Chemical Engineering Science, Vol. 43, No. 12, pp. 3185-3195, 1988. ooo9-X09/88 $3.00 + 0.

00
Printed in Great Britain. 0 1988 Pergamon Press plc

KINETICS OF LOW-PRESSURE METHANOL SYNTHESIS

G. H. GRAAF,+ E. J. STAMHUIS and A. A. C. M. BEENACKERSZ

Department of Chemical Engineering, State University of Groningen, Nijenborgh l&9747 AC Groningen,
Netherlands

(Received 11 June 1987; acceptedfor publication 1 June 1988)

Abstract-ThB kinetics of low-pressure methanol synthesis, starting from CO, CO, and hydrogen over a
commercial Cu-Zn-Al catalyst, were studied in a spinning basket reactor at p= 15-50 bar and
T= 21&245C. The results show that methanol can be formed from both CO and CO,. Besides these two
reactions the water-gas-shift reaction takes place. Based on these three reactions and a dual-site adsorption
mechanism, 48 kinetic rate models are derived. Hydrogen is believed to adsorb dissociatively. The
experimental results support this assumption. Based on X2-statistics and consistency tests a final kinetic rate
model is selected. This kinetic model gives a significantly better agreement with the experimental results than
kinetic models taken from recent literature.

INTRODUCTION Seyfert and Luft (1985) (see Table 2) assumed a

Kinetic data often play an important role in designing
a chemical reactor and methanol synthesis is no
exception to this. Unfortunately, there is still no
agreement in the literature on the kinetics of methanol
synthesis, not even for the same types of catalyst. The
objectives of this paper are to clarify which reactions
are involved in methanol synthesis and to derive
kinetic rate equations for these reactions.
LITERATURE
Although low-pressure methanol synthesis is an
important industrial process, the kinetic studies on
this subject as published in the open literature are very
often conflicting. The role of CO, especially is in-
sufficiently understood. This can be seen in Table 1.
Most models published up till now describe methanol
formation from CO only. The role of CO, in these
models, if present, is restricted to competitive adsorp-
tion on the active sites of the catalyst. Contrary to this
some authors (Dybkjaer, 1985; Chinchen et al., 1984)
claimed that methanol is formed from CO, only.
According to Dybkjaer this is because strong adsorp-
tion of CO, prevents the co-adsorption of CO.
Chinchen et al. based their conclusions on exper-
iments with labelled carbon in CO,. A third group of
authors concluded that methanol is formed from both
CO and CO,. Liu et al. (1985) came to this conclusion
based on experiments with labelled oxygen in CO*.
Denise and Sneeden (1982) and Klier et al. (1982)
reached the same conclusion based on kinetic exper-
iments.
Most of the authors mentioned in Table 1 presented
kinetic rate expressions. The rate expressions pub-
lished more recently are listed in Table 2.
TPresent address: N.V. Nederlandse Gasunie, Laan
Corpus den Hoom 102, 9728 JR Groningen, Netherlands.
*To whom correspondence should be addressed.
Langmuir-Hinshelwood mechanism in which CO and
H, are believed to be non-dissociatively adsorbed on
the same kind of active sites. Methanol is made in a
two-step reaction: in the first step formaldehyde is
formed in an equilibrium reaction; the second step, in
which adsorbed H, and adsorbed formaldehyde react
to form methanol, is believed to be rate-controlling.
Villa et al. (1985) (see Table 2) also assumed a
Langmuir-Hinshelwood mechanism in combination
with non-dissociative adsorption of CO and H,. The
rate-controlling step is believed to be a trimolecular
surface reaction between adsorbed CO and two ad-
sorbed H, molecules as proposed originally by Natta
(1955).
Klier et al. (1982) (see Table 2) presented a kinetic
rate expression based on two synthesis routes. The
first term in their kinetic rate expression describes
methanol formation from CO and H,. Furthermore
they assumed that the active sites can be reduced to
inactive sites by a redox equilibrium involving CO and
CO,. The second term in their kinetic rate expression
describes methanol formation from C02.
The kinetic rate expression proposed by Dybkjaer
(1985) (see Table 2) is based on a dual-site
Langmuir-Hinshelwood mechanism in which H, is
believed to adsorb dissociatively and reacts with ad-
sorbed CO,. Dybkjaer also reported the results of
studies on the chemisorption of H,, H,O, CO and
CO2 on Cu-Zn<r and Cu-Zn-Al catalysts. H, and
H,O are believed to adsorb competitively on one kind
of active site, while CO and CO2 are adsorbed on a
second kind of active site.
In addition, Herman et al. (1979) noted the prob-
ability of a dual-site mechanism, because ZnO is a
good hydrogenation catalyst that activates H, by
dissociative adsorption, while CO is poorly adsorbed
on ZnO, and because univalent copper is known to
adsorb CO but not H,. Matulewicz (1984) concluded
from initial-rate experiments that a dual-site mech-

