A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

doi:10.1016/j.cjche.2023.03.005

中国化学工程学报 ›› 2023, Vol. 61 ›› Issue (9): 9-23.DOI: 10.1016/j.cjche.2023.03.005

• Full Length Article • 上一篇下一篇

A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

Mingxue Yin¹, Bo Jia¹, Kuiyi You², Bo Jin¹, Yangqiang Huang¹, Xiao Luo¹, Zhiwu Liang¹

1. College of Chemistry and Chemical Engineering, The Engineering Research Center of Advanced Catalysis, Ministry of Education, Hunan University, Changsha 410082, China;
2. College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

收稿日期:2022-11-07 修回日期:2023-02-17 出版日期:2023-09-28 发布日期:2023-12-14
通讯作者: Yangqiang Huang,E-mail:yqhuang@hnu.edu.cn;Xiao Luo,E-mail:x_luo@hnu.edu.cn;Zhiwu Liang,E-mail:zwliang@hnu.edu.cn
基金资助:
The financial support from the National Natural Science Foundation of China (22178089) is gratefully acknowledged.

A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

Mingxue Yin¹, Bo Jia¹, Kuiyi You², Bo Jin¹, Yangqiang Huang¹, Xiao Luo¹, Zhiwu Liang¹

1. College of Chemistry and Chemical Engineering, The Engineering Research Center of Advanced Catalysis, Ministry of Education, Hunan University, Changsha 410082, China;
2. College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

Received:2022-11-07 Revised:2023-02-17 Online:2023-09-28 Published:2023-12-14
Contact: Yangqiang Huang,E-mail:yqhuang@hnu.edu.cn;Xiao Luo,E-mail:x_luo@hnu.edu.cn;Zhiwu Liang,E-mail:zwliang@hnu.edu.cn
Supported by:
The financial support from the National Natural Science Foundation of China (22178089) is gratefully acknowledged.

摘要/Abstract

摘要： In this paper, the highly efficient ZnAlLa layered double oxide (ZnAlLa-LDO) catalyst was evaluated and used in methyl carbamate (MC) alcoholysis synthesis of dimethyl carbonate. Under optimal conditions, the MC conversion was 33.5% and the dimethyl carbonate (DMC) selectivity was up to 92.4% at 443 K and in 9 h. The prepared catalysts were well characterized to investigate the effect on the catalytic performance and reaction catalysis mechanism. The experimental results show that the addition of La adjusted the structure and chemical properties of ZnAl composite oxide and that the synergistic effect among Zn, Al and La play a key role in adjusting the acid-base properties and stability of the catalyst, which definitely improved the DMC selectivity and catalytic stability. Based on the proposed reaction mechanism, two kinetic models of the catalytic reaction were established and modified: Langmuir-Hinshelwood and power-rate law kinetic model. The good agreement between kinetic models and experimental data showed that the power-rate law kinetic model based on the elementary reactions is a suitable model for providing a theoretical basis. The pre-exponential factor and activation energy of the main reaction are 5.77×10⁷ and 77.60 kJ·mol^-1, respectively.

关键词: Methanol, Urea alcoholysis, Dimethyl carbonate, Kinetic model

Abstract: In this paper, the highly efficient ZnAlLa layered double oxide (ZnAlLa-LDO) catalyst was evaluated and used in methyl carbamate (MC) alcoholysis synthesis of dimethyl carbonate. Under optimal conditions, the MC conversion was 33.5% and the dimethyl carbonate (DMC) selectivity was up to 92.4% at 443 K and in 9 h. The prepared catalysts were well characterized to investigate the effect on the catalytic performance and reaction catalysis mechanism. The experimental results show that the addition of La adjusted the structure and chemical properties of ZnAl composite oxide and that the synergistic effect among Zn, Al and La play a key role in adjusting the acid-base properties and stability of the catalyst, which definitely improved the DMC selectivity and catalytic stability. Based on the proposed reaction mechanism, two kinetic models of the catalytic reaction were established and modified: Langmuir-Hinshelwood and power-rate law kinetic model. The good agreement between kinetic models and experimental data showed that the power-rate law kinetic model based on the elementary reactions is a suitable model for providing a theoretical basis. The pre-exponential factor and activation energy of the main reaction are 5.77×10⁷ and 77.60 kJ·mol^-1, respectively.

Key words: Methanol, Urea alcoholysis, Dimethyl carbonate, Kinetic model

Mingxue Yin, Bo Jia, Kuiyi You, Bo Jin, Yangqiang Huang, Xiao Luo, Zhiwu Liang. A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol[J]. 中国化学工程学报, 2023, 61(9): 9-23.

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A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

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