Ni-H-Beta Catalysts for Ethylene Oligomerization: Impact of Parent Cation on Ni Loading, Speciation, and Siting

Abstract

Ni-H-Beta catalysts for ethylene oligomerization (EO) were prepared by ion exchange of NH4-Beta and H-Beta zeolites with aqueous Ni(NO3)2 and characterized by H2-temperature-programmed reduction (TPR), NH3-temperature-programmed desorption (TPD), and diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS). Quadruple exchange of NH4-Beta at 70 °C resulted in 2.5 wt.% Ni loading corresponding to a Ni2+/framework aluminum (FAl) molar ratio of 0.52. [NiOH]+ and H+ are the primary charge-compensating cations in the uncalcined catalyst, as evidenced by TPR and DRIFTS. Subsequent calcination at 550 °C in air yielded a Ni-H-Beta catalyst containing primarily bare Ni2+ ions bonded to framework oxygens. Quadruple exchange of H-Beta at 70 °C gave 2.0 wt.% Ni loading (Ni2+/FAl = 0.41). After calcination at 550 °C, the resulting Ni-H-Beta catalyst comprises a mixture of bare Ni2+ ions: [NiOH]+ and NiO species. The relative abundance of [NiOH]+ increases with the number of exchanges. In situ pretreatment at 500 °C in flowing He converted the [NiOH]+ species to bare Ni2+ ions via dehydration. The bare Ni2+ ions interact strongly with the Beta framework as evidenced by a perturbed antisymmetric T-O-T vibration at 945 cm−1. DRIFT spectra of CO adsorbed at 20 °C indicate that the Ni2+ ions occupy two distinct exchange positions. The results of EO testing at 225 °C and 11 bar (ethylene) suggested that the specific Ni2+ species initially presented (e.g., bare Ni2+, [NiOH]+) did not significantly affect the catalytic performance.

Keywords

• Bronsted acidity
• TPR
• DRIFTS
• NH₃ TPD
• perturbed TOT skeletal vibration
• CO adsorption