4.6 Article

Diffusivity and hydrogenation of vanadyl porphyrins in the synthesized NiMo/Zr-SBA-15 and industrial NiMo/?-Al2O3 catalysts

Journal

CHEMICAL ENGINEERING SCIENCE
Volume 261, Issue -, Pages -

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.ces.2022.117958

Keywords

Vanadyl porphyrin; Hydrodemetallation; Hindered diffusion; NiMo/Zr-SBA-15; NiMo/y-Al2O3 catalyst

Funding

  1. National Natural Science Foundation of China [21878329, 21476257]
  2. Science Foundation of China University of Petroleum, Beijing [2462018QZDX04]

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This study validates that the diffusion of vanadyl porphyrins is significantly hindered in catalyst pores, which has a pronounced effect on the reaction. The diffusion effect is larger for vanadyl-TPP than vanadyl octaethylporphine, attributed to its higher intrinsic activity and more severe diffusion resistance. The restrictive correlation is more severe than the theoretical prediction, resulting from the non-spherical configuration of reactants and simultaneous counter diffusion of products.
Hydrogenation reactions of two vanadyl porphyrins are performed over a series of NiMo/Zr-SBA-15 catalysts and an industrial NiMo/gamma-Al2O3 catalyst. The results validate that the diffusion of the porphyrins suffers significant hindrance in the catalyst pores, which make a pronounced effect on the reaction. The hydrogenation of vanadyl-TPP receives a much larger diffusion effect than vanadyl octaethylporphine, which attributes to its higher intrinsic activity and more severe diffusion resistance. The restrictive correlation indicates two vanadyl porphyrins are hindered more severely as diffusing through the orderly NiMo/Zr-SBA-15 catalysts than the theoretical prediction from the Renkin equation, which results from the non-spherical configuration of the reactants and simultaneous counter diffusion of the products. Hydrogenation reactions of the vanadyl porphyrins encounter a stronger internal diffusion restriction in the NiMo/y-Al2O3 catalyst than in the NiMo/Zr-SBA-15 catalysts, attributing to the random structure of the y-Al2O3 support.(C) 2022 Elsevier Ltd. All rights reserved.

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