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Catalytic performance of Brønsted acid
sites during esterification of acetic acid with
ethyl alcohol over phosphotungestic acid
supported on silica
Abd El-Aziz A Said,∗ Mohamed M M Abd El-Wahab and Alian Mohamed Alian
Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Abstract: Different ratios of phosphotungestic acid supported on silica gel were prepared by an impregnation
method with PWA loadings ranging from 1 to 30% w/w and calcined at 350 and 500 ◦ C for 4 h in a static air
atmosphere. The catalysts were characterized by thermogravimety (TG), differential thermal analysis (DTA),
X-ray diffraction, FT-IR spectroscopy and N2 adsorption measurements. The surface acidity and basicity of the
catalyst were investigated by the dehydration–dehydrogenation of isopropanol and the adsorption of pyridine (PY)
and 2,6-dimethyl pyridine (DMPY). The gas-phase estrification of acetic acid with ethanol was carried out at
185 ◦ C in a conventional fixed-bed reactor at 1 atm using air as carrier gas. The results clearly revealed that the
catalyst containing 10% w/w PWA/SiO2 is the most active and delivers reaction selectively to ester with 85% yield.
The Brønsted acid site resulting from hydroxylation of tungsten oxide plays the main role in the formation of ester.
2007 Society of Chemical Industry
Keywords: phosphotungestic acid; silica; structure; surface area; acidity; esterification; acetic acid; ethanol
INTRODUCTION and carbon are good supports, and among them silica
Keggin type heteropoly acids (HPAs), as represented is the most often used.
by phosphotungestic acid, are unique and versatile According to Ohlman et al.8 the thermal stability
catalysts since they possess dual catalytic functions of silica-supported heteropolyanions decreases with
of strong acidity and high oxidizing ability.1 – 5 This respect to that of the bulk acid, particularly at low
allows them to be used as catalysts in various liquid concentrations. The chemical interactions between
phase reactions at moderate temperature6 with yields the HPA and the support are a matter of great
higher than those of other currently used acids such interest because a strong interaction could fix the
as sulfuric and perchloric acids. It is important to HPA to the carrier, avoiding the leaching of HPA
emphasize that the acidity of HPA can be controlled in liquid phase reactions9,10 or maintaining a high
by selecting suitable HPA compounds, the partial HPA dispersion in gas-phase reactions. However,
neutralization of the acid and the dispersion degree of the continuous dissolution of HPA in polar medium
different supports.7 was the most severe problem for the supported
Studies of the HPA catalytic behavior have focused samples.11,12 To overcome this problem, gas-phase
mainly on the acids and their salts. However, reactions may be one alternative method. Recently, we
supported systems are of great practical interest have reported that the gas-phase reaction of acetic acid
because the catalytic activity is directly related to with ethyl alcohol on supported metal oxides13 – 16 and
the surface area in some HPA-catalyzed reactions. phosphomolybdic acid17 showed good results towards
One of the main drawbacks of the Keggin type HPA is ester formation. The main advantages of this method
their low specific surface areas (1–10 m2 g−1 ),4,6 which are the possibility of regeneration of the catalysts and
limit application in gas-solid phase reactions. These reduction of the environmental impact.
disadvantages can be overcome by dispersing the HPA On the other hand, the catalytic gas-phase esterifica-
on high surface area supports. The use of a support tion of acetic with ethyl alcohol on phosphotungestic
allowing the HPA to be dispersed over a large surface acid supported on silica, to our knowledge, has not
must result in an increase in its catalytic activity. It has been reported. In this paper, the acid catalysis of the
been found that silica, mesoporous molecular sieves, silica including H3 PW12 O40 is examined for gas-phase
∗
Correspondence to: Abd El-Aziz A Said, Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
E-mail: a.a.said@acc.aun.ed.eg
(Received 17 December 2006; revised version received 20 March 2007; accepted 26 March 2007)
Published online 15 May 2007; DOI: 10.1002/jctb.1704
esterification of acetic acid with ethyl alcohol and their desorption curves using Nova enhanced data reduction
characterization by physical and chemical methods. software (Version 2.13). A highly pure nitrogen gas
In particular, the results of the esterification reaction was used as adsorbate.