3185
3186 G. H. GRAAF et al.
Table I. Role of CO, in methanol synthesis as reported by several authors

Carbon source Adsorption

Authors for methanol of CO*? Catalyst

Natta (1955) co Zn-Cr

Bakemeier et al. (1970) co Yes Zn-Cr
Leonov et al. (1973) co No Cu-Zn-Al
Schermuly and Luft (1977) co Yes cu-?
Denise and Sneeden (1982) co +co, Cu-Zn-Al
Klier et al. (1982) co + co, Yes Cu-Zn
Monnier et al. (1984) co Yes Cu-Cr
Chinchen et al. (1984) co* Yes Cu-E--AI
Villa et al. (1985) co Yes Cu-Zn-Al
Liu eC al. (1985) co + co, Yes Cu-Zn
Seyfert and Luft (1985) co Yes Cu-Zn
Dybkjaer (1985) co2 Yes Cu-&-Al,
Cu-Zn-Cr

Table 2. Kinetic rate expressions for the methanol formation on Cu-containing

catalysts as found in recent literature

Kinetic rate expression

Authors rCH,oH =

&of i% -SCH,OHI~;,
Seyfert and Luft (1985)
(~,+~,f,,+~3~2+~4fCHJOH+~5fCOfH~+~6fC0~~2
(p=80-140 bar, T=235-265C)

.&of ;, --fcn,o~IK;,
Villa et al. (1985)
(Al+Azfco+A,f,oz+A,~~fH,)3
(p=3&95 bar, r=215-245C)

~,~:(p,mJPccd3 A,A:(PcoPH~ -PPCHK,HIK~,)

Klier et al. (1982)

Dybkiaer (1985)

anism is more likely than a single-site mechanism. He synthesis of methanol. Additionally, new kinetic rate
also concluded that no distinction can be made be- expressions are presented for the reactions involved in
tween molecular H, adsorption and dissociative H, methanol syntheis. Finally, these new rate expressions
adsorption. Liu et al. (1984) reported an inhibiting will be compared with those listed in Tables 2 and 3.
effect of water on the methanol production. The
results of Dybkjaer (1985) are in agreement with this
observation. THEORY
From the authors mentioned in Table 2 only Villa et Reaction schemes and kinetic rate expressions
al. and Dybkjaer presented kinetic rate expressions for Without knowing whether methanol is formed from
the water-gas-shift reaction. These rate expressions CO, CO, or both, the safest way of writing down a
are listed in Table 3. reaction scheme is to include both routes. Because the
From the literature survey presented here it follows Cu-Zn-Al catalysts are known to catalyse the water-
that still no agreement exists in the open literature on gas-shift reaction as well, this reaction should be
the kinetics of methanol synthesis. We are of the modelled too.
opinion that this lack of agreement is mainly caused Therefore the following three reactions are the basis
by the complicating effects of the simultaneously for the derivation of the kinetic rate expressions:
proceeding reactions. Due to the presence of the
water-gas-shift reaction it is in no way a simple matter (A) CON-+ 2H, = CH,OH (1)
to conclude unambiguously whether methanol is
formed from CO, CO, or both. This paper will (B) CO, + H2 = CO +H,O (2)
quantify the relative importance of CO and CO, in the (C) CO, + 3H, = CH,OH + H,O. (3)
 Kinetics of low-pressure methanol synthesis 3187

Table 3. Kinetic rate expressions for the water-gas-shift reaction on

Cu-Zn-Al catalysts as found in recent literature

Kinetic rate expression

Authors r&410=

fco&, -fHzofcoIG
Villa et al. (1985)
A5

(p=3&95 bar, T=215-245C)

From the results of Dybkjaer (1985), Herman et al. (C4) H,C02sl + Hs2 = H,COsl + H,Os2 (17)
(1979) and Matulewicz (1984) all reactions are as- (C5) H,COs1+Hs2=H,COsl +s2 (18)
sumed to be based on a dual-site Langmuir- (C6) H,COsl +Hs2 =CH,OH + sl +s2. (19)
Hinshelwood mechanism. On site 1 CO and CO,
Although these schemes contain some reactions with
adsorb competitively, while on site 2 H, and H,O
equal stoichiometry [e.g. eqs (10) and (18)], these
adsorb competitively. The adsorption of methanol is
reactions are regarded as being different. Assuming
assumed to be negligible. H, is believed to adsorb
the total number of sites 1 and 2 is constant per weight
dissociatively. However, it is quite straightforward to
of catalyst and neglecting terms originating from
derive alternative kinetic rate expressions that are
intermediate products, the following equations are
based on molecular adsorption of H,. It is now
obtained:
possible to write down the elementary reactions
necessary for the overall reactions (AHC). c,1,,0t = c,, + ccor1 + cco2s1 (20)
Adsorption equilibria:
cs2.,01 = &2 + cHs2 + CHzOa2. (21)

co + sl = COsl (4) Kinetic rate expressions can be obtained by choosing

co, + sl = co+1 rate-controlling steps for each overall reaction
(5)
[(AHC)] and assuming that all the other elementary
H, + 2~2 = 2Hs2 (6) reactions are at equilibrium. For instance, if reactions
H,O +s2 = H,Os2. (7) (A2), (B2) and (C2) are chosen to be the rate-con-
trolling steps, the following kinetic rate expressions
are obtained.

