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Applied Catalysis A: General 286 (2005) 5260

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Catalytic synthesis of ethyl-tert-butyl ether on Dawson


type heteropolyacid
Joanna Pozniczek a, Anna Micek-Ilnicka a, Anna Lubanska a,*, Adam Bielanski a,b
a

Polish Academy of Sciences, Institute of Catalysis and Surface Chemistry, Polyoxometalate Laboratory,
ul. Niezapominajek 8, 30-239 Krakow, Poland
b
Faculty of Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Krakow, Poland
Received 12 October 2004; received in revised form 24 February 2005; accepted 28 February 2005

Abstract
Catalytic formation of ethyl-tert-butyl ether (ETBE) by nucleophilic addition of ethanol to isobutene on Dawson-type heteropolyacid
H6P2W18O62nH2O (HP2W) has been studied in the temperature range of 3580 8C. The yield of ETBE reached a maximum of 43% at 40 8C
and then decreased with increasing temperature. Such behaviour is typical for reversible exothermic reactions approaching equilibrium and
results in the decrease of the yield with temperature. At 40 8C the activity of the catalyst depended on the pre-treatment temperature and,
hence, on the content of water of crystallisation. Samples pre-heated at 80 and 95 8C, containing about eight H2O molecules per anion,
exhibited the highest activity. Under these conditions the ETBE yield is slightly above 40%. The samples calcined at 150 and 200 8C,
containing about three H2O per anion, exhibited a yield of about 27%. Parallel sorption experiments of ethanol on octahydrated and
trihydrated HP2W have shown that, in the former case, the sorption of ethanol was nearly twice as large as that in the latter case. The
differences show that the sorption capacity of the samples depends on the secondary structure of the heteropolyacid. These differences have
been assumed also as explanation for the observed levels of catalytic activity. In all experiments carried out at 40 8C the selectivity to ETBE
was over 90% but it decreased to a few percent at 80 8C.
# 2005 Elsevier B.V. All rights reserved.
Keywords: ETBE synthesis; Dawson; Heteropolyacid; Catalyst

1. Introduction
Heteropolyacids (HPA) belong to the strongest mineral
acids which renders them active catalysts for the acidbase
type reactions both in solution and crystalline state.
Independent of some practical applications, they represent
an interesting subject of physicochemical studies, which is
also connected with their unusual sorption properties. Polar
molecules such as H2O, NH3, amines, and alcohols are not
only adsorbed on the external surface of the HPA crystallites
but also penetrate in the bulk where they interact with
loosely bonded protons of the acid, thus forming protonated
* Corresponding author. Tel.: +48 12 6336377x2073;
fax: +48 12 634 05 15.
E-mail address: lubanska@chemia.uj.edu.pl (A. Lubanska).
0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.02.035

monomers or protonated clusters. Generally, the sorption


desorption processes are fast, indicating that at least part of
the absorbed molecules exhibits mobility, remembering to
some extent the mobility of solute molecules in a
concentrated solution. Such behaviour has been called
pseudoliquid phase behaviour [1].
It has been shown [2,3] that it is convenient to describe the
complicated structure of solvated crystalline HPAs on three
levels: the HPA anions forming the primary structure, the
secondary structure which is due to the interactions of protons
and polar molecules penetrating the bulk and the tertiary one
represented by HPA crystallites. These levels of molecular and
super molecular structure should be taken into account when
the catalytic properties of HPAs are discussed.
Misono [2] classified the catalytic reactions occurring on
solid HPAs in three groups:

