Chemical Engineering Sczence. Vol. 46, NO. II, pp. 2809 2813, 1991. cw-2509/91 $3 cm + 0.

00
Printed in Great Britain. c? 1991 Pergamon Press plc

KINETICS OF METHANOL SYNTHESIS OVER

COMMERCIAL COPPER/ZINC OXIDE/ALUMINA
CATALYSTS

J. SKRZYPEK,+ M. LACHOWSKA and H. MOROZ

Institute of Chemical Engineering, Polish Academy of Sciences, PAN, 44- 100 Gliwice, ut. Battycka 5,
Poland

(Rerrioed 19 December 1990; ncceptrd 8 .lanuary 1991)

Abstract-Kinetics of the low-pressure methanol synthesis cwx Polish commercial catalyst CuO (60%
wt)-ZnO (30%)-AI,O, (7.5%) was investigated. The range of parameters applied was wide, especially
concerning inlet concentrations of reactants: xz, (it%80% mol), x&, (340% mol), x& (620% mol). It
was found that methanol synthesis occurs from CO, rather than from CO and that the basic reactions are:
CO, + 3H2 + CH,OH + Hz0 and CO1 + H, it CO + H,O. Dependence of the reaction rates on initial
concentrations of CO, and H, was given by the functions with characteristic maxima. Langmuir-
Hinshelwood type kinetic equations were determined.

INTRODUCTION 1985; Gasser, 1989; Kuznetzov et al., 1984;

Methanol is a very important chemical, manufactured Malinovskaya et al., 1987; Rozovskii, 1989; Tagawa
world-wide. The modern low-pressure methanol et al., 1985). Simultaneously to the methanol syn-
synthesis catalysts are usually based on Cu/ thesis, water-gas shift reaction or reverse water-gas
ZnO/Al,O, or Cu/ZnO/Cr,O,. These mixed oxide shift reaction takes place, depending on reaction
catalysts have been found to be considerably more conditions. Then, two main reactions occur:
active than the individual components. Methanol syn- CO, + 3H, e CH,OH + H,O (1)
thesis has become growing academic interest over the
past decade. The number of publications, particularly CO + H,O si CO, + H,. (2)
on the Cu/ZnO based catalysts, has increased
steadily.
Many studies have been reported on kinetics and EXPERIMENT-AI.
mechanism of methanol synthesis on copper-contain- Catalyst
ing catalysts (Agny and Takoudis, 1985; Amenomiya We used a commercial catalyst sampled from meth-
and Tagawa, 1984; Bos et al., 1989; Chinchen et al., anol plant in Chorzbw. The catalyst was manufac-
1984, 1987; Denise and Sneeden, 1982; Denise et al., tured, on industrial scale, in accordance with Blasiak’s
1989; Dybkjaer; 1985; Gasser and Baiker, 1989; Graaf patent (Blasiak, 1947). Blasiak’s catalysts is character-
et al., 1988; Kuczyliski et al., 1987; Kuznetzov et al., ized by a high CuO content, i.e. 6@65% wt (ZnO:
1984; Malinovskaya, 1987; McNeil et al., 1989; Ren et 25-35% wt; the rest is Al,O,). We used a sample of
al., 1989; Rozovskii, 1980; Schack et al., 1989; Seyfert catalyst of not very high but very stable activity. The
and Luft, 1985; Tagawa et al., 1985; Takagawa and catalyst has been used in the industrial reactor for a
Oshugi, 1987; Villa et aJ., 1985; Weiduan et al., 1989; year. It was slightly deactivated but no further deacti-
Yaling et al., 1989). Several reviews have been pub- vation was observed under otir laboratory conditions.
lished on this subject (Bart and Sneeden, 1987; Ghiotti Its moderate activity and also its dilution with inert
and Boccuzzi, 1987; Kung, 1980; Klier, 1982; material allowed to achieve pseudoisothermal condi-
Chinchen et al., 1988; Kiennemann and Hinderman, tions in the tubular reactor. The catalyst was crushed
1988; Rozovskii, 1989). Unfortunately, there is still no to eliminate the effects of internal diffusion. External
agreement in the literature on the kinetics of this diffusion was also negligible. Before starting the kin-
process. The kinetic studies are often conflicting. etic study the catalyst was carefully reduced by dilute
Moreover, until now there has been no agreement as hydrogen stream. After reduction, the catalyst was
to the basic reactions occurring in the system. The always kept under reaction mixture or inert atmo-
role of CO, is insufficiently understood. It is known sphere.
that some quantity of CO, is necessary for the process
to start and proceed.
Reactor and experimental technique
Many of the papers indicate that methanol syn-
Kinetic experiments were carried out in a tubular
thesis on copper-containing catalysts occurs not from
high-pressure fixed bed reactor. The gaseous feed was
CO, but rather via CO1 hydrogenation (Amenomiya
supplied from a battery of gas cylinders. The reactor
and Tagawa, 1984; Chinchen et al., 1984; Dybkjaer,
consisted of a l-inch diameter stainless steel tube. This
tube was incased in an electrically heated metal block.
‘Author to whom correspondence should be addressed. 50 ml of the catalyst was placed into the reactor tube
2810 J. SKRZYPEK et al.

