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Catalysis, 69 (1991)
Elsevier
Science
Publishers
139-148
B.V..
139
Amsterdam
tel. (+33)
(Received
72445389.
received 5 September
1990)
Abstract
The kinetics of methanol dehydration catalysed by dealuminated H-mordenite were studied using a
packed bed flow reactor at atmospheric pressure in the 473-573 K temperature range. The data were
interpreted in terms of Langmuir-Hinshelwood
rate equations and they suggested that two different
sites are operative during the dehydration, probably an acid site and its adjacent basic site on which
methanol forms respectively [CH,.OH,]+
and [CH,O] _ species which, upon condensation, give dimethyl ether and water. Dimethyl ether and/or water compete with the methanol adsorption particularly at lower reaction temperatures and the surface coverages by activated complexes are always large,
so that one observes a kinetic order with respect to methanol of less than one.
Keywords: methanol dehydration,
ether )
(dimethyl
INTRODUCTION
The acid zeolite-catalysed conversion of methanol into hydrocarbons involves several reaction steps which have been well documented in the literature
111.
140
EXPERIMENTAL
AND DISCUSSION
Under the reaction conditions indicated, DME and water are the only products formed. The thermodynamic constants for the equilibrium
2 CH30H=CH30CH3+H20
have been calculated for temperatures in the range 473-573 K. The derived
values of AGT , the equilibrium constant K,, and the thermodynamic yield Yth
are given in Table 1.
In order to establish the true chemical kinetic expression, the domain of flow
rate, F, where mass transport effects were practically absent, was first determined. Fig. 1. shows the influence of the flow-rate on the conversion of methanol. The rate of the reaction is not dependent on the conversion for values of
flow rate above 10 1 h- in the temperature range 473-573 K. At the highest
temperature (573 K) and methanol pressure (80 Torr, 1 Torr= 133.3 Pa) and
for a flow-rate of 10 1 h-l over 20 mg of catalyst, the conversion was about
141
TABLE 1
Thermodynamic data for dehydration of methanol
Temperature
(K)
A Cl
(J mol-1
YLh
(fro)
473
573
- 17727
- 18735
92.6
52.0
95.1
93.5
(%)
20
0.1
I
0.2
F-l
(h
1-l)
Fig. 1. Variation of the conversion level as a function of the contact time for a methanol partial
pressure of 80 Torr over 0.2 g of catalyst at (A ) 473 K, (m) 523 K and (e ) 573 K.
16%,a value well below the thermodynamic yield (Table 1). Hence, the kinetic
data were established for those reaction conditions where the rate of the reaction was limited neither by transport processes nor by thermodynamics.
142
log1o
1.5
p0
Fig. 2. Logarithmic plots of the methanol dehydration rate versus the methanol partial pressure
at (A ) 473 K, (m) 523 K and (0 ) 573 K (r in mmol converted methanol per h and per g of
catalyst, P, in Torr ).
143
PO/
(tot-r
h gcat
mmol-I)
6
40
80
PO (torr)
Fig. 3. Linear transforms of the methanol dehydration rate as a function of the methanol partial
pressure (Langmuir-Hinselwood model) at (0 ) 473 K, ( n ) 523 K and (A ) 573 K.
served indicates that at 473 K the Langmuir-Hinshelwood model fits the results only if one considers that the reaction products, DME and/or water, remain adsorbed on the active centres. The inhibiting effect of water on the
dehydration of methanol at 473 K was further demonstrated by the data obtained for conversion of methanol/water mixtures. Indeed, at 473 K and P, = 40
Torr, the rate of dehydration decreased from 12.3 to 6.8 mmol h-l g&l when
144
Po/
(tow
h g
cat
mm01 -I.,
0.2
Fig. 4. Linear transform
0. 4
of the inhibiting
0.6
PDME
on methanol
(torr1
dehydration
at
473 K.
the partial pressure of water increased from zero to 5 Torr. In contrast, at 573
K, almost no decrease of the reaction rate occurred on adding water to the
methanol feed.
The kinetic data for the dehydration of pure methanol at two different partial pressures (P, = 10 or 40 Torr ) are collected in an Arrhenius plot in Fig. 5.
This figure shows that the apparent activation energy increased with P,, as
may be expected for a Langmuir-Hinshelwood mechanism.