J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

1. Surface reactions in which no penetration of the reagents


into the bulk takes place. In the ideal case, the adsorbed
molecules interact only with the surface atoms and no
interactions with the bulk occur.
2. Bulk-type I reactions in which polar reagents penetrate
the bulk where their transformation occurs and the
products are given off to the liquid or gas phase. In this
case diffusion and reaction in the bulk is faster than the
surface reaction.
3. Bulk-type II reactions in which a non polar reagent
remaining at the surface reacts with some species
supplied from the bulk, e.g., electrons or protons.
The classification of the reactions becomes more complicated in the case of catalytic reactions occurring between
polar and non-polar molecules, as in the case of the formation of tertiary ethers by the electrophilic addition of
alcohol to tertiary olefin. The most frequently investigated
reaction of this class was the gas phase synthesis of methyltert-butyl ether (MTBE) from methanol and isobutene, reviewed recently [4]. Shikata et al. [5] assumed that in the
case of H3PW12O40 and H6P2W18O62 catalysts the polar
methanol molecules diffuse into the bulk and expand the
HPA crystal lattice, thus enabling the penetration of the nonpolar isobutene into the HPA bulk. As a consequence, the
reaction takes place in the pseudoliquid phase. On the other
hand, the present authors [6] investigated the same reaction
on solid H4SiW12O40 and could not confirm such isobutene
penetration into the bulk of crystallites previously loaded
with methanol. They proposed a model according to which
isobutene, protonated with protons supplied from the bulk,
remains at the surface and reacts with methanol from the
next-to-surface layer of the HPA crystallites.
Tertiary ethers, mainly MTBE but also ETBE and rarely
TAME (tert-amyl methyl ether) are used as important antiknocking additives to automotive fuel. In the recent years
some objections have been risen from environmental
reasons against the use of MTBE. Simultaneously the
interest in the wider application of ETBE is growing. The
latter is considered to degrade faster in soils and water. The
advantage of the ETBE use is also that, one of its substrates,
ethanol, may come from renewable sources, it is from
fermentation processes.
In their study of gas phase formation of MTBE on
Keggin-type HPAs, the authors generally used dehydrated
samples, i.e. devoid of crystallization water. During the
catalysis, the secondary structure was composed of HPA
anions and protonated methanol monomers or protonated
methanol clusters. More recently, Baronetti et al. [7,8]
studied MTBE formation on solid Dawson type HPA and
showed that the activity was influenced by the presence of
crystallization water. This is the substance which formally
does not participate in the catalytic reaction but enters in
HPA secondary structure. In the present research we were
interested in studying this problem in detail by using a
Dawson-type catalysts with different content of crystal-

53

lization water and using the gas phase synthesis of ethyl-tertbutyl ether (ETBE) as the test reaction. Only one paper
appeared in the literature in which a heteropolyacid (blended
with a polymer) was used as the catalyst for ETBE synthesis
[9]. The same results were also described in the more general
context in [10]. However, the reaction has been studied over
acidic resins [11,12] and gallophosphate molecular sieve
cloverite [13] and zeolites [14,15].

2. Experimental and methods


The synthesis of H6P2W18O62nH2O (HP2W) has been
carried out in two steps. The first step consisted of the
preparation of the potassium salt K6P2W18O62, using the
method described in [16]. Small portions of concentrated
H3PO4 (ppa POCh 85 wt.%) were added to the boiling
aqueous solution of Na2WO42H2O (ppa Sigma) with the
final molar ratio 4:1. The solution was boiled under reflux
condenser for 8 h. Subsequently, the potassium salt was
precipitated at room temperature by adding solid KCl. The
precipitate was re-crystallised from water, washed with
diethyl ether, and dried in vacuum. In the second stage, the
potassium salt was transformed into the acid [7] by
dissolving it in a small amount of water and gradually
adding concentrated hydrochloric acid. The released free
HP2W was extracted with diethyl ether. The oily etherate
separated from the solution was subsequently decomposed
on a hot water bath. The remaining acid was dried at 100 8C.
The sample was kept at room temperature in a desiccator
over a saturated solution of Mg(NO3)2. The hydrated sample
was a greenish white, fine powder. Thermal analysis showed
that the composition of the equilibrated sample corresponded to H6P2W18O6228.8 H2O. According to atomic
absorption analysis it contained 0.03 wt.% of potassium.
High resolution 31P NMR of the HP2W sample was
recorded at room temperature on a Bruker AMX 500 NMR
spectrometer equipped with a CP/MAS unit using a hydrated
HP2W dissolved in D2O. Chemical shifts were expressed in
parts per million with respect to 85% H3PO4 as external
standard.
Ethyl alcohol azeotrope (95.6 wt.%, pure, supplied by
POCh Gliwice), 2-methyl propene (isobutene, i-C4H8, p.a.,
Aldrich) and ETBE (99%, Aldrich) were used in the sorption
and catalytic experiments.
TG, DTA, and DTG analyses of the samples were
performed using a STD 2960 TA Instruments Derivatograph
connected with Balzers QMS 300 Thermostar Mass
Spectrometer. A heating rate of 5 8C min1 was applied
in all experiments.
FT-IR spectra of the samples in the spectral region 4000
400 cm1 were recorded with a Bruker IFS 48 Spectrometer
using the KBr technique.
Sorption of water, ethyl alcohol, isobutene, and ETBE
was studied by means of a quartz spring sorption balance
(sensitivity 0.6828 mm mg1) connected with a vacuum

