Abstract
The catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ∼97% can be n-aldehydes. While the product slate contains ∼60% n-aldehydes at /pCO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson–Schulz–Flory behaviour, independent of the /pCO ratio, is found for the sum of C4+ products. We advocate a synergistic interaction between a Mn5O8 oxide and a bulk Co2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies.
Highlights
The catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock
Correspondence and requests for materials should be addressed to N.K. In his seminar ‘Zwolf Jahre Kohlenforschung’ (Twelve Years of Carbon Research, 1926) at the Kaiser-Wilhelm-Institut fur Kohlenforschung in Mulheim-Ruhr[1], Fischer informed the Kuratorium about his incapacity of reproducing the 1913 patent by Badische Anilin and Soda Fabriken (BASF) claiming hydrocarbon chain initiation through CO hydrogenation to occur in an excess of carbon monoxide[2]
Decades after the original discoveries by Mittasch, and Fischer and Tropsch, the influence of the H2/CO pressure on the synthesis kinetics for potassium-promoted iron catalysts was systematically investigated by Dry et al.[6], and Matsumoto and Satterfield[7]
Summary
The catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. Decades after the original discoveries by Mittasch, and Fischer and Tropsch, the influence of the H2/CO pressure on the synthesis kinetics for potassium-promoted iron catalysts was systematically investigated by Dry et al.[6], and Matsumoto and Satterfield[7] These authors established a first-order kinetic dependence on hydrogen and a hydrocarbon chain-lengthening probability insensitive to both the actual H2/CO ratio and the degree of potassium promotion. It seems that similar studies for other catalysts enabling paraffins, olefins and oxygenates formation were not conducted up to date. While aldehydes are presently produced via homogeneous hydroformylation of terminal olefins on an industrial scale, with the possibility of reducing them to terminal alcohols, our results open the door for designing a one-pot heterogeneous process with varying H2/CO ratios to optimize the selectivities of either product class
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