Catalysis, 50 (1989) 265-285

Elsevier Science Publishers B.V., Amsterdam -

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265

Methanol Synthesis from Hydrogen, Carbon

Monoxide and Carbon Dioxide over a CuO/ZnO/
A1203 Catalyst
II. Development of a Phenomenological Rate
Expression
MELANIE A. MCNEIL, CARL J. SCHACK and ROBERT G. RINKER*
Department of Chemical and Nuclear Engineering, University of California, Santa Barbara, CA
(U.S.A.)
(Received 1 August 1988, revised manuscript received 10 January 1989)

ABSTRACT
New steady-state kinetics data for the synthesis of methanol from H,/CO/C02 over a CuO/
ZnO/Al,O,, catalyst were correlated on the basis of reported catalytic mechanisms to formulate a
rate expression for methanol formation. In developing the mechanistic model, it was assumed that
hydrogen adsorption occurs on ZnO in contrast to carbon monoxide adsorption on Cu+ and
carbon dioxide adsorption on Cu. Also, the concentration of sites containing adsorbed hydrogen
was assumed constant during reaction. These assumptions led to the formulation of a rate expression containing the sum of contributions from carbon monoxide and carbon dioxide hydrogenation.

INTRODUCTION

Generally it is agreed that, for a reactant mixture of CO, CO, and Hz, the
main reaction for methanol synthesis is
CO + 2Hz %CH,OH

AH,,,, K= - 21.7 kcal/mol

(1)

Carbon dioxide is almost always added to the synthesis mixture and, as pointed
out by Denny and Whan [ 11, it needs to be accounted for since it can form
methanol according to
COP +3Hz *CH,OH+H,O

AH,,, K= - 11.9 kcal/mol

(2)

The hydrogenation of carbon dioxide proceeds much slower than the hydrogenation of carbon monoxide at industrial conditions of 5-10 MPa and 500-

0166-9834/89/$03.50

0 1989 Elsevier Science Publishers B.V.

266

575 K [ 21 although the opposite has been found to be true at lower temperatures [ 3-61. The reversible water-gas shift reaction also occurs. It, of course,
is obtained by subtracting reaction (1) from (2 ) , giving
COz + H, %CO + H, 0

AH,,,, K= + 9.8 kcal/mol

(3)

and, consequently, is not an independent reaction in this system.

REVIEW

OF PREVIOUSLY

PROPOSED

MECHANISMS

The following review is presented in order to give the reader an overall appreciation of this complex reacting system. A major emphasis of the present
study has been to develop a mechanistic model from the apparently contradictory results presented in previous studies as well as from our own experimental
kinetics data. The key ideas which provide the basis for our model development
are summarized at the end of the review section. Table 1 lists available information on the catalyst types and operating conditions for most of the studies
referred to in this review.
Phenomenological models and rate laws have been proposed in the literature
for methanol synthesis for over 30 years. However, disagreement still exists,
especially concerning the contribution of carbon dioxide during methanol synthesis as well as the identity of the active site or sites on the CuO/ZnO catalyst.
Prior to 1970, no attempt was made to account for the effect of the carbon
dioxide added to the synthesis gas mixture. In fact Nattas model [ 71, which
was the basis of many models developed after 1953 for both high and low pressure methanol synthesis catalysts, did not include any terms to account for the
effect of carbon dioxide. Nattas rate expression is shown below.
YCOPCO
YEI,PzI,- YCH30HPCH30HIKeq
r= (A+%opco

+CYap~z

+~YCH~OH~CH~OH)~

(41

where yi is the fugacity coefficient of species i, pi is the partial pressure of

species i, Keg is the thermodynamic equilibrium constant of reaction (11, and
A, B, C, and D are empirical constants which are functions of temperature and
which are different for each catalyst. Even though this rate expression did not
include any carbon dioxide terms, it fits Nattas data well.
Bakemeier et al. [S] were the first to consider the contribution of carbon
dioxide in their rate equation. They realized that carbon dioxide could participate in the water-gas shift reaction as well as form methanol. The influence
of carbon dioxide was accounted for by using a Langmuir adsorption isotherm;
and methanol desorption was assumed to be the rate determining step. The
resulting rate expression is shown below.
lr=

PCH~OH

~co~&Kes

I+ DeF RTpCdpH2

>I

(5)

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TABLE 1
Catalyst and operating conditions of selected literature studies
Ref.

Catalyst composition

Reaction conditions

Bakemeier et al.
ref. 8, 1970

ZnO 78 wt.-%
Cr,O, 22 wt.-%
BASF S 5-10 red.

Nonisothermal
T=562-612 K, initially
P=20-36 MPa
0.875 kg cat.
Z*lO-6*104 Nm3/m3cat. h

Kagan et al.
ref. lo,1975

CuO/ZnO/AlaO,
SNM-1 catalyst
Unspecified percentages

T=443-513 K
MPa
Unspecified cat. wt.
Unspecified flow-rate

Kieffer et al.
ref. 4, 1981

CuO 60 wt.-%
zno 30 wt.-%
A&O, 10 wt.-%
Lab preparation

T=523-573 K
P=5.2 MPa
3*10-4 kg cat.
6700 I/kg cat. h

Klier et al.
ref. 14,1982

Cu 30 metal-atom-%
Zn 70 metal-atom-%
Lab preparation

P= 7.6 MPa

P=4.9

T=498-523

2.45*10-3 kg cat.
6100 l/kg cat. h

Okamoto et al.
ref. 22, 1984

Cu 30-80 wt.-%
ZnO balance
Lab preparation

T=413-453 K
P=l.Ol*lO-
MPa
unspecified cat. wt.
3.4 and 3.9 slh

Liu et al.
ref. 18,1985

cue 30 wt.-%
ZnO 70 wt.-%
Lab preparation

T= 468-501 K
P= 1.7 MPa

Edwards and Schrader

ref. 40,1985

Cu/ZnO
5/95 mol-%
lo/90 mol-%
CuO/ZnO/CrzO,
5/90/5 mob%
10/80/10 mol-%
Lab preparation

