Applied Catalysis A: General 181 (1999) 145156

Inuence of the carrier on the catalytic performance of impregnated

phosphoric acid in the hydration of ethylene
C.M. Fougreta, M.P. Atkinsb, W.F. Holdericha,*
a

Department of Chemical Technology and Heterogeneous Catalysis, University of Technology RWTH Aachen, Worringerweg 1, D-52074
Aachen, Germany
b
BP Chemicals Research Laboratory, Poplar House, Chertsey Road, Sunbury-On-Thames, Middlesex TW16 7LN, UK
Received 30 November 1998; accepted 4 December 1998

Abstract
The hydration of ethylene was studied at 3008C and 50 bar using phosphoric acid impregnated silica, titania, mixed silica/
titania, zinc oxide/titania, tin oxide/titania, zirconia and niobic acid carriers. The time on stream of ``solid phosphoric acid''
i.e. phosphoric acid on silica is limited because of the crystallization of the silica carrier to b-crystobalite. The addition of
titania to the carrier of the well-known ``solid phosphoric acid'' catalyst results in a decrease of the catalytic activity in the
hydration. The phosphoric acid is strongly bound to the surface of this carrier. The activity of the ``solid phosphoric acid'' is
related to the presence of the liquid form of the deposited phosphoric acid (SLPsupported liquid phase catalyst). The
determination of the amount of free phosphoric acid gives an indication of the state of phosphoric acid on different carrier
materials. This amount was determined by measuring the acid which could be leached out by submerging the catalyst in water.
The activity of carrier materials impregnated with phosphoric acid could not be correlated to the concentration of acid sites at
strengths of 8.2<H03.0. # 1999 Elsevier Science B.V. All rights reserved.
Keywords: Ethylene hydration; Solid phosphoric acid; Carriers impregnated with phosphoric acid; Supported liquid phase catalyst

1. Introduction
Ethanol is one of the largest-volume organic chemicals used in industry and consumer products. Next
to water ethanol is the most important solvent. In
1990, 59% of the synthetically produced ethanol
was used as a solvent [1]. One of the processes used
in the last 50 years for the synthesis of ethanol on an
industrial scale is the direct ethylene hydration over
solid phosphoric acid (SPA) catalysts manufactured
by impregnating silica carriers, e.g. diatomaceous
*Corresponding author. Tel.: +49-241-806560; fax: +49-2418888291; e-mail: hoelderich@rwth-aachen.de

earth or silica gel with phosphoric acid (PA) [2].

Today, the favored carrier material is silica gel. The
active component is liquid phosphoric acid and the
catalyst can be best described as a supported liquid
phase catalyst (SLP) [3]. Unfortunately under reaction
conditions, i.e. 2303008C and 6080 bar [4], the
phosphoric acid is continually lost from the carrier
with consequent loss of catalytic activity. The level of
phosphoric acid on the carrier can be maintained by
the continuous addition of phosphoric acid to the feed
and by discontinuous re-impregnation of the catalyst
in the hydration reactor. Nevertheless, the catalyst
performance deteriorates over a period of 13 years
on stream due to crystallization of the carrier material

0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00416-5

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C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

to b-crystobalite if silica gel is used as carrier material.

For this reason an improvement in the carrier for
supporting phosphoric acid is urgently needed.
Prerequisite for ethylene hydration activity is the
acidity of the catalyst. Tanabe et al. [5] assume that in
the case of metal sulfates as hydration catalysts the
effective acid strength for ethanol formation is
8.2<H03.0 from the point of view of both activity
and selectivity. They report that the conversion correlates well with the acid site concentration at acid
strength H03.0, while the formation of acetaldehyde and polymer byproducts are attributed to the
existence of too strong acid sites of H0<8.2. Giorgini
and Tartarelli [6] found a relationship between the
hydration activity and the acid site concentration at the
acid strength of 8.2<H05.6 for catalysts consisting of a 1:1 mixture of metal phosphates and alumina.
Busca et al. [7,8] characterized catalysts consisting
of a monolayer of phosphoric acid on different carrier
materials. It could be shown that phosphoric acid on
silica has a pure Brnsted acidic nature, whereas on
titania and alumina dual Brnsted and Lewis acid
character is displayed. On the basis of IR data the
Brnsted acidity of impregnated silica is the strongest
[8]. The measurements indicated that the phosphoric
acid is present in a liquid-like form on silica gel. In
contrast the state of phosphoric acid deposited on
titania and alumina is signicantly different, since these
show strong interactions with the phosphoric acid [7].
The scope of this work was to study the inuence of
the carrier material on the catalytic activity of solid
phosphoric acid in the ethylene hydration reaction.
Pure titania, mixed titania/silica, zinc oxide/titania, tin
oxide/titania, zirconia and niobic acid were used as
carrier materials for phosphoric acid and compared
with the activity of phosphoric acid impregnated silica
gel. For each of these catalyst acidities, porosities and
the amount of free phosphoric acid which could be
washed out by water have been investigated.
2. Experimental
2.1. Catalysts
A series of catalysts were prepared from titania and
silica. The kind supply of titania P25 by Degussa AG
and silica gel by BP Chemicals is acknowledged. The

