4.6 Article

Benchmarking Cu/BEA and HBEA catalysts for high-octane gasoline synthesis

Journal

APPLIED CATALYSIS A-GENERAL
Volume 643, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apcata.2022.118799

Keywords

High-octane gasoline; Methanol to hydrocarbons; Deactivation

Funding

  1. U.S. Department of Energy (DOE) [DE-AC36-08GO28308]
  2. U.S. DOE Office of Energy Efficiency and Renewable Energy, Bioenergy Technol-ogies Office

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This study investigates the differences between 5 wt% Cu/H-BEA and H-BEA catalysts during dimethyl ether (DME) homologation in the presence of hydrogen. The results show that Cu enables lower carbon deposition rates, increases the paraffin-to-olefin ratio, and decreases instantaneous site-loss yields, leading to improved product saturation and catalyst stability during DME homologation.
We distinguish rates at which carbon deposition occurs during initiation, rates at which catalytic centers are lost during deactivation, and paraffin-to-olefin ratio during propagation as benchmarks that distinguish 5 wt% Cu/H-BEA and H-BEA (Si/Al = 13.5) catalysts during dimethyl ether (DME) homologation in the presence of hydrogen. Studies that systematically vary initial DME contact time (210, 94, and 45 mol(H+, initial) s (mol (C))(-1)), DME pressure (4 and 22 kPa), and H-2 pressure (1, 24, and 48 kPa) reveal that Cu enables lower carbon deposition rates (on a per proton basis) in the induction period, increases the effluent paraffin-to-olefin ratio during propagation, and decreases instantaneous site-loss yields during termination by 1.5-2x (moles of active sites lost per mole of DME) thus augmenting the degree of product saturation and catalyst stability during DME homologation. These results provide mechanistic insights revealing the critical role of Cu in facilitating DME homologation to high value, high-octane gasoline-range hydrocarbons with higher cumulative turnovers than proton form H-BEA.

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