SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2019, Vol. 27 ›› Issue (3): 549-555.DOI: 10.1016/j.cjche.2018.05.001

• Catalysis, Kinetics and Reaction Engineering • Previous Articles     Next Articles

Non-phosgene synthesis of hexamethylene-1,6-diisocyanate from thermal decomposition of hexamethylene-1,6-dicarbamate over Zn–Co bimetallic supported ZSM-5 catalyst

Yan Cao1,2, Yafang Chi1,2, Ammar Muhammad1,2, Peng He1,2, liguo Wang1,2,3, Huiquan Li1,2,3   

  1. 1 CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    2 National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    3 University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2018-01-25 Revised:2018-04-27 Online:2019-04-25 Published:2019-03-28
  • Contact: Yan Cao,E-mail address:ycao@ipe.ac.cn
  • Supported by:

    Supported by the National Natural Science Foundation of China (21476244,21406245),Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21030600),and the Youth Innovation Promotion Association CAS (2016046).

Non-phosgene synthesis of hexamethylene-1,6-diisocyanate from thermal decomposition of hexamethylene-1,6-dicarbamate over Zn–Co bimetallic supported ZSM-5 catalyst

Yan Cao1,2, Yafang Chi1,2, Ammar Muhammad1,2, Peng He1,2, liguo Wang1,2,3, Huiquan Li1,2,3   

  1. 1 CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    2 National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    3 University of Chinese Academy of Sciences, Beijing 100049, China
  • 通讯作者: Yan Cao,E-mail address:ycao@ipe.ac.cn
  • 基金资助:

    Supported by the National Natural Science Foundation of China (21476244,21406245),Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21030600),and the Youth Innovation Promotion Association CAS (2016046).

Abstract: A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate (HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate (HDC) over Zn-Co bi-metallic supported ZSM-5 catalyst. The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate (DOS), dibutyl sebacate (DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt% concentration of HDC in DOS, 250℃ temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn-Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate (HMI) over Zn-Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6% (98.6% HDI selectively) at 270℃, which further increased the yield of the total HDI (HDItol) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.

Key words: Non-phosgene, Thermal decomposition, Hexamethylene-1,6-diisocyanate, Hexamethylene-1,6-dicarbamate, Bimetallic supported ZSM-5 catalyst

摘要: A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate (HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate (HDC) over Zn-Co bi-metallic supported ZSM-5 catalyst. The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate (DOS), dibutyl sebacate (DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt% concentration of HDC in DOS, 250℃ temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn-Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate (HMI) over Zn-Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6% (98.6% HDI selectively) at 270℃, which further increased the yield of the total HDI (HDItol) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.

关键词: Non-phosgene, Thermal decomposition, Hexamethylene-1,6-diisocyanate, Hexamethylene-1,6-dicarbamate, Bimetallic supported ZSM-5 catalyst