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 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
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
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 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
生物传感器已经成为实时监测特定小分子和精确控制生物系统中基因表达的强大工具。用于1,4-丁二胺生物合成的高通量传感器可以极大地提高1,4-丁二胺高产菌株的筛选效率。为研究调整生物传感器特性的策略,本研究开发了一种以转录调节因子...生物传感器已经成为实时监测特定小分子和精确控制生物系统中基因表达的强大工具。用于1,4-丁二胺生物合成的高通量传感器可以极大地提高1,4-丁二胺高产菌株的筛选效率。为研究调整生物传感器特性的策略,本研究开发了一种以转录调节因子PuuR为基础的1,4-丁二胺生物传感器,其同源的操作子puuO被组装在大肠杆菌组成型启动子PgapA中,以控制下游的高能绿色荧光蛋白(superfolder green fluorescent protein,sfGFP)作为报告蛋白表达。最终该传感器在1,4-丁二胺浓度处于0–50 mmol/L时GFP/OD600值与1,4-丁二胺浓度之间能稳定地表现出线性关系。本研究采用大肠杆菌基因组中不同强度的启动子对1,4-丁二胺生物传感器进行分子改造,探究并改进基于PuuR的1,4-丁二胺生物传感器的功能性质,为高通量筛选高产1,4-丁二胺的工程菌株奠定了基础。展开更多
The Shanxi Sanwei Group Co., Ltd. intends to invest around 820 million RMB in the construction of a 9-kt/a coal gasifica-tion unit and a 30 kt/a polytetrahydrofuran expansion project,
The Shaanxi Bidiou Chemical Company, Ltd. signed with the American Frontech Company a contract on licensing by the American Company the technology to the 30 kt/a 1,4 butanediol （BDO） project. This project is the fir...The Shaanxi Bidiou Chemical Company, Ltd. signed with the American Frontech Company a contract on licensing by the American Company the technology to the 30 kt/a 1,4 butanediol （BDO） project. This project is the first BDO project in Shaanxi province constructed by the Shaanxi Bidiou Chemical Company using the existing methanol and hydrogen as the feedstocks provided by Shaanhua Chemical Fertilizer Company, Ltd.展开更多
The foundation stone laying ceremony for the 25 kt/a 1,4-butanediol project, in which Sichuan Tianhua Company Ltd.,Luzhou Gas Chemicals Group Company Ltd., Sichuan Chemical Company Ltd., Sichuan Investment Holdings Ltd.
The Davy Process Technology （DPT） Company in January 2007 had transferred the technology for production of 1,4- butandiol to two Chinese companies. The first one is the Blue Star Chemical ＆ New Material Stock Co., ...The Davy Process Technology （DPT） Company in January 2007 had transferred the technology for production of 1,4- butandiol to two Chinese companies. The first one is the Blue Star Chemical ＆ New Material Stock Co., Ltd., which will construct a 55 kt/a 1,4-butandiol unit in Nanjing, using maleic anhydride as the starting material to manufacture 1,4- butandiol and tetrahydrofuran by means of the ester hydrogenation technique licensed by DPT. The feedstock needed by this project will be provided by local producer and this unit is scheduled to come on stream by the fourth quarter of 2008. The second licensee is the Shanxi Sanwei Group, which will construct a 70 kt/a 1,4-butandiol unit in Hongtong county using the similar technology to manufacture 1,4-butandiol and g-butyrolactone. The starting material-maleic anhydride-will be sourced from the nearby producer, and construction of this project is slated to be completed by the fourth quarter of 2007.展开更多
An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion ...An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.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.
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%.
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 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.
文摘生物传感器已经成为实时监测特定小分子和精确控制生物系统中基因表达的强大工具。用于1,4-丁二胺生物合成的高通量传感器可以极大地提高1,4-丁二胺高产菌株的筛选效率。为研究调整生物传感器特性的策略,本研究开发了一种以转录调节因子PuuR为基础的1,4-丁二胺生物传感器,其同源的操作子puuO被组装在大肠杆菌组成型启动子PgapA中,以控制下游的高能绿色荧光蛋白(superfolder green fluorescent protein,sfGFP)作为报告蛋白表达。最终该传感器在1,4-丁二胺浓度处于0–50 mmol/L时GFP/OD600值与1,4-丁二胺浓度之间能稳定地表现出线性关系。本研究采用大肠杆菌基因组中不同强度的启动子对1,4-丁二胺生物传感器进行分子改造,探究并改进基于PuuR的1,4-丁二胺生物传感器的功能性质,为高通量筛选高产1,4-丁二胺的工程菌株奠定了基础。
文摘The Shanxi Sanwei Group Co., Ltd. intends to invest around 820 million RMB in the construction of a 9-kt/a coal gasifica-tion unit and a 30 kt/a polytetrahydrofuran expansion project,
文摘The Shaanxi Bidiou Chemical Company, Ltd. signed with the American Frontech Company a contract on licensing by the American Company the technology to the 30 kt/a 1,4 butanediol （BDO） project. This project is the first BDO project in Shaanxi province constructed by the Shaanxi Bidiou Chemical Company using the existing methanol and hydrogen as the feedstocks provided by Shaanhua Chemical Fertilizer Company, Ltd.
文摘The foundation stone laying ceremony for the 25 kt/a 1,4-butanediol project, in which Sichuan Tianhua Company Ltd.,Luzhou Gas Chemicals Group Company Ltd., Sichuan Chemical Company Ltd., Sichuan Investment Holdings Ltd.
文摘The Davy Process Technology （DPT） Company in January 2007 had transferred the technology for production of 1,4- butandiol to two Chinese companies. The first one is the Blue Star Chemical ＆ New Material Stock Co., Ltd., which will construct a 55 kt/a 1,4-butandiol unit in Nanjing, using maleic anhydride as the starting material to manufacture 1,4- butandiol and tetrahydrofuran by means of the ester hydrogenation technique licensed by DPT. The feedstock needed by this project will be provided by local producer and this unit is scheduled to come on stream by the fourth quarter of 2008. The second licensee is the Shanxi Sanwei Group, which will construct a 70 kt/a 1,4-butandiol unit in Hongtong county using the similar technology to manufacture 1,4-butandiol and g-butyrolactone. The starting material-maleic anhydride-will be sourced from the nearby producer, and construction of this project is slated to be completed by the fourth quarter of 2007.
文摘An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.
