Trakarnpruk
et al.(30) loaded CH3COOK on calcined HT and synthesized biodiesel at the condition of a 30:1
methanol/oil molar ratio at 373 K for 6 h and 7 wt % catalyst, with the fatty acid methyl ester
content becoming 96.9%.
Palm oil (PO) is one of the four leading vegetable oils traded on the world market. Cheaper than
canola, rapeseed, or soybean oil, the use of PO would reduce the overhead cost of biodiesel
production and generate a steady supply of diesel fuel substitute. In our early work, KF/Mg−Al
HT(31) had been obtained and was successfully used in the transesterification of PO and the
catalyst showed its activity in this reaction with a FAME yield of 85% under optimum
conditions. In this paper, Ca was added to Mg−Al HT to form a three-metal mixed HT,
Ca−Mg−Al HT. On the basis of Ca−Mg−Al HT, a kind of solid alkyl catalyst was synthesized
and used for biodiesel production with the method of transesterification of PO with methanol.

2 Experimental Section
2.1 Materials
PO and CH3OH were purchased from the Nanjing Runtai market, Nanjing Chemical Reagent
Co., Ltd., and KF·2H2O, Ca(NO3)2·4H2O, Mg(NO3)2·6H2O, Al(NO3)3·9H2O, NaOH, and
Na2CO3 were purchased from Guangdong Guanghua Chemical Factory Co., Ltd.
2.2 Catalyst Preparation
The Ca−Mg−Al hydroxides were prepared by the co-precipitation method. Solution A (200 mL)
contained a certain amount Ca(NO3)2·4H2O, Mg(NO3)2·6H2O, and Al(NO3)3·9H2O, with the
total cation molar concentration being 1 mol/L, while solution B (200 mL) contained NaOH (0.4
mol) and Na2CO3 (0.1 mol). Both solutions were synchronously dropped into 100 mL of water at
338 K, slowly accompanied with vigorous mechanical stirring, while maintaining the pH
between 10 and 11. The resulting mixture was held at 338 K while continuing to stir vigorously
for 48 h and then filtered and washed with water until the pH value of the filtrate was near 7. The
precipitate was dried at 373−398 K overnight and calcined at 723 K for 5 h.
The calcined powder was ground with KF·2H2O, with the mass ratio of 100% (wt/wt calcined
powder), while dropping some water. Then, the paste was dried at 338 K overnight.
2.3 Catalyst Characterization
The catalyst was characterized by powder X-ray diffraction (XRD) and Fourier transform
infrared spectroscopy (FTIR). XRD measurements were performed on a Rigaku D/max-A
instrument with Cu Kα radiation at 50 kV and 30 mA and a scan speed of 0.02°/min.
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2.4 Transesterification
Transesterification experiments were carried out in a 100 mL four-necked flask, provided with a
thermostat and mechanical stirring systems. A total of 30 g of PO and different amounts of
methanol and catalyst were added and heated to a given temperature, accompanied with stirring.
The reactions were undertaken with a refluxing temperature. Other conditions were as follows:
KF/Ca−Mg−Al HT of different cation molar ratios, 6:1−12:1 (molar ratio) of methanol/oil, 5%
(wt/wt oil) of the catalyst amount, and 10 min of the transesterification time. After reaction, the
reactor was cooled to room temperature and the catalyst was removed from the product mixture
by filtration. The excess methanol was distilled with rotary evaporation under subpressure. Phase
separation of the filtrate resulted in the isolation of the methyl esters and glycerol. The top layer
was the biodiesel phase of the methyl esters.
The product mixture was analyzed by the gas chromatograph (Ouhua GC 9160) equipped with a
DB-5Ht capillary column (15 m × 0.25 mm × 0.25 mm) by a flame ionization detector (FID).
Nitrogen was used as a carrier gas with a flow rate of 2 mL/min. The injector and detector
temperatures were 523 and 633 K.
The FAME yield in each experiment was calculated from its content in the composition, as
analyzed by gas chromatography (GC). The yield was defined as the ratio of the weight of
FAME, determined by GC, to the weight of the whole production.
2.5 Central Composite Design (CCD)
A CCD was employed to reduce the total number of experiments needed to determine the best
Ca2+ and Mg2+ ratio for the catalyst preparation. The statistical software used in this paper was
design-expert 7.0, and the prepared cation ratio conditions of each experiment were shown in
Table 1. In addition, the transesterification reactions were undertaken with the following
conditions: reaction temperature, 338 K; methanol/oil molar ratio, 12:1; mass of catalyst, 5%;
and reaction time, 10 min.
Table 1. CCD Conditions for the FAME Yield Catalyzed by KF/Ca−Mg−Al HT
run M1 (Ca/Al molar ratio) M2 (Mg/Al molar ratio)
1 2.00 2.00
2 3.00 1.00
3 3.41 2.00
4 2.00 2.00
5 0.59 2.00
6 2.00 2.00
7 1.00 1.00
8 3.00 3.00
9 2.00 2.00
10 2.00 2.00
11 2.00 0.59
12 2.00 3.41
13 1.00 3.00
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3 Results and Discussion