Bridgewater et al.
ref. 37,1986

cu 72.8 wt.-%
Zn 23.1 wt.-%
Al 4.1 wt.-%
UC C79-4 catalyst

T= 493 K
P=5 MPa
Unspecified cat. wt.
GHSV= 10000 h-l

Chinchen et al.
ref. 13,1987

CuO 60 wt.-%
ZnO 30 wt.-%
Al,O, 10 wt.-%
Unspecified vendor

T=523 K
P=5 MPa
Unspecified cat. wt.
GHSV=1*104-4.105 h-l

Schack et al.
ref. 20, 1989

CuO/ZnO/Al,O,
BASF S 3-85
proprietary percentages

P=2.9-4.3

2.81.10-* kg cat.
Batch reactor
T= 473-523 K
MPa
GHSV= 1800 h-l
T= same
P=same
GHSV=3600 h-
Unspecified cat. wt.

P=5

T=483-513

K
MPa
7.9.10-3 kg cat.
75 slh

*Metal percentages were normalized to exclude oxygen.

*Nm is measured at 1 atm and 273 K; GHSV is gas hourly space velocity; slh is standard liters
per hour (1 atm, 294 K).

268

where A and D are pre-exponential constants, E and F are activation energies,

and m and n are orders of reaction. This expression predicts that the methanol
production rate decreases as the partial pressure of carbon dioxide increases
but does not consider the contribution of carbon dioxide as a reactant.
In an interesting series of papers, Rozovskii and co-workers [9-121 proposed
that carbon monoxide is converted to carbon dioxide through the water-gas
shift reaction and that most of the methanol is consequently formed from carbon dioxide via reaction (2). As stated above, carbon dioxide hydrogenation
occurs faster than carbon monoxide hydrogenation at lower temperatures and
pressures. This might explain why Rozovskii et al. [ 91, who operated at 495 K,
found such a large degree of production from carbon dioxide. While some investigators [ 131 have accepted reaction (2) as the principal path to methanol
formation, the majority feel that reaction (1) is the principal path, at least
under typical synthesis conditions of 5-10 MPa and 500-575 K.
Klier et al. [ 141 were the first to account for the effect of carbon dioxide as
a catalyst promoter and as a reactant to form methanol. Three models were
proposed based on different assumptions concerning how CO, CO, and Hz
compete for the active site. The rate-determining step was postulated to be the
termolecular surface reaction of carbon monoxide with two hydrogen molecules to form methanol. All three rate expressions fit the data adequately. The
one which most satisfactorily fit the data is shown below, and it represents the
general form of the other two models.
r=kAi

+A?'

&oK2,, (PCO~$2 -PCH~OHKJ

WPC02/PCO
I3
[l+K (~con/~coH~(l+Kco~co+Kcoz~c~oz+K~~~~~)~

I-%02-=4

(6)

PCH~OHPI~O

PL

>

where Keq and & are the thermodynamic equilibrium constants of reactions
(1) and (2)) respectively; A, is the sum of the concentrations of oxidized and
reduced active centers; and K is the equilibrium constant of the following
reaction:

Ared+COz,,,%A,, +co,,,

(7)

where Aredand A,, are reduced and oxidized active centers of catalyst, respectively. Klier et al. also found that, under the conditions of their work, the term
multiplied by l/K& was negligible. The contribution of carbon dioxide as a
catalyst promoter was taken into account through the term which represents
the active-site concentration (i.e. the term containing the pcoz/pco ratio). Klier
et al. concluded that the main contribution of carbon dioxide was that of a
catalyst promoter. In fact, the models of Klier et al. show that the methanol

production rate decreases to zero when no carbon dioxide is present in the feed,
because PCOJPCO and therefore the active site concentration are zero. One
main limitation of the models of Klier et al. is that other researchers [X5-17]
have shown that synthesis gas containing no carbon dioxide can still produce
methanol. In fact, Edwards and Schrader [40] ran a synthesis gas mixture of
H2/C!O/C02 =67/33/O over a CuO/ZnO/C!ri03 catalyst and measured rates
four times higher than those obtained by running a 66/28.6/6.6 mixture over
the same catalyst. On the other hand, carbon dioxide or another oxidizing agent
such as water seems to be necessary for optimum synthesis since investigators
[ 2,6,18] have reported that running synthesis gas mixtures without an oxidizing agent over the CuO/ZnO catalyst results in partial deactivation of the catalyst. Herman et al. [ 21 have suggested that the deactivation can be explained
in the following manner: they have reported that the active site for carbon
monoxide hydrogenation consists of Cu+ sites dispersed in ZnO. In a strongly
reducing environment, large copper crystallites form from this Cd+/ZnO
phase, thus reducing the number of active sites, and resulting in irreversible
deactivation.
Another interesting observation regarding carbon dioxide participation was
made by Klier et al. [ 141 who found that increasing the CO,/CO molar ratio
produced methane while no methane was detected for feed gases of CO/H,. In
a seemingly conflicting report, Nappi et al. [ 161 reported that methane production occurs with no carbon dioxide in the feed and increases with increasing
carbon monoxide concentration. Amenomiya [ 191 studied methanol synthesis
from carbon dioxide and hydrogen and reported that no methane is formed
unless the reaction is conducted at temperatures above 570 K. Although no
explanations have been proposed for these varying results, it is worth noting
them.
Liu et al. [ 6,181 have recently published interesting results which raise further questions regarding the contribution of carbon dioxide during methanol
synthesis. Their initial rate studies showed that the methanol production rate
increases as the COJCO ratio increases and does not go through a maximum.
This result is in contrast to studies by Klier et al. [ 141 and separately by Schack
et al. [ 201 who have found that an optimum CO,/CO ratio exists, beyond which
the production rate of methanol is inhibited. However, in Schacks and Kliers
studies, the production rate of methanol was influenced by the reverse synthesis reaction. Liu et al. also found that water inhibits carbon dioxide hydrogenation but not carbon monoxide hydrogenation to methanol. Coupled with that
are the experimental results obtained by Schack et al. [ 201 which suggest that
carbon dioxide inhibits carbon monoxide hydrogenation but not its own hydrogenation to methanol. These results indicate that carbon dioxide and carbon monoxide hydrogenation occur on different sites, The experiments of Liu
et al. using I80 labelled carbon dioxide gave particularly clear evidence sup-

