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Framework modification of microporous silicates via gas‐phase treatment with ZrCl4

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Abstract

The boron forms of the zeolite Beta (B‐Beta) and SSZ‐33 (B‐SSZ‐33) are treated with vapors of ZrCl4 in an attempt to substitute the framework boron for zirconium. The resulting materials Zr‐Beta and Zr‐SSZ‐33 are characterized by X‐ray diffraction (XRD), solid state NMR, FTIR, pyridine adsorption and Raman spectroscopies. In the case of zeolite Beta, Zr substitutes the B present in the framework nearly in a one‐to‐one basis. No evidence is found in support of the tetrahedral Zr fully incorporated into the zeolite framework; Zr is only partially grafted to the zeolite framework giving rise to silanol groups adjacent to the Zr atom. No evidence of extra‐framework zirconia is observed. For SSZ‐33, the amount of zirconium incorporated is significantly less than the amount of boron present in the parent zeolite. Due to the size of ZrCl4, a multidimensional 12‐ring pore system is required for our procedure of Zr incorporation to be effective. Zr‐Beta is an acid catalyst superior in activity to B‐Beta for the isomerization of 1‐butene.

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Authors and Affiliations

  1. Department of Chemical Engineering, University of Delaware, Newark, DE, 19716, USA

    Gopalakrishnan G. Juttu & Raul F. Lobo

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  1. Gopalakrishnan G. Juttu
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  2. Raul F. Lobo
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Juttu, G.G., Lobo, R.F. Framework modification of microporous silicates via gas‐phase treatment with ZrCl4 . Catalysis Letters 62, 99–106 (1999). https://doi.org/10.1023/A:1019047022166

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