The results shown in Figs. 1, 2 and 3 indicate that, when neither diffusion
nor thermodynamics limit the reaction rate, the order relative to methanol, n,
remains between 1 and 0.5. Moreover, n increases with the temperature and
decreases with the methanol partial pressure leading to the belief that the rate
145
\
log10
t
\
0
\
0
\
a
\
0
\
e
\
8,
\
\
l-7
1.9
lo3 K-l
x
2.1
146
[OH]-
(ii) dimethyl ether (or/and water) competes with methanol for the protonic
site
(CH,),O+H+=
[ (CH,),.OH)]+
then the rate expression for methanol dehydration should be r= rZ0,8being the
coverage of dual sites by two methanol molecules. Moreover 8, and & the
surface coverages by [ CH3 .OH,] + and [ CH30] - respectively, are given by:
f31=
a 3,
and
l+b PDME+a,P,
02=
GPO
1+a,p,
From a statistical analysis, it may be shown that f3=& 0,. Hence, the rate
equation for the methanol dehydration should be of the form:
r=k
ala2PZ
l+bPDME+
[a,+
(1+bPDME)a2]Po+a,a,P~
ala2E
1+ (a, +a,)P,+a,azP:
It is obvious that the data presented in Figs. 2 and 3 fit this expression only if
we assume that (al + a*) PO + a, a2 Pz is much greater than one, that is if the
surface coverages by [ CH,.OH,] + and/or [ CHBO] - are important. With such
an assumption, the rate expression becomes:
r=k
APo
l+AP,,
where
A =-
ala2
a1
+a2
147
TABLE2
Kinetic parameters
for dehydration
Temperature
(K)
(mmol h-
523
147
573
739
of methanol.
E
g&i)
(kJ mol-)
80.3
[SIT
al a2 PO
r=k(a,
+as)+a,bPDME
APo
=kl+Abp
DME
al
A good fit was observed by plotting P,,/r versus PDME (Fig. 4).
Such an analysis of the kinetic data allows are to determine the values of the
rate constant, Fz,at 523 and 573 K from the slope of the straight lines of Fig. 3;
they are listed in Table 2 with the corresponding value of the true activation
energy, E=80 kJ mol-. From the latter value, one can calculate the value
k= 20.8 mmol h- g&t for the rate constant at 473 K. Furthermore, the slope
of the straight line of Fig. 4 measures the ratio b/a,K; the value obtained is 6.81
h gcatmmol-l. Hence, b=142 a,, in fair agreement with the assumption that
&ME 3 alp,.
CONCLUSION
Analysis of the kinetic results has shown that the dehydration of methanol
to dimethyl ether proceeds through the combination of two adjacent different
activated complexes, formed by adsorption of methanol on two different active
centres. At 473 K, dimethyl ether and/or water inhibit the reaction by competing with methanol for protons. At temperatures between 473 and 573 K,
the coverages of the active centres by methanol are large.
Thus, a dual site mechanism may be proposed for highly dealuminated Hmordenite, as has been suggested for methanol dehydration on sulphonated
polystyrene catalysts [ 61.
In the case of zeolites, the dual active centre would be one acid site H+ and
its adjacent basic site 02-. On acid sites, methanol would be protonated to
form [ CH3*OHP] + which then rapidly generates [ CH,] + and H20, while on
basic sites methanol would react to form [ CH,O] - and [OH] -. Dimethyl ether
148
may then be formed by combination of two adjacent activated species, the dual
active centre being regenerated through the reactions:
H,O+
[OH]-=[H,O]++O-
and
[H,O]+=H,O+H+
REFERENCES
1 C.D. Chang, Catal. Rev. Sci. Eng., 25 (1983) 1.
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Conf. on Zeolites, 1980, p. 649.
3 T. Mole and J.A. Whiteside, J. Catal., 75 (1982) 284.
4 J. Bandiera, C. Hamon and C. Naccache, in D. Olson and A. Bisio (Editors), Proc. 6th Conf.
on Zeolites, Butterworths, London 1984, p. 337.
5 S.G. Lias, J.F. Liebman and R.D. Levin, J. Phys. Chem. Ref. Data, 13 (1984) 695.
6 B.C. Gates and L.N. Johanson, J. Catal., 14 (1969) 69.