270

porting
separate carbon monoxide and carbon dioxide adsorption, They
sites

for

showed that water inhibited only the carbon dioxide hydrogenation rate while
the carbon monoxide hydrogenation rate was not changed.
Identification of the active site (s ) for methanol synthesis on Cu/ZnO catalysts has also generated considerable controversy. Proposals have included
Cue (X-241, Cul+ [2,25-311 andZn0 [32].
Herman et al. [ 21, Mehta et al. [ 251 and Klier [ 331 have extensively studied
binary and ternary Cu/ZnO catalyst samples (oxidized, reduced and used) in
order to elicit the activation characteristics, electronic structure and surface
composition of these catalysts. Their optical spectroscopy studies of the catalyst led to the proposal that Cul+ dissolved in ZnO is the active site for methanol synthesis.
Klier [ 331 also investigated the activity of pure copper metal and pure ZnO
and found that neither of the two, used individually, can synthesize methanol
in appreciable amounts. Hence, Klier concluded that neither Cue nor ZnO is
active for methanol synthesis. However, this conclusion is only valid for Cue
and ZnO used in isolation. The situation could be quite different when they
are present together, particularly if each site chemisorbs one of the reactants
such as hydrogen on ZnO and carbon monoxide on Cu. Consequently, the
experiments of Klier, on the individual sites, do not unequivocally eliminate
Cue and ZnO as active sites for methanol synthesis.
Numerous groups [ 25,28,34-361 have provided evidence for the existence of
oxidation states of copper in methanol synthesis catalysts during synthesis.
However, Bridgewater and co-workers [24,37] dispute the claim that copper
can exist in an oxidized form under methanol synthesis conditions. Thus, they
also disagree with the proposal of Mehta et al. [25] that Cu+ is the active site
for methanol synthesis. Bridgewaters study compared methanol production
over Raney copper catalysts with production over typical methanol synthesis
catalysts using a synthesis gas which contained carbon dioxide, and found that
catalysts with more copper surface area had more activity. Bridgewater and
co-workers also felt that Kliers work shows the same trend of increasing copper surface area providing increasing activity. It would be interesting to see
what level of methanol production rates would be obtained on Bridgewaters
catalysts without the presence of an oxidizing agent such as carbon dioxide.
Other investigators have also found that increased copper surface area produces increased activity. For example, Chinchen et al. [ 381 measured the copper surface area of Cu/ZnO/Alz03 catalysts by in situ frontal chromatography.
They found a linear relationship between the methanol synthesis activity and
the total copper surface area of the catalyst.
Okamoto et al. [22] seem to provide support for the observations of Bridgewater and Chinchen. Their studies on methanol decomposition indicated
that, as the concentration of Cue dispersed in ZnO decreased, the concentration of Cu+ dispersed in ZnO increased and the activity of their methanol

271
synthesis catalysts decreased. This conclusion was in contrast to their earlier
proposal [ 291 that Cul+ in ZnO was the active site.
On the other hand, support for the proposal of Mehta et al. [ 25 1 that Cult
is the active site for methanol synthesis was provided by Apai et al. 1261 who
surface-stabilized Cul+ ions by vacuum heating Cu/CrzOB evaporated films.
The concentration of Cu + could be variedwith the length of time for vacuum
heating. When these surface-stabilized films were compared to a Cu/Cr,O,
powder which had been reduced in the typical manner, it was found that the
activity of the films was approximately four times greater. Thus, the results of
Apai et al. indicate that Cu+ is the active site for methanol catalysis.
Generally, most of the investigations have been concerned with the adsorption sites for carbon monoxide and carbon dioxide since hydrogen is believed
to adsorb on ZnO and is not believed to be a rate-limiting influence [ 391. Thus,
the main controversy is whether Cue or Cu+ is the active site for methanol
synthesis, although some investigators feel that all or most of the methanol
synthesis pathway occurs on ZnO [ 39,401. This is not an unreasonable conjecture since the high-pressure methanol synthesis catalysts consist of ZnO/Cr,O,
and no copper. However, Klier [33] has pointed out that ZnO is active for
methanol synthesis at 620 K and pressures of 20.4 MPa but not under typical
low-pressure methan synthesis conditions. In any case, the contribution of
ZnO has received some attention in the literature, scant as it may be.
Cheng et al. [32] studied the decomposition of methanol on the different
Crystal faces of ZnO. No decomposition occurred below 580 K which is above
typical methanol synthesis conditions. The main question brought out by Cheng
et al.s work is whether methanol synthesis proceeds through a pathway which
occurs in part on the ZnO surface. In other words, is copper, in whatever form,
only active for the adsorption of carbon monoxide while the rest of the steps
occur on the ZnO surface? If the answer were affirmative, this would agree
with a reaction pathway proposed by Edwards and Schrader [ 401.
There are three factors which seem to exclude ZnO as the principal site for
methanol synthesis: one is the result from the investigation by Denise et al.
[ 411 who found that ZnO is not a unique support. Other supports such as ZrO,
also permit the synthesis of methanol. The second factor is the study by Bridgewater et al. [ 371 in which a Raney Cu/ZnO catalyst was compared to a typical industrial methanol synthesis catalyst. Bridgewater et al. concluded that
the active site in both types of catalyst was the same since the activity per unit
copper surface area was the same. Furthermore, experiments showed that Raney copper, completely free from zinc, was comparatively active for methanol
synthesis. The third factor is that several reports have indicated that ZnO is
not modified during the course of methanol synthesis. Okamoto et al. [29]
have shown, by XPS analysis, that ZnO does not reduce to zinc until temperatures exceed 770 K. Also, Himelfarb et al. [42] performed in situ static X-ray
diffraction studies on a Cu/ZnO/AlzO, catalyst and showed that the reflection