together with the same volume of inert material. Tem- Many of our experiments were performed with
perature was controlled by a moving thermocouple. gaseous mixtures containing only CO,, H, and N,
The effluent stream, after cooling and after pressure (with no CO) under pseudodifferential conditions, i.e.
was reduced to 1 atm, was virtually a two-component for relatively small conversions and also far from
liquid mixture of methanol and water. Liquid pro- equilibrium. In such a situation, conversion degrees
ducts as well as inlet and outlet gases were analysed < 1 and 5 2 were proportional to the reaction rates rl
chromatographically. and r2. The effect of initial concentrations of CO, on
The range of parameters applied was very wide, the rate of methanol formation is presented in Fig. 1.
especially with respect to the inlet concentrations of Characteristic maxima corresponding to 0.2 inlet
reactants: mole fraction of CO1 were obtained. The effects of
initial concentration of CO, on the rate of the reverse
xi,: 0.1-0.8; x&Q 0.05~.35;
water-gas shift reaction are shown in Fig. 2. The
~2,: 0.2; T: 460-550 K;

P: 3 9 MPa; T: 5 lOOkg.s/mol.

KEStil,‘I‘SAND UISCUSSION

We have observed that methanol synthesis on our

catalyst proceeds most probably from CO, rather
than from CO. The argument is as follows. If the feed
consists of only CO, and H, (with no CO) methanol is
formed without any difficulty and selectivity of the
synthesis is very high. However, feed of
when using
various CO and II, concentrations (with no CO,)
methanol is not formed if steam is completely re-
moved from the feed. A very small amount of water
initiates methanol synthesis owing to the thermo-
dynamically preferential water-gas shift reaction
CO + H,OF~CO, + H, @a)
followed by the methanol synthesis from CO, [ reac- 0 0.1 0.2 0.3
tion, eq. (l)]. GO 2
We agree therefore with the results of well known
Rozovskii’s works showing that methanol synthesis Fig. 2. Dependence of the reverse water-gas shift reaction
on copper-containing catalysts proceeds only from rate on initial carbon dioxide concentrations at the temper-
ature of 473 K and r = 6.7 (g cat. h)/mol. 1 = 7 MPa, 2
CO,. Similar conclusions are drawn in many c)ther
= S MPa, 3 = 3 MPa.
research centers in a number of countries.

0.1 0.2 0.3 0.4

Go, 0.2 0.4 0.6 0.8
Gi*
Fig. 1. Dependence of the methanol synthesis rate on initial
carbon dioxide concentrations at the temperature of 473 K Fig. 3. Dependence of the methanol synthesis rate on initial
and T = 6.7 (g cat. h)/mol. 1 = 7 MPa, 2 = 5MPa, 3 hydrogen concentrations at the temperature of 473 K and t
= 3 MPa. = 6.7 (g cat. h)/mol. 1 = 7 MPa, 2 = 5 MPa.
 Kinetics of methanol synthesis over commercial catalysts 2811

