The effect of carbon monoxide on the oligomerization of acetylene in hydrogen over a Ni/SiO₂ catalyst

The effect of small amounts of carbon monoxide on the oligomerization of acetylene over a low loaded Ni/SiO₂ catalyst has been investigated. Although CO does not participate in the reaction it has two beneficial effects if oligomer products are desired. Conversion of acetylene is higher, both initially and over time, and the selectivity to C₄-C₁₀ product is improved relative to C₂ hydrogenation. Higher products are predominantly aliphatic alkenes. CO increases formation of branched products relative to linear ones and dienes relative to alkenes while suppressing benzene and higher aromatics. In the absence of CO, unsaturated products can be largely hydrogenated to alkanes if a Pt/SiO₂ catalyst is located immediately downstream the Ni/SiO₂ but the hydrogenation of dienes and trienes proceeds only as far as alkenes when the feed contains CO. The twin effects of CO can be interpreted on the basis that CO competes for nickel sites that would otherwise be able to accept hydrogen atoms from H₂ or C₂H₂. The Ni/SiO₂ catalyst was sensitive to feed impurities such as phosphine present in some grades of acetylene but deactivation was not complete. Crown