Applied Catalysis A: General 175 (1998) 43±53

Skeletal isomerization of 1-butene on 12-tungstophosphoric

acid supported on zirconia
E. LoÂpez-Salinasa,*, J.G. HernaÂndez-CorteÂza, Ma.A. CorteÂs-JaÂcomea, J. Navarretea,
Ma.E. Llanosa, A. VaÂzqueza, H. ArmendaÂriza, T. LoÂpezb
a
Instituto Mexicano del PetroÂleo, SubdireccioÂn de TransformacioÂn Industrial, Eje Central LaÂzaro CaÂrdenas 152, 07730 MeÂxico DF, Mexico
b
Universidad AutoÂnoma Metropolitana-Iztapalapa, PO Box 55-534, 09340 MeÂxico DF, Mexico

Received 3 January 1998; received in revised form 1 June 1998; accepted 1 June 1998

Abstract

A series of 0±25 wt% H3[W12PO40] (TPA) impregnated on freshly precipitated Zr(OH)4 were prepared. The solids were
characterized by a Hammett indicator method, speci®c surface area and pore size measurements, pyridine adsorption FTIR
and later tested as catalysts in the isomerization of 1-butene. Maximum acid strength of 5±20 wt% TPA/ZrO2 calcined at
673 K is H0ˆÿ9.3, but dried samples (393 K) showed near superacid strength, i.e. H0ÿ13.75. The sites are mainly strong
Lewis acids, but TPA supported on stabilized ZrO2 (calcined at 773 K) shows both strong Brùnsted and Lewis acidity. TPA
addition to hydrated Zr(OH)4 stabilizes the surface area of the ®nal calcined material in comparison with that of pure ZrO2; the
greater the TPA content the higher the resulting surface area. Skeletal rearrangement of 1-butene to isobutylene proceeds on
5±25 wt% TPA/ZrO2 but not on pure ZrO2, the greater the TPA content the higher the initial selectivity towards isobutene. In
contrast, 20 wt% TPA supported on SiO2 formed no isobutylene. # 1998 Elsevier Science B.V. All rights reserved.

Keywords: 12-Tungstophosphoric acid; Zirconia; Solid acid; Skeletal 1-butene isomerization

1. Introduction stabilized zirconia (e.g. depletion of OH groups).

One of the main reasons that has drawn great
attention to the use of hydrated zirconia as a precursor
of a catalyst carrier is the fact that its surface OH
groups are able to undergo a chemical reaction or
strong interaction with incorporated second compo-
nents such as oxo-anions (as described below) and
transition metal cations [1±3], respectively. Upon
thermal activation, hydrated zirconia yields catalysts
with very different properties from those obtained by
incorporating the second component on previously
*Corresponding author. E-mail: esteban@tsekub.imp.mx
For instance, the extensive studies of Hino and Arata
[4±8] showed that sulfate addition to some freshly
precipitated metal oxides such as Fe2O3, TiO2, ZrO2
and HfO2, yielded solids with very strong acid proper-
ties. These solids which have an acid strength higher
than 100% H2SO4 (H0ˆÿ11.9) are called solid super-
acids (SSA). Most attention has been paid to sulfated
zirconia, ®rst reported by Holm and Bailey [9] in
1962, because it has shown the highest acid strength
among sulfated metal oxides (H0ÿ16.04). Jin et al.
[10] ascribed the strong acidity of these solids to the
electron withdrawing surface-bonded (SO4)ˆ anion,
creating a coordinatively unsaturated and electron

