This journal is c The Royal Society of Chemistry 2013 Catal. Sci. Technol.

, 2013, 3, 699--705 699

Cite this: Catal. Sci. Technol., 2013,
3, 699
Esterification of 2-keto-L-gulonic acid catalyzed by a
solid heteropoly acid
Thu Ha Thi Vu,* Hang Thi Au, Tuyet Mai Thi Nguyen, Minh Tu Pham, Tam Thi Bach
and Hong Nhan Nong
The ecacy of a potassium 12-phosphotungstate (KPW) catalyst in the synthesis of methyl 2-keto-L-gulonat
from 2-keto-L-gulonic acid (2-KLGA) and methanol is investigated. The KPW catalyst gives high yields in
short reaction times. The present procedure represents a clean, ecient, practical, simple, mild, time-saving
and eco-friendly method for the synthesis of methyl 2-keto-L-gulonat. The KPW catalyst is found to be a
truly heterogeneous catalyst, highly ecient and reusable in the synthesis of methyl 2-keto-L-gulonat.
1. Introduction
The 2-keto-L-gulonic acid (2-KLGA) esterification reaction plays an
important role in the industrial manufacture of vitamin C.
13
Homogeneous acid catalysts, such as sulfuric acid and heteropoly
acids (HPAs), have been used for the esterification reaction.
46
However, the use of homogeneous acid catalysts for esterification
causes diculties in recovery after the reaction has taken place
and produces toxic wastewater.
7
To overcome this shortcoming of
homogeneous catalysts, heterogeneous catalysts have been used
in esterification reactions in recent years,
8
although the catalytic
activity of heterogeneous catalysts is often lower than that of
homogeneous catalysts.
9
Heterogeneous acid catalysis by a HPA with a Keggin structure
is one of the most important and growing areas of research in
recent years because of its potential economic rewards and green
benefits.
10,11
HPAs with Keggin structures possess special
characteristics that allow for their use as catalysts in esterification
reactions as they have a very high intrinsic acidity.
12
The catalytic
acidity of HPAs is stronger than that of conventional solid acid
catalysts such as acidic oxides and zeolites. The acid strength of
Keggin HPAs decreases in the order: H
3
PW
12
O
40
4H
4
SiW
12
O
40
4
H
3
PMo
12
O
40
4 H
4
SiMo
12
O
40.
13
In addition, the acid sites in HPA
are more uniform and easier to control than those in other solid
acid catalysts.
14
Usually, phosphotungstic acid (HPW) is the
catalyst of choice because of its stronger acidity, higher thermal
stability and lower oxidation potential compared to phos-
phomolybdic acid.
15
However, due to the low surface area
and diculty in the reutilization of the homogeneous tungsten
HPAs, it is advisable to support tungsten HPAs on a carrier with
a high surface area, such as silica, activated carbon, alumina or
clays.
16
Another alternative approach is to prepare HPA-salts by
partially exchanging protons of the parent HPAs with large
cations, such as K
+
and Cs
+
, which have high porosity.
9,15
Thus,
the HPA-salt not only has a high surface area but can also be
reused in the esterification of methyl 2-keto-L-gulonat.
In our present studies, potassium 12-phosphotungstate
(KPW) was prepared by the partially exchanging protons
process. The Keggin structure of KPW was examined by X-ray
Diraction Spectra analysis (XRD). An automated BET sorpt-
ometer was used to study the increasing surface area of the
HPA-salt compared with that of HPA. The surface area of
Amberlyst 15 was also characterized by a BET sorptometer.
The number of acid sites in the catalyst was examined by TPD-NH
3
.
Fourier Transform Infrared Spectroscopy (FTIR) was used to study
the Keggin structure of the KPW catalyst. The catalytic activity
of KPW was tested in the esterification of methyl 2-keto-L-gulonat.
The aim of the present work is to compare the KPW catalyst
performance with other known catalyst systems, such as the
homogeneous catalyst 12-phosphotungstic acid and heterogeneous
catalyst Amberlyst 15 on the esterification reaction.
2. Experimental
2.1. Materials and catalysts
Monohydrous 2-keto-L-gulonic acid (90 wt%), 12-phospho-
tungstic acid (H
3
PW
12
O
40
21H
2
O) and methanol (99.5 wt%)
were purchased from Sigma Aldrich. Amberlyst 15 resin was
obtained from Rohm & Hass Co.
