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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
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].
54
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
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).
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
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
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.
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
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
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
58
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].
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.
60
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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