0926-860X/98/$ ± see front matter # 1998 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00198-7
44 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53
de®cient metal center that behaves as a strong Lewis
acid site. The addition of sulfate to ZrO2 yields not
only a solid acid 104 times stronger than 100% H2SO4
[11] but also stabilizes the tetragonal phase of zirconia
and consequently its speci®c surface area [12]. How-
ever, Babou et al. [13] using quantum chemistry
calculations suggested that the acidity of sulfated
zirconia corresponds, roughly speaking, to that of pure
H2SO4, i.e. this solid is not really superacidic but only
strongly acidic. Recently, we have corroborated these
results by DRIFTS and 1 H MAS NMR spectroscopy
studies on sulfated zirconias [14].
Instead of sulfate, other oxo-anions like tungstate
and molybdate anions impregnated on hydrated zir-
conia produced SSA: WO3/ZrO2 (H0ÿ14.52) and
MoO3/ZrO2 (H0ˆÿ12.7) [15]. The addition of Fe and
Mn to SOˆ 4 =ZrO2 has a promoting effect on its acid
strength, being three orders of magnitude more active
in the isomerization of n-butane than SO4/ZrO2
[16,17]. A recent report on the synthesis of B2O3/
ZrO2 (H0ˆÿ13) obtained by impregnation of boric
acid, which has low acidity (pKaˆ5.0), has con®rmed
that the interaction of oxo-anions with hydrated zir-
conia indeed results in the formation of stronger acid
sites than those of the algebraic sum of the single
components [18].
Heteropolyacids (HPAs) are another class of ef®-
cient catalysts for various reactions in the liquid-
phase, e.g. dehydration, etheretion, esteri®cation
and isomerization. They usually exhibit much higher
catalytic activities than ordinary solid acids such as
zeolite and silica±alumina [19]. HPAs are formed by
the condensation of more than two different oxo-
anions, for instance,
12‰WO4 Šˆ ‡ ‰HPO4 Šˆ ‡ 23H‡
! ‰W12 PO40 Š3ÿ ‡ 12H2 O
The HPAs having the Keggin structure are ther-
mally more stable and easy to synthesize than other
HPAs. Due to their relatively small surface areas (1±
10 m2 gÿ1) [20], HPA compounds are commonly
supported on SiO2, SiO2±Al2O3, TiO2 or activated
carbon when used as catalysts for gas±solid phase
reactions [21]. Supports such as alumina and magnesia
which exhibit surface basicity bring about the decom-
position of HPAs [22,23]. Due to the low acidity of
ZrO2 and its potential interaction with HPAs, their
addition to hydrated ZrO2 could yield strong solid
acids.
Attempting to develop strong solid acid catalysts,
we selected the 12-tungstophosphoric acid (TPA),
since it shows the highest acidity among Keggin-type
HPAs, and impregnated it on freshly precipitated
ZrO2. In this study we report on the preparation
method of x wt% H3[W12PO40]/ZrO2 (xˆ0±25 wt%),
their characterization and catalytic evaluation in the
skeletal isomerization reaction of 1-butene.
2. Experimental
2.1. Preparation of H3[W12PO40]/ZrO2
The solids precipitated from zirconium salts
are complexes with a general formula (ZrOx-
(OH)4ÿ2x
yH2O)n, where the relative amount of oxy-
gen, hydroxide and water depends mainly on the rate
of precipitation [24] and the precursor salt [25,26]. For
the sake of clarity hereinafter they will be referred to
simply as hydrated or freshly precipitated ZrO2. The
hydrated ZrO2 in this study was prepared by slow
precipitation of an aqueous ZrO(NO3)2
xH2O solution
with aqueous NH4OH. The pH of the mixture was kept
as 10 by controlling the addition of the two solutions.
The white gel obtained was repeatedly washed with
deionized water and separated in a centrifuge. After
this, the white paste was dried in an oven at 373 K for
12 h. The impregnation of the heteropolyacid on the
hydrated zirconia was carried out as follows: suf®cient
amounts of an ethanolic solution of 2.510ÿ3 M
reagent grade H3[W12PO40]
6H20 to obtain 5.0,
10.0, 16.6, 20.0 and 25.0 wt% on ZrO2, were poured
onto hydrous ZrO2. The materials were transferred to a
rotary evaporator where ethanol was evaporated at
353 K. After this, the solids were stored in a desiccator
containing both anhydrous CaO and silica gel. These
solids will be hereinafter referred to as 5TPA/Z,
10TPA/Z, 16.6TPA/Z, 20TPA/Z and 25TPA/Z.
2.2. Preparation of H3[W12PO40]/SiO2
Since SiO2 has been the preferred catalyst support
of a variety of heteropoly compounds, SiO2 was
prepared by a sol±gel method for comparison. First
74 cm3 of tetraethyl orthosilicate (TEOS) was dis-
