SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2023, Vol. 55 ›› Issue (3): 148-155.DOI: 10.1016/j.cjche.2022.05.012

• Full Length Article • 上一篇    下一篇

Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor

Zhihao Zhu1,2, Ying Sun1, Haijun Yu1, Meng Li1, Xingming Jie1, Guodong Kang1, Yiming Cao1   

  1. 1. Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS), Dalian 116023, China;
    2. School of Chemistry and Chemical Engineering, Anqing Normal University (AQNU), Anqing 246011, China
  • 收稿日期:2022-02-09 修回日期:2022-05-31 出版日期:2023-03-28 发布日期:2023-06-03
  • 通讯作者: Guodong Kang,E-mail:kangguod@dicp.ac.cn
  • 基金资助:
    All the authors thank the financial support from Dalian Institute of Chemical Physics (DMTO201604), Focus Area Innovation Team Support Plan of Dalian (2021RT03), National Natural Science Foundation of China (21878284), and Regional Development Young Scholars of the Chinese Academy of Sciences.

Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor

Zhihao Zhu1,2, Ying Sun1, Haijun Yu1, Meng Li1, Xingming Jie1, Guodong Kang1, Yiming Cao1   

  1. 1. Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS), Dalian 116023, China;
    2. School of Chemistry and Chemical Engineering, Anqing Normal University (AQNU), Anqing 246011, China
  • Received:2022-02-09 Revised:2022-05-31 Online:2023-03-28 Published:2023-06-03
  • Contact: Guodong Kang,E-mail:kangguod@dicp.ac.cn
  • Supported by:
    All the authors thank the financial support from Dalian Institute of Chemical Physics (DMTO201604), Focus Area Innovation Team Support Plan of Dalian (2021RT03), National Natural Science Foundation of China (21878284), and Regional Development Young Scholars of the Chinese Academy of Sciences.

摘要: Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene (PTFE) membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane (PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120 ℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g-1·h-1. This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.

关键词: PTFE hollow fiber, Microstructure, Membrane contactor, Membrane wetting, Carbonylation of formaldehyde

Abstract: Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene (PTFE) membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane (PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120 ℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g-1·h-1. This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.

Key words: PTFE hollow fiber, Microstructure, Membrane contactor, Membrane wetting, Carbonylation of formaldehyde