Catalyst preparation for vapor phase Beckmann rearrangement via deboronation/desilication of B-ZSM-5

Masahiko Matsukata, Kohsuke Nakagawa, Yasushi Sekine, Eiichi Kikuchi

    Research output: Chapter in Book/Report/Conference proceedingConference contribution

    Abstract

    Vapor phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam is an outstanding achievement of green chemistry. Nest silanols in the vicinity of the external surface of silicalite-1 has been proposed as active sites. In this study, B-ZSM-5(Si/B ratio = 25) was synthesized and the product was agglomerates of nanocrystals. As-made B-ZSM-5 was calcined in air and deboronated by treatment with HCl aq. at 353 K for 3 h. Further, the deboronated sample was desilicated with a mixture of ammonia nitrate and ammonia to develop effective diffusion pathways in the catalyst particles. FT-IR study confirmed the formation of abundant nest silanols. The vapor phase Backmann reaggrangement was performed in a plug flow reactor with a fixed bed of catalyst at WHSV = 8 h-1 and 653 K. The initial catalytic activity was greatly improved by the treatment performed in this study: The pseudo-first-order reaction constant for the parent B-ZSM-5 was 1.8×10-3 s-1, but that for the deboronated/desilicated ZSM-5 was 0.13 s-1.

    Original languageEnglish
    Title of host publicationACS National Meeting Book of Abstracts
    Publication statusPublished - 2008
    Event235th National Meeting of the American Chemical Society, ACS 2008 - New Orleans, LA
    Duration: 2008 Apr 62008 Apr 10

    Other

    Other235th National Meeting of the American Chemical Society, ACS 2008
    CityNew Orleans, LA
    Period08/4/608/4/10

    Fingerprint

    Ammonia
    Caprolactam
    Vapors
    Catalysts
    Nitrates
    Nanocrystals
    Rate constants
    Catalyst activity
    Air
    silanol
    cyclohexanone oxime
    Oximes

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)

    Cite this

    Catalyst preparation for vapor phase Beckmann rearrangement via deboronation/desilication of B-ZSM-5. / Matsukata, Masahiko; Nakagawa, Kohsuke; Sekine, Yasushi; Kikuchi, Eiichi.

    ACS National Meeting Book of Abstracts. 2008.

    Research output: Chapter in Book/Report/Conference proceedingConference contribution

    Matsukata, M, Nakagawa, K, Sekine, Y & Kikuchi, E 2008, Catalyst preparation for vapor phase Beckmann rearrangement via deboronation/desilication of B-ZSM-5. in ACS National Meeting Book of Abstracts. 235th National Meeting of the American Chemical Society, ACS 2008, New Orleans, LA, 08/4/6.
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    abstract = "Vapor phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam is an outstanding achievement of green chemistry. Nest silanols in the vicinity of the external surface of silicalite-1 has been proposed as active sites. In this study, B-ZSM-5(Si/B ratio = 25) was synthesized and the product was agglomerates of nanocrystals. As-made B-ZSM-5 was calcined in air and deboronated by treatment with HCl aq. at 353 K for 3 h. Further, the deboronated sample was desilicated with a mixture of ammonia nitrate and ammonia to develop effective diffusion pathways in the catalyst particles. FT-IR study confirmed the formation of abundant nest silanols. The vapor phase Backmann reaggrangement was performed in a plug flow reactor with a fixed bed of catalyst at WHSV = 8 h-1 and 653 K. The initial catalytic activity was greatly improved by the treatment performed in this study: The pseudo-first-order reaction constant for the parent B-ZSM-5 was 1.8×10-3 s-1, but that for the deboronated/desilicated ZSM-5 was 0.13 s-1.",
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    AU - Matsukata, Masahiko

    AU - Nakagawa, Kohsuke

    AU - Sekine, Yasushi

    AU - Kikuchi, Eiichi

    PY - 2008

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    N2 - Vapor phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam is an outstanding achievement of green chemistry. Nest silanols in the vicinity of the external surface of silicalite-1 has been proposed as active sites. In this study, B-ZSM-5(Si/B ratio = 25) was synthesized and the product was agglomerates of nanocrystals. As-made B-ZSM-5 was calcined in air and deboronated by treatment with HCl aq. at 353 K for 3 h. Further, the deboronated sample was desilicated with a mixture of ammonia nitrate and ammonia to develop effective diffusion pathways in the catalyst particles. FT-IR study confirmed the formation of abundant nest silanols. The vapor phase Backmann reaggrangement was performed in a plug flow reactor with a fixed bed of catalyst at WHSV = 8 h-1 and 653 K. The initial catalytic activity was greatly improved by the treatment performed in this study: The pseudo-first-order reaction constant for the parent B-ZSM-5 was 1.8×10-3 s-1, but that for the deboronated/desilicated ZSM-5 was 0.13 s-1.

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