SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2023, Vol. 53 ›› Issue (1): 402-408.DOI: 10.1016/j.cjche.2022.01.012

• Full Length Article • 上一篇    下一篇

Influence of Ca/P ratio on the catalytic performance of hydroxyapatite for decarboxylation of itaconic acid to methacrylic 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
  • 收稿日期:2021-09-10 修回日期:2022-01-10 出版日期:2023-01-28 发布日期:2023-04-08
  • 通讯作者: Hualiang An,E-mail:anhl@hebut.edu.cn;Xinqiang Zhao,E-mail:zhaoxq@hebut.edu.cn
  • 基金资助:
    This work was supported by the National Natural Science Foundation of China (Grant No. 21978066), Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project (Grant No. 18964308D), and the Key Program of Natural Science Foundation of Hebei Province (Grant No. B2020202048).

Influence of Ca/P ratio on the catalytic performance of hydroxyapatite for decarboxylation of itaconic acid to methacrylic 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:2021-09-10 Revised:2022-01-10 Online:2023-01-28 Published:2023-04-08
  • Contact: Hualiang An,E-mail:anhl@hebut.edu.cn;Xinqiang Zhao,E-mail:zhaoxq@hebut.edu.cn
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (Grant No. 21978066), Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project (Grant No. 18964308D), and the Key Program of Natural Science Foundation of Hebei Province (Grant No. B2020202048).

摘要: Methacrylic acid, an important organic chemical, is commercially manufactured starting from fossil feedstock. The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid. In view of the problems existing in the researches on this route such as use of noble metal catalyst, harsh reaction conditions and low desired-product yield, we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance. The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity. The highest yield of MAA up to 61.2% was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH, 2 MPa of N2, 250 ℃, and 2 h. On this basis, a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established. With the aid of catalyst characterization using X-ray powder diffraction, NH3/CO2 temperature-programmed desorption, N2 physisorption, inductively coupled plasma optical emission spectrometry, and scanning electron microscopy, we found that the distribution of surface acid sites and basic sites, crystal growth orientation, texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio. Furthermore, the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.

关键词: Biomass-derived itaconic acid, Methacrylic acid, Hydroxyapatite catalyst, Ca/P ratio, Decarboxylation reaction

Abstract: Methacrylic acid, an important organic chemical, is commercially manufactured starting from fossil feedstock. The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid. In view of the problems existing in the researches on this route such as use of noble metal catalyst, harsh reaction conditions and low desired-product yield, we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance. The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity. The highest yield of MAA up to 61.2% was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH, 2 MPa of N2, 250 ℃, and 2 h. On this basis, a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established. With the aid of catalyst characterization using X-ray powder diffraction, NH3/CO2 temperature-programmed desorption, N2 physisorption, inductively coupled plasma optical emission spectrometry, and scanning electron microscopy, we found that the distribution of surface acid sites and basic sites, crystal growth orientation, texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio. Furthermore, the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.

Key words: Biomass-derived itaconic acid, Methacrylic acid, Hydroxyapatite catalyst, Ca/P ratio, Decarboxylation reaction