Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies

doi:10.1016/j.cjche.2022.10.011

Chinese Journal of Chemical Engineering ›› 2023, Vol. 58 ›› Issue (6): 1-10.DOI: 10.1016/j.cjche.2022.10.011

Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies

Junyang Liu^1,2, Luming Wang^1,2, Yuhang Bian², Chunshan Li^1,2,3, Zengxi Li¹, Jie Li²

1. School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China;
2. Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. Langfang Technological Center of Green Industry, Langfang 065801, China

Received:2022-04-28 Revised:2022-10-10 Online:2023-08-31 Published:2023-06-28
Contact: Zengxi Li,E-mail:lizengxi@ucas.ac.cn;Jie Li,E-mail:lijiequst@ipe.ac.cn
Supported by:
For this study, we would like to express the gratitude to the National Natural Science Fund for Distinguished Young Scholars (22025803). It was supported by the National Natural Science Foundation of China (22178338), the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2021018). Likewise, and we would thank to the financial support of project “Research and development and industrial application of new catalytic materials for green synthesis of MMA to replace highly toxic HCN” (Hebei, 20374002D).

Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies

Junyang Liu^1,2, Luming Wang^1,2, Yuhang Bian², Chunshan Li^1,2,3, Zengxi Li¹, Jie Li²

1. School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China;
2. Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. Langfang Technological Center of Green Industry, Langfang 065801, China

通讯作者: Zengxi Li,E-mail:lizengxi@ucas.ac.cn;Jie Li,E-mail:lijiequst@ipe.ac.cn
基金资助:
For this study, we would like to express the gratitude to the National Natural Science Fund for Distinguished Young Scholars (22025803). It was supported by the National Natural Science Foundation of China (22178338), the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2021018). Likewise, and we would thank to the financial support of project “Research and development and industrial application of new catalytic materials for green synthesis of MMA to replace highly toxic HCN” (Hebei, 20374002D).

Abstract

Abstract: The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor. The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure. The measurement data were regression with the pseudo-homogeneous (P-H), Eley-Rideal (E-R), and Langmuir-Hinshelwood (L-H) heterogeneous kinetic models. Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components. Among the above three models, the L-H model exhibited the best fitting results. The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation. The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis (TG), scanning electron microscope (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) and so on.

Key words: Kinetics, Esterification, Methyl methacrylate, Cation-exchange resin, Fix bed reactor

摘要： The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor. The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure. The measurement data were regression with the pseudo-homogeneous (P-H), Eley-Rideal (E-R), and Langmuir-Hinshelwood (L-H) heterogeneous kinetic models. Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components. Among the above three models, the L-H model exhibited the best fitting results. The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation. The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis (TG), scanning electron microscope (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) and so on.

关键词: Kinetics, Esterification, Methyl methacrylate, Cation-exchange resin, Fix bed reactor

Junyang Liu, Luming Wang, Yuhang Bian, Chunshan Li, Zengxi Li, Jie Li. Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies[J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 1-10.

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Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies

Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies

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