are presented and their correlation with Brønsted acid
sites on the catalyst surfaces is discussed. Acidity and basicity determination
The acidity and basicity of the catalysts under inves-
tigation were determined by studying the adsorption
EXPERIMENTAL of pyridine (PY), 2,6-dimethyl pyridine (DMPY) and
Materials the dehydration–dehydrogenation of isopropyl alco-
Acetic acid, ethyl alcohol, isopropyl alcohol, pyridine hol (IPA). The decomposition of IPA was carried
and 2,6-dimethyl pyridine were obtained as pure out in a conventional fixed-bed flow Pyrex glass tube
reagents and were used without further purification. reactor, at atmospheric pressure using nitrogen as a
Silica gel (grade, 60–200 mesh), the support material, carrier gas. The reaction conditions were: 0.5g cat-
and phosphotungestic acid were supplied by Merck alyst weight, 2% IPA in the gas feed, 130 ml min−1
(Darmstadt, Germany). The catalysts were prepared total flow rate and 185 ◦ C reaction temperature. The
by impregnation of silica gel with various loadings measurement of propene yield (%) was made after
of phosphotungestic acid (PWA) dissolved in doubly 2 h to achieve steady-state conditions. The adsorption
distilled water. The samples produced were dried in an of PY and DMPY were carried out by injection of
oven at 100 ◦ C for 24 h before being calcined at 300, different volumes at steady state conditions. The exit
350, 400 and 500 ◦ C for 4 h in a static air atmosphere. feed was analysed by direct sampling of the gaseous
The content of PWA added was varied between 1 and products into a Unicam ProGC gas chromatograph
30% w/w (silica supported PWA denoted SPWA). using a flame ionization detector (FID) with a 10%
PEG 400 glass column (2 m).
Apparatus and techniques
Thermal analysis Catalytic activity measurements
Thermogravimetry (TG) and differential thermal anal- The catalytic activity of the catalysts for the vapor-
ysis (DTA) were performed on heating (at 10 ◦ C phase esterification of acetic acid with ethyl alcohol
min−1 ) test samples to 600 ◦ C in a dynamic atmo- was carried out at 185 ◦ C in a conventional fixed-
sphere of air (40 mL min−1 ) using a computerized Shi- bed flow type reactor at atmospheric pressure using
madzu Thermal Analyzer TA6O Apparatus (Japan). dry air as carrier gas. The system comprised two
reactors. One was used without any catalyst and
filled with glass beads (control reactor), to enable
Fourier transform infrared (FT-IR) spectroscopy
a measurement of the ‘control’ conversion (if any),
FT-IR spectra of the prepared catalysts calcined
which was subtracted from that measured in the flow
at 350 and 500 ◦ C for 4 h were recorded in the
reactor. 0.5 g of catalyst was placed in the middle of the
4000–200 cm−1 region with a Nicolet (Madison, WI,
second reactor with quartz wool. Space in the reactor
USA) 710 FT-IR equipped with data station. Dried
pre- and post-heating zone was filled with glass beads
samples of about 10 mg were mixed with 100 mg
to reduce the effect of auto-oxidation of the substrate
of spectral grade KBr and pressed into discs, under
and products in the gas phase. A mixture of ethanol,
hydraulic pressure.
acetic acid and air was introduced into the reactor after
air was bubbled through ethyl alcohol and acetic acid
X-ray diffraction (XRD) saturators. The total flow rate was fixed at 130 mL
XRD analysis of the test samples was performed with min−1 and used 1.6 and 2.1% ethanol and acetic acid
a Philips (The Netherlands) diffractometer (Model in the gas feed, respectively. The gases after reaction
PW 2103, λ = 1.5418 Å, 35 kV and 20 mA) with were chromatographically analysed by FID with a
a source of CuKα radiation (Ni filtered). An on- Unicam ProGC using a 2 m DNP glass column for
line data acquisition and handling system facilitated analysis of the reaction products of ethanol and acetic
automatic JCPDS library search and match for phase acid on the tested catalysts. The connection between
identification purposes. the reactor and the gas chromatograph (GC) was
heated by resistance wire to prevent any condensation.
Nitrogen gas adsorption Measurements of the conversion and yield (%) were
Nitrogen gas adsorption–desorption isotherms were recorded after 2h from the initial introduction of the
measured at −196 ◦ C using a Nova 3200 instrument reactants into the reactor to ensure the attainment of
(Quantachrom Instrument Corporation, USA). Test the reaction equilibrium, (steady state conditions).
samples were thoroughly outgassed for 2 h at 200 ◦ C to
a residual pressure of 10−4 torr, and the weight of the
outgassed sample was that used in calculations. The RESULTS AND DISCUSSION
specific surface area, SBET was calculated by applying Thermal analysis
the Brunauer-Emmett-Teller (BET) equation. The Figure 1 shows TG and DTA curves of the pure silica,
porosity of the catalysts was determined from the pure PWA and PWA supported on silica. It is seen
X-ray diffraction
XRD patterns determined for the various silica
supported PWA samples with different loadings and
calcined at 350 and 500 ◦ C are illustrated in Figs 3(a)
and 3(b). As shown in Fig. 3(a), the XRD patterns
revealed PWA present in an amorphous state on the
SiO2 support. However, it has been reported that at
low loading (≤10 wt %), PWA forms a finely dispersed
species on a silica surface, and interacting species such
as (≡SiOH2 )+ (H2 PW12 O40 )− may form,8 while at
high loading (≥20% w/w) a PWA crystal phase is
developed on silica. These results are consistent with
those reported by Izumi et al.4 and Kozhevnikov et al.2
They did not obtain the characteristics diffraction
peaks of PWA until the loading exceeded 20% w/w.
