Copper-zinc oxide-alumina catalysts synthesis

Chinchen GC, et al. Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts - use of 14C-labeled reactants. Appl Catal. 1987 30(2) 333-8. 

Denny and Whan (26) also reviewed various contrasting reports on the effects of C02 on the synthesis and emphasized that any complete kinetic expression should include a term involving the partial pressure of C02. A rate equation that does contain an empirical C02-dependent term for the copper-zinc oxide-alumina catalysts has been presented in 1980 by Andrew (27) in the form... 

Bowker, M., Hadden, R.A., Houghton, H., Hyland, J.N.K., and Waugh, C.J. (1988) Mechanism of methanol synthesis on copper/zinc oxide/alumina catalysts. J. Catal, 109, 263-273. 

To summarize the qualitative findings, the methanol synthesis activity in the binary Cu/ZnO catalysts appears to be linked to sites that also irreversibly chemisorb CO and not to sites that adsorb CO reversibly. Since irreversible adsorption of CO follows linearly the concentration of amorphous copper in zinc oxide, these sites are likely to be that part of the copper solute that is present on the zinc oxide surface. No correlation of the catalyst activity and the copper metal surface area, titrated by reversible form of CO or by oxygen, could be found in the binary Cu/ZnO catalysts (43). In contrast with this result, it has been claimed that the synthesis activity is proportional to copper metal area in copper-chromia (47), copper-zinc aluminate (27), and copper-zinc oxide-alumina (46) catalysts. In these latter communications (27,46,47), the amount of amorphous copper has not been determined, and obviously there is much room for further research to confirm one or another set of results and interpretations. However, in view of the lack of activity of pure copper metal quoted earlier, it is unlikely that the synthesis activity is simply proportional to the copper metal surface area in any of the low-temperature methanol-synthesis catalysts. 

The best catalyst for the synthesis of methanol from CO + H2 mixtures is copper/zinc oxide/alumina. Intermetallic compounds of rare earth and copper can be used as precursors for low-temperature methanol synthesis as first reported by Wallace et al. (1982) for RCu2 compounds (R = La, Ce, Pr, Ho and Th). The catalytic reaction was performed under 50 bar of CO + H2 at 300°C, and XRD analyses revealed the decomposition of the intermetallic into lanthanide oxide, 20-30 nm copper particles and copper oxide. Owen et al. (1987) compared the catalytic activity of RCux compounds, where R stands mainly for cerium in various amounts, but La, Pr, Nd, Gd, Dy and even Ti and Zr were also studied (table 4). The intermetallic compounds were inactive and activation involved oxidation of the alloys using the synthesis gas itself. It started at low pressures (a few bars) and low temperatures (from 353 K upwards). Methane was first produced, then methanol was formed and it is believed that the activation on, for example, CeCu2, involved the following reaction, as already proposed for ThCu2 (Baglin et al. 1981) ... 

High pressure processes P > 150 atm) are catalyzed by copper chromite catalysts. The most widely used process, however, is the low pressure methanol process that is conducted at 503—523 K, 5—10 MPa (50—100 atm), space velocities of 20, 000-60,000 h , and H2-to-CO ratios of 3. The reaction is catalyzed by a copper—zinc oxide catalyst using promoters such as alumina (31,32). This catalyst is more easily poisoned than the older copper chromite catalysts and requites the use of sulfiir-free synthesis gas. 

The low-pressure methanol synthesis process utilizes ternary catalysts based on copper, zinc oxide, and another oxide, such as alumina or chromia, prepared by coprecipitation. Cu-Zn0-Al203 and Cu-Zn0-Cr203 are usually the most important industrial catalysts. A significant advance was made when a two-stage precipitation was suggested in which ZnAl2C>4, a crystalline zinc aluminate spinel, was prepared prior to the main precipitation of copper-zinc species.372 This alteration resulted in an increase in catalyst stability for long-term performance with respect to deactivation. Catalyst lifetimes industrially are typically about 2 years. 

Low-pressure methanol synthesis relies almost exclusively on catalysts based on copper, zinc oxide, and alumina. The catalysts are produced by ICI (now Johnson Matthay), Siidchemie (now Clariant), Haldor Topsoe, in the past also by BASF, and other chemical enterprises and contain 50-70 atomic % CuO, 20%-50% ZnO, and 5%-20% Al203. Instead of alumina, chromium oxide and rare earth oxides have also been used. The mixed oxide catalysts are usually shipped as 4-6 mm cylindrical pellets with specific surface area of 60-100 m2/g. The catalysts are activated in situ with dilute hydrogen, often derived from off-gases from synthesis gas... 

The modern methanol synthesis catalyst consists of copper, zinc oxide, and alumina. Copper metal is seen as the catalytically active phase, and ZnO as the promoter. It is well known that the interaction between the two components is essential for achieving a high activity, but the nature of the promoting effect is still a matter of debate. Loss of activity is caused by sintering of the Cu crystallites, and, if the feed gas contains impurities such as chlorine and sulfur, by poisoning. 

Because the synthesis reactions are exothermic with a net decrease in molar volume, equiUbrium conversions of the carbon oxides to methanol by reactions 1 and 2 are favored by high pressure and low temperature, as shown for the indicated reformed natural gas composition in Figure 1. The mechanism of methanol synthesis on the copper—zinc—alumina catalyst was elucidated as recentiy as 1990 (7). For a pure H2—CO mixture, carbon monoxide is adsorbed on the copper surface where it is hydrogenated to methanol. When CO2 is added to the reacting mixture, the copper surface becomes partially covered by adsorbed oxygen by the reaction C02 CO + O (ads). This results in a change in mechanism where CO reacts with the adsorbed oxygen to form CO2, which becomes the primary source of carbon for methanol. 

Copper-zinc-alumina mixed oxide catalysts has been investigated in the low-temperature methanol synthesis. Three different copper-containing species were identified in the spent catalysts (i) metallic copper, (ii) CuO, and (iii) copper not detectable by XRD analysis, the latter being probably related to the ZnO matrix. While no correlation existed between the catalytic activity and only one of these... 

The first industrial methanol catalysts, used from 1923, were based on zinc oxide-chromium oxide mixtures. Experimental woik during development of the process had, however, demonstrated the high activity of zinc oxide catalysts containing copper. This was particularly true if a third refractory oxide such as chromia or alumina was also added." Catalysts containing copper are particularly susceptible to poisoning. At that time the synthesis gas was produced from water gas, and contained poisons snch as sulfur and chlorine compounds so that copper catalysts were unsuitable. 

When the hydrocarbon steam reforming process conld provide poison free synthesis gas, the benefits of the more active copper catalysts were quickly reviewed. It was soon shown that the high activity of copper oxide-zinc oxide catalysts, compared with the zinc oxide-chrominm oxide types, particularly when alumina or chromia promoters were added, conld revolutionize methanol production. New, more efficient processes were nrgently needed in view of the increasing demand for methanol and the economies of high capacity units. 

It has been concluded from experimental work with catalysts containing alumina that methanol forms from carbon dioxide and that the catalyst activity is proportional to the copper metal surface area. The presence of carbon dioxide in the gas increases the synthesis rate. The zinc oxide and alumina play little part in the actual reaction apart from stabihzing the reduced copper and protecting it from the effect of any poisons. On the other hand, with catalysts containing chromia, the carbon dioxide leads to a decrease in the reaction rate. ... 

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