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

doi:10.1016/j.cjche.2017.03.032

Chinese Journal of Chemical Engineering ›› 2017, Vol. 25 ›› Issue (12): 1760-1770.DOI: 10.1016/j.cjche.2017.03.032

• 第25届中国过程控制会议专栏 • 上一篇下一篇

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 Ammar^1,2, Yan Cao¹, Peng He¹, Liguo Wang¹, Jiaqiang Chen¹, Huiquan Li¹

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

收稿日期:2016-12-03 修回日期:2017-03-06 出版日期:2017-12-28 发布日期:2018-01-18
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.

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 Ammar^1,2, Yan Cao¹, Peng He¹, Liguo Wang¹, Jiaqiang Chen¹, Huiquan Li¹

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:2017-12-28 Published:2018-01-18
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.

摘要/Abstract

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-5_25(PEG) N Co₃O₄/ZSM-5_25(IWI) N Co₃O₄/ZSM-5_25(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-5_25(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-5_25(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-5_25(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

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-5_25(PEG) N Co₃O₄/ZSM-5_25(IWI) N Co₃O₄/ZSM-5_25(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-5_25(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-5_25(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-5_25(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

Muhammad Ammar, Yan Cao, Peng He, Liguo Wang, Jiaqiang Chen, Huiquan Li. 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[J]. Chinese Journal of Chemical Engineering, 2017, 25(12): 1760-1770.

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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

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

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