272

of ZnO did not change throughout the reaction, thereby showing that ZnO is
not reduced.
The published reports discussed above present conflicting viewpoints on the
identity of the active site(s) on the Cu/ZnO methanol synthesis catalysts.
Most of the above studies have considered carbon monoxide hydrogenation to
be the only significant reaction for methanol production. A possible reason for
the seemingly contradictory results in the literature is that carbon dioxide hydrogenation also occurs to a significant extent under certain reaction conditions (i.e. in the lower temperature and pressure regimes of methanol synthesis) . Perhaps, as mentioned by Liu et al. [ 181,two main sites are necessary for
methanol synthesis, one for activation of carbon monoxide and one for activation of carbon dioxide. If that is the case, then the apparent disagreement
over the identity of the active site could be resolved.
The next point of interest is the identity of the most abundant reaction
intermediate (MARI) during methanol synthesis. In earlier studies, rate laws
were proposed by investigators in which the MARI as well as the rate determining step (RDS) were arbitrarily chosen and many models differed from each
other solely on that basis. Even if such models adequately predicted experimental kinetics trends, they often were not based on physical reality. However,
in the recent literature, a number of investigators have published results on
intermediates actually identified on the catalyst surface.
For example, Edwards and Schrader [40,43,44]
conducted an in situ infrared spectroscopy study with Cu/ZnO and Cu/ZnO/Cr,03
catalysts at 5.0
MPa and 473and 523K. Although these catalysts were limited to about 10mol
percent copper because of an infrared adsorption constraint, the results are
still considered applicable to industrial catalysts (which usually contain at
least 30% copper), because the catalysts with 10 mol percent copper showed
good selectivity for methanol. Edwards and Schrader found spectroscopic evidence for formate, formaldehyde and methoxy intermediates. Based on their
findings, Edwards and Schrader developed a model (but not a rate expression)
in which the hydrogenation of the methoxy intermediate was proposed as the
RDS. The work of Edwards and Schrader represents some of the first good
spectroscopic evidence for formaldehyde as an important intermediate. Their
study indicates that the reaction involving formaldehyde occurs rapidly, which
may explain why formaldehyde has been difficult to measure in the past.
Surface intermediates were also studied for the reaction of carbon dioxide
and hydrogen over a methanol synthesis catalyst. Kieffer et al. [4]identified
formates and acetates as intermediate surface species on a Cu/ZnO/Al,O, catalyst by chemical trapping. Tagawa et al. [21]also studied carbon dioxide
hydrogenation, this time by infrared spectroscopy and temperature-programmed desorption. In both studies, copper formate was proposed as the MARI
for methanol synthesis. The hydrogenation of copper formate was proposed as
the RDS. It is interesting to note that it is copper formate which is the species

273

identified in the above studies while Edwards and Schrader [40] identified
formate on ZnO sites.
In the present study, attempts were made to derive a phenomenological model
and associated rate law that would not only include the contribution of carbon
dioxide to methanol formation, but also be based on the reported chemical and
catalytic mechanisms discussed above. While Klier et al. [ 141 did propose a
rate expression which accounts for the effect of carbon dioxide as a catalyst
promoter as well as a methanol producer, they contended that the main contribution of carbon dioxide is that of a promoter. Moreover, their carbon dioxide hydrogenation rate term is not based on mechanistic factors. While we do
not dispute the fact that carbon dioxide can perform as a catalyst promoter,
we feel that the contribution of carbon dioxide as a reactant must be more
rigorously taken into account. Thus, we attempted to develop a phenomenological model and associated rate law that includes carbon dioxide hydrogenation to methanol and is based on the following features: (i) the surface reaction of the methoxy intermediate with a dissociatively adsorbed hydrogen atom
is the RDS for carbon monoxide hydrogenation; (ii) the methoxy intermediate
on Cu+ sites is the MARI for carbon monoxide hydrogenation; (iii) hydrogen
is dissociatively adsorbed on ZnO sites; (iv) the surface reaction of the formate
intermediate with a dissociatively adsorbed hydrogen atom is the RDS for carbon dioxide hydrogenation; and (v) the formate intermediate on Cue sites is
the MARI for carbon dioxide hydrogenation. It is worth noting that no unequivocal evidence has been reported in the literature which proves that the RDS
and MARI described above are the true RDS and MARI in the methanol synthesis
system. However, the recent spectroscopic evidence in the literature seems to
suggest that the proposed RDS and MARI have at least a measure of credibility.
It must be remembered that in many earlier studies, the RDS and MARI were
chosen without the benefit of such evidence.
EXPERIMENTAL

The reactor system used to perform the kinetics study has been described in
detail, along with the results of the experiments used in this modelling study,
in a separate paper [ 201. Basically, a 0.400 1 continuous stirred reactor (gradientless) was used at temperatures between 483 and 513 K, pressures of 2.89
MPa and 4.38 MPa and varying CO,/CO/H, ratios. A limited number of CO,/
He/H2 experiments were conducted to study the conversion of carbon dioxide
to methanol. BASF methanol synthesis catalyst, type S 3-85, was used in all
experiments.
Before the gradientless reactor was used for experiments, step tests were
performed to confirm that there was essentially perfect mixing in the fluid
phase. Calculations also indicated that heat and mass transfer resistances outside and inside the catalyst particles were negligible.