vA2 &OK,, CfCOfH, -.&+3H/(fHz K;, 11

J (22)
CHoH.A2 = (1 +&of,, f Kc,,_&o,)(l + J$WJ2 + KHIoS*O)

G, Kcoz KHz(fco+fHz -fH,ofcolKk 1

J (23)
H0B2=(1+K~Of~o+.~~2fC0~)(~+K~~fj;l:/2+~~~ofH~~)

k&JkozKHz [fco,fH, -fCHIOHf20/tfH*KDpl)]

&,O, cz = (24)
(l+K,ofco+Kco,~~~)(l+K~~ff,j~+K,,ofH,o)

(= 4h0, c2 1

Reaction (A) Since all the elementary reactions involve sites 1 and 2,
the denominators of all the resulting rate expressions
(Al) COsl +Hs2=HCOsl +s2 (8)
are identical. The kinetic constants kiZr k&, and k&
(A2) HCOsl + Hs2 = H,COsl + s2 (9) are in fact compounded. For example kX2 is calculated
(A3) H,COsl + Hs2 = H,COsl +s2 (10) as follows:
(A4) H,COsl +Hs2=CH,OH +sl +s2. (11)
k
A2 -
- k:,,AzKA,%.tots. (25)
Reaction (B):
In eq. (25) k;,. A2 is the surface reaction rate constant
(Bl) CO& +Hs2 =HCO,sl +s2 U2) based on the elementary reaction (A2), K,, is the
(B2) HCO,sl + Hs2 = COsl + H,Os2. (13) equilibrium constant of the elementary reaction (Al),
Reaction (C): c,r, (,,r is the total number of sites 1 per weight of
catalyst, and s is the number of neighbouring sites 1
(Cl) CO,sl +Hs2=HCO,sl+s2 (14) and 2, which is of relevance because reaction can only
(C2) HCO,sl + Hs2 = H,CO,sl + s2 (15) occur between species adsorbed at adjacent sites 1 and
(C3) H2C02sl +Hs2 =H,CO,sl +s2 (16) 2 (Froment and Bischoff, 1979).
3188 G. H. GRAAF et al.

Based on the reaction schemes given above and Table 4. Driving-force groups of kinetic rate expressions
assuming that adsorption or desorption steps are not for reactions (A), (B) and (C)
rate-controlling there are 48 possible combinations of
Rate-controlling Corresponding driving-force
kinetic rate expressions. Such a combination is called step group
a kinetic model. The only differences between the
kinetic rate expressions are the driving-force groups. (Al)
These driving-force groups are given in Table 4. (A21
643)
6441
Parameter estimation and model discrimination 031)
Each kinetic model given in the previous section (B2)
contains seven kinetic constants, which have to be
(Cl)
estimated from experimental results. These exper-
(C2)
imental results are sets of the following data:
(C3)
I I (C4)
rcHaOn 9 rHrO) K P? Yco 1 Yco2 > YH2. YCH+3H, YHzO.
(C5)
From the temperature, the total pressure and the mole tC6)
fraction fugacities of each component are calculated
by the Soave-Redlich-Kwong equation of state
(Soave, 1972). For a chosen kinetic model the reaction Once a set of optimal constants was found for a
rates for methanol and water can be calculated using given model, the variances of this model for the
these fugacities in combination with the estimated methanol production rate and the water production
values of the parameters (kinetic constants). The rate were calculated:
equilibrium constants Kg, and K& in the kinetic rate
expressions are taken from Graaf et al. (1986). Because 5 &H~OH - r&OH 13
reaction (C) is the stoichiometric sum of reactions (A) p=j=1
(29)
and (B), K& can be written as follows: N-m

K;, = K;, ICOp=. (25)

