4.6 Article

Alkali promoted zinc-aluminum oxide as high temperature water gas shift catalyst

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APPLIED CATALYSIS A-GENERAL
卷 640, 期 -, 页码 -

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ELSEVIER
DOI: 10.1016/j.apcata.2022.118646

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Water gas shift; Catalyst; Zinc oxide; Zinc spinel; Alkali promoter; Potassium promoter

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A new high-temperature water gas shift catalyst based on K-promoted ZnO/ZnAl2O4 has been found to be more effective than traditional Fe/Cr oxide catalysts. This research focuses on the optimization of the catalyst system, including the promotion with alkali metals and the structural characterization. The results show that K promotion significantly increases the catalyst's activity, and the optimum K content is 2.1wt%. The promotion by K is both structural and electronic in nature.
A new kind of high-temperature water gas shift catalyst based on K-promoted ZnO/ZnAl2O4, introduced by Haldor Topsoe as SK-501 Flex (TM), has begun to replace the well-known Fe/Cr oxide catalysts in the industry. In this research article, we focus on optimization of the catalyst system, especially on promotion with alkali metals and on structural characterization using X-ray diffraction. The promotional effect of the alkali metals increases in the order Li < < Na < < Cs < Rb < K. With K, a 20-fold increase of the mass-based intrinsic rate constant compared to an un-promoted sample is observed. The optimum in the K-content, 2.1 wt%, corresponds to a surface concentration of 0.0057 mmol/m2 or 0.0059 mmol/m(2) if K only decorates the ZnAl2O4 spinel surface. This coverage coincides with the surface concentration of Al vacancies on the dominating spinel (111) facet, the so-called kagome layer, with a coverage of 0.00586 mmol/m(2). Potassium decoration of the spinel surface is corroborated by FTIR studies of promoted and un-promoted samples in a CO atmosphere. The promotion by potassium is both structural, inhibiting growth of the spinel crystals as evidenced by XRD and BET surface area measurements, but also electronic since the activity per surface area strongly increases on K-promotion. Finally, our studies include long term tests of thermal stability and tolerance towards H2S.

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