274
MODEL DEVELOPMENT

The group at Lehigh University [ 2,14,25,33,36,45-481

have conducted one
of the most extensive studies on methanol synthesis and the synthesis catalyst
to date. That body of work provides a good starting place for the formulation
of a rate equation which includes reported catalytic mechanisms. Thus, for
example, as proposed by Mehta et al. [25], our carbon monoxide hydrogenation path is based on carbon monoxide adsorbing on Cul+ sites.
As discussed before, catalytic studies by other groups also provided evidence
of the MARI for carbon monoxide hydrogenation. Infrared studies by Edwards
and Schrader [40,43,44]
over binary and ternary catalysts suggested that the
methoxy intermediate was a plausible candidate as the MARI for carbon monoxide hydrogenation. Thus, our model was developed with the methoxy intermediate as the MARL In addition, based on Edwards and Schraders study, the
hydrogenation of the methoxy intermediate was chosen as the RDS for the carbon monoxide hydrogenation rate term in our model.
Regarding the site for hydrogen adsorption, we chose ZnO sites based on
Edwards and Schraders infrared analysis [ 40,43,44]. Since Kung [391 has
indicated that hydrogen adsorption is rapid, we assumed that the concentrations of ZnO sites and adsorbed hydrogen on ZnO sites remain constant during
synthesis. Consequently, each hydrogenation path could be represented by a
single-site model (e.g. the Cul+ site for carbon monoxide adsorption and the
Cue site for carbon dioxide adsorption ) .
Based on the preceding points, the rate equation for carbon monoxide hydrogenation was formulated as follows:
H, +ZnO%H*ZnO*H
H*ZnO*H+ZnO%2

(8)
ZnO*H

(9)

co + cul+ %co*cul+

(10)

CO*Cul+ +H*ZnO%CHO*Cu+
CHO*Cul+ + H*ZnO%CH,

+ ZnO

(11)

O*Cul+ + ZnO

CH, O*Cul+ + H*ZnO %CH, O*Cul+ + ZnO

(12)
(13)

RDS:

CHBO*Cul++H*ZnO%CH,OH*Cul+ZnO

(14)

CH,OH*Cul+%CH,OH+Cul+

(15)

Reactions (8) and (9)are based on Edwards and Schraders infrared analysis [ 401. Reactions (11)- (13 ) were combined to give
CO*Cu++3

H*ZnO%CH,O*Cul++3

ZnO

(16)

275

A site balance gives

L=Cu+

+CO*Cu+

+CHBO*Cul+ + CH,OH*Cul+

(17)

Rearranging reactions (8), (9), (lo), (15) and (16) to solve for [H2*ZnO],
[H*ZnO], [CO*Cul+ 1, [ CH30*Cu1+ ] and [ CH,OH*Cul+ 1, respectively, leads
to
[H*ZnO*H] =KH2pH2 [ZnO]

(18)

[H*ZnO] =KgzKgp$

[ZnO]

(19)

(20)

[CO*Cul+] =Kcopco[Cu+
[CH,O*Cu+]

Ko,[H*Zn0]3[CO*Cu1+]

(21)

[Zn013

[CH30*Cu1+] =KCHKCOK~~K~2pCOp3H/22[C~1+]

(22)

[CH,OH*Cul+]

(23)

=KMpCH30H[C~1+]

wherep; is the partial pressure of species i in the gas phase and the concentration of each surface species is given in brackets. The rate of reaction for the
RDS is given by
~.=$K~~K~P~~O~~~~*~~~+

[ZnO] -k,KmpCHzoH

0 cuI+ [ZnO]

(24)

where 0; is the fractional surface coverage by species i. Converting eqns. (18)(23) in terms of fractional surface coverage and substituting into eqn. (24)
leads to
kiKwKL,K&Kco
(PCOP~H~-PCH~OH/&)
r=1+K~HKf(~K~2K
p
p312
co co Hz + Kc, PCO + KCH~OHPCHZOH

(25)

for the carbon monoxide hydrogenation rate term, where k; is the forward rate
constant lumped with [ ZnO ] (since [ ZnO ] is considered constant), and Keg
is the thermodynamic equilibrium constant of the overall reaction (1). Based
on the kinetics experiments, the Kcopco and the KCH30HpCH30H terms were
found to contribute negligibly to the denominator term. Klier et al. [ 141, Kuczynski [ 171, and Villa et al. [49] also claimed that the methanol adsorption
term is negligible. However, it was found necessary to include adsorption terms
in the denominator accounting for hydrogen and carbon dioxide adsorption on
Cul+ sites. The final version of the rate expression for carbon monoxide hydrogenation becomes

(26)
The Ku, in the denominator of eqn. (26) is primed as a reminder that, in
this case, hydrogen is adsorbing on a Cu + site and not a ZnO site.

276

Before developing the carbon dioxide hydrogenation rate term, it was necessary to determine a possible site for carbon dioxide activation since both Liu
et al.s [6,18] and our own kinetics experiments have indicated that carbon
dioxide adsorbs on a different site than carbon monoxide. A possible site for
carbon dioxide activation was suggested by the investigation of Okamoto et al.
[22]. In this study, both the reverse carbon dioxide and reverse carbon monoxide hydrogenation reactions were investigated in order to determine the nature of the active site(s) of the methanol synthesis catalyst. Okamoto et al.
found that, as the Cul+ concentration increased, the catalyst activity decreased. Metallic copper was considered the major species active for the dehydrogenation reactions. Okamoto proposed that electron transfer was occurring between Cue and ZnO which apparently contributes to the activity of the
Cu. Herman et al. [ 21 and Mehta et al. [ 251 also noticed fine particles of
copper metal dispersed in ZnO along with Cult ions. The optical d-hump transition of the copper particles in the experiments of Herman et al. was slightly
shifted from that of free metallic copper, indicating that a small amount of
electron transfer between the copper and zinc oxide was occurring [ 2). However, in that study, it was not felt that this effect contributed to the activity of
the catalyst.
Based on the above studies as well as on Okamoto et al.s [22] and Fleisch
and Mievilles [23] XPS analysis showing that Cu2+ sites are non-existent in
the reduced catalyst, carbon dioxide hydrogenation is assumed to occur on Cue
sites. Based on Okamoto et al.s [22,29], Kliers [33] and Denise et als [41]
investigations, we also feel that it is microcrystalline copper particles and not
large amorphous copper agglomerates that are the active sites for carbon dioxide hydrogenation. It is noteworthy that Denise et al. [41] suggested the possibility of an oxidized form of copper as active for carbon monoxide hydrogenation and copper metal as active for carbon dioxide hydrogenation.
Again, as in the case for carbon monoxide hydrogenation, the RDS and MARI
for carbon dioxide hydrogenation were chosen based on reported spectroscopic
evidence. Copper formate has been detected as a surface intermediate in carbon dioxide hydrogenation to methanol by Kieffer et al. [ 41 and Tagawa et al.
[ 211. Edwards and Schrader [ 401 also noted a surface formate species during
reaction over a Cu/ZnO catalyst for a synthesis gas containing CO/CO,/H,,
although they attributed it to a formate absorbed on a ZnO site. Based on these
studies, our carbon dioxide hydrogenation rate term includes copper formate
as the MARI and the hydrogenation of a copper formate species as the RDS. The
rate equation for carbon dioxide hydrogenation is formulated from the following steps:
Hz + ZnO %H*ZnO*H
H*ZnO*H+ZnO+s2

