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

McCaig, Joseph; Lamb, H. Henry

doi:10.3390/catal12080824

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

Journal Article · 27 July 2022 · Catalysts

DOI: https://doi.org/10.3390/catal12080824 · OSTI ID:1981113

McCaig, Joseph ^[1]; Lamb, H. Henry ^[2]

North Carolina State University, Raleigh, NC (United States); North Carolina State University, Raleigh, NC (United States)
North Carolina State University, Raleigh, NC (United States)

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.

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Research Organization:: American Institute of Chemical Engineers (AIChE), New York, NY (United States); North Carolina State University, Raleigh, NC (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0007888

OSTI ID:: 1981113

Journal Information:: Catalysts, Journal Name: Catalysts Journal Issue: 8 Vol. 12; ISSN 2073-4344

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Ni-H-Beta Catalysts for Ethylene Oligomerization: Impact of Parent Cation on Ni Loading, Speciation, and Siting

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