The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent...The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.展开更多
2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the t...2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.展开更多
A new industrial production method of 2, 3-butanediol is discussed in this paper. C2-4 bio-polyol is prepared by combining biological fermentation and chemical cleavage, with corn starch as raw material. In this indus...A new industrial production method of 2, 3-butanediol is discussed in this paper. C2-4 bio-polyol is prepared by combining biological fermentation and chemical cleavage, with corn starch as raw material. In this industrial method, high purity 2,3-butanediol can be obtained after distillation and purification. Low production cost of this method provides an effective support for 2, 3-butanediol large-scaled application.展开更多
The kinetics of the oxidation of 1,2-butanediol or mephenesin by ditelluratocuprate（Ⅲ）（DTC） was investigated spectrophotometrically at temperatures between 283.2―303.2 K in alkaline media. The reaction rate show...The kinetics of the oxidation of 1,2-butanediol or mephenesin by ditelluratocuprate（Ⅲ）（DTC） was investigated spectrophotometrically at temperatures between 283.2―303.2 K in alkaline media. The reaction rate showed first order dependence in DTC and fractional order in 1,2-butanediol or mephenesin. It was shown that the pseudo- first-order rate constant kobs increased with an increase in concentration of OH– and a decrease in concentration of TeO42–. The reaction has a negative salt effect. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between the complex and 1,2-butanediol or mephenesin was proposed. The rate equations derived from the mechanism can explain all the experimental phenomena. The activation parameters for the rate-determining step were also calculated.展开更多
The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were ...The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.展开更多
基金Supported by the National Natural Science Foundation of China(21673132).
文摘The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.
基金Supported by the National "973" project (No. 613740102)
文摘2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.
文摘A new industrial production method of 2, 3-butanediol is discussed in this paper. C2-4 bio-polyol is prepared by combining biological fermentation and chemical cleavage, with corn starch as raw material. In this industrial method, high purity 2,3-butanediol can be obtained after distillation and purification. Low production cost of this method provides an effective support for 2, 3-butanediol large-scaled application.
基金Supported by the Natural Science Foundation of Hebei Province,China(No.295066)
文摘The kinetics of the oxidation of 1,2-butanediol or mephenesin by ditelluratocuprate（Ⅲ）（DTC） was investigated spectrophotometrically at temperatures between 283.2―303.2 K in alkaline media. The reaction rate showed first order dependence in DTC and fractional order in 1,2-butanediol or mephenesin. It was shown that the pseudo- first-order rate constant kobs increased with an increase in concentration of OH– and a decrease in concentration of TeO42–. The reaction has a negative salt effect. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between the complex and 1,2-butanediol or mephenesin was proposed. The rate equations derived from the mechanism can explain all the experimental phenomena. The activation parameters for the rate-determining step were also calculated.
基金supported by the Foundation of Liaoning Provincial Department of Education (990321076)
文摘The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.