3.1 Transesterification
3.1.1 Transesterification of Different Catalysts
Table 2 showed the FAME yields catalyzed by Mg−Al HT, Ca−Al HT, Ca−Mg−Al HT, calcined
Ca−Mg−Al HT, pure KF crystal, KF/Ca−Al HT, KF/Mg−Al HT, and KF/Ca−Mg−Al HT (2:3:1
Ca/Mg/Al). The reactions were carried out under the conditions as follows: methanol/oil molar
ratio, 12:1; mass of catalyst, 5%; and reaction temperature, 338 K. The results proved that the
doping of KF highly raised the activity of the HT catalysts. In addition, it also showed that the
transesterification reaction, catalyzed by the new catalyst KF/Ca−Mg−Al HT(2:3:1 Ca/Mg/Al),
could obtain a very high FAME yield (98%) in 10 min while needing 1 or 3 h to obtain a
relatively high FAME yield with other two catalysts. In connection with the XRD patterns
(Figure 4), it was believed that the new catalyst combined the advantages of KF/Mg−Al HT and
KF/Ca−Al HT and brought itself higher activity.
Table 2. FAME Yield over Different Catalysts
catalyst reaction time FAME yield (%)
Mg−Al HT 5h 3.6
Ca−Al HT 5h 4.4
Ca−Mg−Al HT 5h 5.6
calcined Ca−Mg−Al HT 5h 10.3
KF 5h <1
KF/Mg−Al HT 3h 73.3
KF/Ca−Al HT 1h 96.6
KF/Ca−Mg−Al HT (2:3:1 Ca/Mg/Al) 10 min 98.0
2+ 2+
3.1.2 Influence of the Ca and Mg Molar Ratio on Biodiesel Yield
In Figure 1, during a 10 min transesterification reaction, the FAME yields were about 90% or
more when catalyzed by KF/Ca−Mg−Al HT catalysts, except that by the cation ratio of 3:3:1,
which was 84.5%. Figure 1a showed that, when Ca was added to the Mg−Al HT, the activity of
the catalyst enhanced greatly after the same loading step. Before the Ca2+/Mg2+ ratio was 1.5:3,
the FAME yield increased significantly, while an increasing trend was apparently slowed down
with the cation ratio rising from 1.5:3 to 2.5:3 and was decreased when the cation ratio was up to
2.5:3. Similar to Figure 1a, Figure 1b showed that, when Mg was added to the Ca−Al HT, the
activity of the catalyst also rose after the same loading step. When the panels a and b of Figure 1
were compared, it was clearly seen that Ca increased the activity of the KF/Mg−Al HT much
more than Mg increased the activity of the KF/Ca−Al HT. In addition, both panels a and b of
Figure 1 could prove that the synergistice effect of Ca2+ and Mg2+ largely improved the catalytic
activity of the kind of KF/HT catalyst. In combination with Figure 3, it was believed that the
obvious layer structure of KF/Ca−Mg−Al HT made it more active than KF/Ca−Al HT and the
active crystals, which were formed by the added Ca2+, made it more active than KF/Mg−Al HT.
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Figure 1. (a) Influence of the Ca2+ molar ratio on the FAME yield (3:1 Mg2+/Al3+). (b) Influence
of the Mg2+ molar ratio on the FAME yield (3:1 Ca2+/Al3+). Reaction conditions: temperature,
338 K; methanol/oil molar ratio, 12:1; catalyst amount, 5%; time, 10 min.

When the cation ratio became 3:3:1, the reduction of the FAME yield might be caused by the
following reason: when the cation ratio became 3:3:1, it meant that the ratio of the divalent
cation/trivalent cation was 6:1, which made too much divalent cation and hindered their
combination with the trivalent cation to form the layer structure.
To evaluate the efficiency of the Ca2+ and Mg2+ molar ratios, CCD experiments were employed,
as shown in Table 1, and the regression equation of the experiments was as follows:
FAME yield =55,64314 + 36,22700M1 + 8,58818M2 – 3,04475 M1M2 -7,58669 M12 -
1,10519M22

The model used to evaluate the FAME yield fitted with the experimental data well (Figure 2 a,
0.05 > probability > F), which proved that, on the basis of the significance of the effects of
factors in the experimental interval and possible interactions, the interpretation was correct.
Details of the experimental results on the FAME yield through response surface analysis were
shown in Figure 2b. According to the model, an optimal Ca2+ and Mg2+ ratio was obtained as
follows: Ca/Mg/Al was 2.2:0.8:1, and at the same reaction conditions the FAME yield predicted
was 99.4%. According to the CCD analysis results, the transesterification reaction was
undertaken with the following conditions: reaction temperature, 338 K; reaction time, 10 min;
methanol/oil molar ratio, 12:1; catalyst, KF/Ca−Mg−Al HT (2.2:0.8:1 Ca/Mg/Al; KF mass ratio
of 100%); amount, 5% (wt/wt oil); and FAME yield, 99.6%, which was not different from the
predicted value. Therefore, the model obtained by the CCD method had some guiding
significance.