titania powder was extruded, dried at 1208C, calcined

in air at 3008C and crushed. The particles in the range
0.40.5 mm were used as the carrier. The industrially
used silica carrier pellets were crushed in order to
obtain the same particle size. The mixed titania silica
carriers were prepared via impregnation of the titania
pellets with a solution of tetraethyl orthosilicate in
ethanol or impregnation of silica with a tetraethyl
orthotitanate solution. The pellets were dried at
1208C and calcined at 5508C. The mixed titania silica
carrier with 1.8 wt% TiO2 content was kindly supplied
by Grace Davison.
The mixed zinc oxides/titania (molar ratio2/1)
and the tin oxide/titania (1/1) carriers were prepared
from the chlorides by precipitation [9,10]. The zirconia was supplied by Degussa AG and the niobic acid
by CBMM. These carriers were pressed into tablets
and crushed to split; the particles in the range 0.4
0.5 mm were used as supports.
The carrier pellets were impregnated with different
amounts of aqueous phosphoric acid by the incipient
wetness method and dried at 1208C for 16 h.
Calcination experiments were carried out in air. The
catalysts were calcined for 6 h with a heating rate of
28C/min.
2.2. Catalyst characterization
X-ray diffraction patterns of the powdered samples
were measured on a Siemens D 5000; elementary
analyses were carried out with a Spectroame D
ICP-AES spectrometer. Catalyst surface areas were
measured by nitrogen sorption on a Coulter Omnisorp
100 at 77 K. The acidic sites were titrated with n-butyl
amine in the presence of Hammett-indicators [11].
The 31 P-MASNMR measurements were carried out
on a Bruker AC 300 spectrometer at a resonance
frequency of 121.5 MHz. The free phosphoric acid
was determined by titration of the polyphosphoric acid
that was leached out when the ne powdered catalysts
were submerged into room-temperature water for
10 min [12]. The aqueous suspension was ltered
off and the leached phosphoric acids were titrated
with 0.1 M NaOH.
2.3. Ethylene hydration
The ethylene hydration was carried out in an integral copper lined continuous ow reactor with an

C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

internal diameter of 4.75 mm with 50 bar and 3008C

as standard test conditions. For each run 2.5 g of the
catalyst was used. The ethylene feed rate was monitored through a mass ow meter heated to 708C. The
water was fed to the reactor from a HPLC pump at a
rate of 4.0 ml/h providing an ethylene to water molar
ratio of 2:1. The feed was evaporated at the reactor
inlet at the reaction temperature. The laboratory unit
was equipped with a high pressure separator for the
condensation of the corrosive efuents. The gaseous
efuents were passed through a heated stainless steel
pressure control valve. Samples of the efuents were
taken at intervals after 2, 4, 6 and 8 h on stream. The
analysis of the products was carried out using a GC
having a 2 m Porapak QS column with a thermal
conductivity detector. Calculation of the conversion
and selectivities were based on water.
3. Results and discussion
3.1. Formation of silicon phosphate phases by
calcination
The industrially used phosphoric acid on silica gel
catalyst (SPA), deteriorates over a period of 13 years
time on stream (TOS) by crystallization of the carrier
material to b-crystobalite. In addition, the formation
of silicon phosphate phases can be observed in shorter
times under ethylene hydration conditions.
The crystallization was investigated by calcining
the samples of solid phosphoric acid catalyst containing phosphoric acid between 7.9 and 47.5 wt% for 6 h
(Table 1). The X-ray diffraction patterns showed that
the dried samples were amorphous. After calcination
between 2008C and 6008C no crystallization was
observed for solid phosphoric acid samples containing

