In a stainless steel autoclave,the synthesis kinetics of dimethyl carbonate(DMC) from urea and methanol was separately investigated without catalyst and with Zn-containing catalyst.Without catalyst,for the first react...In a stainless steel autoclave,the synthesis kinetics of dimethyl carbonate(DMC) from urea and methanol was separately investigated without catalyst and with Zn-containing catalyst.Without catalyst,for the first reaction of DMC synthesis(the reaction of urea with methanol to methyl carbamate(MC)),the reaction kinetics can be described as the first order with respect to the concentrations of both methanol and urea.For the second reaction of DMC synthesis(the reaction of MC with methanol to DMC),the results exhibit characteristics of zero-order reaction.For Zn-containing catalyst,the first reaction is neglected in the kinetics model since its rate is much faster than the second reaction.The macro-kinetic parameters of the second reaction are obtained by fitting the experimental data to a pseudo-homogenous model,in which a side reaction in forming process of DMC is incorporated since it decreases the yield of DMC drastically at high temperature.The activation energy of the reaction from MC to DMC is 104 kJ/mol while that of the side reaction of DMC is 135 kJ/mol.The highest yield of DMC is 23%.展开更多
A new MoO3/SO4 2--TiO2 catalyst was prepared by a conventional impregnation of SO4 2-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbon...A new MoO3/SO4 2--TiO2 catalyst was prepared by a conventional impregnation of SO4 2-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate(DMC)with phenol.A series of MoO3/SO4 2--TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction(XRD),Fourier transform infrared spectrometer(FTIR),NH3-temperature programmed desorption(NH3-TPD)and X-ray photoelectron spectroscopy(XPS).The results show that MoO3 loading is related to the activity of transesterification reaction.With the increase of MoO3 loading,the activity of transesterification reaction increases.The sulfur species in the catalyst have an influence on the molybdenum species,and lead to an increase in the electropositive of molybdenum,which promotes the catalytic activity of MoO3/SO4 2--TiO2.Among the series of catalysts prepared,MoO3/SO4 2--TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction.Under the reaction conditions of 453 K and 12 h,the conversion of DMC is 30.5 %,and the yields of MPC and DPC reach 21.2 % and 8.7 %,respectively.展开更多
基金Project(2010ZC034) supported by the Science Foundation of Yunnan Province,ChinaProject(20105314120005) supported by the Research Fund for Doctor Program of Higher Education of China+2 种基金Project(11-12-609) supported by the Open Foundation of State Key Laboratory of Coal Conversion,ChinaProject(KKJD201051012) supported by the Scientific Research Fund of Yunnan Provincial Education Department,ChinaProject(2009-096) supported by the Analysis and Measure Foundation of Kunming University of Scienceand Technology,China
文摘In a stainless steel autoclave,the synthesis kinetics of dimethyl carbonate(DMC) from urea and methanol was separately investigated without catalyst and with Zn-containing catalyst.Without catalyst,for the first reaction of DMC synthesis(the reaction of urea with methanol to methyl carbamate(MC)),the reaction kinetics can be described as the first order with respect to the concentrations of both methanol and urea.For the second reaction of DMC synthesis(the reaction of MC with methanol to DMC),the results exhibit characteristics of zero-order reaction.For Zn-containing catalyst,the first reaction is neglected in the kinetics model since its rate is much faster than the second reaction.The macro-kinetic parameters of the second reaction are obtained by fitting the experimental data to a pseudo-homogenous model,in which a side reaction in forming process of DMC is incorporated since it decreases the yield of DMC drastically at high temperature.The activation energy of the reaction from MC to DMC is 104 kJ/mol while that of the side reaction of DMC is 135 kJ/mol.The highest yield of DMC is 23%.
基金Project(20936003)supported by the National Natural Science Foundation of ChinaProject(2012CB723105)supported by the National Basic Research Program of China
文摘A new MoO3/SO4 2--TiO2 catalyst was prepared by a conventional impregnation of SO4 2-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate(DMC)with phenol.A series of MoO3/SO4 2--TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction(XRD),Fourier transform infrared spectrometer(FTIR),NH3-temperature programmed desorption(NH3-TPD)and X-ray photoelectron spectroscopy(XPS).The results show that MoO3 loading is related to the activity of transesterification reaction.With the increase of MoO3 loading,the activity of transesterification reaction increases.The sulfur species in the catalyst have an influence on the molybdenum species,and lead to an increase in the electropositive of molybdenum,which promotes the catalytic activity of MoO3/SO4 2--TiO2.Among the series of catalysts prepared,MoO3/SO4 2--TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction.Under the reaction conditions of 453 K and 12 h,the conversion of DMC is 30.5 %,and the yields of MPC and DPC reach 21.2 % and 8.7 %,respectively.