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J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

system. The elongation of the spring was measured with a


cathetometer, the sensitivity of which was 0.01 mm.
Constant flow glass microreactor (f = 10 mm) was used
for the catalytic experiments. The helium carrier gas was
first saturated with ethanol vapour (ethanol of azeotropic
composition with 4.43 wt.% of water) and subsequently
mixed with a stream of isobutene. The composition of the
reaction mixture was fixed at the isobutene/ethanol molar
ratio equal to 0.7 ( pC4H8 = 3.7 kPa, pC2H5OH = 5.6 kPa).
An excess of alcohol was used in order to prevent the
formation of isobutene oligomers at the catalysts surface.
The catalytic reactor was connected on line with Hewlett
Packard Ser. II. A gas chromatograph and a Porapak QS
column was used for the chromatographic analyses. Samples
of 0.453 g (0.177 cm3) of H6P2W18O6228.8 H2O
(0.926  104 mole)
were
mixed
with
0.090 g
(0.0339 cm3) of quartz grains (f = 0.19 mm) thus obtaining
a catalyst layer thickness of 0.5 cm. The microscopically
determined diameter of the HP2W crystallites was of the
order 2.5  102 cm. Under these conditions, the value of
2:5bdp
2:47  102 < 5  102
1  bLp
fulfilled the van den Bleek criterion of diluting the catalyst
with inert material [17] (b is the inert bed fraction, dp the
diameter of catalyst particles, Lb the bed length). The space
velocity was 0.109 mole/(h  gcat).
Before the catalytic experiments the samples were
activated in situ in a stream of helium for 0.5 h between
80 and 300 8C. In a series of independent experiments, the
composition of the samples was determined after activation.

3. Results
Fig. 1 shows the 31P NMR spectrum of the HP2W sample.
The peak at 12.225 ppm characteristic of the a isomer and
the doublet at 11.499 and 10.737 ppm characteristic of
the b isomer were observed. Similar results were found by
Briand et al. [18]. The contents of a = 87.4% and b = 12.6%
were calculated from the intensities ratio. The absence of a
peak at +0.742 ppm indicated that no contamination with
phosphoric acid or phosphates was present.
Fig. 2a and b show the TG, DTG and DTA curves of the
hydrated H6P2W18O62 sample kept over a saturated solution
of Mg(NO3)2. The total weight loss corresponded to 31.8
H2O per mole of acid. Assuming that the last portion of
water removed above 250 8C (3.01 mole H2O per mole
HPA) corresponded to the water of constitution bonded in
the form of OH groups, the formula of the initial sample was
as follows: H6P2W18O6228.8 H2O.
The BET specific surface area calculated from the N2
sorption isotherm at 77 K determined for the dehydrated
sample of HP2W was equal to 3.6 m2 g1.
Sorption of water and ethanol vapours as well as sorption
of isobutene and ETBE was studied at 40 8C, i.e., at the

Fig. 1.

31

P NMR spectrum of the HP2W sample.

temperature at which most of the catalytic experiments were


carried out. Samples of anhydrous H6P2W18O62 and those
with eight H2O and about three H2O molecules of
crystallisation water per mole of HPA were used. The
samples were dehydrated in situ in the sorption balance by
evacuating at 210 8C (anhydrous and trihydrated samples,
depending on the evacuation time) or at 110 8C (octahydrated sample). The results are given in Table 1. Sorption of
both water and ethanol vapours was rapid, with most of the
absorbate being taken up within a few minutes. Table 1 also
shows the amount of irreversibly bonded absorbate (after
evacuation at 40) as well as the results of the second
absorptiondesorption cycle carried out on the same sample.
Fig. 3 shows the behaviour of octahydrated samples in
contact with isobutene (a) and ETBE vapours (b). In both
cases a rapid increase in weight is observed, followed by a
slower decrease indicating desorption of some reaction
products, presumably of TBA in the first case and the
products of ETBE decomposition in the second one.