The acidic heteropoly salt (KPW) was prepared according to
the literature procedure
18
by adding dropwise the required
amount of an aqueous solution of H
3
PW
12
O
40
(0.1 M) to
an aqueous saturated solution of KCl at 40 1C with stirring.
National Key Laboratory for Petrochemical and Refinery Technologies, Hanoi,
Vietnam. E-mail: ptntd2004@yahoo.fr; Fax: +84 439335410; Tel: +84 422189067
Received 16th July 2012,
Accepted 25th October 2012
DOI: 10.1039/c2cy20497e
www.rsc.org/catalysis
Catalysis
Science & Technology
PAPER
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The precipitate obtained was filtrated and washed with distilled
water and then dried at 70 1C for 10 hours and after that in an
oven at 120 1C for 5 hours.
2.2. Techniques
Powder X-ray diraction (XRD) spectra of KPW and H
3
PW
12
O
40
(HPW) were recorded on a D8 Advance diractometer (XRD) with
monochromatic CuK
a
radiation using a Brucker Tensor 37.
The nature of the acid sites of these catalysts was deter-
mined by NH
3
-TPD on an Autochem 2020 (micrometric) at the
temperature range of 100 1C to 600 1C at a rate of 10 1C min
1
,
using nitrogen as a gas carrier.
The thermal stability of the catalyst was examined by
thermogravimetric/dierential thermal analysis (TG/DTA) using
a Perkin Elmer instrument. The samples were heated at a rate of
10 1C min
1
. The TG and DTA curves were recorded.
The BrunauerEmmettTeller (BET) surface area and porosity
of the catalysts were measured from the N
2
adsorption isotherm
at 77 K using a BET Sorptometer (Automated BET Sorptometer
201-A, USA).
Infrared spectra were recorded on a Brucker FTIR spectrometer
with samples prepared as KBr disks in the 4004000 cm
1
range.
The yield of the esterification reaction was determined by
HPLC chromatography. HPLC was performed using a Model
1200 Agilent, a model UV (210 nm) and a C18 column.
The chemical composition of the KPW catalyst was analysed
using X-ray fluorescence, XRF (Model: Bruker S4 Pioneer, USA).
2.3. Catalytic reactions
The catalytic activity of KPW was tested in 2-keto-L-gulonic acid
esterification, which was carried out under atmospheric pres-
sure in a 250 ml bottom glass reactor. The 2-KLGA was mixed
with methanol at various molar ratios of 2-KLGA: methanol:
1 : 24, 1 : 48, 1 : 96, 1 : 192, 1 : 384, 1 : 720, 1 : 1440 (mol : mol
1
).
The mixtures were heated to 65 1C and then the catalyst was
added to the 2-KLGAmethanol solutions with the weight ratio
of catalyst to 2-KLGA of 1 : 10 (g: g
1
). The esterification reaction
time was started by charging the catalyst. The product of the
reaction was periodically taken out at 5 min, 15 min, 30 min,
60 min, 120 min, 180 min, 240 min, 300 min, 360 min and
420 min and analyzed by HPLC analysis.
Catalyst recycling experiments were performed as follows:
after the reaction, the heterogeneous KPW catalyst was recovered
from solution by simple filtration. The catalyst was washed with
copious amounts of methanol solvent. Then the catalyst was
reused in the reaction. The ecacy on the esterification reaction
when using the KPW catalyst was determined after each recycling.
2.4. Scale up reaction
APPARATUS. The experiments were performed in a 2000 ml round
bottomglass reactor dipped in a constant temperature water bath.
The reactor was equipped with a temperature indicator (Pt-100)
and speed monitoring facility. It was also equipped with a
condenser to avoid any possible loss of methanol.
ESTERIFICATION REACTION. In the scaled up esterification reaction,
the molar ratio of 2-KLGA: methanol was 1 : 24 (mol mol
1
),
which is the highest concentration of 2-KLGA in methanol at
65 1C. A mixture solution was prepared by mixing 200 g of a
2-keto-L-gulonic acid solution with 1000 ml of a CH
3
OHsolution.
The mixture was stirred at a rate of 500 r min
1
and heated to
65 1C. 20 g of the catalyst was then added to the mixture. The
esterification reaction time was started by charging the catalyst.
The products of the reaction were periodically taken out at
5 min, 15 min, 30 min, 60 min, 120 min, 180 min, 240 min,
300 min, 360 min and 420 min. The products were diluted
30 times by methanol and were analyzed by HPLC analysis.
