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A Steady-State Kinetic Model for Methanol Synthesis and the Water Gas
Shift Reaction on a Commercial Cu/ZnO/Al2O3 Catalyst
K. M. Vanden Bussche1 and G. F. Froment2
Laboratorium voor Petrochemische Techniek, Universiteit Gent, Krijgslaan 281, B9000 Gent, Belgium
Received January 30, 1995; revised December 18, 1995; accepted January 30, 1996
rCH3 OH =
f CO f H2 2 f CH3 OH /K 2
,
(A + B f CO + C f H2 + D f CH3 OH )3
Press, Inc.
INTRODUCTION
rCH3 OH
m n
2
AeE/RT pCO
pH2 1 pCH3 OH pCO pH
K 2
2
=
,
1 + DeF/RT pCO2 pH2
!
0.34
0.5
pCH
pCO
pH2
3 OH
rCH3 OH = k
0.5
.
0.66
pCH
pCO pH2 K 2
3 OH
1
Present address: Koninklijke/Shell Laboratorium, P.O. Box 38000,
NL-1030BN Amsterdam, The Netherlands. E-mail: busschel@ksla.nl.
2
To whom correspondence should be addressed.
1
0021-9517/96 $18.00
c 1996 by Academic Press, Inc.
Copyright
All rights of reproduction in any form reserved.
3
2
K redox
( pCO2 / pCO )3 pCO pH
pCH3 OH /K 2
2
= const
[1 + K redox ( pCO2 / pCO )]3 (F + K CO2 pCO2 )n
3
+ k 0 pCO2 (1/K 1 ) pCH3 OH pH2 O pH
.
2
These equations later served as a base for the work of McNeil et al. (6), who expanded on the mechanism of the direct hydrogenation of CO2 and the possible role of ZnO
as a hydrogen reservoir. Despite the much larger number
of parameters in the resulting model, the latter authors did
not manage to show a significantly better agreement between the experimental and the simulated results than that
already obtained by Klier et al. (5).
Villa et al. (7) realized that a thorough modeling of the
methanol synthesis system should also involve a description
of the water gas shift reaction. Assuming thereby again that
the hydrogenation of CO is the only route to methanol, this
resulted in the following set of equations
rCH3 OH =
rRWGS =
f CO f H22 f CH3 OH /K 2
(A + B f CO + C f H2 + G f CO2 )3
f CO2 f H2 f CO f H2 O K 3
,
M2
equations:
rCH3 OH,1
3/2
3/2
0
K CO2 f CO2 f H2 f CH3 OH f H2 O f H2 K 1
kps,1c
=
1/2
1/2
(1 + K CO f CO + K CO2 f CO2 ) f H2 + K H2 O K H2 f H2 O
rCH3 OH,2
1/2
3/2
0
kps,2c
K CO f CO f H2 f CH3 OH f H2 K 2
=
1/2
1/2
(1 + K CO f CO + K CO2 f CO2 ) f H2 + K H2 O K H2 f H2 O
rRWGS
0
K CO2 f CO2 f H2 f H2 O f CO K 3
kps,3b
=
1/2
1/2
.
(1 + K CO f CO + K CO2 f CO2 ) f H2 + K H2 O K H2 f H2 O
3
k1 pCO2 pH2 1 pCH3 OH pH2 O K 1 pCO2 pH
2
rCH3 OH =
pCO2 + K H2 O pCO2 pH2 O + K 00 pH2 O
MODEL FOR METHANOL SYNTHESIS AND THE WATER GAS SHIFT REACTION
FIG. 1. Schematic view of the bench scale reactor system used in the kinetic data acquisition.
FIG. 2. Reaction scheme for the synthesis of methanol and the water
gas shift reaction.
