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
The production of 2,3-butanediol by Klebsiella pneumoniae from glucose supplemented with different salts was studied. A suitable medium composition was defined by response surface experiments. In a medium containing g...The production of 2,3-butanediol by Klebsiella pneumoniae from glucose supplemented with different salts was studied. A suitable medium composition was defined by response surface experiments. In a medium containing glu-cose and (NH4)2HPO4, the strain could convert 137.0g of glucose into 52.4g of 2,3-butanediol and 8.4g of acetoin in shaking flasks. The diol yield amounted to 90% of its theoretical value and the productivity was 1—1.5g·L-1·h-1. In fed-batch fermentation, the yield and productivity of diol were further enhanced by maintaining the pH at 6.0. Up to 92.4g of 2,3-butanediol and 13.1g of acetoin per liter were obtained from 215.0g of glucose per liter. The diol yield reached 98% of its theoretical value and the productivity was up to 2.1g·L-1·h-1.展开更多
The removal of solid impurities and separation of target products from a fermentation broth is becoming more tedious with the utilization of lignocelluloses as source of substrate.2,3-Butanediol,an important chemical ...The removal of solid impurities and separation of target products from a fermentation broth is becoming more tedious with the utilization of lignocelluloses as source of substrate.2,3-Butanediol,an important chemical used widely is also a main product of sugar-based fermentation carried out by Klebsiella pneumoniae.In this study,we investigated the use of salting-out extraction(SOE) that employed a K2HPO4/ethanol system consisting of 21% ethanol and 17% K2HPO4(mass fraction) to separate 2,3-butanediol from the viscous Jerusalem artichoke-based fermentation broth.After SOE,about 98% of solid matters was removed,and the viscosity decreased from 72.5 mPa s in the original fermentation broth to 4.4 mPa s in the top phase.The partition coefficient and yield of 2,3-butanediol reached 13.4 and 99%,respectively,and 89% of soluble proteins was removed from the broth.The results showed that SOE is an efficient way for isolating 2,3-BD from a highly viscous fermentation broth by removing much of the solid matters within the broth.展开更多
A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differentia...A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.展开更多
The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out ...The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)4]were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO(or TPA)with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.展开更多
The decarbonization of the chemical industry and a shift toward circular economies because of high global CO_(2) emissions make CO_(2) an attractive feedstock for manufacturing chemicals.Moreover,H_(2) is a low-cost a...The decarbonization of the chemical industry and a shift toward circular economies because of high global CO_(2) emissions make CO_(2) an attractive feedstock for manufacturing chemicals.Moreover,H_(2) is a low-cost and carbon-free reductant because technologies such as solar-driven electrolysis and supercritical water(scH_(2)O) gasification enable sustainable production of molecular hydrogen(H_(2)).We review the recent advances in engineering Ralsto-nia eutropha,the representative species of“Knallgas”bacteria,for utilizing CO_(2) and H_(2) to autotrophically produce 2,3-butanediol(2,3-BDO).This assessment is focused on state-of-the-art approaches for splitting H_(2) to supply en-ergy in the form of ATP and NADH to power cellular reactions and employing the Calvin-Benson-Bassham cycle for CO_(2) fixation.Major challenges and opportunities for application and future perspectives are discussed in the context of developing other promising CO_(2) and H_(2)-utilizing microorganisms,exemplified by Zymomonas mobilis.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.
文摘The production of 2,3-butanediol by Klebsiella pneumoniae from glucose supplemented with different salts was studied. A suitable medium composition was defined by response surface experiments. In a medium containing glu-cose and (NH4)2HPO4, the strain could convert 137.0g of glucose into 52.4g of 2,3-butanediol and 8.4g of acetoin in shaking flasks. The diol yield amounted to 90% of its theoretical value and the productivity was 1—1.5g·L-1·h-1. In fed-batch fermentation, the yield and productivity of diol were further enhanced by maintaining the pH at 6.0. Up to 92.4g of 2,3-butanediol and 13.1g of acetoin per liter were obtained from 215.0g of glucose per liter. The diol yield reached 98% of its theoretical value and the productivity was up to 2.1g·L-1·h-1.
基金Supported by the National High Technology Research and Development Program of China (2009AA05Z443)
文摘The removal of solid impurities and separation of target products from a fermentation broth is becoming more tedious with the utilization of lignocelluloses as source of substrate.2,3-Butanediol,an important chemical used widely is also a main product of sugar-based fermentation carried out by Klebsiella pneumoniae.In this study,we investigated the use of salting-out extraction(SOE) that employed a K2HPO4/ethanol system consisting of 21% ethanol and 17% K2HPO4(mass fraction) to separate 2,3-butanediol from the viscous Jerusalem artichoke-based fermentation broth.After SOE,about 98% of solid matters was removed,and the viscosity decreased from 72.5 mPa s in the original fermentation broth to 4.4 mPa s in the top phase.The partition coefficient and yield of 2,3-butanediol reached 13.4 and 99%,respectively,and 89% of soluble proteins was removed from the broth.The results showed that SOE is an efficient way for isolating 2,3-BD from a highly viscous fermentation broth by removing much of the solid matters within the broth.
基金Supported by Research Funds from Chinese Education Department (2003406)Bureau of Science and Technology of Jiangsu Province (BG2006025)
文摘A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.
文摘The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)4]were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO(or TPA)with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.
基金This work was authored by Alliance for Sustainable Energy,LLC,the Manager and Operator of the National Renewable Energy Laboratory for the U.S.Department of Energy(DOE)under Contract No.DE-AC36-08GO28308Funding provided by U.S.Department of Energy Office of Energy Efficiency and Renewable Energy,Bioenergy Technologies Of-fice(BETO)Funding for YJB was provided by the Center for Bioenergy Innovation(CBI),a U.S.Department of Energy Bioenergy Research Cen-ter supported by the Office of Biological and Environmental Research in the DOE Office of Science.
文摘The decarbonization of the chemical industry and a shift toward circular economies because of high global CO_(2) emissions make CO_(2) an attractive feedstock for manufacturing chemicals.Moreover,H_(2) is a low-cost and carbon-free reductant because technologies such as solar-driven electrolysis and supercritical water(scH_(2)O) gasification enable sustainable production of molecular hydrogen(H_(2)).We review the recent advances in engineering Ralsto-nia eutropha,the representative species of“Knallgas”bacteria,for utilizing CO_(2) and H_(2) to autotrophically produce 2,3-butanediol(2,3-BDO).This assessment is focused on state-of-the-art approaches for splitting H_(2) to supply en-ergy in the form of ATP and NADH to power cellular reactions and employing the Calvin-Benson-Bassham cycle for CO_(2) fixation.Major challenges and opportunities for application and future perspectives are discussed in the context of developing other promising CO_(2) and H_(2)-utilizing microorganisms,exemplified by Zymomonas mobilis.
