TY - GEN
T1 - Catalyst preparation for vapor phase Beckmann rearrangement via deboronation/desilication of B-ZSM-5
AU - Matsukata, Masahiko
AU - Nakagawa, Kohsuke
AU - Sekine, Yasushi
AU - Kikuchi, Eiichi
PY - 2008/12/1
Y1 - 2008/12/1
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.
AB - 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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M3 - Conference contribution
AN - SCOPUS:77955620995
SN - 9780841269859
T3 - ACS National Meeting Book of Abstracts
BT - American Chemical Society - 235th National Meeting, Abstracts of Scientific Papers
T2 - 235th National Meeting of the American Chemical Society, ACS 2008
Y2 - 6 April 2008 through 10 April 2008
ER -