SCHEME I. Reaction scheme for the synthesis of methanol and the
reverse water gas shift reaction. rds, rate determining step.
species (2225). On the oxidized copper surface, carbonate structures are formed by further adsorption of CO2
(2628). These carbonates are quickly hydrogenated, first
to bicarbonate structures and subsequently to Cu formate,
formaldehyde, methoxy species, and finally methanol. In
this sequence, shown in the left-hand side of Fig. 2, the rate
determining step is the hydrogenation of the formate, which
is generally accepted to be the longest living intermediate
in methanol synthesis on copper (15, 20, 29).
At two stages in the hydrogenation of CO2 to methanol,
surface oxygen is released from the molecule. This species
is also hydrogenated by the available hydrogen atoms,
yielding hydroxyl groups and subsequently water, which
is known to desorb relatively slowly. In fact, the right-hand
side of Fig. 2 describes the reverse water gas shift reaction, proceeding according to a redox mechanism. In this
sequence of reactions, the dissociative adsorption of CO2
is rate determining, as was shown by Nakamura et al. (17),
Fujita et al. (30), and Ernst et al. (31). Their results, for
equimolar mixtures of CO2 and H2, are all the more valid
under industrial conditions, since the ratio pCO2 / pH2 then
only amounts to 0.05.
Scheme I shows the different elementary reaction steps
to be considered and introduces the nomenclature for the
equilibrium (Ki) and rate (ki) constants.
Derivation of the corresponding set of kinetic equations
is performed under the hypothesis of pseudo-steady-state
of the concentration of the different surface intermediates
(13). The concentration of free active sites, cs, can be obtained from a balance over the total number of sites, ct, from
which the concentrations of the surface intermediates have
been eliminated. This balance for ct is given by
cOs
cH Os
cHCO2 2s
cCO3 2s
cHs
cs
+
+ 2 +
+
+
.
1=
ct
ct
ct
ct
ct
ct
cs
ct
2
,
in which
a = K 20 K 3 K 4
b =1+
K H2 pCO2
pH2 +
K 20 K H2 O pH2 O pCO2
,
K H2 K 8 K 9
pH2
[1]
K H2 O p H2 O p
+ K H2 pH2 + K H2 O pH2 O ,
K 8 K 9 K H2 pH2
and
K 20 = K 2 ct .
This balance is not linear in cs and has to be solved as a
quadratic equation in cs /ct. Only the positive root has to
be considered. Simple analysis reveals that the normalized
concentration of free active sites,
b + b2 + 4a
cs
=
,
=
ct
2a
[2]
MODEL FOR METHANOL SYNTHESIS AND THE WATER GAS SHIFT REACTION
1 pH2 O pCH3 OH
0
0
rMeOH = k5a K 2 K 3 K 4 K H2 pCO2 pH2 1
3
3
K 1 pH
p
CO
2
2
pH O pCO
rRWGS = k10 pCO2 1 K 3 2
,
pCO2 pH2
in which
0
k5a
k10
= k5a
ct2
= k 1 ct ,
and represents a function of partial pressures and parameter groups, given by [1] and [2]. The use of fugacities,
rather than partial pressures, was considered, applying the
SoaveRedlichKwong equation of state (36). The compressibility factors were never outside the 0.99 to 1.01 range
and found to give negligible changes in the results.
The equilibrium constants K1 and K3 are thermodynamically determined. The values were taken from Graaf et al.
(1986):
log10 k1 =
log10 1/K 3 =
3066
10.592
T
2073
+ 2.029.
T
PARAMETER ESTIMATION
K H2 ,
K H2 O ,
K 20 K H2 O
,
K8 K9
K 20 K 3 K 4
K H2 ,
0
k5a
K 20 K 3 K 4 K H2 ,
K H2 O
K 8 K 9 K H2
k10 ,
and
K 20 K H2 O
,
K H2 K 8 K 9
never yielded any statistically significant contribution. The
surface converge by these species was, therefore, considered to be negligible and discarded from the factor. By
leaving out these bridging compounds, however, the a term
in equation [1] becomes identical to 0 and the normalized
concentration of free active sites is reduced to
B(i) 1
1
equations (e.g., for CO and CO2) had to be considered.