(27)
H*ZnO

(28)

co, + CuO%co, *cue

(29)

CO2 *Cue + H*ZnO% CHOz *Cue+ ZnO

(36)

RDS:

CHOz*Cuo+H*ZnOfsCH,O,*Cuo+ZnO

(31)

CH, O2*Cue + H*ZnO%CH3 0, *Cue +ZnO

(32)

CHB02*Cuo + H*ZnO%C!H, OHO*CuO + ZnO

(33)

CH3 OHO*CuGCH,

OH + O*Cu

(34)

O*Cu + H*ZnO%HO*CuO + ZnO

(35)

HO*CuO+ H*ZnO %H, O*Cu + ZnO

(36)

H,0*Cu%H20+Cuo

(37)

L= Cue + HCO, *Cue + CO, *Cue + H, O*Cu

(33)

Reactions (32 )- (37 ) were combined and the following rate equation was developed for carbon dioxide hydrogenation.

(39)
where the double primes denote the fact that these are carbon dioxide hydrogenation rate terms. It is noteworthy that the Kco2 in the carbon monoxide
hydrogenation rate term [ eqn. (26) ] is not equal to Kho2 since different sites
are involved. As in the case of carbon monoxide hydrogenation, the k$contains
the [ZnO] term which is taken as constant and the K& is the equilibrium
constant for reaction (2 ) .
The contribution of unity in the denominator of eqns. (26) and (39) was
found to be negligible and was dropped before adding the two equations to form
the overall rate expression shown below.
~;K~HK~,K~K~~(P~oP~~-P~H~oH/K~~)
r=Kc~K?i:K?i!2&o~co~~;
+~FKH%KHKc:~~K~H~~[Pco~PH~

+&o~Pco~+K;I~PH~

(49)

-PcH~oHPH~o/(~cIP~z)

K~~22K~12KC02K
CHOYPCOZPHZ 12+ Go2

P go:! + K+o

P&O

RESULTS

If the constants in the numerators of each hydrogenation rate term in eqn.

(40) are divided into their respective denominators, a six-parameter model is
formed, i.e.,

278

r=(PcoP&z

-PCH~OH/&)+

u&O&2

+@H,

[Pco~PH~-PCH~OHPH~O/(~~P~~)

+'%O,

~Pco,PX~

+bp:o,

(41)

+CP&O

The parameters in this model were fit to the experimental data with the aid
of a multiple nonlinear regression subroutine, LMDIF, obtained from the Sandia Laboratories in New Mexico. First, the parameters for the carbon dioxide
hydrogenation rate term, a, b, c, were fit by using data which was obtained
by replacing carbon monoxide with helium in the feed [ 201. An average of 0.6
mol percent carbon monoxide was formed during these runs, most likely through
the reverse water-gas shift reaction. Although the resulting carbon monoxide
could react to form methanol, contribution from this source was assumed negligible. Only the carbon dioxide hydrogenation rate term in eqn. (41) was used
to fit a, b, and c. Then, with these parameters fixed, the remaining parameters, a, b, and c, were fit to the data from the CO/H,/CO,
experiments with
the complete eqn. (41) . Table 2 lists the values of these parameters under the
conditions of our experiments.
The overall sum of the squares of the residuals for a, b, and c was of the order
of 10W1for each temperature while the overall residuals for a, b, and c varied
between lo-l3 for the 513 K data to 10-l for the 483 K data. The lumped
parameter containing the Koo2 term, c or c , corresponding to carbon monoxide
or carbon dioxide hydrogenation, respectively, was always the largest parameter. This result agrees with the finding of Klier et al. [ 141 that the adsorption
strength of carbon dioxide is-higher than for hydrogen or carbon monoxide.
Kuczynski [ 171 reported that the pcopH2 term in his model was negligible, at
least at pressures of 6 MPa. However, as shown in the values of parameter a in
Table 2, that term was significant in our model for each temperature and for
both pressures, 2.89 and 4.38 MPa. Experimental data for 513 K at 2.89 and
4.38 MPa and for varying H,/CO/CO,
inlet compositions are presented in
Table 3.
DISCUSSION

As shown in eqn. (40), inhibition terms involving carbon dioxide and hydrogen adsorption on Cul+ appear in the denominator of the carbon monoxide
TABLE 2
Parameter values for the methanol synthesis rate law, eqn. (41)
Temp [K]

483
488
498
513

3.167.lo6
2.145.lo6
1.000-10~
3.762.105

4.595.105
8.902*107
6.302*106
1.536*107

1.493*109
6.086*108
1.031~108
2.993*107

4.687.lo6
1.237.lo6
3.512-10'
8.939-10"