Therefore, the XRD patterns obtained for pure PWA
and SiO2 containing 10, 15, 20 and 30% w/w of Figure 3. X-ray diffraction of pure SiO2 , pure PWA and PWA
PWA calcined at 350 ◦ C show only one broad peak supported on silica (different % w/w loadings). (a) calcined at 350 ◦ C
as observed for pure SiO2 and supported PWA up in air for 4 h; (b) calcined at 500 ◦ C in air for 4 h.
Table 1. Variation of specific surface area (SBET ), total pore volume (TPV) and average pore diameter (APD) with calcination temperature for
PWA-SiO2 catalysts
Calcination Temp. SBET TPV APD SBET TPV APD SBET TPV APD SBET TPV APD
PWA % Mixing m2 g−1 cc/g Å m2 g−1 cc/g Å m2 g−1 cc/g Å m2 g−1 cc/g Å
Pure SiO2 288 0.351 397 285 0.360 376 283 0.345 379 281 0.361 373
5 270 0.361 328 274 0.378 384 280 0.384 353 285 0.394 342
7 258 0.353 363 264 0.374 397 272 0.380 363 281 0.394 332
10 254 0.342 341 259 0.312 358 268 0.350 382 277 0.386 331
15 236 0.333 330 245 0.296 345 255 0.328 375 265 0.359 350
20 208 0.227 423 211 0.214 433 217 0.208 365 247 0.340 413
30 166 0.224 430 170 0.182 484 178 0.172 373 218 0.309 409
silica network. These observations are in accordance Acidity and basicity determination
with earlier findings indicating the reliability of the Determination of the surface acidic and basic sites
preparation method.32 – 34 Results for the catalytic dehydration–dehydrogenation
of IPA over PWA supported on silica calcined at 350
and 500 ◦ C are shown in Fig. 4. IPA dehydration has
Surface area and porosity
been used by several authors35,36 as a test reaction
The surface area of PWA supported on silica gel
to determine the acidity of different catalysts and
samples calcined at 300, 350, 400 and 500 ◦ C
it proceeds quickly on weak acid sites.37 In the
was determined on the basis of nitrogen adsorption
working conditions used, it was found that IPA reacts
and desorption measurements. The isotherms show
on the bare support and on the PWA supported
type II BDDT classification closed hysteresis loops
catalysts selectively to propene. In samples calcined
at intermediate relative pressures. The pore size
at 350 ◦ C, the addition of 3% w/w PWA, as indicated
distribution of these samples was determined from
in Fig. 4, sharply increases the conversion of IPA to
the desorption data. The specific surface area of the
propene. This increase reaches a maximum for the
investigated catalysts, SBET , was calculated from these
addition of 10% w/w, and remains constant up to
measurements and is shown in Table 1.
an addition of 30% w/w. Figure 4 also shows the
It is clear from Table 1 that pure SiO2 calcined
results of the decomposition reaction of IPA catalyzed
at 300–500 ◦ C has SBET values between 288 and
by PWA/SiO2 calcined at 500 ◦ C. It is seen that the
281 m2 g−1 . Results also show that the addition of
addition of PWA into SiO2 increases the yield of
PWA catalyst into the SiO2 support led to a continuous
propene steadily, passing through a maximum at 7%
decrease in SBET values up to the addition of 30% w/w
w/w, followed by a continuous decreases up to 30%
PWA for all calcination temperatures. In contrast,
w/w addition. It is clear from the above results that
samples containing 20 or 30% w/w exhibited a
the catalysts calcined at 350 ◦ C exhibits higher activity
remarkable decrease in surface area. At even higher
towards propene formation than the catalysts calcined
coverage, crystallization of PWA takes place, filling
at 500 ◦ C.
the pores of the support. The much lower surface
area at 20 or 30% w/w addition is due to the strong
influence on the number of pores and the formation
of a monolayer PWA surface, which has lower surface 100 350 °C
area. It is worth noting from the above results that the 500 °C
SBET of the prepared catalysts increased on increasing
80
the calcination temperature. This behavior may be
% Conversion
The above results show that catalyst containing −−−→ C3 H6 + + H+ .. O2− ku (4)
10% w/w PWA has sufficient acid sites to produce
the dehydration pathway for IPA better than that In this mechanism, 2-propanol is first protonated at
of unsupported acid. The difference between the the acidic sites (step 1) of the heteropoly oxometalat
performances of the supported catalysts is explained leading to perturbation of the electron density
on the basis of PWA interaction with the support via distribution in the protonated species and a weakening
the creation of more acidic sites, which encourage ultimate scission of the C–O bond.30,43 The resulting
the dehydration reaction and the effect of percentage carbocation C3 H7 + (step 2) is found to be associated
loading on the dispersion of the acid and in turn, with the (presumably terminal) oxygen atoms of the
the catalyst performance. The selectivity to propene heteropoly oxometalate anions30,43 (step 3). After that
as a function of percentage mixing of PWA is 100%. the dehydration cycle may be completed via one
Selectivities were not influenced by IPA conversion in reaction path, i.e. propene (step 4) production.
