Mesoporous silicon sulfonic acid as a highly efficient and stable catalyst for the selective hydroamination of cyclohexene with cyclohexylamine to dicyclohexylamine in the vapor phase

doi:10.1007/s11705-020-1973-2

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (3) : 654-665 https://doi.org/10.1007/s11705-020-1973-2

RESEARCH ARTICLE

Mesoporous silicon sulfonic acid as a highly efficient and stable catalyst for the selective hydroamination of cyclohexene with cyclohexylamine to dicyclohexylamine in the vapor phase

Jingbin Wen¹, Kuiyi You^1,²(

), Minjuan Chen¹, Jian Jian³, Fangfang Zhao¹, Pingle Liu^1,², Qiuhong Ai^1,², He’an Luo^1,²(

)

¹. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China
². National & Local United Engineering Research Center for Chemical Process Simulation and Intensification, Xiangtan University, Xiangtan 411105, China
³. School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China

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Abstract

In this work, a new mesoporous silicon sulfonic acid catalyst derived from silicic acid has been successfully prepared by the chemical bonding method. The physicochemical properties of mesoporous silicon sulfonic acid catalysts have been systematically characterized using various techniques. The results demonstrate that sulfonic acid groups have been grafted on silicic acid by forming a new chemical bond (Si–O–S). The mesoporous silicon sulfonic acid exhibits excellent catalytic performance and stability in the vapor phase hydroamination reaction of cyclohexene with cyclohexylamine. Cyclohexene conversion of 61% and 97% selectivity to dicyclohexylamine was maintained after running the reaction for over 350 h at 280 °C. The developed mesoporous silicon sulfonic acid catalyst shows advantages of low cost, superior acid site accessibility, and long term reactivity stability. Moreover, a possible catalytic hydroamination reaction mechanism over silicon sulfonic acid was suggested. It has been demonstrated that the sulfonic acid groups of the catalyst play an important role in the hydroamination. The present work provides a simple, efficient, and environmentally friendly method for the hydroamination of cyclohexene to valuable dicyclohexylamine, which also shows important industrial application prospects.

Keywords mesoporous silicon sulfonic acid catalytic hydroamination cyclohexene dicyclohexylamine vapor phase

Corresponding Author(s): Kuiyi You,He’an Luo

Just Accepted Date: 14 July 2020 Online First Date: 13 November 2020 Issue Date: 10 May 2021

Cite this article:

Jingbin Wen,Kuiyi You,Minjuan Chen, et al. Mesoporous silicon sulfonic acid as a highly efficient and stable catalyst for the selective hydroamination of cyclohexene with cyclohexylamine to dicyclohexylamine in the vapor phase[J]. Front. Chem. Sci. Eng., 2021, 15(3): 654-665.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1973-2
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I3/654

Fig.1 Scheme 1 Synthetic routes of DCHA.

Fig.2 Scheme 2 One-step catalytic hydroamination of cyclohexene to DCHA over mesoporous SSA in the vapor phase.

Fig.3 Scheme 3 Preparation of mesoporous SSA catalyst.

Fig.4 Experimental equipment for the vapor phase hydroamination reaction.

Tab.1 Comparison of the catalytic performance of various catalysts in the hydroamination reaction^a)

Fig.5 Effects of reaction temperature on the catalytic hydroamination reaction. Reaction conditions: catalyst was SSA; molar ratio of cyclohexene to cyclohexylamine was 1:4; time on stream was 6 h; residence time was 16.7 s; GHSV was 215.6 h^–1.

Fig.6 Effects of molar ratio of cyclohexene to cyclohexylamine on the catalytic hydroamination reaction. Reaction conditions: catalyst was SSA; the reaction temperature was 280 °C; time on stream was 6 h; residence time was 16.7 s; GHSV was 215.6 h^–1.

Fig.7 Effects of residence time on the catalytic hydroamination reaction. Reaction conditions: catalyst was SSA; the molar ratio of cyclohexene to cyclohexylamine was 1:4; the reaction temperature was 280 °C; time on stream was 6 h.

Fig.8 Stability test of SSA catalyst in the hydroamination reaction. Reaction conditions: molar ratio of cyclohexene to cyclohexylamine was 1:4; reaction temperature was 280 °C; residence time was 16.7 s; GHSV was 215.6 h^–1.

Fig.9 XRD patterns of SA and SSA samples.

Fig.10 FTIR spectra of (a) SA, (b) fresh SSA, (c) spent SSA, and (d) regenerated SSA.

Fig.11 (A) N₂ adsorption-desorption isotherms and (B) pore diameter distribution curves of SA and SSA samples.

Tab.2 Textural and acidic properties of catalysts

Fig.12 (A) Pyridine-adsorbed FTIR spectra and (B) NH₃-TPD curves of samples: (a) SA, (b) fresh SSA, (c) spent SSA, and (d) regenerated SSA.

Fig.13 TG/DTG curves of SA and SSA samples: (A) TG curves; (B) DTG curves.

Fig.14 ²⁹Si solid-state MAS NMR spectra of SA and SSA samples.

Tab.3 Elemental analysis of samples

Fig.15 Scheme 4 Possible catalytic hydroamination reaction mechanism of cyclohexene with cyclohexylamine over mesoporous SSA catalyst.

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