1.133.lo6
2.864.lo6
7.877*105
2.368*106

2.423.lo8
1.072.lOa
2.140.lo7
7.702*106

279

hydrogenation rate term. Based on the data from our kinetic study, it was
found necessary to include these two inhibition terms. A plausible reason for
the necessity of adding the hydrogen adsorption term is that the reduction of
Cu + to Cu* by hydrogen, which eliminates sites for carbon monoxide activation, occurs to a significant extent during methanol synthesis. The necessity
of adding an inhibition term involving carbon dioxide adsorption on Cul + sites
indicates that carbon dioxide adsorbs strongly on these sites, which in turn
inhibits carbon monoxide from adsorbing. Recall that oxidation of Cu+ to
Cu2+ has already been ruled out [ 22,231.
The carbon dioxide hydrogenation rate term in eqn. (40) contains a term in
the denominator for carbon dioxide adsorption on Cue sites, As we show later,
the carbon dioxide adsorption term does not appear to diminish the carbon
dioxide hydrogenation rate under the conditions of our experimental kinetics
study [ 201. However, the modelling studies presented here indicate that the
carbon dioxide adsorption term must be present in order to correctly predict
the experimental plots of overall methanol production rate versus carbon dioxide percentage in feed.
The predicted overall methanol production rate versus mol percent carbon
dioxide in the feed is shown in Figs. 1 and 2 and is compared to the experimental rate at 513 K and at pressures of 2.89 MPa and 4.89 MPa. The accumulated
error in these experiments was calculat.ed to be i 5%. Duplicate runs at 2 mol
percent carbon dioxide in the feed exhibited a 3.4% difference in methanol
production rate at 2.89 MPa and a 0.8% difference at 4.38 MPa.
An explanation for the maximum in the overall methanol production rate
versus mol percent carbon dioxide in the feed is of particular interest. Two
possibilities are: (i) Klier et al.s proposal [ 141 that carbon dioxide adsorbs
strongly on the Cul+ sites necessary for CO activation, thus causing inhibition
of the carbon monoxide hydrogenation rate and/or (ii) Liu et al.s proposal
[6,18] that the water formed in the methanol synthesis reaction and/or the
water-gas shift reaction via reaction (2) or (3)) respectively, adsorbs strongly
on sites necessary for carbon dioxide activation, thus causing inhibition of the
carbon dioxide hydrogenation rate. However, as shown in Fig. 3, which is a plot
of methanol production rate versus mol percent carbon dioxide in a carbon
monoxide free feed, the carbon dioxide hydrogenation rate directly increases
with increasing carbon dioxide, at least up to 8 mol percent carbon dioxide in
the feed. Although this result could be misleading due to the limited amount
of data available, it indicates that carbon monoxide and not carbon dioxide
hydrogenation is being inhibited, thus leading to the maximum in Fig. 2. These
results suggest that, as proposed by Klier et al. [ 141, carbon dioxide is adsorbing on &I strongly enough to inhibit the methanol production rate. While
water might inhibit the carbon dioxide hydrogenation rate, not enough was
formed to be an inhibitor under our synthesis conditions, perhaps due to participation in the water-gas shift reaction.

data for steady-state

methanol

synthesis

513
513
513
513

2.89

513
513
513
513
513
513

513
513
513
513
513
513
513
513
513

4.38
4.38
4.38
4.38
4.38
4.38
4.38
4.38
4.38

2.89

2.89

2.89
2.89

2.89

2.89

2.89

2.89

2.89

Temperature
(R)

Pressure
(MPa)

8.64
8.65
8.62
8.63
8.62
8.61
8.64
8.64
8.64

8.61
8.63
8.66
8.62
8.65
8.65
8.62
8.63
8.61
8.61
20.03
25.90
29.08
32.66
9.96
20.22
20.03
19.35
18.77

20.08
25.98
32.59
29.99
9.98
20.22
19.39
18.79
19.73
20.08
2.03
2.03
2.04
2.03
2.03
1.00
2.03
5.01
7.98

1.02
4.99
8.00
3.49
1.98

1.97

1.97
1.98

1.98

1.98

72.08
68.89
65.30
88.00
78.78
77.94
75.64
73.26

7.47
7.46
1.42
7.69
8.07
7.64
7.65
7.70
7.89

7.25
1.48
1.25
7.55
7.62
7.44
7.57
7.51
7.46

77.94

7.09

72.04
65.44
68.03
88.04
78.76
75.62
73.21
76.76
77.94

Flow-rate

7.78
8.07
8.25
7.89
4.91
7.02
7.66
6.99
6.10

5.25
5.33
5.19
5.36
3.55
4.82
5.11
4.52
4.56
4.82

CH,OH

0.38
0.32
0.29
0.25
0.64
0.30
0.38
0.55
0.77

0.25
0.20
0.18
0.19
0.45
0.18
0.42
0.55
0.33
0.26

H,O

2.05
2.38
2.38
2.43
2.02
1.10
5.37
8.72
3.66
2.06
2.60
2.62
2.54
2.67
1.84
1.06
2.58
5.23
8.16

17.11
23.98
31.76
28.59
7.78
17.96
16.91
16.67
17.19
17.80
14.21
20.60
23.94
27.95
6.37
15.36
14.35
14.20
14.13

CO

CO,

of carbon monoxide

component

conversion

Reactor outlet, percentage

77.94

H,

CO,

Flow-rate

CO

component

Reactor inlet, percentage

All experiments were performed with 7.9*10- kg of catalyst. The overall molar fractional
0.320 at 2.89 MPa and from 0.237 to 0.401 at 4.38 MPa

Experimental

TABLE 3

75.03
68.39
64.98
61.24
86.24
76.26
75.03
73.03
70.84

75.34
68.11
60.49
63.43
86.20
75.94
72.19
69.54
74.26
75.06

H,

7.34
7.60
7.73
7.66
5.00
6.17
7.40
6.80
6.07

4.70
4.88
4.90
4.91
3.38
4.64
4.80
4.32
4.32
4.54

kmol. 106)
( kgs

CH,OH rate

ranged from 0.198 to

281

2IlfI
0

III/I
2

Mel

Percent

6
CO,

in the

6
Feed

Fig. 1. Predicted (-_) compared to experimental (m) methanol production rate versus mol percent carbon dioxide in the feed at 513 K and 2.89 MPa. The CO:HP mol ratio was held constant
at 1.0:3.9.