 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53
solved in 48 cm3 of anhydrous ethanol, heated at
353 K and stirred for 2 h in re¯ux conditions. After
this, the solution was cooled down to 268 K in an ice-
salt bath. A mixture made up of 48 cm3 of H2O,
37 cm3 of ethanol and 2 cm3 of 1 N H2SO4 was added
dropwise to the TEOS±ethanol solution. The resulting
mixture was kept for 3 h at 268 K. Then, the sol was
heated at 353 K at re¯ux conditions for 12 h. After
this, the mixture was dried in a rotary evaporator at
393 K. 16.6 and 20.0 wt% TPA were impregnated on
dried SiO2 as described above for Zr(OH)4. These
solids will be referred to as 16.6TPA/S and 20TPA/S.
2.3. Characterization techniques
The measurement of Hammett acid strength (H0)
was carried out by exposing previously evacuated
samples (0.1 g) at 393 K for 4 h to a benzene solution
of selected Hammett indicators: (2-bromo-4,6-di-
nitroaniline, pKaˆÿ6.6; anthraquinone, pKaˆÿ8.2;
2,4,6-trinitroaniline, pKaˆÿ10.1; p-nitrotoluene,
pKaˆÿ11.35; p-nitrochlorobenzene, pKaˆÿ12.7;
2,4-dinitrotoluene, pKaˆÿ13.75).
The nature of the acid sites (Brùnsted or Lewis) was
determined in a Fourier transform infrared (FTIR)
Nicolet 710SX spectrometer by means of pyridine
adsorption. The equipment was furnished with a cell
with interchangeable windows in which the samples,
previously pressed into thin self-supported wafers,
were placed in order to be evacuated (110ÿ6 Torr)
in situ at the calcination temperature for 30 min, and
then, after cooling down to room atmosphere, to
adsorb pyridine.
The thermal programmed desorption of NH3 (NH3-
TPD) was used to estimate the amount and strength of
acid sites formed on the surface of TPA/Z. First, a
sample of previously calcined TPA/Z was heated
(10 K minÿ1) in ¯owing helium (Linde UHP,
99.999%) until reaching the indicated temperature
and kept for 60 min. After this, the sample was
allowed to cool down to room temperature and
exposed to ¯owing NH3 (20% in He) for 30 min.
Later, the system was purged at 303 K for 30 min
with helium in order to eliminate weakly adsorbed
NH3. The temperature of the sample rose linearly
(10 K minÿ1) from ambient to the indicated tempera-
tures. NH3 concentration was monitored by means of a
thermal conductivity detector. The amount of NH3
45
was quanti®ed by comparing the areas under the curve
in the sample with those of known amounts of NH3
injected after each run. The NH3-TPD analysis was
carried out in an AMI-3 apparatus from Altamira
Instruments. The amount of acid sites per Keggin unit
(KU) in TPA/Z catalysts was calculated by dividing
the difference between the amount of total acid sites
and that of pure ZrO2 by the amount of (KU) contained
in each catalyst, i.e., assuming that all TPA were
accessible to ammonia molecules and that the acid
sites in pure ZrO2 would be added to those generated
by incorporating the TPA.
Speci®c surface areas using the BET method with
N2 adsorption at 77 K and pore size distribution by
means of N2 adsorption±desorption isotherms were
measured in an ASAP-2000 apparatus from Micro-
meritics.
Catalytic evaluation of TPA/Z, and other solids for
comparison, was carried out in a ®xed bed ¯ow
microreactor connected to a gas chromatograph
equipped with a silica fused capillary column (KCl/
Al2O3, 50 m, i.d. 0.32 mm) and a ¯ame ionization
detector. 1-Butene, N2 and H2 were of reagent grade
(99.99% Matheson and Infra, respectively) and were
further puri®ed by passing them through a dryer
containing molecular sieve. The previously calcined
catalysts were heat-treated in situ at 673 or 773 K, as
indicated, in a stream of N2 for 1 h before reaction and
then cooled to reaction temperature. Isomerization of
1-butene was carried out with 0.1 g (mesh 150±200) of
catalyst at 673 K, 101.33 KPa, 1-butene/H2
(molar)ˆ1 and a total WHSVˆ25.2 hÿ1. The conver-
sion of 1-butene is de®ned as the percentage of 1-
butene converted to all products.
3. Results and discussion
3.1. Acid strength enhancement
The highest acid strength of ZrO2 calcined in air at
773 K for 3 h is H0 between ‡1.5 and ‡3.3 [27].
Accordingly, ZrO2 is considered a weakly acidic oxide
made up mainly of Lewis-type acid sites [28]. On the
other hand, solid H3[W12PO40]
6H2O contains acid
sites stronger than H0ˆÿ8.2 [29]. Table 1 shows the
Hammett acid strength of various TPA/Z catalysts heat
treated at indicated temperatures. The TPA/Z materi-
46 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53