J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

55

Fig. 3. Sorption (&) and desorption (~) of isobutene (a) and ethyl-tertbutyl ether (b) on H6P2W18O628 H2O at 40 8C. The final content of
adsorbate is given in the graph as C4 or ETBE molecules per Dawson unit
(DU).

Fig. 2. Thermal analysis of H6P2W18O6228.8 H2O; heating rate: 58 min1.


(a) TG and DTG; (b) DTA.

The course of a typical catalytic test is shown in Fig. 4.


The predominant product in the gas phase was ETBE, while
in some experiments small amounts of tert-butyl alcohol
(TBA) and isobutene dimer were detected. The pristine
samples H6P2W18O6228.8 H2O were activated before the
catalytic run between 80 and 300 8C. Their composition

after activation at particular temperatures was determined in


a separate series of experiments and the results are given in
Table 2. During the catalytic test, the content of water vapour
in the gas leaving the reactor was monitored chromatographically and compared with that in the feed.
The FT-IR spectra in the 1200400 cm1 region of
Dawson anion skeletal vibrations are very much similar to
those obtained by Baronetti et al. [19]. They contain four
characteristic modes at about 1091, 961, 913 and 777 cm1
ascribed to nPOa ; nWOd ; nWOb W and nWOc W , respectively [1,20]. The exact positions of the particular IR
bands in the pristine sample as well as those of samples
calcined up to 600 8C, and the samples, which after
standardisation were catalytically tested, are given in
Table 3. The changes in the IR spectra due to the different
treatments of the samples are manifested not only by some

Table 1
Sorption and desorption experiments on Dawson acid at 40 8C
Composition of the
adsorbent

Sorption I
mole adsorbate=mole HP2W

Irreversible sorption I
mole adsorbate=mole HP2W

Sorption II
mole adsorbate=mole HP2W

Total irreversible sorption


mole adsorbate=mole HP2W

Sorption of H2O
HP2W
HP2W3H2O
HP2W8H2O

3.0
3.5
8.2

0.2
1.3
2.2

5.0
2.3
7.9

3.3
2.3
3.3

Sorption of C2H5OH
HP2W
HP2W3H2O
HP2W8H2O

3.1
3.3
8.1

0.9
2.1
2.3

2.4
4.1
8.4

1.1
3.0
3.3

J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

56

Fig. 4. Typical catalytic run carried out at 40 8C. (a) Yield of ETBE and
TBA; (b) selectivity to ETBE formation. Sample pre-heated in situ at 95 8C.

shifts of the frequency values but also by changes in the


intensity ratio of particular bands (the absorbance corresponding to the stretching vibration of P Oa bond at
1091 cm1 has been assumed as unity).

4. Discussion
The TG analysis (Fig. 2) shows that on heating
H6P2W18O62nH2O decomposes in two main stages. In
the first stage, between room temperature and 200 8C, the
weight loss corresponds to 28.8 mole H2O per mole of acid.
Between about 200 and 250 8C a plateau appears on TG
curve. Above the latter temperature the second stage of
sample decomposition begins characterised by an endothermic DTA peak at 300 8C and a parallel DTG effect at the
same temperature. The weight loss corresponds to 3.01 mole
H2O per HPA anion. Above about 400 8C no change of mass
is detected. A DTA exothermic effect at about 600 8C not
accompanied by any change in weight, indicates a phase
Table 2
Composition of the activated samples (activation time 30 min)
Activation
temperature
(8C)