147

up to 15.6 wt% phosphoric acid. At a calcination

temperature of 10008C b-crystobalite formation could
be observed. The crystallinity of the formed b-crystobalite of the sample containing 7.9 wt% phosphoric
acid was much higher than the one containing
15.6 wt% phosphoric acid. The calcination of the
samples containing 31.6 and 47.5 wt% phosphoric
acid between 2008C and 6008C resulted in the formation of silicon phosphate phases. The reections of
the XRD patterns could be identied as Si3(PO4)4
(JCPDS-No.: 22-1380), Si5P6O25 (JCPDS-No.: 400457) and Si3(PO4)4 (JCPDS-No.: 18-1167), but the
samples also contained large amounts of amorphous
material. With an increasing content of phosphoric
acid the crystallinity of the samples rose, but no
denite relationship between crystallinity and the
calcination temperature could be determined. Calcination at 10008C of samples containing more than
31.6 wt% resulted in the formation of amorphous
silicon phosphate glass.
The formation of b-crystobalite occurred only in
samples containing relatively low amounts of phosphoric acid; these samples did not form silicon phosphate phases during calcination.
3.2. Hydration over phosphoric acid impregnated
silica, titania and mixed silica/titania
The inuence of titania as the carrier for phosphoric
acid on catalytic performance was studied by
comparison with the industrially used solid phosphoric acid on silica gel catalyst. The conversion of
silica gel impregnated with different amounts of
phosphoric acid (SPA) is shown in Fig. 1. Only the
catalysts containing 39% and 50% phosphoric acid
showed the formation of acetaldehyde as the only
byproduct.

Table 1
Structure of the SPA samples with different PA concentrations after calcination for 6 h (Aamorphous, Ssilicon phosphate phases, Cbcrystobalite, Gglass)
Tcalc. (8C)
SPA
SPA
SPA
SPA

1
2
3
4

(7.9% PA)
(15.8% PA)
(31.6% PA)
(47.5% PA)

Dried

200

250

300

350

400

450

500

600

1000

A
A
A
A

A
A
S
S

A
A
S
S

A
A
S
S

A
A
S
S

A
A
S
S

A
A
S
S

A
A
S
S

A
A
S
S

C
C
G
G

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C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

Fig. 1. Conversion in the hydration of ethylene over solid phosphoric acid (SPA) as a function of the time on stream (TOS), temperature
3008C, p50 bar, 4 ml/h water, molar ratio ethylene/water2/1.

Comparing the activities of the different catalysts

after 2 h time on stream (Fig. 2), a parabolic dependence on the acid loading could be observed. The
catalysts showed water conversions between 13% and
22% and selectivities of more than 97% after 2 h on
stream. For the catalyst containing 39 wt% phosphoric
acid the highest ethanol yield but also the lowest
selectivity was observed.
In comparison Maki et al. [13] investigated the SPA
ethylene hydration activity in dependence of the acid
loading at ambient pressure and 2008C. It is reported

that the activity increased drastically with the acid

loading investigated up to 72 wt% of H3PO4. Nevertheless, reported rates of ethanol formations under
these conditions were corresponding to the conversions of less than 0.2%. The difference in the catalyst
activity in terms of dependence of the H3PO4 content
compared to our results must be explained by the
differences in the conditions applied in the experiments like temperature and especially pressure which
strongly inuences the diffusion in the pores. An
important feature is the amount of steam fed into

Fig. 2. Conversion in the hydration of ethylene over solid phosphoric acid (SPA) and PA impregnated titania (TPA), temperature 3008C,
p50 bar, 4 ml/h water, molar ratio ethylene/water2/1.