Table 1
Hammett acid strength of TPA/Z catalysts

TPA/Z catalysts Hammett acid strength (H0)

TPA (wt%) Calc. T (K) ÿ6.6 ÿ8.1 ÿ9.3 ÿ10.1 ÿ11.35 ÿ12.70 ÿ13.75
16.6 393 ‡ ‡ ‡ ‡ ‡ ‡ ‡
5.0 673 ‡ ‡  ± ± ± n.a.
10.0 673 ‡ ‡  ± ± ± n.a.
16.6 673 ‡ ‡ ‡ ± ± ± n.a.
20.0 673 ‡ ‡ ‡ ± ± ± n.a.
10.0 773 ‡ ± ± n.a. n.a. n.a. n.a.
16.6 773 ‡ ± ± n.a. n.a. n.a. n.a.
20.0 773 ‡ ± ± n.a. n.a. n.a. n.a.
n.a.: not analyzed.

als show superacid strength (H0ÿ13.75) when dried

at 393 K. However, when the samples are calcined at
673 K the maximum acid strength decreases to
H0ˆÿ9.3. Calcination at 773 K further decreases
the maximum acid strength to H0ÿ6.6.

3.2. Nature of acid sites

In order to throw light on the type of acid sites

(Lewis or Brùnsted) on TPA/Z, a 20TPA/Z calcined at
673 K was exposed to pyridine and the IR spectra were
recorded from 1700 to 1400 cmÿ1 (Fig. 1). Spectrum
(a) taken after pyridine adsorption at ambient tem-
perature, shows:
(1) very weak bands at 1637, 1546 and 1533 cmÿ1,
ascribed to Brùnsted acidity [30],
(2) intense bands at 1610 and 1442 cmÿ1, ascribed
to strong Lewis acidity [30] and
(3) two weak bands at 1595 and 1577 cmÿ1, arising
from weak Lewis acid sites.
The band at 1488 cmÿ1 has been ascribed to both Fig. 1. FTIR spectra of pyridine adsorbed on 20 wt% TPA
Lewis and Brùnsted acid sites [30]. When the sample supported on hydrated zirconia and then calcined at 673 K.
is evacuated at 373 K for 15 min (spectrum (b)) the Spectrum recorded after evacuating at: (a) room temperature, (b)
bands ascribed to Brùnsted and weak Lewis sites 373 K, (c) 473 K, (d) 573 K, and (e) 673 K. (f) Reference spectrum
mostly disappear. However, the bands at 1610 and taken before pyridine adsorption.
1422 cmÿ1 are visible when evacuating at 473, 573
and 673 K for 15 min (spectra (c), (d) and (e), respec- 773 K. Accordingly, the TPA Keggin structure can
tively). These results indicate that these bands arise be retained below 723 K [31,32].
from very strong Lewis acid sites. A broad band at ca. Nevertheless, it has been reported that pure TPA is
1540 cmÿ1 appears when the sample is heat treated at characterized by mainly Brùnsted-type acidity [19].
673 K (spectrum (e)) and is probably associated to the The impregnation of TPA on a freshly precipitated
structural transformation of metastable tetragonal to ZrO2 which upon further calcination undergoes dehy-
monoclinic ZrO2, which occurs between 673 and droxylation and concomitant structure transformation
 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53
Fig. 2. FTIR spectra of pyridine adsorbed on 20 wt% TPA
supported on zirconia previously calcined at 773 K. Spectrum
recorded after evacuating at: (a) room temperature, (b) 373 K, (c)
473 K, (d) 573 K, and (e) 673 K. (f) Reference spectrum taken
before pyridine adsorption.
implies that some (OH) groups may react with TPA
protons to form water. In fact, careful experiments by
NH3-TPD, temperature programmed reduction and
temperature programmed exchange, have shown that
protons can be removed from the anhydrous
H3[W12PO40], but only when accompanied by loss
of anionic oxygen atoms [32,33]. To clarify this
behavior, a 20 wt% TPA supported on a previously
calcined ZrO2 (at 773 K) was examined by pyridine
adsorption FTIR. Fig. 2 shows that the bands ascribed
to Brùnsted acid sites (1639 and 1538 cmÿ1) are not
only more prominent than the corresponding ones in
Fig. 1, but also can be clearly observed up to 673 K,
indicating that these Brùnsted sites are strong. In this
case, the near absence of surface (OH) groups on
ZrO2, allowed protons to remain attached to the
heteropolyanion unit until reaching a temperature at
which protons react with oxometalate anionic oxygen
and depart as water [32]. Assuming that some TPA
protons react with (OH) groups in hydrated zirconia, it
would be reasonable to expect that some terminal
47
Fig. 3. NH3 temperature programmed desorption patterns of: (a)
ZrO2, (b) 5TPA/Z, (c) 10TPA/Z, (d) 16.6TPA/Z, (e) 20TPA/Z and
(f) 25TPA/Z.
WˆO bonds of TPA might react with partially dehy-
droxylated …Zr…ÿO†3 †‡ species to form anchored TPA
species, e.g. the formation of Zr±O±W bonds. These
TPA species would exert an electron withdrawing
effect on surface Zr4‡ cations, making them to behave
as strong Lewis acid sites. Accordingly, the strongly
acidic properties of TPA/Z could be attributed to
electron-withdrawing effects similar to those ascribed
to Zr-bonded sulfate groups [10±12].
3.3. Amount of acid sites on H3[W12PO40]/ZrO2
The relationship between the amount of supported
TPA and the total number of acid sites on ZrO2 was
examined by means of the NH3-TPD method. Fig. 3
shows the NH3-TPD patterns of 0, 5, 10, 16.6, 20 and
25TPA/Z calcined at 673 K for 4 h. Single ZrO2 shows
a desorption pattern made up of two broad peaks with
maximum intensity at 443 and 543 K (pattern (a)). The
desorption patterns of 5-20TPA/Z show similar shapes
to that of ZrO2, but the intensity of desorption peaks
48 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53

