SCI和EI收录∣中国化工学会会刊

Chin.J.Chem.Eng. ›› 2017, Vol. 25 ›› Issue (12): 1760-1770.DOI: 10.1016/j.cjche.2017.03.032

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An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst: An indirect utilization of CO2

Muhammad Ammar1,2, Yan Cao1, Peng He1, Liguo Wang1, Jiaqiang Chen1, Huiquan Li1   

  1. 1. Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, CAS, Beijing 100190, China;
    2. University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2016-12-03 Revised:2017-03-06 Online:2018-01-18 Published:2017-12-28
  • Contact: Yan Cao,Fax:+86 10 62621355.E-mail addresses:ycao@ipe.ac.cn;Huiquan Li,E-mail addresses:hqli@ipe.ac.cn.
  • Supported by:

    National Natural Science Foundation of China (21476244 and 21406245) and Youth Innovation Promotion Association CAS.

An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst: An indirect utilization of CO2

Muhammad Ammar1,2, Yan Cao1, Peng He1, Liguo Wang1, Jiaqiang Chen1, Huiquan Li1   

  1. 1. Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, CAS, Beijing 100190, China;
    2. University of Chinese Academy of Sciences, Beijing 100049, China
  • 通讯作者: Yan Cao,Fax:+86 10 62621355.E-mail addresses:ycao@ipe.ac.cn;Huiquan Li,E-mail addresses:hqli@ipe.ac.cn.
  • 基金资助:

    National Natural Science Foundation of China (21476244 and 21406245) and Youth Innovation Promotion Association CAS.

Abstract: The utilization of CO2 as rawmaterial for chemical synthesis has the potential for substantial economic and green benefits. Thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) is a promising approach for indirect utilization of CO2 to produce hexamethylene-1,6-diisocyanate (HDI). In this work, a green route was developed for the synthesis of HDI by thermal decomposition of HDC over Co3O4/ZSM-5 catalyst, using chlorobenzene as lowboiling point solvent. Different metal oxide supported catalysts were prepared by incipientwetness impregnation (IWI), PEG-additive (PEG) and deposition precipitation with ammonia evaporation (DP) methods. Their catalytic performances for the thermal decomposition of HDC were tested. The catalyst screening results showed that Co3O4/ZSM-525 catalysts prepared by different methods showed different performances in the order of Co3O4/ZSM-525(PEG) N Co3O4/ZSM-525(IWI) N Co3O4/ZSM-525(DP). The physicochemical properties of Co3O4/ZSM- 525 catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS. The superior catalytic performance of Co3O4/ZSM-525(PEG) catalyst was attributed to its relative surface content of Co3+, surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co3O4/ZSM-525(PEG) catalyst, 250 ℃ temperature, 2.5 h time, 800 ml·min-1 nitrogen flow rate and 1.0 MPa pressure, the HDC conversion and HDI yield could reach 100% and 92.8% respectively. The Co3O4/ZSM-525(PEG) catalyst could be facilely separated from the reaction mixture, and reused without degradation in catalytic performance. Furthermore, a possible reaction mechanism was proposed based on the physicochemical properties of the Co3O4/ZSM-525 catalysts.

Key words: Hexamethylene-1,6-dicarbamate (HDC), Hexamethylene-1,6-diisocyanate (HDI), Thermal decomposition, Co3O4/ZSM-5, Heterogeneous catalyst

摘要: The utilization of CO2 as rawmaterial for chemical synthesis has the potential for substantial economic and green benefits. Thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) is a promising approach for indirect utilization of CO2 to produce hexamethylene-1,6-diisocyanate (HDI). In this work, a green route was developed for the synthesis of HDI by thermal decomposition of HDC over Co3O4/ZSM-5 catalyst, using chlorobenzene as lowboiling point solvent. Different metal oxide supported catalysts were prepared by incipientwetness impregnation (IWI), PEG-additive (PEG) and deposition precipitation with ammonia evaporation (DP) methods. Their catalytic performances for the thermal decomposition of HDC were tested. The catalyst screening results showed that Co3O4/ZSM-525 catalysts prepared by different methods showed different performances in the order of Co3O4/ZSM-525(PEG) N Co3O4/ZSM-525(IWI) N Co3O4/ZSM-525(DP). The physicochemical properties of Co3O4/ZSM- 525 catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS. The superior catalytic performance of Co3O4/ZSM-525(PEG) catalyst was attributed to its relative surface content of Co3+, surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co3O4/ZSM-525(PEG) catalyst, 250 ℃ temperature, 2.5 h time, 800 ml·min-1 nitrogen flow rate and 1.0 MPa pressure, the HDC conversion and HDI yield could reach 100% and 92.8% respectively. The Co3O4/ZSM-525(PEG) catalyst could be facilely separated from the reaction mixture, and reused without degradation in catalytic performance. Furthermore, a possible reaction mechanism was proposed based on the physicochemical properties of the Co3O4/ZSM-525 catalysts.

关键词: Hexamethylene-1,6-dicarbamate (HDC), Hexamethylene-1,6-diisocyanate (HDI), Thermal decomposition, Co3O4/ZSM-5, Heterogeneous catalyst