C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

the reactor. In comparison Maki et al. used a partial

pressure of 0.4 bar steam whereas 33 bar steam were
present in this work. The amount of steam is important
because steam is not only reactant, in addition it is the
solvent of the active compound and therefore its
amount inuences the concentration of it.
Therefore the dependence of the conversion on the
H3PO4 content must be explained by the theory of the
SLP catalysts. A parabolic dependence of the activity
on the loading of the liquid or dissolved active compound is a feature of many SLP catalysts [3]. The
liquid is distributed between the capillaries and the
surface of larger cavities of the carrier. For catalysts
containing only small amounts of liquid active compounds the lm is uniformly distributed and thin
enough to make liquid diffusion negligible. Every
liquid element is accessible for the reactants and with
an increasing liquid loading the activity rises. At a
higher loading a concentration gradient appears
depending on the depth of the liquid element though
the liquid distribution is still uniform. The accessibility of the liquid becomes restricted due to liquid
diffusion restrictions and the activity increase gets less
large with rising liquid loading. At very high loadings
liquid distribution becomes non-uniform. Agglomeration to macroscopic liquid clusters occurs which are
surrounded by well-dispersed liquid. The bulk of the
acid gets inaccessible for the reactants, blocks the
pores and the activity decreases.

149

The phosphoric acid impregnated titania catalyst

(TPA) showed a similar parabolic activity dependence
on the acid loading. But the activity was in comparison
much lower. Maximum water conversion was 4.9% for
a catalyst containing 16 wt% phosphoric acid (Figs. 2
and 3).
The poor performance of the titania supported
catalysts suggests that titanium is an effective poison.
The role of titania as a poison could be demonstrated
by examining the performance of mixed titania/silica
carriers impregnated with ca. 20 wt% phosphoric acid
(TSPA, Figs. 4 and 5). The catalysts containing only
small amounts of titania showed water conversions of
up to 18%, but there was a drastic decrease in the
hydration activity with rising titania content. The
phosphoric acid impregnated catalyst made from carrier containing only 1.5 wt% silica was nearly inactive.
3.3. Characterization of phosphoric acid
impregnated silica, titania and mixed silica/titania
The compositions of the silica, titania and mixed
silica/titania carriers impregnated with phosphoric
acid are presented in Table 2.
It is known that the acidity is a prerequisite for the
activity of ethylene hydration catalysts. A correlation
between the acid site concentration and activity was
observed for metal sulfates [5] and alumina supported

Fig. 3. Conversion in the hydration of ethylene over PA impregnated titania (TPA) as a function of the time on stream (TOS), temperature
3008C, p50 bar, 4 ml/h water, molar ratio ethylene/water2/1.

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C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

Fig. 4. Conversion in the hydration of ethylene over PA impregnated mixed titania/silica (TSPA) as function of the time on stream (TOS),
temperature 3008C, p50 bar, 4 ml/h water, molar ratio ethylene/water2/1.

Fig. 5. Conversion in the hydration of ethylene over PA impregnated mixed titania/silica (TSPA) in dependence on the TiO2 content,
temperature 3008C, p50 bar, 4 ml/h water, molar ratio ethylene/water2/1.

metal phosphates [6]. In order to compare these results

with phosphoric acid impregnated carriers, the acid
site concentrations were determined by titration with
n-butyl amine in the presence of Hammett-indicators.
In the case of solid phosphoric acid catalysts no acid
sites of H05.6 were present. The acid site concentration rose with decreasing phosphoric acid content
between 5.6<H03.0 (Fig. 6). In contrast to the
results of Tanabe et al. [5] and Giorgini and Tartarelli

[6], the correlation between the acid site concentration

and the activity for ethylene hydration could not be
observed for solid phosphoric acid. Activity was not a
function of the acid concentration, neither for the acid
sites of 5.6<H03.0 nor for the acid sites of other
acid strengths.
The titration of the phosphoric acid impregnated
titania (TPA) catalysts showed that they had stronger
acidic sites than phosphoric acid/silica (SPA) with a

C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

Table 2
Results of the elementary analysis for the solid phosphoric acid
(SPA), PA impregnated titania (TPA) and PA impregnated mixed
titania/silica (TSPA)
Sample

Carrier

H3PO4 (wt%)

TiO2 (wt%)

SiO2 (wt%)

SPA
SPA
SPA
SPA
SPA

1
2
3
4
5

100
100
100
100
100

9.2
21.8
33.0
38.8
49.5

TPA
TPA
TPA
TPA
TPA
TPA

1
2
3
4
5
6

100
100
100
100
100
100

4.0
8.0
15.9
24.8
27.2
29.4

TSPA
TSPA
TSPA
TSPA

1
2
3
4

98.5
7.8
4.4
1.8

1.5
92.2
95.6
98.2

21.4
19.3
19.8
20.9

maximum acidity of H08.2 (Fig. 7). In comparison

to the SPA catalysts the amounts of acid sites with acid
strength 5.6<H03.0 were smaller. In contrast to
these ndings the acid site concentrations of
4.8<H03.3 and of 3.0<H03.3 were larger. No
correlation between the acidity and the activity could
be observed.

