Highly efficient catalyzed by imidazolium-based dual-sulfonic acid functionalized ionic liquids for liquid phase Beckmann rearrangement: experiments and COSMO-RS calculations

Xin Guo; Zhiyuan Wang; Ye Yang; Jiahui Zhang; Yanduo Liu; Zhiyuan Mu; Siqi Jiang; Chunxiao Ren; Dan Lv; Yufeng Hu; Zhichang Liu

Green Chemical Engineering (Mar 2024)

Highly efficient catalyzed by imidazolium-based dual-sulfonic acid functionalized ionic liquids for liquid phase Beckmann rearrangement: experiments and COSMO-RS calculations

Xin Guo,
Zhiyuan Wang,
Ye Yang,
Jiahui Zhang,
Yanduo Liu,
Zhiyuan Mu,
Siqi Jiang,
Chunxiao Ren,
Dan Lv,
Yufeng Hu,
Zhichang Liu

Affiliations

Xin Guo: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China
Zhiyuan Wang: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China
Ye Yang: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China
Jiahui Zhang: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China
Yanduo Liu: School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, 230026, China
Zhiyuan Mu: School of Light Industry and Engineering, South China University of Technology, Guangzhou, 510641, China
Siqi Jiang: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China
Chunxiao Ren: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China
Dan Lv: School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, 230026, China
Yufeng Hu: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China; Corresponding author.
Zhichang Liu: State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing, 102249, China; Corresponding author.

Journal volume & issue: Vol. 5, no. 1
pp. 108 – 118

Abstract

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A production technique with the high yield and environmentally friendly process need be developed for ε-Caprolactam (CPL) in the chemical industry. This technology is highly desired to design and synthesize high−performance catalysts for liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) to CPL. In this work, 3-methyl-1-(propyl-4-sulfonyl) imidazolium methanesulfonate ([PHSO3MIM][MSA]) with highly efficient and excellent yield is synthesized successfully. When the optimum molar ratio of ZnCl2 over [PHSO3MIM][MSA] was 0.02, it exhibits the high selectivity (94%) of CPL at 90 °C for 1 h. Interestingly, Fourier-transform infrared (FT-IR) investigations show that the functional Brønsted−Lewis acidic types of ionic liquids (ILs) are formed by the uniformly distributed ZnCl2 and [PHSO3MIM][MSA]. In addition, the hydrogen bond (H-bond) is formed between CHO and ILs. After ten reaction cycles, no significant structure changes are observed in the recovered [PHSO3MIM][MSA]·ZnCl2. The solubilities of ILs are predicted by using COSMO-RS model, the results show that [PHSO3MIM][MSA] is a promising candidate for the liquid phase Beckmann rearrangement of CHO into CPL. Finally, a theoretical model of the H-bond interactions between ILs and CHO is further confirmed to support the advance of reaction mechanism. A feasible way is provided for the CPL production technique in the liquid phase Beckmann rearrangement reaction.

Published in Green Chemical Engineering

ISSN: 2666-9528 (Online)
Publisher: KeAi Communications Co. Ltd.
Country of publisher: China
LCC subjects: Technology: Chemical technology: Chemical engineering; Science: Chemistry: Organic chemistry: Biochemistry
Website: https://www.keaipublishing.com/en/journals/green-chemical-engineering/

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