Process and safety study of tert-butyl hydroperoxide

doi:10.1016/j.cjche.2025.01.010

Chinese Journal of Chemical Engineering ›› 2025, Vol. 82 ›› Issue (6): 185-195.DOI: 10.1016/j.cjche.2025.01.010

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Process and safety study of tert-butyl hydroperoxide

Dongjin Yu¹, Yuantong Hao², Chunsheng Cheng^1,2,3, Xu Ming², Jie Hu², Xiaohua Ma²

1. School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China;
2. Chemical Industry Safety Technology& Engineering Center, Shenyang Research Institute of Chemical Industry, Shenyang 110021, China;
3. School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, China

Received:2024-10-28 Revised:2024-12-03 Accepted:2025-01-05 Online:2025-03-16 Published:2025-08-19
Contact: Chunsheng Cheng,E-mail:chengchunsheng@sinochem.com;Xu Ming,E-mail:mingxu@sinochem.com
Supported by:
We gratefully acknowledge the financial support provided by the National Key Research and Development Program of 14th Five-Year Plan, China ( 2021YFC3001101).

Process and safety study of tert-butyl hydroperoxide

Dongjin Yu¹, Yuantong Hao², Chunsheng Cheng^1,2,3, Xu Ming², Jie Hu², Xiaohua Ma²

1. School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China;
2. Chemical Industry Safety Technology& Engineering Center, Shenyang Research Institute of Chemical Industry, Shenyang 110021, China;
3. School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, China

通讯作者: Chunsheng Cheng,E-mail:chengchunsheng@sinochem.com;Xu Ming,E-mail:mingxu@sinochem.com
基金资助:
We gratefully acknowledge the financial support provided by the National Key Research and Development Program of 14th Five-Year Plan, China ( 2021YFC3001101).

Abstract

Abstract: Process safety for synthesis of tert-butyl hydroperoxide (TBHP) by tert-butyl alcohol (TBA) to react with H₂O₂ was studied in this paper. On-line Raman spectroscopy and gas chromatography jointed analysis method was researched to monitor and analyze the changes of each components during the process to study reaction mechanism. The reaction kinetics was reproduced by apparent thermodynamics study and simulation for whole process, and the kinetics model of TBHP synthesis was obtained and with the first reported. The process safety parameter of the maximum temperature of the synthesis reaction (MTSR) and yield were predicted by response surface methodology (RSM) method and go through experimental verification further. It was found that the sulfuric acid and the concentration of TBA had great influences to reaction selectivity and yield. According to our research results, we supposed that the mechanism of TBHP synthesis would be followed by SN₁+SN₂. Focus on process safety, process risk assessment was done and pipe reaction to optimize TBHP synthesis was developed to change the batch process to pipe continuously. The yield of TBHP was 91.1%, conversion of TBA was 93.1%, and the selectivity of TBHP was 97.8%. The process safety parameters of heat accumulation and MTSR decreased 40.5% and 37.7% respectively comparison of the pipe continuous reaction and batch process. This study will provide guidance for intrinsic safety improvement of peroxidation reactions.

Key words: TBHP, Mechanism, Risk, On-line Raman, Intrinsically safety

摘要： Process safety for synthesis of tert-butyl hydroperoxide (TBHP) by tert-butyl alcohol (TBA) to react with H₂O₂ was studied in this paper. On-line Raman spectroscopy and gas chromatography jointed analysis method was researched to monitor and analyze the changes of each components during the process to study reaction mechanism. The reaction kinetics was reproduced by apparent thermodynamics study and simulation for whole process, and the kinetics model of TBHP synthesis was obtained and with the first reported. The process safety parameter of the maximum temperature of the synthesis reaction (MTSR) and yield were predicted by response surface methodology (RSM) method and go through experimental verification further. It was found that the sulfuric acid and the concentration of TBA had great influences to reaction selectivity and yield. According to our research results, we supposed that the mechanism of TBHP synthesis would be followed by SN₁+SN₂. Focus on process safety, process risk assessment was done and pipe reaction to optimize TBHP synthesis was developed to change the batch process to pipe continuously. The yield of TBHP was 91.1%, conversion of TBA was 93.1%, and the selectivity of TBHP was 97.8%. The process safety parameters of heat accumulation and MTSR decreased 40.5% and 37.7% respectively comparison of the pipe continuous reaction and batch process. This study will provide guidance for intrinsic safety improvement of peroxidation reactions.

关键词: TBHP, Mechanism, Risk, On-line Raman, Intrinsically safety

Dongjin Yu, Yuantong Hao, Chunsheng Cheng, Xu Ming, Jie Hu, Xiaohua Ma. Process and safety study of tert-butyl hydroperoxide[J]. Chinese Journal of Chemical Engineering, 2025, 82(6): 185-195.

Dongjin Yu, Yuantong Hao, Chunsheng Cheng, Xu Ming, Jie Hu, Xiaohua Ma. Process and safety study of tert-butyl hydroperoxide[J]. 中国化学工程学报, 2025, 82(6): 185-195.

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Process and safety study of tert-butyl hydroperoxide

Process and safety study of tert-butyl hydroperoxide

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