Composition of the
activated sample

Approximate sorption of H2O


vapour at the initial period of
the run, mole H2O/mole HP2W

80
95
128
150
200
300

H6P2W18O628.6
H6P2W18O628.0
H6P2W18O625.4
H6P2W18O623.0
H6P2W18O622.8
P2W18O59

1.76
3.29
2.67
2.74
5.21

H2O
H2O
H2O
H2O
H2O

transformation of this material, consisting of its re-crystallisation or decomposition into an other solid phase or phases.
In the first stage of the decomposition, the typical
behaviour of a solid containing crystallisation water is
observed. The presence of these water molecules, responsible for the secondary structure of the heteropolyacid, is
characterised by the deformation vibration of H2O, dH2 O , at
1645 cm1 and broad stretching bands at about 3570 and
3445 cm1 due to the hydrogen bonds. These bands vanish
partly or totally when the sample is evacuated and are easily
regenerated on exposure to the atmospheric humidity.
The TG curve in Fig. 2, although monotonically
decreasing from room temperature to 200 8C, shows several
inflexion points characterised by DTG peaks at 68, 107, and
147 8C and also DTA peaks at 68, 105 (shoulder) and
148 8C. It can also be inferred from the DTG curve that the
local minima of the decomposition rate of the sample
correspond to about 98, 129, and 250 8C. At 98 8C the
sample contained 10.5 moles of crystallisation water per one
of acid, at 129 8C it contained 6.0 mole H2O per mole of
acid, and at 250 8C the sample was anhydrous H6P2W18O62.
In the first case, the H2Oproton molecular ratio is close to
2:1 and in the second case 1:1 which suggests an enhanced
stability of the hydrates H6P2W18O6212 H2O and
H6P2W18O626 H2O, containing dioxonium H5O2+ or
H3O+ oxonium ions, respectively. According to the
theoretical calculations of Sambeth et al. [21], the stability
of protonated water clusters in the H6P2W18O62 structure
increases in the sequence H2O < H3O+ < H5O2+.
The very good accordance of the weight loss of 3.01 mole
H2O with the stoichiometry of the Dawson heteropolyacid
H6P2W18O62 indicates that the second stage of sample
decomposition above 250 8C is related to dehydroxylation
(departure of the constitution water). The composition of the
remaining product corresponds to the average formula
P2W18O59. Shikata et al. [22] observed dehydroxylation at
300 8C. The fact that the IR spectrum of the samples heated
to 300 and 360 8C preserves, although somewhat changed,
all the typical skeletal vibrations of the pristine sample
indicates that the dehydroxylation product P2W18O59 in
principle preserves the typical structure of the Dawson
anion. The shift of the nWOd vibrations from 1091 to
1087 cm1 and of the nWOb W vibration from 913 to
933 cm1 as well as the change in absorbances ratio
(Table 3), are most probably due to the removal of protons
and the formation of oxygen vacancies in the polyoxometalate. These observations are in accordance with Briand
et al. [18] who stated that the XRD pattern of hydrated
H6P2W18O62 calcined at 400 8C, although showing the same
reflections, exhibited an increase of the background and an
intensity loss of the peaks. Only a calcination at 600 8C
resulted in a significant modification of the XRD pattern.
In our case the changes in the heteropolyacid, due to the
calcination at 300 8C were also manifested by the fact that
the calcined sample was only partly soluble in cold and hot
water, in contrast to the completely soluble pristine sample

J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

57

Table 3
FT-IR vibrations and the ratios of absorbances for the samples heated at temperature 95600 8C in separate experiments and the samples which after pre-heating
at 95360 8C were catalytically tested at 40 8C
Temperature (8C) of
Calcination

Reaction

Pristine
95
215
300
400
600
95
150
200
300

40
40
40
40

nPOa

nWOd

nWOb W

nWOc W

A1091:A961:A913:A777

1091
1091
1087
1086
1087
1086
1091
1091
1091
1086

961
962
964
961
962
966
961
961
962
961

913
914
914
933(sh)
943(sh)
938(sh)
912
913
913
924

777
780
791
787
777
777
779
782
781
781

1.00:1.07:1.05:1.84
1.00:1.21:1.00:1.72
1.00:1.86:1.64:3.00
1.00:1,56:1.50:2.72
1.00:1.69:1.50:2.86
1.00:1.70:1.77:3.58
1.00:1.08:1.04:1.79
1.00:1.07:1.05:1.80
1.00:1.12:1.08:1.83
1.00:1.54:1.42:2.43

and the samples calcined at 200 and lower temperatures.