For the parameter estimation a direct-search al- (30)
gorithm was developed in which the parameters are
adjusted towards optimum values. The adjustment The values of these variances are due to experimental
steps were taken as fractions of the parameter values inaccuracies and to a lack of fit of the kinetic model
ranging from 0.5 to 0.01. The objective functions were used.
chosen as follows: The variances of all models were tested for their
equality with Bartletts X2-test (Bartlett, 1937). As has
been pointed out by Dumez et al. (1977) this test is not
a true adequacy test: models that are retained may not
+ WF (Go - Go 1;1 (27) be adequate but simply the best of a series of in-
adequate models. For this reason a model that passed
FCH,OH -&OH
OF SARR = the X2-test was subsequently tested by two other
r&H,OH j methods:
PHz0 -kO
+WF I 1. (28) (a) Physico-chemical constraints.
I Go lj/
(b) Residual analysis.
In these equations WF is a weighting factor; for
WF = 0 only the methanol production rate is con- (a) The estimates of the kinetic parameters must
sidered in fitting the parameters, for WF = 1 both have physico-chemical meanings. This led to certain
methanol and water production rates with equal rules for the estimates of kinetic parameters which are
weights are considered, and for WF = cc only the summarized below (Boudart, 1972; Vannice et al.,
water production rate is considered. 1979; Kapteyn, 1980).
OF,,, was used because the statistical methods Reaction rate constants:
applied in this paper are based on variances and thus
k = Aexp[-EE,/(RT)J (31)
on sums of squares of residuals. However, a well-
known disadvantage of the sum-of-squares regression rule 1: k>O (32)
is that large reaction rates and large residuals have the
ruie 2: E, > 0. (33)
greatest contribution in the fitting procedure. This
problem vanishes using OF,,,, in which the sums of Adsorption equilibrium constants:
absolute values of the relative residuals are minimized.
For the final results of the chosen kinetic model K = exp (A%:,,IR) exp C- AHLJ(R W (34)
OF SARRwas used. rule 3: K > 0 (35)
 Kinetics of low-pressure methanol synthesis
rule 4: - AH& > 0 (36)
rule 5: 0 < - AS&,, -z S&,. (37)
(b) The residuals &oH - r,&,H and i;120-rnao
should be normally distributed with zero mean. Also,
the residuals should have no trend effects as a function
of any of the independent variablesf,, f& ,fH2, fCHsOH
and hilo.
EXPERIMENTAL
Equipment
The kinetic study was carried out with a spinning
basket reactor as described by Tjabl et al. (1966). A
commercial catalyst was used (Haldor Topsoe Mk
101). Properties of this catalyst were reported by
Dybkjaer (1981). A simplified flow scheme of the
equipment is given in Fig. 1. The reactant feeds
(prefabricated mixtures of CO, CO, and Hz) were
drawn from gas cylinders (1). The pressure in the
reactor (3) was adjusted with a pressure reducer (2).
The spinning basket reactor was heated electrically
and thermostatted by a proportional thermal con-
troller (4). A small part of the product stream was led
to an on-line GLC (1 I). The flow rate of this part was
measured with a soap bubble meter (10) and regulated
with two needle valves placed in series (9). The remain-
ing part of the product stream was passed through a
condenser of -40C (7) and a gas-liquid separator (6).
The methanol and the water formed in the reactor
were condensed almost completely and stored in a
cooled vessel (8). The gas flow through the reactor was
adjusted with a needle valve (13) which was placed
between a pressure reducer (12) and a back pressure
regulator (14). The gas flow was measured with a wet
gas meter (15). The product lines were heated electri-
cally where necessary in order to avoid unwanted
condensation of methanol and water (see Fig. 1). The
Fig. 1. Flow scheme of the equipment used for the kinetic experiments:
reducer, 3 = spinning basket reactor, 4 = thermostat,
8 = storage vessel, 9 = needle valves, 10 = soap bubble meter, 11= GLC, 12 = pressure reducer, 13 = needle
valve, 14 = back pressure regulator, 15 = wet gas meter, 16 = bypass, 17 = needle valve.
3189
reactant feed could be sampled for analysis through a
reactor bypass (16) using a needle valve (17).
Analysis
A schematic drawing of the GLC apparatus is given
in Fig. 2. Gas samples of 1 ml were injected. The
column temperature as well as the sampling valve
temperature were maintained at 100C. Helium was
used as a carrier gas. The column (2 mm i.d., 6 m long,
packed with Porapak Q) was connected to a thermal
conductivity detector and a flame ionization detector
placed in series. Calibrations of the detectors were
carried out each day in order to assure accurate
analysis. Hydrogen was not determined directly in the
analysis, but from the material balance:
Y Hz -- 1-_Cy, GZH,). (38)
I
Measurements
The kinetic experiments were always carried out
under steady-state conditions. External mass- and
heat-transfer limitations were negligible during the
experimental conditions chosen. This was both calcu-
lated and experimentally verified. At temperatures
above 245C intra-particle diffusion limitations were
observed. Therefore, these experimental results will
not be dealt with in this paper. A subsequent paper on
the subject of the intra-particle diffusion limitations in
methanol synthesis will be presented in the near
future.
For each experiment the material balances over the
reactor for hydrogen, carbon and oxygen were calcu-
lated. The deviations in these material balances were
always very small, usually less than 5%.
A broad range of experimental conditions was
examined in order to gain a good insight into the
1 =gas-cylinder, 2=pressure
5 = manometer, 6 = gas-liquid separator, 7 = cooler,
3190 G. H. GRAAF et al.