3. Results and discussion
3.1. Chemical composition
The chemical composition of the KPW catalyst was determined
by XRF analysis (as shown in Table 1). The results confirm that
the potassium element is present in the catalyst structure. The
presence of potassium in the catalyst structure can change the
physicochemical properties of the catalyst from a homoge-
neous catalyst to a heterogeneous catalysts.
15
From the results
in Table 1, we can calculate the content of potassium ions in
KPW. The structure formula of KPW is K
2.2
H
0.8
PW
12
O
40
.
3.2. Catalyst characterization
3.2.1 TG/DTA ANALYSIS. The thermal stability of KPW was
investigated by means of thermogravimetric (TG) and dierential
thermal analysis (DTA) (Fig. 1). The TG curve of the KPW catalyst
shows that there is one weight loss step which is attributed to
crystallization water desorption between room temperature to
150 1C. In the DTA curve, one endothermic peak was observed
at 70 1C which associated with the mass losses observed in the TG
curve. No endothermic peaks or weight losses were observed in
the DTA and TG analysis between 150600 1C. These results
indicate that the KPW catalyst has a high thermal stability which
can be uses in the esterification reaction of 2-KLGA and methanol.
3.2.2 SURFACE AREA. Table 2 summarizes the results from the
BET surface area measurements of the KPW, HPW and Amberlyst
15 catalysts. The specific surface area of the KPW and HPW
catalysts are 96.37 m
2
g
1
and 11.55 m
2
g
1
, respectively. The
KPW catalyst shows a relatively higher specific surface area
compared to the HPW catalyst. Specifically, the specific surface
area of the heteropoly acid was dramatically increased from
11.55 to 96.37 m
2
g
1
after the exchange process of protons and
Table 1 The chemical composition of the KPW catalyst
Element Chemical composition (%)
W 94.6
K 3.67
P 1.04
Se 0.20
As 0.14
Si 0.122
Al 0.106
Ge 590 (ppm)
V 430 (ppm)
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potassium cations. This is attributed to the potassium cations of
the KPW, which improved the surface area of the catalyst.
3.2.3 FTIR. The FTIR spectra of the KPW catalyst (as shown
in Fig. 2) exhibits the characteristic frequencies of the Keggin
structure (as shown in Fig. 3) in the range of 1100600 cm
1
.
It is found that the KPW catalyst presents strong bands at
1080.7 cm
1
and 986.0 cm
1
, which are characteristic of the
PO
a
and WO
d
absorption bands, respectively. The peaks at
891.3 cm
1
and 808.0 cm
1
are characteristic of WO
b
W bridges
(inter bridges between corner-sharing octahedra) and WO
c
W
bridges (intra bridges between edge-sharing octahedra), respec-
tively (as shown in Fig. 2).
10,11,15
The results of the FTIR spectra
indicate that the Keggin structure is retained in the KPW catalyst.
Fig. 1 TG/DTA of the KPW catalyst.
Table 2 BET specific areas of HPW, KPW and Amberlyst 15 dry
KPW HPW Amberlyst 15 dry
S
BET
(m
2
g
1
) 96.37 11.55 45.00
S
pores
(m
2
g
1
) 43.07
V
pores
(cm
3
g
1
) 0.06
+
pores
(nm) 5.20 o2 25
Fig. 2 FTIR spectra of the KPW catalyst.
Fig. 3 Keggin structure.
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3.2.4 X-RAY DIFFRACTION. The Keggin structure of the catalyst
was also confirmed using XRD analysis. Fig. 4 shows the XRD
patterns of HPW (a) and KPW before use (b). The strong
reflections at 2y values of 19.81, 26.11, 29.51 and 36.21 were
assigned to the Keggin structure of the HPW catalyst (as shown
in Fig. 4(a)).
17,18
The characteristic peaks of the KPW catalyst
were at 2y 21.11, 26.21, 30.11, and 36.41, which was quite similar
to that of HPW, indicating that the Keggin structure was
retained in the KPW catalyst (as shown in Fig. 4(b)).
19
A shift
in the reflections between the KPW and HPW catalysts was due
to the ion exchange between a potassium ion and a proton. This
behavior can be explained by the fact that the atom dimension
of the potassium ion is larger than that of a proton and
therefore caused the shift in the reflection.
3.2.5 ACIDITY MEASUREMENTS TPD OF NH
3
. The ammonia
adsorptiondesorption technique usually enables the determi-
nation of the strength of the acid sites present on the catalyst
surface together with the total acidity.