This might indicate the partial condensation of anions and
the formation of non-soluble aggregates.
Under the conditions of our catalytic reaction, the catalyst
remains in contact with molecules of ethanol, water,
isobutene, and ETBE. In separate experiments we have
studied the sorption of these reagents on the catalysts.
Taking into account that the most active catalysts contained
certain amounts of crystallization water, the sorption
experiments were not only carried out with anhydrous
HP2W but also with hydrated samples with compositions
close to H6P2W18O623H2O and H6P2W18O628H2O.
The sorption of water and ethanol vapours on anhydrous
and trihydrated H6P2W18O62 is fast at 40 8C and, after a few
minutes in the former case and about 30 min in the latter
case it reaches a constant level. The amounts of H2O and
C2H5OH taken up at equilibrium (Table 1) correspond to the
coverage of the sample with 11 or 18 monolayers,
respectively. Considering the low relative pressures of both
adsorbates ( p= p0 0:26 for water and p= p0 0:31 for
ethanol), no such coverage can be expected and volume
sorption has to be assumed.
It is quite striking that, although the final increase in
weight differs depending on the kind of adsorbate, the
numbers of molecules per anion are very much similar. In
both cases, 3 moles of adsorbate are taken up per mole of
HP2W. This ratio indicates that one molecule of either water
or alcohol is bonded to two protonic centres, e.g.:

or that oxonium ions H3O+ are formed, e.g.


[(H3O+)3H3P2W18O62], but only half of the protonic sites
are accessible.

Table 1 shows that, also in the case of sorption on


octahydrated HP2W, the uptake of both water and ethanol is
stoichiometrically identical. However, it was rather unexpected to observe that higher amounts were absorbed on
octa- than on trihydrated samples. This difference has to be
explained by the differences in the secondary structure. In
fact, the model of the secondary structure of hydrated
Dawson HPA proposed recently by Sambeth et al. [21]
presents a rather loose structure in which HPA anions are
joined by bridges formed by protonated clusters. The
penetration of adsorbed water or ethanol molecules into such
a structure must be much easier than the penetration into the
anhydrous acid which forms a much more compact structure
in which Dawson anions are kept together by stronger and
definitely shorter hydrogen bonds.
The data given in Table 1 show that in most cases sorption
of water and alcohol on hydrated and dehydrated
H6P2W18O62 is partly irreversible and that the amount of
irreversibly bonded molecules slightly increases when
adsorptiondesorption cycles are repeated.
The behaviour of isobutene as adsorbate is completely
different from that of polar water and ethanol molecules. At
40 8C it is practically not adsorbed on dehydrated
H6P2W18O62. On the octahydrated sample it rapidly
adsorbed (Fig. 3a), and adsorption reached about seven iC4H8 moles per mole of acid. After some 510 min, the
weight of the sample began to decrease to a few tenth of mol
of i-C4H8 per mole of HP2W. This residual amount is
reversibly bonded. A possible explanation for the observed
weight decrease is the reaction between isobutene and water
originating from the catalyst (water of crystallisation)
leading presumably to the formation of tert-butyl alcohol,
TBA, which is desorbed. In fact, the formation of small
amounts of TBA was observed as by-product of the catalytic
synthesis of ETBE. The desorption of isobutene in the form
of the dimer seems less probable. The fact that on the second
exposure of the sample to i-C4H8 only a very small amount
adsorbed, seems to indicate that in the first run isobutene
molecules were adsorbed on the water molecules that are
forming the secondary structure in the hydrated sample.
These water molecules accessible to i-C4H8 were mostly

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J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