fC0 fHzO

K P; fco,fcl,

Pig. 2. GLC apparatus used: I= sampling valve,

2 = Porapak Q column, 3 = TCD, 4 = FID, 5 = integrator,
6 = recorder.

kinetics. These conditions are briefly summarized in

00
0 10 20 3.0 L.0 50 sc
Table 5. It was assumed that the spinning basket 1030/W
reactor behaved as a perfect mixer. Justification of this md kg

assumption is given by Tjabl et al. (1966).

Reaction rates for water and methanol were calcu- Fig. 3. Water formation in methanol synthesis: (0)
lated from simple mixed-flow material balances over p = 50 bar, (0) p = 30 bar; (a) p = 15 bar. Symbols = results
of feed 7 (see Table 5). Lines = calculated with model A3B2C3
the reactor:
after correcting for the difference in activity of the catalyst
used in feed 7 (with respect to methanol).
, 4 P
PCH,OH= YCH,OHWR (39)

result from the direct synthesis of methanol from CO,,

In eqs (39) and (40), p and T correspond to the
conditions at which 4, is measured, being atmospheric
pressure and room temperature.
RESULTS
Water formation in methanol synthesis
The amount of water formed in the methanol
synthesis as a function of the gas flow rate shows some
peculiar features (see Fig. 3). Here, the quantity put at
the vertical axis is a dimensionless measure for the
amount of water related to the water-gas-shift equilib-
rium. If the water-gas-shift reaction is at equilibrium,
its numerical value will be one. Under certain con-
ditions more water is formed than is predicted thermo-
dynamically. We see only one possible explanation for
this phenomenon: in addition to the water-gas-shift
reaction a second water-yielding reaction proceeds.
Since no by-products in detectable amounts were
formed in these experiments, the surplus of water must
which indeed yields water.
Still another interesting feature can be detected
from Fig. 3. In some experiments (marked with an
arrow in Fig. 3) the water content is about the same as
predicted from the chemical equilibrium of the water-
gas-shift reaction. In this situation no driving force is
left for this reaction. Furthermore, it should be empha-
sized that the water-gas-shift reaction is not a fast
reaction compared with the methanol formation reac-
tions. Otherwise, the water content would be close to
equilibrium under all conditions. For these reasons,
the contribution of the water-gas-shift reaction to the
amount of water formed will be negligible for the
experiments marked with an arrow in Fig. 3: all the
water formed will be the result of the methanol
formation from CO,. Since hydrogenation of CO
yields only methanol, we can now calculate the
amounts of methanol formed from CO and CO,,
respectively. The results of these calculations are listed
in Table 6. They prove unambiguously that methanol
is produced from both CO and CO,. It also follows
that none of the two independent synthesis routes is
relatively negligible.

Table 5. Experimental conditions in the present study (catalyst Cu-Zn-Al)

Feed composition
P 1039%lW
Feed Yco YCO, YH, (bar) (& (m3s-lkg-)

1 0.065 0.26 1 0.674 15, 30, 50 483.5, 499.3, 516.7 1-6

2 0.053 0.047 0.900 15, 30, 50 483.5, 499.3, 516.7 16
3 0.220 0.155 0.625 15, 30, 50 483.5, 499.3, 516.7 16
4 0.120 0.02 1 0.859 15, 30, 50 483.5, 499.3, 516.7 l-6
5 0.179 0.067 0.754 15, 30, 50 483.5, 499.3, 516.7 l-6
6 0 0.115 0.885 15, 30, 50 483.5 0.3-7
7 0.092 0.105 0.803 15, 30, 50 499.3 0.14
 Kinetics of low-pressure methanol synthesis 3191

Table 6. Relative amounts of methanol formed from CO and from CO, for experiments with feed 7
(see Table 5)