curves also reach maxima which correspond to 0.1 istic maxima are also obtained. For methanol syn-
inlet mole fraction of CO,. thesis the maximum corresponds to the 0.7 inlet mole
Plots of the reaction rates against initial concentra- fraction of hydrogen.
tions of H, are illustrated in Figs 3 and 4. Character- The effects presented above indicate considerable
slowing down in the reaction rates probably
due to
Table 1. Initial feed composition the strong chemisorption of CO, and H,. On the
other hand, these effects enabled one to predict the
xco. XH1 XC0 final kinetic equations.
0.22 0.76 0
A whole series of experiments was done in order
0.20 0.68 0 to determine the final form of kinetic expressions.
0.23 0.49 0 The experiments were performed using gaseous
0.21 0.35 0 mixtures consisting of both CO,-Hz-N, and
0.23 0.12 0
CO-CO,-Hz-N2 of various reactant concentrations
0.35 0.63 0
0.25 0.67 0 for T = 473, 493 and 513 K; P = 5 and 7 MPa; F’
0.10 0.67 0 = 0.2 mol/min. Larger integral conversion degrees
0.04 0.64 0 were achieved under such conditions. The final kinetic
0.11 0.63 0.14 equations are of Langmuir-Hinshelwood’s type with
0.06 0.75 0.18
0.04 0.60 0.07
the surface reactions between CO, and I-I, as rate-
controlling steps.

(Pzl,Pco,)
- ( l/K,,) (PCHIOH
PH*OIPHJ
11 = k, KtdGx,z
( 1 + KH,PHz+ KcozPcoz + &H~OHPCH,OH + KH~OPH~O+ KCOPCO)~1

1
(JkPcoA - (1/K,,)(PCOP",O)
(1 + KH,FH, + Go, PCO, + KCH~OHPCH~OH + KH~OPH~O f KCOPCO)~

k,, = 3 x lo9 kmol/(kg cat. h)

E, = 25 kcal/mol (104.7 kJ/mol)
k,, = 2.5 x lo9 kmol/(kg cat-h)
E, = 25 kcal/mol (104.7 kJ/mol)

K Hz:
K,, = 0.14 x 1O-s atm-’ (1.38 x lo-l4 m’/N)
AH, = 18 kcal/mol (75.4 kJ/mol)

K co11
K,, = 0.44 x 10-s atm-’ (4.34 x lo-l4 m2/N)
AH, = 18 kcal/mol (75.4 kJ/mol)

K CHJOH:
K,, = 0.1 I x 10m9 atm- ’ (1.09 x lo-l5 m2/N)
AH, = 7 kcal/mol (29.3 kJ/mol)

K HaO:

K,, = 0.35 x 10-satm-’ (3.45 x lo- l4 m’/N)

AH, = 18 kcal/mol (75.4 kJ/mol)

Kc,:
K,, = 0.50 x 10WIO atm-’ (4.93 x lo-l6 m2/N)
AH, = 18 kcal/mol (75.4 kJ/mol)
2812 J. SKRZYPEK et al.

25
1

s-
b2
*
x
* 2
z-
&I.5
r
3
E \
* *
P 1

*
0.E
Fig. 6. Parity plot for integral conversion r2
.;:
I I I I
C 0.2 0.4 0.6 0.B 1

X""z
for the fked containing only CO, ‘and Hz with-
Fig. 4. Dependence of the reverse water-gas shift reaction out co.
rate on initial hydrogen concentrations at the temperature of (2) The relations between the reaction rates and the
473 K and 5 = 6.7 (g cat. h)/mol. 1 = 7 MPa, 2 = 5 MPa. inlet concentrations of COz and H, (for a feed
without CO) are functions with characteristic
maxima for both methanol synthesis and re-

J 0 0 0 0
verse water-gas
(3) The Langmuir-Hinshelwood
with the surface reaction
as a rate-controlling
shift

between
reaction.
kinetic equations
CO, and H,
step are proposed.

NOTATION

E activation energy, kcal/mol

FO inlet total feed of reactants, kmol/h
AHi adsorption enthalpy, kcal/mol
Ki equilibrium constant, atm ’
adiorption
K,j equilibrium reaction constant
J k reaction rate constant, kmol/(h. kg cat)
0 0.02 0.04 0.06 0.08 0.7 c1.1: molar flux of reactant, kmol/h
ni
51exp preexponential factor, kmol/(h ‘kg cat)
kj,
P partial pressure of reactant, Pa
Fig. 5. Parity plot for integral conversion c1
T temperature, K
r reaction rate, kmol/(h kg cat)-
The quality of the fit was shown in Figs 5 and 6, X mole fraction
where the estimated values of conversion degrees 5 1,
t2 are plotted against the experimental values. One Greek letters
should emphasize that from the mathematical point of 51 conversion degree for reaction 1
view these kinetic equations well reflect the reaction ( = %,,o,lFO)
rates with their characteristic maxima (Figs 14). 52 conversion degree for reaction 2 ( = nHJO
- ~c”,o”l~*)
CONCLlJSlONS

(1) Low-pressure methanol synthesis on Polish

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