Table 2
Total amount and density of acid sites in TPA/Z catalysts calcined at 673 K, as a function of the TPA content

TPA/Z catalysts Acid sites per KU Total acid sitesa Surface areaa Density of acid sitesb
(wt% TPA) (mol NH3/mol KU) (mmol NH3 gÿ1) (m2 gÿ1) (mmol NH3 mÿ2)

0.0 ± 617 132 4.7

5.0 9.1 776 149 5.2
10.0 5.7 812 159 5.1
12.5 5.2 843 173 4.9
16.6 5.3 922 183 5.2
20.0 5.6 1007 181 5.6
20.0c ± 518 132 3.9
25.0 11.8 1628 n.a. ±
a
Measured after calcining at indicated temperatures for 4 h. KU: Keggin unit. n.a.: not analyzed.
b
Total acid sites divided by surface area.
c
TPA impregnated on previously calcined ZrO2.

increases as the TPA content rises. Additionally, the
peak at high temperature becomes more prominent as
the TPA content increases (compare pattern (d) with
(a)). Clearly, the addition of the TPA to hydrated
zirconia increases the number of acid sites expressed
per gram of solid. For instance, the number of acid
sites on 25TPA/Z is 2.6 times greater than that in pure
ZrO2. In Table 2, the amount of acid sites per KU in
10±20 TPA/Z calcined at 673 K is approximately ®ve.
Accordingly, unsupported TPA absorbed ®ve ammo-
nia molecules per KU, after heating and evacuating at
473 K [32]. Since only three ammonia molecules are
needed to neutralize the TPA polyanion, the excess
ammonia may correspond to acid sites formed on
zirconia because of TPA interaction. However, when
TPA/Z catalysts were calcined at 773 K a dramatic
increase in the number of acid sites per KU as well as
in the density of acid sites is observed (Table 3). These
results can be rationalized by assuming that the KU
decomposes between 623 and 773 K [31,32]. These
results suggest that TPA addition does not increase the
total number of acid sites per unit area, but modi®es
their distribution.
In order to elucidate the contribution of ZrO2 sup-
port on the acidic properties of TPA/Z catalysts,
16.6 wt% TPA was impregnated on a freshly prepared
SiO2. The number and the density of acid sites present
on 16.6TPA/S as well as those in pure SiO2 are
reported in Table 4. Unlike in the case of the TPA/
Z catalysts, the addition of TPA to SiO2 neither
increases the total number of acid sites nor their
density. These results strongly suggest that the inter-
action of TPA with ZrO2 plays a crucial role in the
development of acid sites.

