The Role of Nickel and Brønsted Sites on Ethylene Oligomerization with Ni-H-Beta Catalysts

Abstract

The present work studies the adsorption of ethylene on Ni-H-Beta particles to unravel the roles of nickel and Brønsted sites in the catalytic oligomerization of ethylene. Three models (i.e., two based on the Cossee–Arlman mechanism and one based on the metallacycle mechanism) are examined in terms of the nature of the active sites and the adsorption mechanism involved in the ethylene coordination step. The results are consistent with the participation of two active sites in the formation of [Ni(II)-H]+ Cossee–Arlman centers and also suggest that ethylene dissociates upon adsorption on [Ni(II)-H]+ sites. Further characterization of Ni-H-Beta catalysts prepared at different nickel loadings and silica-to-alumina ratios reveals that highly dispersed Ni2+ exists on the catalyst surface and interacts with the catalyst’s lattice oxygen and free NiO crystals. At the same time, the kinetic results indicate that Brønsted sites may form isolated nickel-hydride ([Ni(II)-H]+) centers on the catalyst surface. In addition, the presence of residual, noncoordinated Ni2+ and Brønsted sites (not involved in the formation of [Ni(II)-H]+ sites) shows a reduced probability of the formation of nickel-hydride sites, hindering the conversion rate of ethylene. A mechanism for forming [Ni(II)-H]+ centers is proposed, involving ethylene adsorption over Ni2+ and a Brønsted site. This research has important implications for improving ethylene oligomerization processes over nickel-based heterogeneous catalysts.