Mol

Percent

6
CO,

in the

Feed

Fig. 2. Predicted (-_) compared to experimental (m) methanol production rate versus mol percent carbon dioxide in the feed at 513 K and 4.38 MPa. The CO:H, mol ratio was held constant
at 1.0:3.9.

00

iJlJ
1
2

4
Mol

Percent

7
CO2

10

11

12

13

14

I the Feed

Fig. 3. Experimental methanol production rate versus mol percent carbon dioxide in the feed over
a range of temperatures at two pressures. Carbon monoxide was replaced with helium in the feed.
The He:H, mol ratio was held constant at 1.0:3.9. ( V ) 483 K, 2.89 MPa; (V ) 483 K, 4.38 MPa;
(W) 488 K, 2.89 MPa; (A ) 498 K, 2.89 MPa; (A ) 498 K, 4.38 MPa; (0) 513 K, 2.89 MPa; (0)
513 K, 4.38 MPa.

282

7/

1
10

Mol

I,

I
20

,I,

I
30

Percent CO in the Feed

Fig. 4. Predicted (-) compared to experimental ( n ) methanol production rate versus mol percent carbon monoxide in the feed at 513 K and 2.89 MPa. The carbon dioxide mol percent in the
feed was held constant at 2% and the balance was hydrogen.

IIllI

10

20

Mel

Percent CO in the Feed

30

Fig. 5. Predicted (-) compared to experimental (m) methanol production rate versus mol percent carbon monoxide in the feed at 513 K and 4.38 MPa. The carbon dioxide mol percent in the
feed was held constant at 2% and the balance was hydrogen.

Figs. 4 and 5 compare the experimental and predicted rate versus mol percent carbon monoxide in the feed under the same conditions as above. The
accumulated experimental error was calculated to be k 5%. In both cases, our
model is able to predict the experimental trends adequately. The maxima in
Figs. 4 and 5 are relatively flat indicating that carbon monoxide negligibly
inhibits its own hydrogenation rate. This could be a possible explanation for
our finding that the Kcopco term in the denominator of the carbon monoxide
hydrogenation rate term was negligible.
Eqn. (41) fit all of the experimental data (66 points) to within an absolute
error of ? 18%, with the exception of 4 points which were about 25% off. The
quality of the fit is illustrated in Fig. 6, which shows the predicted reaction rate
versus the experimental value. The average deviation between the two is 8.4%.
Our overall rate expression includes the effect of carbon dioxide as a methanol producer via the carbon dioxide hydrogenation rate term as well as a
methanol production rate inhibitor through the inhibition term in the denom-

283

Measured Methanol Production Rate (kmol/kg

set) x10

Fig. 6. Scatter plot of predicted versus measured methanol production rate over a range of temperatures at two pressures. (0 ) 483 K, 2.89 MPa; ( 0 ) 483 K, 4.38 MPa; (a ) 488 K, 2.89 MPa;
( 0 ) 488 K, 4.38 MPa; (A ) 498 K, 2.89 MPa; ( A ) 498 K, 4.38 MPa; (7 ) 513 K, 2.89 MPa; (V )
513 K, 4.38 MPa.

inator of the carbon monoxide hydrogenation rate term. These dual qualities
distinguish our model from that of Natta [ 71, since the effect of carbon dioxide
was not considered in his model, and from that of Bakemeier et al. [S] whose
model only took carbon dioxide inhibition into account. The model of Klier et
al. [ 141 does take into account both of the above contributions of carbon dioxide. However, our model differs from that of Klier et al. in several significant
respects. In the absence of carbon dioxide our model predicts that methanol
production will occur while the model of Klier et al. predicts that the methanol
production rate will decrease to zero. Several studies reported in the literature
have confirmed methanol production in the absence of carbon dioxide, although to a lesser degree than in the presence of carbon dioxide [ 15-171.
Carbon dioxide hydrogenation in our model is also treated differently from
that of Klier et al. In their models, carbon dioxide hydrogenation is accounted
for by an empirical term. In our case, we developed a carbon dioxide hydrogenation expression based on mechanistic information reported in literature. To
the best of our knowledge, our rate expression is the first which develops a
carbon dioxide hydrogenation rate term based on reported mechanistic
information.
Additionally, in our model, Cul+ only activates carbon monoxide methanol
synthesis whereas, in Klier et al.s model [ 141, Cul+ can activate carbon monoxide, carbon dioxide and hydrogen. However, in another report, Klier [33]
had suggested that hydrogen may also be activated on ZnO with one of the two
forms being the significant kinetic form. In fact, Herman et al. [2] originally
proposed that the adsorption of hydrogen occurs on the ZnO surface.
Finally, Klier et al. [ 141 propose the termolecular surface reaction of an
adsorbed carbon monoxide with two adsorbed hydrogen molecules as the RDS.

284

However, one would expect termolecular surface reactions to be relatively rare.

None of the elementary steps proposed in our model contains reactions which
are higher than bimolecular. In the development of our reaction rate model
some elementary steps were lumped together for convenience. Although the
lumped steps have orders higher than two, they obviously do not represent
what is occurring at the molecular level.
CONCLUSIONS

A model and resultant rate expression were developed which includes both
carbon monoxide and carbon dioxide hydrogenation rate terms. In our judgement, the rate expression given by eqn. (40) adequately models our kinetics
data and also retains most of the salient features of mechanistic studies presented in the literature. Reiterating, the important reported mechanistic features included in our proposed phenomenological model are: (i) the surface
reaction of the methoxy intermediate with a dissociatively adsorbed hydrogen
atom is the RDS for carbon monoxide hydrogenation; (ii) the methoxy intermediate on Cult sites is the MARI for carbon monoxide hydrogenation; (iii)
hydrogen dissociatively adsorbs on ZnO sites; (iv) the surface reaction of the
formate intermediate with a dissociatively adsorbed hydrogen atom is the RDS
for carbon dioxide hydrogenation; and (v) the formate intermediate on Cue
sites is the MARI for carbon dioxide hydrogenation.

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