The effect of sodium on the structure–activity relationships of cobalt-modified Cu/ZnO/Al2O3 catalysts applied in the hydrogenation of carbon monoxide to higher alcohols

• Bulk and surface properties of the catalysts were characterized after 40 h TOS.
• Cu acts as reduction promoter for enhanced Co0 formation at low temperatures.
• Low Na content: initial deactivation and Cu–Co surface alloy formation as active sites in higher alcohol synthesis.
• High Na content: constant performance and formation of Co/Co2C interfaces as active sites in higher alcohol synthesis.

A series of Co-modified Cu/ZnO/Al2O3 methanol synthesis catalysts with different Na loadings was prepared and applied in higher alcohol synthesis (HAS) at 280 °C, 60 bar and a ratio of H2/CO = 1. The bulk and surface properties of the catalysts were characterized after reduction and after 40 h time on stream (TOS) without exposing the catalysts to air during the transfer and the measurements. Increased presence of metallic Co0 after reduction at 350 °C was confirmed by X-ray photoelectron spectroscopy indicating metallic Cu0 to act as a reduction promoter. Catalysts with low Na loadings (⩽0.6 wt%) showed strong initial deactivation presumably due to coking of isolated Co0 surface sites favoring hydrocarbon formation. The selectivity to higher alcohols gradually increased during the first 10 h TOS indicating enhanced Cu–Co surface alloy formation considered as active sites for HAS. In contrast, with high Na loadings (⩾0.8 wt%) deactivation did not occur and stable performance with constant CO conversion and product distribution was observed indicating significantly altered structural properties. High Na loadings caused the stabilizing amorphous oxide matrix to collapse resulting in strong sintering of the metallic Cu particles, and an increased carbidization of metallic Co0 forming bulk Co2C was observed by X-ray diffraction. Close contact between metallic Co0 and Co2C, which is known to facilitate molecular CO adsorption, is assumed to generate additional active sites for HAS.

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