(i) = A (i)exp
The integration of the two equations, containing the proR
Tav
T
posed kinetic expressions, was performed applying fourthin which Tav equals 501.57 K.
and fifth-order Runge Kutta methods.
Calculating the frequency factors back to the original
The parameter estimation was based on minimization of
context of Arrhenius or Vant Hoff,
2
n
X
X
A(i) exp(B(i)/RT ),
wi
(yi j,obs yi j,calc )2 ,
i=1
j=1
where B(i) represents either E or (1H) or a combination of those, the parameter values of Table 2 are obtained,
3
The data set was too extensive to be incorporated in full in the text.
It is available from the corresponding author.
TABLE 1
Parameter Values and Corresponding Approx. 95% Confidence Intervals for the Kinetic Model
K H2
A
B
K H2 O
A
B
K H2 O
K 8 K 9 K H2
0
k5a
K 20 K 3
K 4 K H2
k10
Standard
deviation
Value
B
A
B
A
B
Upper limit
95% conf. int.
t0.95 value
30.82
17,197
0.375
1864
30.08
13,545
31.56
20,850
81.97
9.23
558.17
124,119
10.18
3058
538.23
118,125
578.11
130,112
54.86
40.59
3,453.38
260.29
2,943.21
3,963.55
13.27
Lower limit
95% conf. int.
7,070.34
36,696
259.75
6102.8
6,561.23
24,734
7,579.45
48,657
27.22
6.01
1.65
94,765
0.02
1694
1.61
98,084
1.69
91,446
82.31
55.96
0
K 20 K 3 K 4 K H2 pCO2 pH2 1(1/K ) pH2 O pCH3 OH pH
p
k5a
2 CO2
p
(1+(K H2 O /K 8 K 9 K H2 )( pH2 O / pH2 )+ K H2 pH2 +K H2 O pH2 O )3
rRWGS =
k10 pCO2 [1 K 3 ( pH2 O pCO / pCO2 pH2 )]
p
,
(1+(K H2 O /K 8 K 9 K H2 )( pH2 O / pH2 )+ K H2 pH2 +K H2 O pH2 O )
[3]
in which the pressures are expressed in bar and the reaction
rates in mol/kgcat/s.
EVALUATION OF THE MODEL
TABLE 2
Parameter Values for the Steady-State Kinetic
Model
A
B
0.499
17,197
K H2 O
A
B
6.62 1011
124,119
K H2 O
K 8 K 9 K H2
3,453.38
A
B
1.07
36,696
A
B
1.22 1010
94,765
K H2
0
k5a
K 20 K 3
K 4 K H2
k10
MODEL FOR METHANOL SYNTHESIS AND THE WATER GAS SHIFT REACTION
TABLE 3
Operating Conditions for the Simulation
of the Bench Scale Reactor
S.
0 1Sads
Parameter 1, describing the square root of the hydrogen adsorption constant, satisfies both criteria, since 1Sads
and S respectively amount to 11.56 and 145 J/mol/K. The
water adsorption constant, i.e., parameter 2, also passes the
test, with values of 195 and 207 J/mol/K, respectively (S values taken from Stull et al. (35)).
A third and final rule pertains to the sign of B(i). It has
to be positive for the adsorption constants, reflecting the
heat of adsorption. Parameters 1 and 2 satisfy this criterion.
The exponential of the reaction rate constants on the other
Catalyst
Density (kg/m3s )
Porosity (m3g /m3s )
Mass (g)
Pellet diameter (ms)
Reactor
Diameter (mr)
Length (mr)
Operating conditions
T (K)
pt (bar)
m (105 kg/s)
Feed composition
CO (mol%)
H2O (mol%)
MeOH (mol%)
H2 (mol%)
CO2 (mol%)
Inert (mol%)
1775
0.5
34.8
0.0005
0.016
0.15
493.2
50
2.8
4.00
0.00
0.00
82.00
3.00
11.0
WGS
hydrog.
