Applied Catalysis, 30 (198’7) 333-338 333

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

MECHANISM OF METHANOL SYNTHESIS FROM CO,/CO/H2 MIXTURES OVER COPPER/ZINC OXIDE/

ALUMINA CATALYSTS: USE OF 14C-LABELLED REACTANTS

G.C. CHINCHEN, P.J. DENNY, D.G. PARKERa, M.S. SPENCER*and D.A. NHAN
Imperial Chemical Industries, plc, Agricultural Division, Billingham, Cleveland
TS23 ILB, England.
aImperial Chemical Industries, plc, Advanced Materials Business Group, Hilton,
Cleveland, England.

(Received 1 September 1986, accepted 20 December 1986)

ABSTRACT
14
The addition of CO or14C02 tracers to C02/CO/H2 reactant mixtures for methanol
svnthesis over a commercial coooer/zinc oxide/alumina catalvst was used to deter-
m"ine the origin of the carbon in the product.. For pCD2/pCO ratios from 0.02 to
1 the fraction of methanol made from carbon dioxide rises from %0.7 to $1, so
carbon dioxide is the major reactant under industrial conditions. There is no
carbon-containing surface intermediate common to methanol synthesis and the water-
gas shift reaction.

INTRODUCTION
In much of the discussion [I,21 on the mechanism of methanol synthesis over
copper/zinc oxide catalysts it has been tacitly assumed that carbon monoxide is
the main source of carbon for the product methanol. However, earlier Russian work
[3], some with "C tracers, indicated that methanol was made from carbon dioxide
only and recent studies [4-71 also indicate that carbon dioxide is the primary
reactant. As methanol can be made from CO/H2 and C02/H2 mixtures [8,9], isotope-
labelling studies under industrially-relevant conditions are the best method
for determining the source of methanol in the reaction of C02/CO/H2 mixtures.
In this paper both labelled CO and CO2 were used over a range of feed compositions
in a flow system with an industrial copper/zinc oxide/alumina catalyst.

EXPERIMENTAL
The industrial methanol synthesis catalyst, made by co-precipitation [IO] and
of composition 60% Cu/30% ZnO/lO% A1203 by weight, was the same as in earlier
work [4-6, 11, 121. It was reduced in situ under 2% H2/N2 mixture and the reduction
temperature was raised from 423 to 503 K over about 5 h. The runs were carried
out in microreactor units similar to those described before [4-61 except that
the pre-mixed feed gases could be switched between a standard mixture and a
14
mixture containing either CO or 14C02. All runs were carried out at 50 bar and

0166-9834/87/$03.50 0 1987 Elsevier Science Publishers B.V.

TABLE 1

Experimental results at 50 bar and 523 K.

Run No. Inlet gas composition 14C Relative Exit gas composition Specific radioactivity
1% label space 1% /uC mmole-'
co velocity MeOH H20 CO2 CO H2 MeOH co
co2 CO2

Al 10.1 10.2 1.00 6.1 1.3 9.8 6.9 75.9 0.085 0.071 0.043
CQ2
A2 10.1 10.2 4.48 2.2 1.3 9.42 10.0 77.3 0.1145 0.1045 0.0125
CO2
A3 10.1 10.2 8.30 1.3 1.2 9.35 10.3 77.9 0.129 0.121 <O.OOl
CO2

Bl 10.0 10.0 co 10.3 2.1 1.7 6.5 10.5 79.2 0.0080 0.012 0.025
B2 6.85 9.2 co 30.0 0.79 1.1 6.7 9.2 80.2 0.0015 0.0023 0.013
B3 6.85 9.2 co 10.9 1.4 0.93 6.55 9.5 79.6 0.0040 0.0046 0.0145
84 4.0 16.2 9.9 2.1 0.8 3.9 16.2 75.0 0.044 0.031 0.0041
CO2
85 0.45 23.0 28.8 0.47 - 0.49 21.3 75.7 0.300 0.190 0.0041
CO2
B6 %O.Ol 21.7 28.0 22.7 77.3 4.88 4.54 0.012
co2
 335

523 K. Diluted catalyst beds were used in most runs to reach high space velocities
and also to keep the reactor isothermal. Throughout each run the exit concent-
rations of methanol, water, carbon monoxide and carbon dioxide were determined
conventionally [4-61 by on-line gas chromatography. A sample of condensate (i.e.,
water and methanol) was taken throughout each run by the use of a methanol/
solid carbon dioxide cold trap on the gas exit line. The water contents of con-
densate samples were measured by micro-Carl Fischer analysis.
Radiochemical analyses of liquid and gas products were performed separately.
The condensate samples (5 u.~,)were taken up in IO ml PCS (Amersham-Searle) and
counted in standard low-potassium glass vials on a Nuclear Chicago Mark III Model
6880 liquid scintillation spectrometer. Two methods were used to count the gas
samples, by radio gas-liquid chromatography and by absorption as barium carbonate.
Radio GLC was carried out on a Pye-Unicam GCD with katharometer detector, tempera-
ture programmer and a Panax-Reigate gas flow proportional counter. For the barium
carbonate method, carbon dioxide was absorbed by barium hydroxide from the exit
gas. The resultant barium carbonate sample was filtered, dried and a known weight
was then treated in an ultrasonic bath with 3 ml water. 10 ml of scintillation
cocktail was added to produce a gel which was then counted by the liquid
scintillation counter.
The radioactive carbon dioxide was prepared by the action of concentrated
sulphuric acid under high vacuum on a known weight of Ba '4603. The14C0 was
2
admitted to an evacuated gas cylinder and then pressured to 120 bar with a
synthesis gas mixture. Radioactive carbon monoxide was prepared by pyrolysis of
[14C] calcium carbonate with zinc dust and it was shown by radio-glc to be
>99.9% radiochemically pure. The gas was admitted to an evacuated gas cylinder
and pressurised as above.