20
Fig. 5 shows the NH
3
-
TPD profiles of HPW and KPW before use and Table 3 presents
the amount of NH
3
desorbed per g. It was observed that the
number of strong Bronsted and Lewis acid sites of these
catalysts (desorption peaks are distributed beyond 500 1C) is
more than that of the weak and intermediate acid sites of the
catalyst.
5,21,22
In the catalyst, the number of strong acid sites is
about 3 and 2.5 times as high as the number of weak and
intermediate sites, respectively. It is evident from Table 3
that the total acidity for KPW is lower than that for HPW due
to the ion exchange between a potassium ion and proton in the
catalysts.
3.3 Catalyst performance
3.3.1 ELIMINATION OF MASS TRANSFER RESISTANCE. To evaluate the
external mass transfer resistance, the esterification reactions
were carried out at stirrer speeds from 50 to 500 r min
1
while
keeping the rest of the reaction conditions the same. The
results are shown in Fig. 6. It was found that the speed of the
rotating rate had no eect on the esterification rate in the range
of 300500 r min
1
. All further experiments were performed at
500 r min
1
, at which external diusion was eliminated.
In the concept of internal diusion, Xu et al. demonstrated
that the internal diusion can be considered negligible in
the esterification reaction of 2-KLGA when using the Amberlyst
catalyst with particle sizes of 0.7 mm at a stirrer speed of
500 r min
1
.
23
The smaller the particle size, the lower the
eect of internal diusion on the esterification reaction. In our
case, the size of the KPW powder catalyst is much smaller
than that of the Amberlyst catalyst. Therefore, the internal
diusion can be considered negligible in the esterification
reaction of 2-KLGA.
Fig. 4 Wide-angle XRD pattern of (a) HPW catalyst, (b) KPW catalyst before using.
Fig. 5 NH
3
temperature-programmed-desorption profiles of (a) KPW and
(b) HPW.
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3.3.2 EFFECT OF THE INITIAL REACTANT MOLAR RATIOS. 2-KLGA can
be dissolved in methanol at 65 1C with molar ratios of 2-KLGA
to methanol up to 1 : 24 (mol : mol
1
). Therefore, the eect of
the molar ratios of 2-KLGA: methanol on the equilibrium yield
of the esterification reaction was investigated at various molar
ratios of 2-KLGA: methanol: 1 : 24, 1 : 48, 1 : 96, 1 : 192, 1 : 384,
1 : 720 and 1 : 1440 (mol : mol
1
). The results are presented in
Fig. 7. It was found that identical results were observed with
each fraction obtained. This indicated that the molar ratios of
2-KLGA: methanol have no eect on the equilibrium yield of
the esterification reaction with ratios up to 1 : 24 (mol mol
1
).
In addition, by using a large excess of alcohol, the products of
the esterification reaction can be directly pumped into the
column of the HPLC to determine the yield of the reaction
without diluting with methanol. Thus, further experiments
were performed at a 2-KLGA: methanol molar ratio of 1 : 1440
(mol : mol
1
).
3.3.3 CATALYTIC ACTIVITY STUDIES. The catalytic activity of the
heterogeneous KPW catalyst was demonstrated on the esterification
of 2-KLGA and compared with that of other known catalyst systems:
the homogeneous HPW catalyst and commercial heterogeneous
Table 3 Data from the NH
3
temperature-programmed-desorption results of the
catalysts
Temperature
(1C)
Concentration
(mL NH
3
g
1
)
Concentration
(mmol NH
3
g
1
)
HPW
Peak 1 175.9 1.0367 0.0525
Peak 2 591.4 3.1022 0.1570
Total 4.1389 0.2095
KPW before use
Peak 1 159 0.1808 0.0092
Peak 2 297.9 0.0826 0.0042
Peak 3 578.7 0.6447 0.0326
Total 0.9081 0.0460
Fig. 6 The eect of the rotating rate on the yield of the esterification reaction
(the molar ratio of 2-KLGA: methanol of 1: 1440 (mol mol
1
), reaction time:
180 min, 65 1C).
Fig. 7 The yield of the esterification reaction at various molar ratios of 2-KLGA to
methanol.
Fig. 8 The eect of dierent catalysts on the yield of esterification of 2-KLGA with
methanol: (a) HPW catalyst, (b) KPW catalyst, (c) Amberlyst catalyst (the weight
ratio of catalyst to 2-KLGA is 1: 10 (g: g
1
)).
Fig. 9 Evaluation the catalytic heterogeneity of the KPW catalyst: (a) the
esterification reaction when using the KPW catalyst, (b) the esterification reaction
with the filtrate of the KPW catalyst after 120 min.