Table 3
Total amount and density of acid sites in TPA/Z catalysts calcined at 773 K, as a function of the TPA content

TPA/Z catalysts Acid sites per KU Total acid sitesa Surface areaa Density of acid sitesb
(wt% TPA) (mol NH3/mol KU) (mmol NH3 gÿ1) (m2 gÿ1) (mmol NH3 mÿ2)

0.0 ± 500 82 6.1

5.0 14.8 757 91 8.3
10.0 15.4 1029 110 9.4
12.5 15.0 1150 141 8.2
16.6 12.5 1218 123 9.9
20.0 6.1 924 134 6.9
20.0a ± 369 82 4.5
25.0 10.9 1435 n.a. ±
a
Measured after calcining at indicated temperatures for 4 h. n.a.: not analyzed.
b
Total acid sites divided by surface area.
 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53 49

Table 4
Total amount and density of acid sites in SiO2 and 16.6TPA/S catalysts as a function of the calcination temperature

TPA/S catalysts Total acid sitesa (mmol NH3 gÿ1) Surface areaa (m2 gÿ1) Density of acid sitesb (mmol NH3 mÿ2)

673 K 773 K 673 K 773 K 673 K 773 K

SiO2 79 109 383 288 0.2 0.4

16.6TPA/S 80 68 469 345 0.2 0.2
a
Measured after calcining at indicated temperatures for 4 h.
b
Total acid sites divided by surface area.

3.4. Textural properties
Table 5 shows the effect of the addition of the TPA
on the speci®c surface area, pore volume and mean
pore diameter of TPA/Z catalysts. Pure ZrO2 calcined
at 673 K shows a surface area of 132 m2 gÿ1. The
addition of the TPA results in a considerable stabiliza-
tion of the surface area of ZrO2. For instance, 20TPA/
Z calcined at 673 K shows a 37% increase in surface
area in comparison with that of ZrO2. A similar
stabilization effect can be observed in a series of
TPA/Z calcined at 773 K, in spite of the fact that in
comparison with those calcined at 673 K, a 40±60%
reduction in speci®c surface area occurred. A similar
stabilization effect takes place on a freshly precipi-
tated SiO2, dried at 393 K and later impregnated with
the TPA solution. For instance in Table 5, 16.6TPA/S
shows a surface area 22% and 20% higher than that of
pure SiO2, calcined at 673 and 773 K, respectively. It
has been reported that the addition of sulfate anions to
freshly precipitated ZrO2 results in solids with much
higher surface areas when calcined at 773±873 K in
comparison with unsulfated ZrO2, thus showing a
stabilizing effect on the structure of the calcined
zirconia [34].
Pore size distributions of ZrO2 and those of
5±20TPA/Z calcined at 673 K are shown in Fig. 4.
Here, ZrO2 shows an almost unimodal distribution
of 75 AÊ mean pore diameter. Upon TPA additions to
ZrO2, the resulting solids become bimodal with a
clear increase in the population of 30±40 A Ê pores.
These results can be explained considering that
one KU has about 10 A Ê diameter, and its location
in the bigger pores (ca. 75 A Ê ) could yield smaller
pores, e.g. those in the lower mesoporous region
(30±40 A Ê ).

Table 5
Specific surface area, pore volume and mean pore diameter of TPA/Z and TPA/S catalysts as a function of TPA content and calcination
temperature

TPA Calc. Support Surface area Pore volume Mean pore

(wt%) T (K) (m2 gÿ1) (cm3 gÿ1) Ê)
diameter (A

0.0 673 ZrO2 132 0.289 69

5.0 673 ZrO2 149 0.277 63
10.0 673 ZrO2 159 0.287 61
16.6 673 ZrO2 183 0.279 55
20.0 673 ZrO2 181 0.277 57
0.0 773 ZrO2 82 0.203 73
5.0 773 ZrO2 91 0.246 87
10.0 773 ZrO2 110 0.254 77
16.6 773 ZrO2 123 0.249 69
20.0 773 ZrO2 134 0.249 65
0.0 673 SiO2 383 0.139 23
16.6 673 SiO2 469 0.181 25
0.0 773 SiO2 216 0.104 25
16.6 773 SiO2 345 0.167 25
50 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53