% CH,OH % CH,OH
l~3LXJL,ol(&0*fH,) lOSKi YCHlOH YH.0 from CO from CO,

6.9 7.54 0.0109 0.0061 44 56

8.2 7.54 0.0122 0.0074 39 61
7.5 7.54 0.0110 0.0067 39 61

Parameter estimation and model discrimination Table 7. Kinetic models that passed the X*-test
In a first series of computations the results of feeds
l-5 of Table 5 were used, because replicated exper- P&,0,) (r&J)+
Kinetic model (~1 (%)
iments showed a constant catalyst activity. At each
temperature the data of about 30 experiments were A3BlC2 7.9 28.7
collected. The parameter estimation was carried out at A3BlC3 6.4 26.8
A3B2C3 6.4 24.2
each temperature for all 48 kinetic models given in
Table 4. However, the results of these calculations These deviations are defined by the objective
were very dependent on the initial guess values of the function, OFsARR [eq. (28)].
parameters. A careful1 analysis of this phenomenon
showed that ill-guessed initial parameter values led to
solutions in which one of reactions (A) and (C) [eqs (1) Table 8. Relative catalyst activities with respect to methanol
and (3)] was completely neglected. As was shown and water
above, this is essentially wrong. For this reason the
data were screened for experiments in which the Activity for Activity for
Kinetic model methanol water
water-gas-shift reaction was approximately at equilib-
rium (within 10%). As explained above the amounts of A3BlC2 1.45 + 0.27 1.75 +0.30
methanol produced from CO and from CO, were A3BlC3 1.34+0.05 1.38 kO.07
calculated from these experiments. The ratio of the A3B2C3 1.36 +0.04 1.35kO.05
kinetic factors could be calculated from these results
for all kinetic models. For instance, the kinetic models
A2BlC2 and A2B2C2 yield the following equation: with the catalyst activity during experiments with
feeds l-5). For each experiment of feed 6 (18 exper-
k&z Kc,, GL, y,,oDF,,
t(= (41) iments) and each kinetic model of Table 7 the relative
kA2 &OK,, = (YCH,OH - y,,o)DFc, . methanol activity and water activity were calculated.
The parameter estimation was carried out again, with The activity of methanol or water is defined as being
k& Kcoz K,, = akaz K,,K,, while a was not involved the ratio of the observed rate of formation and the
in the fitting procedure but calculated from the exper- calculated rate of formation using one of the kinetic
iments for which the water-gas-shift reaction was models in combination with the estimated values of
approximately at equilibrium. WF was chosen to be the parameters. The results of these calculations are
0.5. It should be noted that the fitting results were listed in Table 8.
almost independent of values of the WF ranging from For the correct kinetic model equal catalyst ac-
0.1 to 2. This revised approach gave considerably tivities might be expected for both methanol and
better results: based on the X2-test at a 95% confidence water. Based on the results listed in Table 8 in
level six models were retained from the original 48 combination with those listed in Table 7 we conclude
models. For these six models the parameter estimation that the best kinetic model is A3B2C3.
was repeated for all three temperatures simul- In Fig. 4 rates of methanol and water production as
taneously. Here it was assumed that all parameters predicted by model A3B2C3 are compared with the
follow an Arrhenius temperature dependency. Initial experimental results of feed 6. As can be seen there is a
guess values of the parameters were based on the good agreement between the model calculations and
results of the parameter estimation at each tempera- the experimental data. The same agreement can be
ture. The data consisted of the results of 89 exper- seen in Fig. 3: the solid lines were calculated with
iments. Now, a was no longer excluded from the fitting model A3BZC3 in combination with a correction for
procedure. Based on the X2-test three models were catalyst activity (with regard to methanol).
retained at a 95% confidence level. These models are A thorough residual analysis on model A3B2C3,
given in Table 7. which is not given here, showed that trending effects of
In order to discriminate between these three rival the residuals as a function of any of the independent
models, the results of the experiments with feed 6 (see variables were absent. The residuals were also nor-
Table 5) were used. These results were not used for the mally distributed with zero mean.
parameter estimation, because the catalyst activity It turns out that the kinetic model can be simplified,
was different during these experiments (compared because the number of free sites 2 is negligible, which
 3192 G. H. GRAAF et al.

kr,. c3 = (4.36 + 0.25) x 10

- 65,200 + 200
x exp (48)
RT >

Kco=(7.99f 1.28) x lo-

IO3r 58,100 f 600

Skg-'
x exp (49)
mol
RT >
K,,=(1.02+0.16)x lo-

67,400 f 600
x exp (50)
( RT >
K,,o/K~~=(4.13f1.s1)x lo--
OO
V 10
8 2.0 301 L-0
I 5.0 I
6.0 104,500+ 1100
103~,IW x exp (51)
RT >
n?< kQ
The Arrhenius diagrams are given in Figs 5 and 6. The
Fig. 4. Reaction rates for methanol and water: (0) and (a), results of the parameter estimation per temperature
p=50 bar, (Cl) and (m) p=30 bar, (0) and (A) p=15 bar. are also plotted in Figs 5 and 6. The differences
Open symbols = reaction rates for methanol, results of feed 6 between these results and the results obtained from the
(see Table 5). Closed symbols= reaction rates for water,
results of feed 6 (see Table 5). Lines = calculated with model
parameter estimation for all temperatures are justified
A3B2C3 after correcting for the difference in activity of the by the confidence intervals.
catalyst used in feed 6 (with respect to methanol). The confidence intervals in eqs (46) and (47) were
calculated from

means that
SSR to.991= SSR,r + SSR,i, m FIm,N-m.0.99,.
N-m
1Q Kg2fH:12 + KH2&*0. (42)
(52)
Model A3B2C3 can now be expressed kinetically as