Figure 2. (a) Normal plot of residuals. (b) Three-dimensional response surface for the FAME
yield in relation to the Ca2+ and Mg2+ molar ratio.

3.1.3 Influence of the Methanol/Oil Molar Ratio

Both panels a and b of Figure 3 showed the influence of the methanol/oil molar ratio on FAME
yields with different catalysts. Because the transesterification reaction is an equilibrium reaction,
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an excess of methanol will increase the oil conversion by shifting this equilibrium to produce
FAME. From both panels a and b of Figure 3, the FAME yields increased as the methanol/oil
molar ratio increased from 6:1 to 12:1. This could be explained by the pushing effect of excess
methanol on the reaction balance. Unlike the situation catalyzed by KF/Mg−Al HT;(31)
however, the methanol/oil molar ratio did not influence the FAME yield significantly, which
might be a result of the fact that the high activity catalysts were provided more basic sites, which
made the reaction much faster and gave a relatively higher FAME yield. From panels a and b of
Figure 3, a lower methanol/oil molar ratio, such as 9:1, could be used to cut cost without
significant biodiesel yield falling.

Figure 3. (a) Influence of the methanol/oil molar ratio on the FAME yield (0.5:3:1 to 3:3:1
Ca/Mg/Al). (b) Influence of the methanol/oil molar ratio on the FAME yield (3:0.5:1 to 3:3:1
Ca/Mg/Al).

3.1.3 Recycle Using Catalyst

Table 3 showed the FAME yield catalyzed by calcined and uncalcined fresh catalysts and reused
and regenerated ones. When the FAME yield catalyzed by the uncalcined and calcined fresh
catalysts was compared, the uncalcined ones gave a higher FAME yield. In combination with the
XRD patterns and our former research on KF/Mg−Al HT,(31) it was believed that the layer
structure of the catalyst helped raise the activity of the catalyst. It was clearly seen that the
FAME yield decreased apparently when the reaction was catalyzed by the fresh catalyst and the
used once one without any disposal and the FAME yields catalyzed by the used once and twice
catalysts were not as discrepant as that of the first and second time. In combination with the
XRD patterns (Figure 6), the huge decline of the FAME yield might not be caused by the loss of
the active crystal (in Figure 6, there are still strong XRD peaks belonging to them) but by the
adsorption of the byproduct, glycerin, which decreased the effective contact surface of the
catalyst with the reactants. In Figure 7, the used catalyst showed clear FTIR peaks belonging to
the −OH of glycerin. After calcinations, the glycerin adsorbed was burnt and the active site
emerged again; therefore, the FAME yield went up again, reaching 78.6%, which was much
higher than the results by the used once catalyst. According to the XRD patterns, calcination
might also reform the active crystal, which seemed greatly reduced after the reaction 3 times.
Table 3. FAME Yield Catalyzed by Fresh and Reused Catalyst (3:2.5:1 Ca/Mg/Al)
used fresh used used after loaded, calcined at after use 3 times and then
times (%) once (%) twice (%) 873 K, fresh (%) calcined at 873 K (%)
FAME 95.93 51.88 40.61 90.35 78.62
yield
3.2 Catalyst Characterization
Figure 4 showed the XRD patterns of different catalysts. In pattern A, peak a was the typical HT
peak, which meant that the sample had a layered structure, and peak b belonged to the active
crystal (KMgF3) of KF/Mg−Al HT.(30) In pattern B, according to the early research of our team,
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peak c belonged to the active crystal (KCaF3, CaAlF5, and KCaCO3 F) of KF/Ca−Al HT. In
pattern C, it was clearly seen that the KF/Ca−Mg−Al HT synchronously had peaks a, b, and c,
which meant that this catalyst had the high active crystals that showed in KF/Mg−Al HT and
KF/Ca−Al HT as well as the layered structure. These two parts, active crystal and layered
structure, made the new catalyst show high catalysis activity in the transesterification reaction of
oil with methanol. Therefore, the layered structure, KMgF3, KCaF3, CaAlF5, and KCaCO3F were
the active components of the KF/Ca−Mg−Al HT catalyst.