consumed in the first run and, hence, the second adsorption


was very much limited.
Fig. 3b shows that ETBE sorption on octahydrated
H6P2W18O62 exhibits a similar pattern as that of isobutene.
The initial rapid uptake is also followed by a decrease in
weight, indicating most probably a decomposition of ETBE
into isobutene and ethanol, which partly desorbed from the
sample. However, in contrast to the sorption of isobutene,
quite an appreciable portion of ETBE (about 65%) remains
and cannot be removed even by evacuation. On repeated
adsorption, the coverage is similar as in the first adsorption.
In a separate experiment the catalytic decomposition of
ETBE over octahydrated HP2W at 40 8C has been
confirmed.
The main product of the catalytic reaction of isobutene
and ethanol on H6P2W18O62 was ethyl tert-butyl ether,
independently of temperature in the range investigated (30
80 8C). Besides ETBE, small amounts of tert-butyl alcohol
and (above 40 8C) isobutene dimer were obtained.
Fig. 4a and b show a typical catalytic run carried out at
40 8C over H6P2W18O6228.8H2O previously heated in situ
at 95 8C for 0.5 h in a flow of helium. Isobutene conversion
stabilised at 44 mol.% after about 30 min and remained
constant during the rest of the run lasting 9 h without deactivation. The selectivity to ETBE calculated both from
conversion of isobutene and ethanol was higher than 90%.
The yield of TBA was about 2 mol.% and isobutene dimer
was not detected in the run presented.
The effect of reaction temperature has been studied on a
series of samples preheated at 95 8C. Fig. 5 shows yield and
selectivity to ETBE as a function of temperature. The yield
of ETBE, which was equal to 36.7 mol.% at 35 8C, reaches a
maximum of 43.0 mol.% at 40 8C and then decreases with
increasing temperature. Such a behaviour is characteristic
for reversible exothermic reactions when equilibrium is
approached. The dotted curve in Fig. 5 presents the
equilibrium yield of ETBE calculated from equilibrium
values experimentally determined by Iborra et al. [23].
Maxima at 40 8C appear also on the curves representing the
yield of ETBE and selectivity to ETBE. For this reason, this
temperature has been chosen in the further experiments in
which the effect of preheating temperature was studied. The
selectivity which was high (about 90%) at lower temperatures
decreased to 2.7% at 80 8C. This is due to the increased
production of by-products such as isobutene dimer, tert-butyl
alcohol, and other non-identified substances detected by gas
chromatography. Due to their formation, the conversion of
isobutene at 80 8C was still as high as 21.0 mol%.
The effect of the pre-treatment temperature of the catalyst
on the ETBE yield and selectivity is shown in Fig. 6. All tests
in this series of experiments were carried out at 40 8C. The
highest activity corresponding to ETBE yield above
40 mol.% was observed over the samples preheated at 80
and 95 8C. Pre-heating at 150 and 200 8C resulted in the
decrease of the yield to about 27 and to 24.6 mol.% for the
sample calcined at 300 8C.

Fig. 5. The effect of reaction temperature on the ETBE yield (a) and
selectivity of ETBE formation (b). HP2W catalyst pre-heated at 95 8C.
Dotted line presents the equilibrium yield of ETBE calculated using the
equilibrium constants determined by Iborra et al. [23].

The two different levels of activity in Fig. 6a can be


understood if the catalytic results are compared with both the
composition of the samples activated by pre-heating

Fig. 6. The effect of catalyst pre-treatment temperature on ETBE yield (a)


and selectivity of ETBE formation (b). Reaction temperature: 40 8C.

J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

(Table 2) and the sorptive properties of the samples of


approximately the same composition as in the catalytic runs
(Table 1). First, it should be observed that the most active
samples pre-heated at 80 and 95 8C contained 89 moles of
crystallisation water per mole of HPA, while in the samples
preheated at 150 and 200 8C the content of crystallisation
water decreased to about 3 H2O moles per mole HPA. The
sorption capacity of octahydrated HPA, as shown above, was
more than twice as large as that of trihydrated HPA. Hence,
the difference in the catalytic behaviour can be ascribed to
the differences in the sorption capacities of the samples due
to the different secondary structure. The problem of the acid
strength of the catalysts with different contents of water
remains open for further studies.
In our experiments, the ethanol used had the composition
close to that of an azeotropic mixture and, hence, the
possibility of water vapour sorption by the catalyst in the
course of catalytic run should be taken into account. This
was monitored by comparing the water content in the gas
leaving the catalytic reactor with that in the feed.
Fig. 7 shows, as an example, the amounts of water
remaining at the catalyst as determined in particular
chromatographic analyses for the sample calcined at
95 8C. It is seen that the highest consumption of water
vapour from the feed by the catalyst occurred during the first
60 min of reaction and then decreased to low values, which
do not contribute to the essential change of the sample
composition. The integration of the area below such a curve
allows a rough estimate of the amount of water taken up
during the catalytic run. The details of the procedure for
determining the deficit of reagents are given in [6]. The
results obtained in this way are given in the last column of
Table 2.
The fact that in our catalytic experiments water was
present both in the solid phase of catalyst as the crystallisation water and in the gas phase, to which it was
introduced together with ethanol as the component of the
azeotropic mixture, also raises the question of its participation in the catalytic process. On the one hand, its presence
enables the formation of tert-butyl alcohol, TBA, as side
product, and on the other hand, it is a factor which

Fig. 7. Sorption of water vapour from the feed by the catalyst during the
run. Catalyst pre-heated at 95 8C; reaction temperature: 40 8C.

