Investigation of the active centers and structural modifications for TS-1 in catalyzing the Beckmann rearrangement

Xin Jin; Rusi Peng; Wen Tong; Jinpeng Yin; Hao Xu; Peng Wu

doi:10.1016/j.cattod.2022.05.033

Investigation of the active centers and structural modifications for TS-1 in catalyzing the Beckmann rearrangement

Xin Jin
, Rusi Peng
, Wen Tong
, Jinpeng Yin
, Hao Xu^*
, Peng Wu

^*Corresponding author for this work

School of Chemistry and Molecular Engineering

East China Normal University

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

The Beckmann rearrangement (BR) of cyclohexanone oxime (CHO) to produce caprolactam (CPL) has been studied over various titanosilicates. TS-1 showed superior catalytic performance, compared to Ti-MWW, Ti-Beta and Ti-MOR. Based on the close relationship between Ti content and CHO conversion, and the Na⁺-exchange experiments, the silanol groups, adjacent to the “open” Ti sites, were proved to be the active centers for the BR reaction of CHO to produce CPL, in addition to those generated by defects including terminal silanols, hydrogen-bonded silanols and silanol nests. Moreover, monolithic TS-1 (M-TS-1) microspheres showed higher catalytic activity than the conventional TS-1. The diffusion properties of M-TS-1 were further enhanced via the chemical modifications to achieve longer lifetime for the Beckmann rearrangement under optimized reaction conditions.

Original language	English
Pages (from-to)	193-202
Number of pages	10
Journal	Catalysis Today
Volume	405-406
DOIs	https://doi.org/10.1016/j.cattod.2022.05.033
State	Published - 1 Dec 2022

Keywords

Beckmann rearrangement
Chemical modification
Lewis acid
Silanol
TS-1

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@article{af443ada48a04fce896bf386d183e05b,

title = "Investigation of the active centers and structural modifications for TS-1 in catalyzing the Beckmann rearrangement",

abstract = "The Beckmann rearrangement (BR) of cyclohexanone oxime (CHO) to produce caprolactam (CPL) has been studied over various titanosilicates. TS-1 showed superior catalytic performance, compared to Ti-MWW, Ti-Beta and Ti-MOR. Based on the close relationship between Ti content and CHO conversion, and the Na+-exchange experiments, the silanol groups, adjacent to the “open” Ti sites, were proved to be the active centers for the BR reaction of CHO to produce CPL, in addition to those generated by defects including terminal silanols, hydrogen-bonded silanols and silanol nests. Moreover, monolithic TS-1 (M-TS-1) microspheres showed higher catalytic activity than the conventional TS-1. The diffusion properties of M-TS-1 were further enhanced via the chemical modifications to achieve longer lifetime for the Beckmann rearrangement under optimized reaction conditions.",

keywords = "Beckmann rearrangement, Chemical modification, Lewis acid, Silanol, TS-1",

author = "Xin Jin and Rusi Peng and Wen Tong and Jinpeng Yin and Hao Xu and Peng Wu",

note = "Publisher Copyright: {\textcopyright} 2022 Elsevier B.V.",

year = "2022",

month = dec,

day = "1",

doi = "10.1016/j.cattod.2022.05.033",

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volume = "405-406",

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journal = "Catalysis Today",

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TY - JOUR

T1 - Investigation of the active centers and structural modifications for TS-1 in catalyzing the Beckmann rearrangement

AU - Jin, Xin

AU - Peng, Rusi

AU - Tong, Wen

AU - Yin, Jinpeng

AU - Xu, Hao

AU - Wu, Peng

PY - 2022/12/1

Y1 - 2022/12/1

N2 - The Beckmann rearrangement (BR) of cyclohexanone oxime (CHO) to produce caprolactam (CPL) has been studied over various titanosilicates. TS-1 showed superior catalytic performance, compared to Ti-MWW, Ti-Beta and Ti-MOR. Based on the close relationship between Ti content and CHO conversion, and the Na+-exchange experiments, the silanol groups, adjacent to the “open” Ti sites, were proved to be the active centers for the BR reaction of CHO to produce CPL, in addition to those generated by defects including terminal silanols, hydrogen-bonded silanols and silanol nests. Moreover, monolithic TS-1 (M-TS-1) microspheres showed higher catalytic activity than the conventional TS-1. The diffusion properties of M-TS-1 were further enhanced via the chemical modifications to achieve longer lifetime for the Beckmann rearrangement under optimized reaction conditions.

AB - The Beckmann rearrangement (BR) of cyclohexanone oxime (CHO) to produce caprolactam (CPL) has been studied over various titanosilicates. TS-1 showed superior catalytic performance, compared to Ti-MWW, Ti-Beta and Ti-MOR. Based on the close relationship between Ti content and CHO conversion, and the Na+-exchange experiments, the silanol groups, adjacent to the “open” Ti sites, were proved to be the active centers for the BR reaction of CHO to produce CPL, in addition to those generated by defects including terminal silanols, hydrogen-bonded silanols and silanol nests. Moreover, monolithic TS-1 (M-TS-1) microspheres showed higher catalytic activity than the conventional TS-1. The diffusion properties of M-TS-1 were further enhanced via the chemical modifications to achieve longer lifetime for the Beckmann rearrangement under optimized reaction conditions.

KW - Beckmann rearrangement

KW - Chemical modification

KW - Lewis acid

KW - Silanol

KW - TS-1

UR - https://www.scopus.com/pages/publications/85132371782

U2 - 10.1016/j.cattod.2022.05.033

DO - 10.1016/j.cattod.2022.05.033

M3 - 文章

AN - SCOPUS:85132371782

SN - 0920-5861

VL - 405-406

SP - 193

EP - 202

JO - Catalysis Today

JF - Catalysis Today

ER -

Investigation of the active centers and structural modifications for TS-1 in catalyzing the Beckmann rearrangement

Abstract

Keywords

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