?J
kbs,,, Kc, C&offi~,-.Lx,odfA: K;, )I
CH30H
= A3
(1 + Kcofco + Kco&oz) Cfh;2+(K~,olk~~~K,,ol (43)
k6, B2 Km &o,_G, -_A,,o&o/K;z 1
&zO.BZ =
(1 +KcoJzo + &oJLod CfX2 +(K.r,olk~~2)f.,01 (44)

k;S.ca &o,Cfco,f%2 - fCu,o&,ol(fH3j2K;~)l

J
CHsoH*C3= (1 + Kc0 fco + K cozfcoz) IX: +W,,JKAI:)f,,ol
(45)

( = &,o. c3 1

The reaction rate constants are marked with the In this equation Ftm.N-,,,0.991 is Fishers F-value with
subscript ps (pseudo), because they now contain the [m. N-m] degrees of freedom at a 99% significance
adsorption equilibrium constant of hydrogen. The level (Fisher, 1958). The confidence intervals were
parameter estimation was carried out again for this obtained by varying one parameter at a time and
simplified form of model A3B2C3. It should be noted holding all the other parameters at their optimal
that the model predictions as presented in Figs 3 and 4 values.
did not change noticeably after the simplification The results of the parameter estimation were used to
mentioned above. The following results were obtained: check whether the kinetic model follows the physico-
chemical constraints. It can be seen from eqs (46H51)
&,, A3 = (2.69kO.14) x IO that rules 14 [eqs (32)-(36)] are obeyed.
From the pre-exponential factors of the adsorption
- 109,900 f 200 constants the entropies of adsorption for CO and CO,
x exp (46)
RT > were calculated from eq. (34). Together with the
boundary values from eq. (37) these adsorption
entropies are listed in Table 9.
Clearly, the adsorption entropies have reasonable
- 123,400 + 1600
x exp (471 values. For hydrogen and water, only the ratio of
RT > adsorption constants was determined: this gives no
 Kinetics of low-pressure methanol synthesis 3193

T
oc
2LO 230 220 210 L
L I I I I

3
i

-2

i04 k
-112
- mot E? k$bar
0.8 -0.8
0.7 - 0.7
0.6 - 0.6
0.5 - 0.5

- i

Fig. 5. Reaction rate constants vs temperature: (0) k&,,,(n) kb,.,,, (0) VP,..,. Symbols =regression per
temperature. Lines = regresslon with all temperatures.

From the results of feed 6 the adsorption of

hydrogen, which was assumed to be dissociative, can
be studied to a greater extent. Because feed 6 did not
contain CO, it may be assumed that methanol is
formed almost exclusively from CO*. This was con-
firmed by model calculations, which are not given
here. After rearrangement of eq. (45) the following
equation is obtained:
$ii
k;,, ca Km2 Cfc,,f,:/ -fc,ofH,ol(f~~2K;,)1
r&O(l +&of,, + KC02fC02)fH:/2

Thus on plotting the left-hand side of eq. (53) against

Fig. 6. Adsorption constants vs temperature: (0) Kc,,, (A)
Kc,,, (0) K,,oIK,, I/*.Symbols = regression per temperature.
Lines = regression with all temperatures.
a straight line should be obtained. As can be
f*O /fix2
seen from Fig. 7, the results are in complete agreement
with our expectations, thus supporting the assump-
tion that hydrogen is adsorbed dissociatively.

Comparison with literature

Table 9. Adsorption entropies of CO and CO, Parameter estimation was also carried out with the
S&(500 K)t models taken from the literature given in Tables 2 and
-AS,,,
3 using the experimental data of feeds 1-5. Because
Compound (J mole1 K- ) (J mol- K-l)
Seyfert and Luft (1985) and Klier et al. (1982) have not
co 116.7 213.2 presented kinetic rate expressions for the water-gas-
CO, 133.9 243.9 shift reaction, these literature models were completed
with the kinetic rate expression for this reaction as
tTaken from Stull et al. (1969).
given by Villa et al. (1985).
The optimal parameters were determined for these
useful information about the adsorption entropies, models. Using these optimal parameters the devi-
however. Therefore, we may conclude that the kinetic ations for the methanol and water production rates
model A3B2C3 obeys all the physico-chemical con- were calculated. These values are summarized in
straints. Table 10.
3194 G. H. GRAAF et al.

The experiments further support the assumption of

dissociative hydrogen adsorption.
At least for the commercial catalyst applied in this
5.0 study, the kinetic model proposed here explains the
L.H.5 ~1531
experimental results with a significantly improved
1 LO
accuracy as compared with the kinetic models pro-
3.0
posed by Seyfert and Luft (1985), Villa et al. (f985),
Klier et al. (1982) and Dybkjaer (1985).

