4.7 Article

Promoting effect of alkali metal on the catalytic performance of hierarchical Pt/Beta in the aromatization of n-heptane

Journal

MICROPOROUS AND MESOPOROUS MATERIALS
Volume 343, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.micromeso.2022.112189

Keywords

Hierarchical Beta zeolite; Alkali metal modification; n -Heptane aromatization; Pt dispersion; Acid sites passivation; Pt/Beta-Rb

Funding

  1. National Key Research and Development Program of China [2020YFB0606404]
  2. National Natural Science Foundation of China [22172184, U2003123, 21991092, U1910203]
  3. Strategic Priority Research Program of the Chinese Academy of Sciences [XDA21020500]
  4. CAS/SAFEA Inter- national Partnership Program for Creative Research Teams

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The catalytic performance of Pt/Beta-Me catalysts modified with different alkali metals in the aromatization of n-heptane was investigated. The results showed that the modification with alkali metals can enhance the Pt dispersion, suppress cracking reactions and carbonaceous deposition, and promote the dehydroaromatization of alkanes, leading to improved catalytic stability and selectivity. The extent of modification effect varied with different alkali metals, with Rb having the highest promoting effect.
Previous research showed that hierarchical Beta zeolite supported Pt was an effective catalyst for the aromati-zation of alkanes and the modification with K could further enhance its catalytic performance; however, the intrinsic effect of alkali metal on the alkanes aromatization over Pt/Beta was still rather obscure. In this work, a series of hierarchical Pt/Beta-Me catalysts were prepared by modifying the Beta zeolite with different alkali metal nitrates (MeNO3, Me = Li, Na, K and Rb) through ion-exchange and used in the aromatization of n-heptane; the effect of alkali metal on the catalytic performance of Pt/Beta-Me was then systematically investigated. The results indicate that the alkali metals used to modify the Pt/Beta-Me catalysts can not only passivate the strong Bronsted acid sites of Beta zeolite, but also enhance the Pt dispersion and induce an electron-rich chemical environment for the supported Pt species. Accordingly, the modification with alkali metal can effectively sup-press the cracking reactions and carbonaceous deposition and meanwhile promote the dehydroaromatization of alkanes, in favor of enhancing the catalytic stability and aromatization selectivity of Pt/Beta-Me. The extent of promoting effect of various alkali metals follows the order of Rb > K > Na > Li. In particular, the Pt/Beta-Rb catalyst exhibits excellent performance in the aromatization of n-heptane, with a much higher selectivity to aromatics (78.2%) and larger turnover number of aromatic products (Pt-based TON, 19.4 x 103) than the un-modified Pt/Beta-H one (27.7% and 4.8 x 103, respectively). These results help to clarify the role of alkali metal played in the catalysis of Pt/Beta-Me for n-heptane aromatization and pave the way for designing more efficient catalysts in the aromatization of alkanes.

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