Figure 4. XRD pattern of different catalysts: (A) KF/Mg−Al HT (mass ratio of 100%), (B)
KF/Ca−Al HT (mass ratio of 100%), and (C) KF/Ca−Mg−Al HT (2:3:1 Ca/Mg/Al; mass ratio of
100%).

Figure 5 showed the XRD patterns of KF/Ca−Mg−Al HT with different cation molar ratios.
When the Ca2+ molar ratio was increased, the peaks at 20°, 23°, 28.5°, 35°, and 47°, which
belonged to the active centers CaAlF5, KCaF3, and KCaCO3F, enhanced. At the same time, the
peaks belonging to the layer structure and KMgF3 decreased. This phenomenon might be caused
by the following reasons: when the Ca2+ molar ratio increased, more Al3+ combined with it and
partly destroyed the layer structure, the Mg2+ relative molar ratio decreased instantaneously, and
then less KMgF3 was formed. However, when Ca/Mg/Al reached 3:3:1, the peaks of the active
crystals and layer structure all went down, because too much divalent cations were added and
there were not enough trivalent cations to act with them, and then Ca2+ and Mg2+ aggregated
respectively and reduced the amount of content that could interact with KF to form the active
structure.

Figure 5. XRD patterns of KF/Ca−Mg−Al HT with different cation molar ratios (Ca2+ ratio rose).

In Figure 6, the peaks belonging to the active structure of the KF/Ca−Mg−Al HT were not
reduced after use once. It was shown that, after use twice, the active centers (peaks at 20°, 23°,
28.5°, 35°, and 47°) nearly disappeared and the layer structure (peaks at 11.6°, 23.4°, 35°, 39.6°,
and 47.1°) was destroyed completely. This meant that this catalyst should be regenerated after
been used twice. After use once, the peaks belonging to the active centers of the catalysts did not
weaken obviously; however, the FAME yields decreased greatly (from 96 to 58%). This could be
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explained by the following reason: in combination with the active site of the catalyst was the
precondition that methanol reacted with oil; however, the byproduct glycerin could also combine
with the catalyst, which largely reduced the contact opportunity of the methanol and catalyst,
which can be seen from Figure 7. In Figure 7, it can been seen that, in comparison to the calcined
fresh catalyst (curve B), the used once catalyst (curve A) showed two clear peaks around 2800
cm−1, which belonged to the −OH of glycerol, and after calcined (curve C), the two peaks
disappeared, which meant that the glycerol has been burnt during the calcinations.

Figure 6. XRD patterns of catalysts before and after use.

Figure 7. FTIR profiles of different catalysts: (A) catalyst used once, (B) fresh calcined catalyst,
and (C) used calcined catalyst.

Figure 8 showed the XRD patterns of KF/Ca−Mg−Al HT, in which Ca/Mg/Al was 1:3:1 and
3:1:1, respectively. These two samples could delegate the catalyst, which had excess Ca2+ or
Mg2+. From this figure, it was seen that the sample with excess Mg2+ had more obvious HT
typical peaks of the layer structure, while the one with excess Ca2+ scarcely had any, which
meant that the Ca2+ may affect the formation of the lay structure of HT and too much Ca2+ would
destroy the regular layer structure. However, the catalyst with more Ca2+ showed much stronger
peaks of CaAlF5, KCaF3, and KCaCO3F. In combination with the FAME yield catalyzed by
these two catalysts, the FAME yield was a little higher for the Ca2+-excess catalyst than the
Mg2+-excess one. Then, it was believed that the active center CaAlF5, KCaF3, and KCaCO3F
played a more important role in building the catalyst activity than KMgF3. In addition, the
samples with excess Ca2+ showed distinct peaks belonging to CaCO3 (23°, 29.5°, 31.5°, and
36°), which meant that the Ca2+ actually aggregated and formed a non-active center.
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Figure 8. XRD patterns of KF/Ca−Mg−Al HT with different Ca2+ and Mg2+ molar ratios.

4 Conclusion
The results of this study confirmed that KF/Ca−Mg−Al HT was a very highly effective catalyst
for the transesterification reaction of PO with methanol. Catalyzed by this kind of catalyst, the
biodiesel yield could obtain over 90% in 10 min under the following reaction conditions:
reaction temperature, 338 K; methanol/oil molar ratio, 12:1; and catalyst amount, 5% (wt/wt oil).
The catalyst with an optimal cation ratio (2.2:0.8:1) was obtained by the CCD method, and at the
same reaction conditions, the FAME yield could reach 99.6%. This catalyst largely shortened the
reaction time of the biodiesel production and showed a hopeful future of the new producing
method of biodiesel.

Acknowledgment
The authors are grateful to the National High Technology Research and Development Program
of China (2009AA03Z222 and 2009AA05Z437) and “Six Talents Pinnacle Program” of Jiangsu
Province of China (2008028) for financial support.

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