arrangements depending on the catalyst type and

Fig. 4. Pore size distribution of: (a) ZrO2, (b) 5TPA/Z, (c) 10TPA/
Z and (d) 20TPA/Z.
3.5. Isomerization of 1-butene
Isomerization of n-butenes (1-, cis- and trans-but-2-
ene) can occur by both double bond shift and skeletal
reaction conditions. Rearrangements of the carbon
skeleton (Wagner±Meerwein arrangements), e.g. to
obtain isobutylene from 1-butene, require very strong
acid sites.
Table 6 shows the results of 1-butene isomerization
using 0±25 TPA/Z and 16.6TPA/S (as a comparison).
Pure ZrO2 (calcined at 673 K) shows 50% conversion
and a cis/trans 2-butene ratio of 1.43. No isobutylene
formed on ZrO2, indicating the absence of strong acid
sites. It has been reported that a sulfated zirconia
shows more than twice the conversion of 1-butene
to 2-butene at 394 K compared with unsulfated zirco-
nia [35]. The overall conversion increased to 71% on
5TPA/Z and brought about the formation of isobuty-
lene (6.8% selectivity at 5 min). Increasing the amount
of the TPA on ZrO2 from 10 to 20 wt% increases the
isobutylene selectivity from 9.5 to 17.1%, respec-
tively. Composition of n-butenes at 673 K after
5 min using 20TPA/Z catalyst is (1-Cˆ ˆ ˆ
4 : t-C4 : c-C4 )
1:1.3:1, while that at equilibrium is 1:1.8:1 [36].
The increase in isobutylene selectivity as a function
of the TPA content is associated with relatively more
strong acid sites, as discussed in Section 3.3, which
are responsible for the double bond isomerization. In
spite of its higher acid site density and acid site
number per KU, the 25TPA/Z catalyst did not show

Table 6
Conversion of 1-butene and selectivity towards products using TPA/Z and TPA/S catalysts
a
TPA Calc. Support 1-Cˆ
4 conversion Selectivity (mol%)a
(wt%) T (K) (mol%)
Cˆ
3 iC4 nC4 iCˆ
4 t2Cˆ
4 c2Cˆ
4 Othersc