151

The results of the titration of mixed oxides impregnated with phosphoric acid to an acid loading of ca.
20 wt% are presented in Fig. 8. The strongest acid
sites (H0<5.6) could be observed for the phosphoric
acid impregnated carrier containing of 98.5 wt% TiO2
and the impregnated commercial silica/titania carrier
with a titania content of 1.8 wt%. The acid site concentrations at acid strengths which are reported to be
prerequisite for catalytic activity [5,6] could not be
correlated with the hydration activity.
The correlation between acid amount and the hydration activity reported by Tanabe et al. [5] and Giorgini
and Tartarelli [6] could not be conrmed, neither for
the series of the silica and the titania carriers with
different phosphoric acid loadings nor for comparisons between the SPA and the TPA catalysts.
The nitrogen sorption measurements of the SPA and
TPA catalysts showed that the BET surface area
(SBET) and the cumulative pore volume decreased
with increasing phosphoric acid loading as it is to
be expected (Table 3). At the same time the average
pore width of the SPA catalysts, calculated by the BJH
method, increased. It may be likely that the smaller
pores of the catalyst were lled with the liquid phosphoric acid. In contrast the average pore width of the
titania carrier decreased from 21 to 19 nm by phosphoric acid impregnation. The pore width did not
change for the TPA catalysts at higher phosphoric
acid loading. However, the ethylene hydration activity

Fig. 6. Acid site distribution of the solid phosphoric acid samples with different PA loadings.

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C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

Fig. 7. Acid site distribution of the PA impregnated titania samples with different PA loadings.

Fig. 8. Acid site distribution of the titania/silica carriers with different TiO2 contents impregnated with 20 wt% PA.

of the SPA and TPA catalysts could not be explained

by the results of the surface determination. Modications of the impregnation process and post-synthetical
modications of the solid phosphoric acid allowed to
vary the average pore diameter in between 16 and
34 nm. The catalytic tests showed that the reaction is
restricted by the diffusion of the reactants. The average pore diameters of the catalysts play an important

role. The results will be reported in a separate paper

[14].
The high BET surface area of the catalyst TSPA 4
could be explained by the high surface area of the
silica/titania carrier (324 m2/g).
The nature of the phosphorus environment on silica
and titania was investigated with 31 P-MASNMR
(Fig. 9). The spectrum of a solid phosphoric acid

C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

153

Table 3
Results of the nitrogen measurements on the SPA, TPA and TSPA samples
Sample

PA content (wt%)

SBET (m2/g)

Average pore
width (nm)

Cumulative pore
volume (ml/g)

Silica gel
SPA 1
SPA 2
SPA 3
SPA 4
SPA 5

9.2
21.8
33.0
38.8
49.5

205
133
87
57
36
28

16
16
17
19
19
19

0.92
0.62
0.51
0.38
0.29
0.22

Titania pellets
TPA 1
TPA 2
TPA 3
TPA 4
TPA 5

4.0
8.0
15.9
24.8
27.2

51
42
37
24
15
12

21
19
19
18
19
19

0.31
0.25
0.23
0.18
0.12
0.10

TSPA 3
TSPA 4

19.8
20.9

71
148

16.5
12.5

0.44
0.74

catalyst showed that the phosphorus was present as

isolated phosphate (0.0 ppm). Traces of pyrophosphate (10.8 ppm) were also present.
The spectrum of the TPA catalyst was completely
different. Signals at 22.0, ca. 15 and 6.6 ppm
indicated that the phosphorus was present mainly as
condensed phosphates. In addition the catalyst contained small amounts of isolated phosphates
(0.2 ppm) and phosphorus pentoxide (51.9 ppm).
The spectra showed that under the same preparation
procedure phosphoric acid interacts differently with
different carriers. Silica acts as an inert carrier for
phosphoric acid conrming the IR results of Busca et
al. [7,8]. The titania carrier showed interactions with
impregnated phosphoric acid. Busca et al. [7] assumed
that the absence of H-bonded phosphate species, even
after hydration, was evidence for the formation of a
``localized'' monomeric species bonded ionically to
the support surface. However, our NMR investigations
show that the phosphorus species are mainly oligomeric in nature.
In order to further investigate the interactions of the
phosphoric acid with the carrier, the amount of free
phosphoric acid was measured using the method
described by Cavani et al. [12] who measured the
inuence of the water content of phosphoric acid
impregnated Kieselguhr in the alkylation of benzene
and the oligomerization of propene. The method is
based on the fact that higher condensed phosphates

