Cooperative catalytic effects between the penta-coordinated Al and Al2O3 in Al2O3-AlPO4 for aldol condensation of methyl acetate with formaldehyde to methyl acrylate

doi:10.1016/j.cjche.2021.11.025

Chinese Journal of Chemical Engineering ›› 2022, Vol. 52 ›› Issue (12): 172-183.DOI: 10.1016/j.cjche.2021.11.025

Cooperative catalytic effects between the penta-coordinated Al and Al₂O₃ in Al₂O₃-AlPO₄ for aldol condensation of methyl acetate with formaldehyde to methyl acrylate

Zhenyu Wu^1,2, Zengxi Li^1,2, Chunshan Li^1,2,3

1. School of Chemical Science, 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, Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. Zhongke Langfang, Institute of Process Engineering, Chinese Academic of Sciences, Hebei 065000, China

Received:2021-07-08 Revised:2021-11-08 Online:2023-01-31 Published:2022-12-28
Contact: Zengxi Li,E-mail:lizengxi@ucas.ac.cn;Chunshan Li,E-mail:csli@ipe.ac.cn
Supported by:
This work was supported by Key Research Program of Frontier Sciences (No. QYZDB-SSW-SLH022), National Natural Science Foundation of China (No. 21676270, No. 21878293, No. 22178338), the Joint Fund of the YulinUniversity and the Dalian National-Laboratory for Clean Energy (Grant YLU-DNL Fund 2021018), and Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (Grant No. 2017-K08).

Cooperative catalytic effects between the penta-coordinated Al and Al₂O₃ in Al₂O₃-AlPO₄ for aldol condensation of methyl acetate with formaldehyde to methyl acrylate

Zhenyu Wu^1,2, Zengxi Li^1,2, Chunshan Li^1,2,3

1. School of Chemical Science, 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, Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. Zhongke Langfang, Institute of Process Engineering, Chinese Academic of Sciences, Hebei 065000, China

通讯作者: Zengxi Li,E-mail:lizengxi@ucas.ac.cn;Chunshan Li,E-mail:csli@ipe.ac.cn
基金资助:
This work was supported by Key Research Program of Frontier Sciences (No. QYZDB-SSW-SLH022), National Natural Science Foundation of China (No. 21676270, No. 21878293, No. 22178338), the Joint Fund of the YulinUniversity and the Dalian National-Laboratory for Clean Energy (Grant YLU-DNL Fund 2021018), and Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (Grant No. 2017-K08).

Abstract

Abstract: The bare amorphous Al₂O₃-AlPO₄ and Cs/Al₂O₃-AlPO₄ catalysts were developed for the aldol condensation of methyl acetate with formaldehyde to methyl acrylate. The structure and property of catalyst were characterized by XRD, XPS, BET, Pyridine-IR, FT-IR, ²⁷Al-MASNMR, NH₃-/CO₂-TPD and SEM. The correlation between structural features and acid-base properties was established, and the loading effect of the cesium species was investigated. Due to cooperative catalytic effects between the penta-coordinated Al and Al₂O₃, the weak-II acid and medium acid site densities and the product selectivity were improved. While the basic site densities of these catalysts were almost in proportion to the conversion of methyl acetate. The loaded Cs could form new basic sites and change the distribution of acid sites which further enhance the catalytic performance. As a result, the 10Cs/8AlP was proved to be an optimal catalyst with the yield and selectivity of 21.2% and 85% for methyl acrylate respectively. During the reaction, a deactivation behavior was observed on 10Cs/8AlP catalyst due to the carbon deposition, however, it could be regenerated by thermal treatment in the air atmosphere at 400 ℃.

Key words: Methyl acrylate (MA), Aldol condensation, Al₂O₃-AlPO₄, Penta-coordinated aluminum, Cooperative effects

摘要： The bare amorphous Al₂O₃-AlPO₄ and Cs/Al₂O₃-AlPO₄ catalysts were developed for the aldol condensation of methyl acetate with formaldehyde to methyl acrylate. The structure and property of catalyst were characterized by XRD, XPS, BET, Pyridine-IR, FT-IR, ²⁷Al-MASNMR, NH₃-/CO₂-TPD and SEM. The correlation between structural features and acid-base properties was established, and the loading effect of the cesium species was investigated. Due to cooperative catalytic effects between the penta-coordinated Al and Al₂O₃, the weak-II acid and medium acid site densities and the product selectivity were improved. While the basic site densities of these catalysts were almost in proportion to the conversion of methyl acetate. The loaded Cs could form new basic sites and change the distribution of acid sites which further enhance the catalytic performance. As a result, the 10Cs/8AlP was proved to be an optimal catalyst with the yield and selectivity of 21.2% and 85% for methyl acrylate respectively. During the reaction, a deactivation behavior was observed on 10Cs/8AlP catalyst due to the carbon deposition, however, it could be regenerated by thermal treatment in the air atmosphere at 400 ℃.

关键词: Methyl acrylate (MA), Aldol condensation, Al₂O₃-AlPO₄, Penta-coordinated aluminum, Cooperative effects

Zhenyu Wu, Zengxi Li, Chunshan Li. Cooperative catalytic effects between the penta-coordinated Al and Al₂O₃ in Al₂O₃-AlPO₄ for aldol condensation of methyl acetate with formaldehyde to methyl acrylate[J]. Chinese Journal of Chemical Engineering, 2022, 52(12): 172-183.

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Cooperative catalytic effects between the penta-coordinated Al and Al₂O₃ in Al₂O₃-AlPO₄ for aldol condensation of methyl acetate with formaldehyde to methyl acrylate

Cooperative catalytic effects between the penta-coordinated Al and Al₂O₃ in Al₂O₃-AlPO₄ for aldol condensation of methyl acetate with formaldehyde to methyl acrylate

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