0.0 673 ZrO2 50 0.4 0.0 0.0 0.0 42.1 57.5 0.1
5.0 673 ZrO2 71 0.5 0.3 0.4 6.8 49.1 42.9 0.0
10.0 673 ZrO2 72 1.5 0.4 2.5 9.5 46.6 39.5 0.2
16.6 673 ZrO2 75 3.4 1.3 1.3 16.2 41.6 34.1 2.2
16.6 673 ZrO2b 71 1.1 0.2 0.6 13.0 45.0 40.1 0.0
20.0 673 ZrO2 75 2.7 1.3 1.3 17.1 42.2 35.4 2.8
25.0 673 ZrO2 76 3.6 1.6 1.6 17.1 39.1 33.6 3.4
10.0 773 ZrO2 72 0.0 0.0 0.3 6.9 50.0 42.4 0.1
16.6 773 ZrO2 73 2.0 0.3 0.7 13.0 45.2 38.0 0.9
20.0 773 ZrO2 74 2.1 0.5 1.2 13.2 44.9 37.9 0.2
16.6 673 SiO2 56 0.0 0.0 0.0 0.0 50.1 48.2 1.7
20.0 673 SiO2b 32 0.0 0.0 0.0 0.0 50.7 49.3 0.0
a
Taken after 5 min of reaction.
b
TPA was impregnated on a previously calcined ZrO2 (SiO2) at 773 K for 4 h.
c ÿ1
Mainly pentanes. Reaction conditions: 673 K, 1-Cˆ ˆ ˆ
4 =H2 (molar)ˆ1, 101.3 KPa, WHSVˆ2 h , 0.1 g-cat. 1-C4 : 1-butene, C3 : propene, iC4:
isobutane, nC4: n-butane, iCˆ 4 : isobutylene, t2C ˆ
4 : trans-2-butene, c2Cˆ
4 : cis-2-butene.
 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53
any further increase in isobutylene selectivity beyond
that of 20TPA/Z. The reason may be that a great
portion of the total acid sites developed in 25TPA/Z
is weak (see Fig. 3(f)) and does not contribute to the
formation of isobutylene. A similar ceiling value has
been reported for 25 wt% H3[W12PO40] and 25 wt%
H3[W12SiO40] supported on SiO2 in the alkylation of
benzene with ethylene at 473 K [28]. Recently, San-
tiesteban et al. [37] reported that in highly acidic WOx/
ZrO2 catalysts only a small portion (0.005 meq per
gram of catalyst) of the total strong acid sites were
responsible for the n-pentane isomerization activity.
Calcination at 773 K of TPA/Z decreased the selec-
tivity towards isobutylene by 27%, 20%, and 23% for
10.0, 16.6 and 20.0TPA/Z, respectively, relative to
calcination at 673 K. This decline is probably asso-
ciated with the loss of the stronger acid sites as a
consequence of the partial crystalline structure mod-
i®cation from the metastable tetragonal to the mono-
clinic phase from 673 to 773 K [38]. The
decomposition of the Keggin structure at 773 K
[31], can also decrease the catalytic activity. Although
the fragments of the KU yield a greater acid site
density (see Table 3) on TPA/Z calcined at 773 K,
they are weaker than those in TPA/Z calcined at
673 K.
Heteropolyacids and their salts are commonly sup-
ported on acidic or neutral carriers, e.g. SiO2, activated
carbon, or TiO2, since basic materials, e.g. MgO,
Al2O3, decompose them, damaging the catalytic activ-
ity [28,39]. In Table 4, 16.6TPA/S, unlike the TPA/Z
catalysts, shows no indication of isobutylene forma-
tion and overall activity is considerably lower than that
of 5±25TPA/Z catalysts.
To generate superacid properties on SO4/ZrO2,
sulfation has to be carried out on freshly precipitated
Zr(OH)4 and not on calcined ZrO2 [10]. Accordingly,
surface OH groups are necessary to exchange with
[SO4]= and ®x them to ZrO2 to generate superacid
centers [40]. To examine whether a similar effect
occurs on the preparation of TPA/Z catalysts,
16.6 wt% TPA was impregnated on a freshly precipi-
tated zirconia and on one previously calcined at
673 K. TPA/ZrO2 is less active and less selective
for isobutylene than TPA/Zr(OH)4. Likewise,
20 wt% TPA/calcined SiO2 at 673 K is less active
than 16.6 wt%/uncalcined SiO2, the overall conver-
sions being 32% and 56%, respectively. As a compar-
51
ison, a sulfated alumina catalyzes the skeletal
isomerization of 1-butene at 698 K yielding about
27% isobutene after 2 h [41].
The product distribution as a function of time-on-
stream for 20TPA/Z is shown in Fig. 5. Though over-
all conversion does not diminish markedly, isobuty-
lene selectivity falls sharply with time, probably
associated to selective poisoning of strong acid sites.
In addition to butenes, 2.7% of propene, 1.3% of i-
butane and 1.3% of n-butane, were detected at 5 min,
but they almost disappeared after 1 h of reaction.
These results suggest that two types of catalytic sites
may initially operate on TPA/Z catalysts. Site (A) is
responsible for the skeletal rearrangement of 1-butene
and for the cracking reactions. This site has strong acid
properties and deactivates rapidly due to coke deposits
making both isobutylene and cracking by-products
decrease with time-on-stream. On the other hand,
double-bond isomerization does not demand a strong
acid site and proceeds on site (B). Thus when coke
deactivates (A) sites, (B) sites continue to participate
in the double-bond shift isomerization in agreement
with the increase of 2-butene formation as isobutylene
and other by-products decrease. Accordingly, propy-
lene and C‡ 5 by-products are produced via dimeriza-
tion and cracking reactions …2Cˆ 4 ! octenes !
isomerized octenes ! cracking products† [42]. On
the other hand, recent studies strongly point out that
isobutylene is formed via a monomolecular mechan-
ism in which the precise intermediate species is not yet
well stabilized [43].
4. Conclusions
The impregnation of H3[W12PO40] on ZrO2 yields
strong solid acids (H0ÿ9.3, calcined at 673 K). The
sites are predominantly Lewis acids when TPA was
supported on hydrated ZrO2 and then calcined at
673 K, but both Brùnsted and Lewis acid sites are
observed when TPA was supported on a previously
calcined ZrO2. The addition of the TPA stabilizes the
surface area of the resulting solid acid in comparison
with that of pure ZrO2. For instance, 16.6TPA/Z shows
1.4 times more surface area than that of ZrO2. 5-
25TPA/Z exhibit high catalytic activity in the 1-butene
isomerization at 673 K. Particularly, skeletal isomer-
ization, e.g. isobutylene formation, increases with
52 E. LoÂpez-Salinas et al. / Applied Catalysis A: General 175 (1998) 43±53
Fig. 5. Product distribution as a function of time-on-stream in the isomerization of 1-butene using 20TPA/Z at 673 K. (*) trans-2-butene,
(*) cis-2-butene, () isobutylene.
TPA content until leveling off at 20 wt% TPA. TPA
supported on SiO2 shows no isobutylene formation.
Acknowledgements
This study was funded in part by a FIES 95-02-III
project.
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