take longer to be hydrolyzed while simple species

such as ortho- and pyro-phosphoric acids are easily
leached from the catalyst when it is submerged in
water. The amount of free phosphoric acid recovered
can be taken as representative for the kinds of acid
present, or in our case, for the strength of the interactions between the phosphoric acid and the different
carriers.
The results are presented in Figs. 10 and 11. It can
be shown that in the case of the SPA catalysts the
amount of free phosphoric acid increased with the
amount of impregnated phosphoric acid (Fig. 10). In
the case of the mixed silica/titania carriers impregnated with about 20 wt% H3PO4 the amount of free
phosphoric acid decreases with the titania content
(Fig. 11). From these results and the catalytic activity
of the catalysts (Fig. 5) we conclude that the free
phosphoric acid is a prerequisite for the catalytic
activity in the hydration reaction. The introduction
of titania into the carrier material poisons the catalyst
by strong interaction with the phosphoric acid present.
3.4. Hydration of ethylene over other phosphoric
acid impregnated carrier materials
In order to investigate the catalytic performance of
other phosphoric acid impregnated carrier materials,
zinc oxide/titania, tin oxide/titania, zirconia and niobic acid carriers were impregnated and tested in the

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C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

Fig. 9.

31

P-MASNMR spectra of solid phosphoric acid (SPA 4) and of PA impregnated titania (TPA 3).

Fig. 10. Determination of the free phosphoric acid of the solid phosphoric acid samples.

hydration reaction. The mixed oxides and the zirconia

were impregnated with 20 wt% phosphoric acid.
These catalysts showed very low water conversions
in the hydration of ethylene (Table 4). In the case of
the impregnated mixed oxides, diethyl ether was

found as the main byproduct, together with traces

of acetone and polymers.
The niobic acid was impregnated with 50 wt%
phosphoric acid. Initial activity was high but the
catalyst deactivated rapidly. Conversion decreased

C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

155

Fig. 11. Determination of the free phosphoric acid of the PA impregnated mixed titania/silica samples in dependence on the TiO2 content.

lower activity for ethylene hydration under the industrial conditions than solid phosphoric acid.

from 12% after 2 h TOS to 1.7% after 4 h TOS. As

byproducts diethyl ether and traces of acetone were
detected after 2 h. The deactivation could not be
explained by leaching, since the pH of the efuents
were neutral.
In contrast to our results, Okazaki et al. [15]
reported that niobic acid treated with small amounts
of phosphoric acid was remarkably more active than
solid phosphoric acid. Under the conditions used,
2208C and low pressures, conversions of less than
0.05% were observed. In our study niobic acid impregnated with high amounts of phosphoric acid showed a

3.5. Determination of free phosphoric acid and

correlation with the catalytic activity
The amount of free phosphoric acid present in the
catalysts studied here was determined in order to
check the assumption that for effective activity, the
phosphoric acid has to have as low interaction with the
carrier as possible, i.e. that it has to be in a liquid-like
form (SLP catalyst).

Table 4
Ethylene hydration over different PA impregnated carriers, temperature 3008C, p50 bar, 4 ml/h water, molar ratio ethylene/water2/1
Carrier

PA content (%)

TOS (h)

TiO2/ZnO

20

Conversion (%)
Selectivity (%)

2.0
100

3.4
43.4

1.8
76.1

1.2
100

TiO2/SnO

20

Conversion (%)
Selectivity (%)

6.1
27.1

1.2
27.0

0.8
100

ZrO2

20

Conversion (%)
Selectivity (%)

1.3
100

0.3
100

Nb2O5
xH2O

50

Conversion (%)
Selectivity (%)

12.1
99.5

1.7
100

3.2
100

1.4
100

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C.M. Fougret et al. / Applied Catalysis A: General 181 (1999) 145156

Table 5
Determination of the free phosphoric acid for different PA
impregnated carriers
Carrier

TiO2/ZnO TiO2/SnO ZrO2

Nb2O5
xH2O

PA content (wt%)
Free PA (mg/g)

