SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2024, Vol. 67 ›› Issue (3): 9-15.DOI: 10.1016/j.cjche.2023.11.018

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Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

Shutong Pang, Hualiang An, Xinqiang Zhao, Yanji Wang   

  1. Hebei Provincial Key Laboratory of Green Chemical Technology and Efficient Energy Saving, Tianjin Key Laboratory of Chemical Process Safety, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
  • Received:2023-06-18 Revised:2023-11-27 Online:2024-06-01 Published:2024-03-28
  • Contact: Hualiang An,E-mail address:anhl@hebut.edu.cn;Xinqiang Zhao,E-mail address:zhaoxq@hebut.edu.cn.
  • Supported by:
    This work was supported by National Natural Science Foundation of China (21978066), Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project (18964308D), and the Key Program of Natural Science Foundation of Hebei Province (B2020202048).

Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

Shutong Pang, Hualiang An, Xinqiang Zhao, Yanji Wang   

  1. Hebei Provincial Key Laboratory of Green Chemical Technology and Efficient Energy Saving, Tianjin Key Laboratory of Chemical Process Safety, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
  • 通讯作者: Hualiang An,E-mail address:anhl@hebut.edu.cn;Xinqiang Zhao,E-mail address:zhaoxq@hebut.edu.cn.
  • 基金资助:
    This work was supported by National Natural Science Foundation of China (21978066), Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project (18964308D), and the Key Program of Natural Science Foundation of Hebei Province (B2020202048).

Abstract: The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route, for it can get rid of the dependence on fossil resource. In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali, we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance. The results showed that the ionic liquid [Bmim]BF4 can affect the crystal growth of hydroxyapatite, provide fluoride ion for fluorination of hydroxyapatite, and adjust the surface acidity and basicity, morphology, textural properties, crystallinity, and composition of hydroxyapatite. The [Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system, thus changing the degree of fluoridation of hydroxyapatite. High fluoride-ion concentration can lead to the formation of CaF2 and thus significantly decrease the catalytic performance of hydroxyapatite. The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis, leading to different catalytic performance. The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows: a mass ratio of [Bmim]BF4 to calcium salt =≥0.2:1, a hydrothermal time of 12 h, and a hydrothermal temperature of 130℃. A maximal methacrylic acid yield of 54.7% was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions (250℃ and 2 MPa of N2) in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

Key words: Ionic liquid, Hydroxyapatite, Itaconic acid, Methacrylic, Decarboxylation reaction

摘要: The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route, for it can get rid of the dependence on fossil resource. In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali, we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance. The results showed that the ionic liquid [Bmim]BF4 can affect the crystal growth of hydroxyapatite, provide fluoride ion for fluorination of hydroxyapatite, and adjust the surface acidity and basicity, morphology, textural properties, crystallinity, and composition of hydroxyapatite. The [Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system, thus changing the degree of fluoridation of hydroxyapatite. High fluoride-ion concentration can lead to the formation of CaF2 and thus significantly decrease the catalytic performance of hydroxyapatite. The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis, leading to different catalytic performance. The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows: a mass ratio of [Bmim]BF4 to calcium salt =≥0.2:1, a hydrothermal time of 12 h, and a hydrothermal temperature of 130℃. A maximal methacrylic acid yield of 54.7% was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions (250℃ and 2 MPa of N2) in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

关键词: Ionic liquid, Hydroxyapatite, Itaconic acid, Methacrylic, Decarboxylation reaction