The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffrac...The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.展开更多
A novel lanthana-promoted nickel catalyst supported on silica for the liquid phase hydrogenation of m-dinitrobenzene to m-phenylenediamine was prepared by an incipient wetness sequential impregnation method. It was ...A novel lanthana-promoted nickel catalyst supported on silica for the liquid phase hydrogenation of m-dinitrobenzene to m-phenylenediamine was prepared by an incipient wetness sequential impregnation method. It was found that Ni-La/SiO2 catalyst exhibited high activity and stability for m-dinitrobenzene hydrogenation. Over this catalyst, the conversion of m-dinitrobenzene and the yield of m-phenylenediamine were up to 97.1% and 93.5%, respectively, at 373 K and 2.6 MPa hydrogen pressure after reaction for 1 h.展开更多
Using tetraethyl orthosilicate(TEOS)as the pre-cursor of silica,the silica aerogel and xerogel,which were used as supports of nickel-based catalysts for liquid hydroge-nation of m-dinitrobenzene to m-phenylenediamine,...Using tetraethyl orthosilicate(TEOS)as the pre-cursor of silica,the silica aerogel and xerogel,which were used as supports of nickel-based catalysts for liquid hydroge-nation of m-dinitrobenzene to m-phenylenediamine,were prepared by the sol-gel method combined with supercritical drying(SCD)and conventional drying,respectively.Then,a series of nickel-based catalyst samples supported on these supports were prepared by the incipient wetness impregna-tion method with an aqueous solution of nickel nitrate as well as lanthanum nitrate as impregnation liquids.Based on the characterization results of nitrogen adsorption-desorption(BET),X-ray diffraction(XRD),temperature programmed reduction(TPR),temperature-programmed desorption of hydrogen(H2-TPD),and catalytic activity evaluation,the physico-chemical properties and catalytic performances of the catalysts were investigated.The results show that the nickel crystallites on the binary nickel catalyst using silica aerogel as support are of smaller particle size.However,com-pared with the sample supported on silica xerogel,the nickel catalyst supported on the silica aerogel exhibits lower activity and selectivity for the hydrogenation of m-dinitrobenzene because it has a lesser amount of active sites and weaker absorption ability to reactants caused by sintering of the nickel crystallites.The addition of promoter La2O3 could increase the activity and selectivity of the catalysts.Among all the nickel-based catalyst samples prepared,the La2O3 promoted ternary nickel-based catalyst supported on silica xerogel exhibits the highest activity and selectivity for the hydrogenation of m-dinitrobenzene to m-phenylenediamine,which could be attributed to its highest active surface area and appropriate absorption strength to reactants.Over this prom-ising catalyst,the conversion of m-dinitrobenzene and the yield of m-phenylenediamine could reach 97.0%and 93.1%,respectively,under proper reaction conditions of hydrogen pressure 2.6 MPa,temperature 373 K,and reaction time 1 h.展开更多
文摘The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.
文摘A novel lanthana-promoted nickel catalyst supported on silica for the liquid phase hydrogenation of m-dinitrobenzene to m-phenylenediamine was prepared by an incipient wetness sequential impregnation method. It was found that Ni-La/SiO2 catalyst exhibited high activity and stability for m-dinitrobenzene hydrogenation. Over this catalyst, the conversion of m-dinitrobenzene and the yield of m-phenylenediamine were up to 97.1% and 93.5%, respectively, at 373 K and 2.6 MPa hydrogen pressure after reaction for 1 h.
文摘Using tetraethyl orthosilicate(TEOS)as the pre-cursor of silica,the silica aerogel and xerogel,which were used as supports of nickel-based catalysts for liquid hydroge-nation of m-dinitrobenzene to m-phenylenediamine,were prepared by the sol-gel method combined with supercritical drying(SCD)and conventional drying,respectively.Then,a series of nickel-based catalyst samples supported on these supports were prepared by the incipient wetness impregna-tion method with an aqueous solution of nickel nitrate as well as lanthanum nitrate as impregnation liquids.Based on the characterization results of nitrogen adsorption-desorption(BET),X-ray diffraction(XRD),temperature programmed reduction(TPR),temperature-programmed desorption of hydrogen(H2-TPD),and catalytic activity evaluation,the physico-chemical properties and catalytic performances of the catalysts were investigated.The results show that the nickel crystallites on the binary nickel catalyst using silica aerogel as support are of smaller particle size.However,com-pared with the sample supported on silica xerogel,the nickel catalyst supported on the silica aerogel exhibits lower activity and selectivity for the hydrogenation of m-dinitrobenzene because it has a lesser amount of active sites and weaker absorption ability to reactants caused by sintering of the nickel crystallites.The addition of promoter La2O3 could increase the activity and selectivity of the catalysts.Among all the nickel-based catalyst samples prepared,the La2O3 promoted ternary nickel-based catalyst supported on silica xerogel exhibits the highest activity and selectivity for the hydrogenation of m-dinitrobenzene to m-phenylenediamine,which could be attributed to its highest active surface area and appropriate absorption strength to reactants.Over this prom-ising catalyst,the conversion of m-dinitrobenzene and the yield of m-phenylenediamine could reach 97.0%and 93.1%,respectively,under proper reaction conditions of hydrogen pressure 2.6 MPa,temperature 373 K,and reaction time 1 h.
