The extraction conditions of aluminum by the disproportionation process of A1C1 in vacuum were investigated using alumina and graphite as raw materials, including reaction temperature, pre-reaction and condenser struc...The extraction conditions of aluminum by the disproportionation process of A1C1 in vacuum were investigated using alumina and graphite as raw materials, including reaction temperature, pre-reaction and condenser structure. The results show that the extent of the reaction between alumina and carbon increases with increasing reaction temperature at 1643-1843 K; however, the extraction rate of aluminum increases firstly, and reaches the highest at 1743 K, and then decreases with rise in reaction temperature. The pre-reaction of alumina and carbon increases the extraction rate of aluminum. The impurities C, AlaC3 and A1203 in the aluminum product are reduced with reducing the contact surface of the aluminum with CO and with decreasing the condensation temperature, depending on the structure of the condenser.展开更多
以年总操作费用(TAC)、CO_(2)排放量(GEC)和精馏塔热力学效率(η)为目标,提出了基于粒子群算法(PSO)的优化方法,并将该方法应用于三氯氢硅(SiHCl_(3),TCS)歧化制取硅烷(SiH_(4),MS)反应精馏塔的优化设计。在Aspen Plus V7中建立流程进...以年总操作费用(TAC)、CO_(2)排放量(GEC)和精馏塔热力学效率(η)为目标,提出了基于粒子群算法(PSO)的优化方法,并将该方法应用于三氯氢硅(SiHCl_(3),TCS)歧化制取硅烷(SiH_(4),MS)反应精馏塔的优化设计。在Aspen Plus V7中建立流程进行模拟,使用平衡级模型,对RD-2IC(带有2个中间冷凝器的反应精馏塔)和高压分离塔的双塔构型建立稳态模型,考察了塔压、塔板数、回流比、进料位置、反应段持液量和中间冷凝器气相分率等影响因素,初步确定了各参数的最优值,为进一步深度优化提供了初值和可行域。结果表明,与单因素灵敏度分析结果相比,PSO算法优化后的TAC节省了54.50%、GEC减少了38.13%、η提高了22.55%。展开更多
The formation conditions of C, Al4C3 and Al2O3 in the Al Cl disproportionation process in vacuum to produce aluminum was investigated by thermodynamics analysis. It is demonstrated that the required temperatures for t...The formation conditions of C, Al4C3 and Al2O3 in the Al Cl disproportionation process in vacuum to produce aluminum was investigated by thermodynamics analysis. It is demonstrated that the required temperatures for the reactions to form these impurities, the disproportionation of CO and the reactions of metallic aluminum with CO, decrease with decreasing pressure. The lg pCO-1/T diagram of metallic aluminum-CO system agrees with the experimental results, indicating that the reaction rate is very high and this system in vacuum is approximately in equilibrium; therefore, the equilibrium diagram can be used to predict the possible reactions in this system in vacuum.展开更多
Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semicond...Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.展开更多
Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS （tetraethyl orthosilicate）....Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS （tetraethyl orthosilicate）.Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM （scanning electron microscopy）.The conversion of toluene and para-xylene selectivity were influenced remarkably by the n（SiO2）/n（Al2O3） ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.展开更多
The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. Th...The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3（g） reacts with Al2O（g） or Al（g） generated from the carbothermal reduction of alumina to form AlCl（g）, and the AlCl（g） disproportionates to aluminum and AlCl3（g） at a lower temperature and the reaction rate of AlCl（g） reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl（g） disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.展开更多
The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction me...The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.展开更多
The selective synthesis of p-diethylbenzene （p-DEB） by disproportionation of ethylbenzene （EB） in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst...The selective synthesis of p-diethylbenzene （p-DEB） by disproportionation of ethylbenzene （EB） in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst. The industrial feed having different compositions of ethylbenzene and xylene isomers was used for the experimentation. Hence, they were expected to hinder the movement of reactant molecules both on the external surface and within the zeolite channels. It was observed that irrespective of the different feed compositions the concentration of the xylene isomers was intact in the product. There is no other byproducts formation like para-ethylmethyl benzene. The effects of varying the concentration of aromatic compounds in the feed on ethylbenzene conversion and product distribution over the parent and modified H-ZSM-5 catalyst have been discussed. Ethylbenzene disproportionation reaction follows the pseudo first order reaction with an activation energy of 8.6 kcal/mol.展开更多
A new method of synthesizing single-component molecular conductor [Ni(dmit)2] by the reaction 2(Me4N)[Ni(dmit)2]2 [Ni(dmit)2] + (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2] exhibits a semiconductive behavior above 167...A new method of synthesizing single-component molecular conductor [Ni(dmit)2] by the reaction 2(Me4N)[Ni(dmit)2]2 [Ni(dmit)2] + (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2] exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.展开更多
