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Zn-Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene–1,6–diisocyanate by thermal decomposition of hexamethylene–1,6–dicarbamate
引用本文:Muhammad Ammar,Yan Cao,Peng He,Li-Guo Wang,Jia-Qiang Chen,Hui-Quan Li. Zn-Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene–1,6–diisocyanate by thermal decomposition of hexamethylene–1,6–dicarbamate[J]. 中国化学快报, 2017, 28(7): 1583-1589. DOI: 10.1016/j.cclet.2017.03.015
作者姓名:Muhammad Ammar  Yan Cao  Peng He  Li-Guo Wang  Jia-Qiang Chen  Hui-Quan Li
作者单位:a Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, CAS, Beijing 100190, China;b University of Chinese Academy of Sciences, Beijing 100049, China
基金项目:This work was supported by National Natural Science Foundation of China (Nos. 21476244 and 21406245) and Youth Innovation Promotion Association CAS.
摘    要:A set of mono-and bimetallic(Zn-Co) supported ZSM-5 catalysts was first prepared by PEG-additive method. The physicochemical properties of the catalysts were investigated by FTIR, XPS, XRD, N_2adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the Zn Co_2O_4 spinel oxide was formed on the ZSM-5 support and provided effectual synergetic effect between Zn and Co species for the bimetallic catalyst. Furthermore, bimetallic supported ZSM-5 catalyst exhibited weak, moderate and strong acidic sites, while the monometallic supported ZSM-5 catalyst showed only weak and moderate or strong acidic sites. Their catalytic performances for thermal decomposition of hexamethylene–1,6–dicarbamate(HDC) to hexamethylene–1,6–diisocyanate(HDI) were then studied. It was found that the bimetallic supported ZSM-5 catalysts,especially Zn-2Co/ZSM-5 catalyst showed excellent catalytic performance due to the good synergetic effect between Co and Zn species, which provided a suitable contribution of acidic sites. HDC conversion of 100% with HDI selectivity of 91.2% and by-products selectivity of 1.3% could be achieved within short reaction time of 2.5 h over Zn-2Co/ZSM-5 catalyst.


Zn-Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene-1,6-diisocyanate by thermal decomposition of hexamethylene-1,6-dicarbamate
Muhammad Ammar,Yan Cao,Peng He,Li-Guo Wang,Jia-Qiang Chen,Hui-Quan Li. Zn-Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene-1,6-diisocyanate by thermal decomposition of hexamethylene-1,6-dicarbamate[J]. Chinese Chemical Letters, 2017, 28(7): 1583-1589. DOI: 10.1016/j.cclet.2017.03.015
Authors:Muhammad Ammar  Yan Cao  Peng He  Li-Guo Wang  Jia-Qiang Chen  Hui-Quan Li
Affiliation:a Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, CAS, Beijing 100190, China;b University of Chinese Academy of Sciences, Beijing 100049, China
Abstract:A set of mono- and bimetallic (Zn-Co) supported ZSM-5 catalysts was first prepared by PEG-additive method. The physicochemical properties of the catalysts were investigated by FTIR, XPS, XRD, N2 adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the ZnCo2O4 spinel oxide was formed on the ZSM-5 support and provided effectual synergetic effect between Zn and Co species for the bimetallic catalyst. Furthermore, bimetallic supported ZSM-5 catalyst exhibited weak, moderate and strong acidic sites, while the monometallic supported ZSM-5 catalyst showed only weak and moderate or strong acidic sites. Their catalytic performances for thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) to hexamethylene- 1,6-diisocyanate (HDI) were then studied. It was found that the bimetallic supported ZSM-5 catalysts, especially Zn-2Co/ZSM-5 catalyst showed excellent catalytic performance due to the good synergetic effect between Co and Zn species, which provided a suitable contribution of acidic sites. HDC conversion of 100% with HDI selectivity of 91.2% and by-products selectivity of 1.3% could be achieved within short reaction time of 2.5 h over Zn-2Co/ZSM-5 catalyst.
Keywords:Hexamethylene-1  6-dicarbamate (HDC)  Hexamethylene-1  6-diisocyanate (HDI)  Thermal decomposition  Bimetallic supported ZSM-5 catalyst  Synergetic effect  
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