59

Fig. 8. The effect of the content of water in the feed on ETBE yield (a) and
selectivity of ETBE formation (b). Reaction temperature: 40 8C.

determines the secondary structure of the heteropolyacid,


the importance of which has been shown in the present study.
Although the effect of water will be the object of further
studies, some facts will be discussed here.
The effect of water originating from the feed on the
course of the ETBE synthesis is shown in Fig. 8. The
catalysts were preheated at 95 8C and the reaction was
carried out at 40 8C using ethanol containing 0.25, 0.32, and
4.40 wt.% of water. It is seen that the highest yield and
selectivity of ETBE were obtained when the azeotropic
preparation of alcohol with 4.40 wt.% water was used. A full
explanation for the synergetic effect of water cannot be
proposed at this moment. However, it is not excluded that in
the case of the nearly absolute ethanol crystallisation
water is extracted from the catalyst, thus destroying the
secondary structure of the catalyst and lowering its activity.
It should be stressed that no any essential changes in the
IR spectra of the Dawson anion in the samples calcined
below 100 8C and also at 150 and 200 8C were observed as
compared to those of the fully hydrated heteropolyacid
(Table 3). The only exception were small shifts in the
nWOc W vibration. Heating of the samples to 300600 8C
caused more appreciable changes in the IR spectra. The shift
of the nWOd and nWOb W vibrations, the strongly
decreasing intensity of the structural vibrations, as well as
the appearance of some new bands indicates the formation of
a new phase. We ascribe these changes to the defected
structure of Dawson ions due to the dehydroxylation
process.

60

J. Pozniczek et al. / Applied Catalysis A: General 286 (2005) 5260

The distinct growth of the absorbances ratio AWOc W :


AWOd in the sample calcined at 600 8C might indicate that
in the strongly disordered crystal lattice the ratio of the
number of WOcW chains (Oc being the corner oxygen
atoms joining two W3O10 subunits in the Dawson anion) to
the number of terminal oxygens is higher than 18:18 = 1,
which corresponds to the strict stoichiometry. Such a
situation might appear if a certain number of WOcW
chains would be formed between neighbouring anions at the
expense of vanishing terminal Od atoms. Such a process
would be realised, for example, by forming an oxygen
vacancy (dehydroxylation process) at the W Od site in one
anion and subsequent filling it by a terminal Od atom of the
neighbouring anion.

5. Conclusions
Dehydration of Dawson-type heteropolyacid H6P2W18
O6228.8H2O proceeds in two stages. In the first stage, up to
about 200 8C, the crystallisation water is gradually lost
forming octa- and trihydrates. Anhydrous H6P2W18O62 acid
is stable up to about 250 8C. Above this temperature
dehydroxylation of the acid occurs during which 3.0 moles
of the so-called water of constitution are removed.
Anhydrous and trihydrated HP2W absorbed only about 3
moles of H2O or C2H5OH per mole of heteropolyacid, while
the octahydrated form sorbed up to about 8 moles of water or
alcohol per mole of HP2W. This increase in the sorption
capacity is ascribed to the differences in the secondary
structure of the hydrate, which appears to be looser in the
case of octahydrated sample than in the anhydrous or
trihydrated acid. Non-polar isobutene is not sorbed on the
anhydrous heteropolyacid. On the other hand, it is sorbed on
hydrated samples but the rapid sorption is followed by a
slower reaction between isobutene and water molecules
originating from the solid, thus producing tert-butyl alcohol
(TBA) that gets desorbed.
The main product of the catalytic reaction between
isobutene and ethanol is ethyl-tert-butyl ether. The highest
conversion of isobutene observed at 40 8C was 43.0%. The
selectivity to ETBE was then as high as 90%. The
investigation of the thermal pre-treatment of the catalyst
has shown that the most effective catalyst was the sample
which contained 8 moles of water per mole of HP2W. This
sample was characterised by the highest sorption properties.
Hence we deal in this case with a distinct influence of the
heteropolyacid secondary structure on the catalytic activity.

Acknowledgements
This work was financially supported by KBN (Committee for Scientific Research of Poland) Grant No. 4 T09A 099
23. The authors express their gratitude to Professor G.
Baronetti for friendly providing details of the procedure of
H6P2W18O62 synthesis. The authors thank Dr. E. Szneler for
carrying out the 31P NMR analysis.

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