FIG. 5. (a) Simulated concentration profiles in an adiabatic reactor for the conditions specified in Table 3. (b) Simulated temperature profiles in
an adiabatic reactor for the conditions specified in Table 3.
(overdimensioned) catalyst bed. At lower inlet temperatures, the reaction is kinetically limited, while at higher Tin
the thermodynamic equilibria set the upper limits for the
exit conversion.
Finally, it is interesting to observe the model response
upon variation of the ratio of pCO and pCO2 at constant pH2 ,
pt, and temperature. Experiments of this nature were performed by Klier et al. (5) over a Cu/ZnO catalyst, at 75 bar
and temperatures between 225 and 250 C in an isothermal
reactor. As shown by the points in Fig. 8, the authors found
a maximum conversion to methanol at (2 : 28 : 70) mol% of
(CO2 : CO : H2). According to Klier et al., CO acts as the
main source of carbon in methanol, while CO2 ensures a
certain surface oxidation level. The lower conversions at
lower CO2 concentrations are due to overreduction of the
surface, while at higher CO2 levels, this species strongly
covers the active sites, decreasing catalyst activity.
FIG. 6. (a) Simulated concentration profile of CH3OH at various inlet pressures. (b) Simulated temperature profile at various inlet pressures.
(c) Simulated concentration profile of CO2 at various inlet pressures.
MODEL FOR METHANOL SYNTHESIS AND THE WATER GAS SHIFT REACTION
FIG. 7.
(a) Simulated temperature profile at various inlet temperatures. (b) Simulated concentration profile of CH3OH at various inlet temperatures.
The curve in Fig. 8 results from the simulations of the experiments performed by Klier et al. (5) at 250 C, using the
current kinetic model, that was not tuned to Kliers data. It is
worthy of note that the pressure as well as the composition
of the gas are well outside the experimental window used
to estimate the kinetic parameters. Although the present
model considers only CO2 as a precursor to methanol, it
is perfectly able to qualitatively predict the evolution observed by Klier et al. (5). This behavior can, therefore,
equally well be ascribed to a shift in the methanol equilibrium position upon the introduction of water (or CO2), the
strong adsorption of water, and the changing level of surface oxidation. In terms of the present work, the evolution is
solely due to the changing oxygen (or water) concentration
in the system.
In summary, these results show that the proposed model
describes the influence of pressure, temperature, and gas
phase composition in a physically acceptable way, even
Based upon a detailed reaction scheme derived from literature data and own experimental work (21), a steadystate kinetic model was developed for methanol synthesis
and the water gas shift reaction. Unlike some other kinetic
models available in the literature, the current model effectively couples the rate of both overall reactions through the
common surface oxygen intermediate.
The experiments used to determine the kinetic parameters, were performed on an industrial Cu/ZnO/Al2O3 catalyst at pressures between 15 and 51 bar and for temperatures
varying between 180 and 280 C.
All parameters are statistically significant and satisfy
each of the physico-chemical criteria postulated by Boudart
FIG. 8. Conversion to methanol for different ratios of yCO /yCO2 at yH2 = 0.7. pt = 75 bar; T = 250 C; r, experimental results by Klier et al. (5);
line, simulated using the current kinetic model.
10
(34). Furthermore, the kinetic equations describe the influence of inlet temperature, pressure, and feed composition
in a physically acceptable way. The mechanistically sound
foundations of the model allow for accurate predictions of
catalyst behavior outside the original experimental window.
ACKNOWLEDGMENTS
The experimental assistance of V. Vanrysselberghe is gratefully acknowledged. Part of the present work was performed within the framework of the IUAP Center of Excellence Grant, provided by the Belgian
Ministerie voor de Programmatie van het Wetenschapsbeleid. The authors
are grateful to ICI for providing a sample of their 51-2 catalyst.
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