the conversion range covered (1–30% w/w). The following conclusions can be drawn from
Significant changes in the number and nature of catalytic dehydration of IPA over PWA supported
(Brønsted or Lewis) acid sites have been observed on silica:
with changes in PWA content. Yet, IPA dehydration
selectivities were not affected by these structural (i) The catalysts calcined at 350 ◦ C possess higher
changes, suggesting either that only one type of acid activity towards propene formation than the
site (Brønsted or Lewis) catalyzes the dehydration catalysts calcined at 500 ◦ C; (ii) the decrease in
reaction or that the different types of sites present acidity of the catalysts calcined at 500 ◦ C may
lead to identical selectivities. However, the ability of be attributed to decomposition of the Keggin
the catalyst to break the C–OH bond during the structure to WO3 ; and (iii) the prepared catalysts
chemisorption itself by polarizing the C–O bond and exhibit an acidic character with selectivity 100%,
leaving the O–H bond intact may be important in which reflects that there are no basic sites available
catalyzing the dehydration reaction. This is facilitated on the catalyst surfaces.
by the presence of acidic groups.29 In agreement with
such a suggestion; Okuhara et al.38 reported that, on Adsorption of pyridine and 2,6-dimethyl pyridine over
Nax H3−x PW12 O40 , the formation of ethylene from 10% w/w PWA supported on SiO2 calcined at 350 and
ethyl alcohol requires fission of the C–O bond on 500 ◦ C
the Brønsted acid sites. Moreover, it is known that It is known that the chemisorption of pyridine (PY)
propene formation requires Brønsted acid sites.39 and 2,6-dimethyl pyridine (DMPY) can be used
Based on the above discussion, one may conclude as basic probe molecules to determine the acidity
that, the dehydration activity of the catalysts is mainly of catalyst.44 It was reported that PY is selectively
due to; (i) the Brønsted acidity of the catalysts, aided adsorbed on both Brønsted (B) and Lewis (L) acid
to a large extent by the water adsorption, which sites.45,46 On the other hand, DMPY is selectively
is known to create Brønsted sites;39 (ii) the flexible adsorbed on Brønsted acid site47,48 but not Lewis sites
nature of the secondary structure of heterocompounds, because of the steric hindrance of two methyl groups.
which allows the polar molecule, e.g. isopropanol, to So the difference between PY and DMPY adsorption
penetrate the bulk of the solid;38 and (iii) the existence is a measure of the Lewis acid sites.
of the Keggin structure, which has an influence in The poisoning of the active surface sites of 10% w/w
stabilizing the reaction intermediates. PWA supported on silica catalysts (SPWA10) in IPA
Accordingly, it is highly probable that the active conversion was performed through saturation of the
sites in the conversion of 2-propanol are Brønsted in acid sites with PY or DMPY according to the following
nature and it is most likely that the reaction proceeds procedures. After measuring the conversion activity
via a carbonium ion mechanism. Such a mechanism of the SPWA10 catalyst at 185 ◦ C the catalyst was
was recommended by Hayashi and Moffat40 – 42 for the injected with different volumes of PY or DMPY in the
dehydration of alcohols over heteropoly compounds. stream of the reactants using N2 as a carrier gas. The
According to the above discussion, the dehydration results obtained are shown in Figs 5 and 6. Figure 5
reaction mechanism may be systemized as: shows the influence of PY or DMPY additions on
the distribution products of IPA reaction on SPWA10
C3 H7 OH + H+ . . . . O2− ku calcined at 350 ◦ C. The results indicate that PY and
DMPY suppressed IPA dehydration activity. Thus,
−−−→ C3 H7 OH2 + . . . O2− ku (1)
the chemisorbed PY and DMPY decrease the yield of
+
C3 H7 OH2 the propene by ≈90 and 80%, respectively.
From the above results, we see that the volume of PY
−−−→ C3 H7 + + H2 O (2)
required to inhibit the activity of the catalysts towards
+
C3 H7 + O 2−
ku propene is higher than that of DMPY by about 10%.
+ This value corresponds to the presence of Lewis acid
−−−→ C3 H7 + . . . . . . O2− ku (3)
sites. Thus, the SPWA10 catalyst is an acidic catalyst
+
C3 H7 + . . . . . . O 2−
ku with major Brønsted acid sites and minor Lewis
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