The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed ...The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed to be 1 and 1.3 by the integral test method and the numerical differential method, respectively. The activation energies of the two steps were(56.94 ± 5.90) k J·mol-1and(72.07 ± 3.47) k J·mol-1with the frequency factors exp(12.53 ± 1.42) min-1and(14.254 ± 0.84) mol-0.33·L0.33·min-1, respectively. Based on the kinetic model obtained, the progress of the reaction can be calculated under given conditions.展开更多
The utilization of CO_2 as raw material 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 ind...The utilization of CO_2 as raw material 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 CO_2 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 Co_3O_4/ZSM-5 catalyst, using chlorobenzene as low boiling point solvent. Different metal oxide supported catalysts were prepared by incipient wetness 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 Co_3O_4/ZSM-5_(25) catalysts prepared by different methods showed different performances in the order of Co_3O_4/ZSM-5_(25)(PEG)N Co_3O_4/ZSM-5_(25)(IWI)N Co_3O_4/ZSM-5_(25)(DP). The physicochemical properties of Co_3O_4/ZSM-5_(25) catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS.The superior catalytic performance of Co_3O_4/ZSM-5_(25)(PEG)catalyst was attributed to its relative surface content of Co^(3+), surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co_3O_4/ZSM-5_(25)(PEG)catalyst, 250 °C 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 Co_3O_4/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 Co_3O_4/ZSM-5_(25) catalysts.展开更多
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 cataly...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(BMIMBF_4) 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 °C 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 °C, which further increased the yield of the total HDI(HDI_(tol)) 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.展开更多
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, N2adsorption-desorption m...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, N2adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the Zn Co2O4 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.展开更多
基金the National Key Technology R&D Program(2013BAC11B03)the Knowledge Innovation Fund of Chinese Academy of Science(KGCX2-YW-215-2)the National Natural Science Foundation of China(21476244)
文摘The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed to be 1 and 1.3 by the integral test method and the numerical differential method, respectively. The activation energies of the two steps were(56.94 ± 5.90) k J·mol-1and(72.07 ± 3.47) k J·mol-1with the frequency factors exp(12.53 ± 1.42) min-1and(14.254 ± 0.84) mol-0.33·L0.33·min-1, respectively. Based on the kinetic model obtained, the progress of the reaction can be calculated under given conditions.
基金National Natural Science Foundation of China(21476244 and 21406245)Youth Innovation Promotion Association CAS
文摘The utilization of CO_2 as raw material 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 CO_2 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 Co_3O_4/ZSM-5 catalyst, using chlorobenzene as low boiling point solvent. Different metal oxide supported catalysts were prepared by incipient wetness 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 Co_3O_4/ZSM-5_(25) catalysts prepared by different methods showed different performances in the order of Co_3O_4/ZSM-5_(25)(PEG)N Co_3O_4/ZSM-5_(25)(IWI)N Co_3O_4/ZSM-5_(25)(DP). The physicochemical properties of Co_3O_4/ZSM-5_(25) catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS.The superior catalytic performance of Co_3O_4/ZSM-5_(25)(PEG)catalyst was attributed to its relative surface content of Co^(3+), surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co_3O_4/ZSM-5_(25)(PEG)catalyst, 250 °C 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 Co_3O_4/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 Co_3O_4/ZSM-5_(25) catalysts.
基金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)the Youth Innovation Promotion Association CAS(2016046)
文摘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(BMIMBF_4) 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 °C 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 °C, which further increased the yield of the total HDI(HDI_(tol)) 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.
基金supported by National Natural Science Foundation of China(Nos.21476244 and 21406245)Youth Innovation Promotion Association CAS
文摘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, N2adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the Zn Co2O4 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.