RESULTS AND DISCUSSION

The mean values of results obtained for each run in two series of experiments
are given in Table 1. As described above,
runs at lower space velocities were
14
also carried out but, because of extensive scrambling of C between methanol,
carbon monoxide and carbon dioxide, these runs gave no mechanistic information.
The catalyst used in the first series of runs had had some prior use under
standard synthesis conditions and it was of lower activity than fresh catalyst.
The values of specific radioactivity of reaction products (Table 1) show
qualitatively that at all inlet gas compositions the values for methanol are
14
more closely linked to those of CO2 than of CO. Scrambling of C between CO
and CO2 via reactions 1 and 2 is slow enough at high space velocities for the
distinction to be made. Reaction 1 has

14
co + '2c02 = '4c02 + '2co (I)
336

Specific
Radioactivity
j&/mm01

0.08-

0.06-

o inlet CO

Space Velocity(h -')

FIGURE 1 Specific radioactivities of carbon monoxide, carbon dioxide and methanol

as a function of space velocity. Reactant mixture lC% CO/IO% CO/80% H2, containing

14C02 at 50 bar, 523 K.

H20 + 14C0 = H2 t 14C02 (2)

12
co + o(a) f
+ '2co2 (3)

been observed on Cu/ZnO/A1203 catalysts at ambient temperatures [13,14]. At low

conversions the dilution of labelled carbon dioxide by reaction (3) is also small.
Thus methanol is made predominantly from C02, even when (Run B6) the initial CO2
content is only ~100 ppm. The results from the first series of runs (Al - A3)
are shown in Figure 1 and it is clear that carbon dioxide is essentially the sole
source of methanol in a 10% C02/10% CO/BO% H2 gas mixture.
Estimates of the fraction (0) of methanol made from CO2 were made from the
specific radioactivity of methanol and the mean values (inlet to outlet) for
carbon monoxide and carbon dioxide. Errors in 0 were largest for small CO2 con-
centrations or large conversions, due to large differences between inlet and

exit activities of C02, and no values of 0 could be calculated for runs Al or B6.

The dependence of 0 on mean pC02/pco ratio is shown in Figure 2, which also gives
the variation of coverage (e) of adsorbed oxygen derived from earlier work [5,6]
with the same catalyst. Clearly methanol formation from carbon monoxide occurs
only at very low CO2 and O(a) concentrations. The effects of O(a) are discussed

elsewhere [4-6, 111, but relevant points are:

 337

Fraction
ofCH,OH
from CO,@)
Coverage(B)
of o,,,

FIGURE 2 Variation of fraction of methanol derived from carbon dioxide (0) as a

function of mean pC02/pCo. X, runs with 14C02; 0, runs with 14C0. ------,
variation of coverage of adsorbed oxygen (8) with pCo /p [5,61.
2 co

(a) Adsorbed oxygen promotes CO2 chemisorption [6,15] and hence CO2 hydrogenation

to methanol.
(b) Any adsorbed CO reacts with Ota), a fast reaction [16-191, rather than with
hydrogen.
The approach of the water-gas shift reaction, (4) to equilibrium

H20 + CO = H2 + CO2 (4)

in these experiments was estimated by the calculation of Y by equation (5). The

values were all in the range 23-59,

compared with the value of the equilibrium constant, K3 = 75.9 at 523 K. Thus
a significant fraction of any carbon-containing surface intermediate in the shift
reaction would be formed from CO as well as C02, As methanol is formed almost
entirely from CO2 at the higher pC02/pC0 ratios, there cannot be a common carbon-
containing surface intermediate common to both the shift reaction and methanol
synthesis. This is in agreement with the dissociative mechanism involving Ota)

proposed [6] for the shift reaction.

338

CONCLUSIONS
1 Methanol is made on Cu/ZnO/A1203 catalysts predominantly from carbon dioxide
in all practical CO,/CO/H, gas mixtures.
2 Methanol formation from carbon monoxide occurs only at very low levels of carbon
dioxide and adsorbed oxygen on the copper.
3 There is no carbon-containing surface intermediate common to both methanol
synthesis and the water-gas shift reaction over Cu/ZnO/A1203 catalysts.

ACKNOWLEDGEMENTS
The authors thank C. Plant, B.M. Glanville, R.A. McReddie and P. Jackson for
experimental assistance.

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