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
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
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
A reconstructed Cu-ZnO catalyst with improved stability was fabricated by organic acid treatment method for the liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol.According to the characterization resu...A reconstructed Cu-ZnO catalyst with improved stability was fabricated by organic acid treatment method for the liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol.According to the characterization results of the fresh Cu-ZnO and reconstructed Cu-ZnO,three different forms of ZnO were suggested to be presented on the catalysts:ZnO having strong interaction with Cu species,ZnO that weakly interacted with Cu species and isolated ZnO.The first form of ZnO was believed to be beneficial to the formation of efficient active site Cu^(+),while the latter two forms of ZnO took the main responsibility for the deactivation of Cu-ZnO catalysts in the liquid-phase hydrogenation of diesters.The reconstruction of the Cu-ZnO catalyst by the organic acid treatment method resulted in a new Cu-ZnO catalyst with more Cu^(+)and less ZnO species that leads to deactivation.Furthermore,the deactivation mechanism of Cu-ZnO catalysts in liquid-phase diester hydrogenation in continuous flow system was proposed:the deposition of the polyesters on the catalysts via transesterification catalyzed by weakly interacted ZnO and isolated ZnO leads to the deactivation.These results provided meaningful instructions for designing highly efficient Cu-Zn catalysts for similar ester hydrogenation systems.展开更多
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.
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 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.
基金We are grateful for the financial support from the National Natural Science Foundation of China(Grant Nos.21878227 and 22278309).
文摘A reconstructed Cu-ZnO catalyst with improved stability was fabricated by organic acid treatment method for the liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol.According to the characterization results of the fresh Cu-ZnO and reconstructed Cu-ZnO,three different forms of ZnO were suggested to be presented on the catalysts:ZnO having strong interaction with Cu species,ZnO that weakly interacted with Cu species and isolated ZnO.The first form of ZnO was believed to be beneficial to the formation of efficient active site Cu^(+),while the latter two forms of ZnO took the main responsibility for the deactivation of Cu-ZnO catalysts in the liquid-phase hydrogenation of diesters.The reconstruction of the Cu-ZnO catalyst by the organic acid treatment method resulted in a new Cu-ZnO catalyst with more Cu^(+)and less ZnO species that leads to deactivation.Furthermore,the deactivation mechanism of Cu-ZnO catalysts in liquid-phase diester hydrogenation in continuous flow system was proposed:the deposition of the polyesters on the catalysts via transesterification catalyzed by weakly interacted ZnO and isolated ZnO leads to the deactivation.These results provided meaningful instructions for designing highly efficient Cu-Zn catalysts for similar ester hydrogenation systems.