Acknowledgements-We thank Haldor Topsoe A/S, Lyngby,

Copenhagen, Denmark for delivering their methanol syn-
thesis catalyst Mk 101 and the N.V. Nederlandse Gasunie,
1 I I , I 1 I
Groningen, Netherlands, for delivering gas mixtures for
OO 0.7 0.2 03 calibration purposes.
fCl,o/fCI:2
NOTATION
I2
bar
A pre-exponential factor
Fig. 7. Adsorption of hydrogen and water: (0) p = 50 bar, A I...6 kinetic constants in literature ex-
( 0) p = 30 bar, (A) p = 15 bar. Symbols = results of feed 6 (see pressions
Table 5). Line = best fit based on SSR. concentration, mol kg-
c
DF driving force
energy of activation, J mol-
Table 10. Accuracies of the kinetic models taken from recent partial fugacity, bar
literature compared with the model proposed in this study :
j experiment index
k reaction rate constant
Kinetic model from Ki adsorption equilibrium constant,
bar- ; e.g. for CO:

If I
Seyfert and Luft (1985) 10.8 100
Villa et al. (1985) 12.3 100 COG1
K co= __
Klier et al. (1982) 10.0 57
CCOSl EP
Dybkjaer (1985) 14.7 167
This study 6.4 24 K Al ... K A4 elementary reaction equilibrium
K B1 . . . K 82 constant
These deviations are defined by the objective function
K cl- K C6 e.g.
OFSARR [es- (WI.

K, chemical equilibrium constant based

Comparing these results with the results of mode1 on partial pressures
A3B2C3 it is obvious that the latter describes the m number of parameters
kinetics in methanol synthesis much better. This was N number of experiments
confirmed by the X2-test: using this criterion the four OF objective function
models from the literature were rejected, thus Pi partial pressure, bar
favouring model A3B2C3. p total pressure, bar
r reaction rate per weight of catalyst,
CONCLUSIONS mols-kg-
Experimental evidence shows that methanol can be R gas constant (8.314), JmolmKP
formed simultaneously from both CO and CO2 in S number of neighbouring sites
low-pressure methanol synthesis. S variance
The experimental results on the methanol syn- S entropy, J mol - 1 K -
thesis kinetics can be explained by a dual-site T temperature, K
Langmuir-Hinshelwood mechanism, based on dis- W weight of catalyst, kg
sociative hydrogen adsorption and three independent WF weighing factor
reactions: methanol formation from CO, methanol Y mole fraction
formation from CO, and the water-gas-shift reaction. ratio of kinetic constants
Depending on which elementary reaction step is : relative error
rate-controlling in each of these three parallel reac- AH enthalpy change, J mol-
tions, 48 different kinetic models are possible. Based AS entropy change, Jmol- K-
on X2-statistics and consistency tests a final model was $ gas flowrate at standard temperature
selected. and pressure (25C, 1.013 bar), m3 s-
The kinetic parameters could be determined as
functions of temperature between 210 and 245C. The Superscripts
values of these parameters are not in conflict with the 0 indicates standard pressure (1 ,013 bar)
physico-chemical constraints. indicates calculated value
 Kinetics of low-pressure methanol synthesis 3195

Subscripts butene dehydrogenation. Ind. Engng Chem. Fundam. 16,

ads adsorption 298-301.
Dybkjaer, I., 1981, Topsoe methanol technology. Chem.
Al . ..A4 indicates rate-controlling step of
Econ. Engng Rev. 13(6), 17-25.
methanol from CO reaction Dybkjaer, I., 1985, Design of ammonia and methanol syn-
Bl...B2 indicates rate-controlling step of the thesis reactors. Paper presented at the NATO conference
water-gas-shift reaction on chemical reactor design and technology, Canada.
Cl...C6 indicates rate-controlling step of Fisher, R. A., 1958, Statistical Methodsfor Research Workers,
13th edition. Hafner, New York.
methanol from CO, reaction
Froment, G. F. and Bischoff, K. B., 1979, Chemical Reactor
co indicates component CO Analysis and Design, p. 98. J. Wiley, New York.
CO, indicates comnonent CO, Graaf, G. H., Siitsema, P. J. J. M., Stamhuis, E. J. and Joosten,
CH,OH indicates component CH;OH G. g. H., 1986, Chemical equilibria in methanol synthesis.
Chem. Engng Sci. 41, 2883-2890.
EQ at,equilibrium
Herman, R. G., Klier, K., Simmons, G. W., Finn, B. P., Bulko,
gas gaseous component J. B. and Kobylinski, T. P., 1979, Catalytic synthesis of
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Ps
on a low-temperature catalyst. Kinet. Katal. 14, 970-975.
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