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Amberlyst 15 catalyst. The yield of the esterification reaction
when using dierent catalysts is presented in Fig. 8. From a
comparison of the results between line (a) and line (b) in Fig. 8,
the yield of the esterification reaction using the KPW catalyst is
slightly lower than that of the esterification reaction using
the homogeneous HPW catalyst. In return, the heterogeneous
process is an environmentally friendly process and greatly
minimizes the steps needed for the separation and recovery of
the product.
5,14,24,25
In a comparison of the results between line
(b) and line (c) in Fig. 8, the yield of the esterification reaction
using the commercial heterogeneous KPW catalyst is slight
higher than that of the reaction using the heterogeneous
Amberlyst catalyst. Thus, due to the useful properties of the
KPW catalyst, it can be regarded as a good heterogeneous
catalyst for the esterification of 2-KLGA.
3.3.4 HETEROGENEITY CATALYST. In order to prove that the
esterification reaction of 2-KLGA using KPW catalysts is truly
a heterogeneous process, we investigated the yield of the
esterification reaction with and without filtration of the KPW
catalyst. Fig. 9(a) shows that the yield of the esterification
reaction using the KPW catalyst depends on time. Another
esterification reaction of 2-KLGA was carried out with the
KPW catalyst at 120 minutes. The KPW catalyst was filtered
out of the reaction mixture and then the reaction was resumed
with the filtrate, in the absence of any externally added catalyst.
The results on the yield of the reaction are shown in Fig. 9(b).
From Fig. 9(a) it was observed that the yield of the reaction
using the KPW catalyst increases with increasing time. From
the result in Fig. 9(b), the yield of the reaction also tended to
increase with increasing time from 0 to 120 min. There was no
increase in the yield of the esterification after filtration of the
KPW catalyst from 120 to 300 min. These results prove that the
KPW catalyst is a real heterogeneous catalyst.
3.3.5 CATALYST RECYCLING. To investigate the catalyst recycling,
the KPW catalyst, used in the first cycle of the esterification
reaction for 300 min, was separated by filtration, washed with
methanol and dried 100 1C for 3 h and returned to a fresh
reaction mixture under identical conditions as the first cycle.
The reaction was repeated to check the second and the third
cycle of the KPW catalyst. The results of initial rates of ester-
ification are shown in Fig. 10. There was no dierence in the
initial rate of the esterification reaction between each cycle,
meaning that the KPW catalysts possess high stability. Thus,
the KPW catalyst can be reuses in the esterification reaction of
2-KLGA.
Fig. 11 shows the XRD patterns of the KPW catalyst after
recycling 3 times. It was found that the characteristic peaks of
KPW after recycling 3 times also tended to be the same as those
of the fresh KPW. There was no dierence in the reflections
between the KPW catalyst before and after recycling 3 times,
indicated that the KPW catalyst can be recycled in the ester-
ification reaction of 2-KLGA.
3.3.6 SCALE UP ESTERIFICATION REACTION. Fig. 12 shows the yield
of the esterification reaction with and without scale up. From a
comparison of the results between line (a) and line (b) in Fig. 12, Fig. 10 The eect of time on the initial rate of esterification in three cycles.
Fig. 11 XRD pattern of the KPW catalyst after recycling 3 times.
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the equilibrium yield of the scaled up reaction is 96% at 360
min, which is quite similar to that of the esterification reaction
without scale up, indicating that with scale up, the esterification
reaction did not aect the equilibrium condition of the reaction.
4. Conclusion
The KPWcatalyst was successfully synthesised by an ion exchange
process between a potassium ion and proton. It was found that
the KPW catalyst shows a high eciency for the esterification of
2-KLGA. The KPW catalyst is a real heterogeneous catalysts in the
esterification reaction. The catalytic activity of the heterogeneous
KPW catalyst is slightly lower than that of the homogeneous
HPW catalyst and is approximate to that of the commercial
heterogeneous Amberlyst catalyst. The KPW catalysts are eective,
environmentally friendly and recyclable. The present procedure
also represents a clean, practical, simple and mild method for the
esterification of 2-KLGA with excellent equilibrium yields of
approximately 96% at 360 min.
Acknowledgements
This work was supported by the National Key Programs on
Research of the sciences and technology for developing the
pharmaceutical industry to 2020 of the Ministry of Industry and
Trade, Vietnam.
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Fig. 12 Yield of the esterification reaction using the KPW catalyst with and
without scale up: (a) with scale up; (b) without scale up.
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