20
23.7

50
50.4

20
14.9

20
9.4

The results are presented in Table 5. A direct

correlation between the catalytic activity for ethylene
hydration and the amount of free phosphoric acid
could not be concluded, but it could be demonstrated
that an estimation in relation to the hydration activity
can roughly be done.
4. Conclusions
The direct investigation of the crystallization process of solid phosphoric acid is not possible since the
catalyst carrier crystallizes to b-crystobalite at the
earliest after one year on stream. Calcination experiments with solid phosphoric acid showed that the
formation of b-crystobalite occurs only at about
10008C if the catalyst contains low amounts of phosphoric acid.
The addition of titania to the silica gel carrier
material poisons the catalyst even though the acid site
concentration of the material increases with an acid
strength between 8.2<H03.0. Nitrogen sorption
isotherms indicate that the phosphoric acid is distributed more uniformly on titania than on silica. The
small pores of the silica carrier are lled up with the
phosphoric acid solution whereas this typical effect of
a liquid in a pore system cannot be detected on titania
impregnated with phosphoric acid. The nature of the
phosphoric acid is changed to oligomeric phosphate
species by impregnation on titania as could be shown
with 31 P MASNMR spectroscopy. In contrast to
these ndings the nature of the phosphoric acid is
not changed when impregnated on silica. It can be
assumed that the liquid-like state of phosphoric acid
on carrier materials is a prerequisite for the catalytic
activity in the hydration of ethylene. The determination of the amount of free phosphoric acid gives an
indication on the liquid-like state of phosphoric acid

on silica, titania and mixed silica/titania carrier materials, and as a consequence, on the activity in the
ethylene hydration.
The lack in activity of the phosphoric acid impregnated zinc oxide/titania, tin oxide/titania, zirconia and
niobic acid carriers can be explained by the interactions between the phosphoric acid impregnated and
those carriers. The strength of the interactions can be
estimated easily by the determination of the free
phosphoric acid.
Acknowledgements
The authors wish to acknowledge BP Chemicals for
nancial support and the allowance to publish the
results as well as Dr. B. Zibrowious for the performance of the MASNMR spectra.
References
[1] J.I. Kroschwitz, M. Howe-Grant (Eds.), Kirk-Othmer
Encyclopedia of Chemical Technology, vol. 9, Wiley, New
York, 1994, p. 842.
[2] A.F. Millidge, in: S.A. Miller (Ed.), Ethylene and its
Industrial Derivatives, Ernest Benn Ltd., London, 1969, p.
713.
[3] J. Villardsen, H. Livbjerg, Catal. Rev.-Sci. Eng. 17 (1978)
203.
[4] G.M. Wells, Handbook of Petrochemicals and Processes,
Gower Publishing, Hants, 1991, p. 154.
[5] K. Tanabe, M. Misono, Y. Ono, H. Hattori, New Solid Acids
and Bases, Elsevier, Amsterdam, 1989, p. 248.
[6] M. Giorgini, R. Tartarelli, Chim. Ind. (Milan) 58 (1976) 611.
[7] G. Busca, G. Ramis, V. Lorenzelli, P.F. Rossi, A. La Ginestra,
P. Patrono, Langmuir 5 (1989) 911.
[8] G. Ramis, P.F. Rossi, G. Busca, V. Lorenzelli, A. La Ginestra,
P. Patrono, Langmuir 5 (1989) 917.
[9] K. Tanabe, C. Ishiya, I. Matsuzaki, I. Ichikawa, H. Hattori,
Bull. Chem. Soc. 45 (1972) 47.
[10] M. Itoh, H. Hattori, K. Tanabe, J. Catal. 43 (1976) 192.
[11] H.A. Benesi, J. Phys. Chem. 61 (1957) 970.
[12] F. Cavani, G. Girotti, G. Terzoni, Appl. Catal. A 97 (1993)
177.
[13] Y. Maki, K. Sato, A. Isobe, N. Iwasa, S. Fujita, M.
Shimokawabe, N. Takezawa, Appl. Catal. A 170 (1998) 269.
[14] C.M. Fougret, M.P. Atkins, W.F. Holderich, in preparation.
[15] S. Okazaki, M. Kurimata, T. Iizuka, K. Tanabe, Bull. Chem.
Soc. Jpn. 60 (1987) 37.