A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourl...A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourly space velocity(WHSV)into account is incorporated into the model,which reasonably accounts for the loss in activity because of coke deposition on the surface of catalyst during long-term operation.The kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza- tion method.Sets of plant data at different operating conditions are applied to make sure validation of the model and the results show a good agreement between the model predictions and plant observations.The simulation analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail,giv- ing the guidance to select suitable operating conditions.展开更多
Mechanically activated disproportionation of Nd 12 Fe 82 B 6 alloy by ball milling in hydrogen atmosphere was experimentally investigated. The aspects of thermodynamics and kinetics for the mechanically activated disp...Mechanically activated disproportionation of Nd 12 Fe 82 B 6 alloy by ball milling in hydrogen atmosphere was experimentally investigated. The aspects of thermodynamics and kinetics for the mechanically activated disproportionation of the NdFeB alloy were discussed. Both the evolution of the disproportionation reaction and the corresponding microstructure change of the alloy during milling were characterized by X ray diffraction (XRD) analysis. The results show that the matrix phase Nd 2Fe 14 B of the as cast Nd 12 Fe 82 B 6 alloy can be disproportionated into a mixture of Nd hydride (H 5Nd 2), FeB/Fe 2B, and α Fe, by ball milling under hydrogen pressure of 0.2 MPa. The as disproportionated phases are of the size about 20 nm, suggesting that ball milling in hydrogen is an effective route for low temperature disproportionation processing of the NdFeB alloy to ensure a full nano structured as disproportionated microstructure. This is the basis for synthesizing Nd 2Fe 14 B/ α Fe nano composites with magnetic exchange coupling effect by subsequent desorption recombination processing.展开更多
基金Project(51264023)supported by the National Natural Science Foundation of ChinaProject(KKSY201207016)supported by Yunnan Provincial Science and Technology Department,China
文摘The extraction conditions of aluminum by the disproportionation process of A1C1 in vacuum were investigated using alumina and graphite as raw materials, including reaction temperature, pre-reaction and condenser structure. The results show that the extent of the reaction between alumina and carbon increases with increasing reaction temperature at 1643-1843 K; however, the extraction rate of aluminum increases firstly, and reaches the highest at 1743 K, and then decreases with rise in reaction temperature. The pre-reaction of alumina and carbon increases the extraction rate of aluminum. The impurities C, AlaC3 and A1203 in the aluminum product are reduced with reducing the contact surface of the aluminum with CO and with decreasing the condensation temperature, depending on the structure of the condenser.
文摘以年总操作费用(TAC)、CO_(2)排放量(GEC)和精馏塔热力学效率(η)为目标,提出了基于粒子群算法(PSO)的优化方法,并将该方法应用于三氯氢硅(SiHCl_(3),TCS)歧化制取硅烷(SiH_(4),MS)反应精馏塔的优化设计。在Aspen Plus V7中建立流程进行模拟,使用平衡级模型,对RD-2IC(带有2个中间冷凝器的反应精馏塔)和高压分离塔的双塔构型建立稳态模型,考察了塔压、塔板数、回流比、进料位置、反应段持液量和中间冷凝器气相分率等影响因素,初步确定了各参数的最优值,为进一步深度优化提供了初值和可行域。结果表明,与单因素灵敏度分析结果相比,PSO算法优化后的TAC节省了54.50%、GEC减少了38.13%、η提高了22.55%。
基金Project(51364020)supported by the National Natural Science Foundation of China
文摘The formation conditions of C, Al4C3 and Al2O3 in the Al Cl disproportionation process in vacuum to produce aluminum was investigated by thermodynamics analysis. It is demonstrated that the required temperatures for the reactions to form these impurities, the disproportionation of CO and the reactions of metallic aluminum with CO, decrease with decreasing pressure. The lg pCO-1/T diagram of metallic aluminum-CO system agrees with the experimental results, indicating that the reaction rate is very high and this system in vacuum is approximately in equilibrium; therefore, the equilibrium diagram can be used to predict the possible reactions in this system in vacuum.
基金financially supported by the National Key Research and Development Program of China (No.2021YFA0718900)the National Natural Science Foundation of China (No.62074014)the Xiaomi Scholar project。
文摘Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.
基金Supported by the Key Natural Science Foundation for Universities of Jiangsu Province（06KJA53012） the National Natural Science Foundation of China（20776069 20976084）
文摘Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS （tetraethyl orthosilicate）.Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM （scanning electron microscopy）.The conversion of toluene and para-xylene selectivity were influenced remarkably by the n（SiO2）/n（Al2O3） ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.
基金Project (u0837604) supported by the Joint Funds of the National Natural Science Foundation of China and Yunnan Province
文摘The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3（g） reacts with Al2O（g） or Al（g） generated from the carbothermal reduction of alumina to form AlCl（g）, and the AlCl（g） disproportionates to aluminum and AlCl3（g） at a lower temperature and the reaction rate of AlCl（g） reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl（g） disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.
基金Supported by the Joint Funds of the National Natural Science Foundation of China(No.u0837604) the Funds for Applied Basic Researches of Yunnan Province(No.2010CD022)
文摘The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.
文摘The selective synthesis of p-diethylbenzene （p-DEB） by disproportionation of ethylbenzene （EB） in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst. The industrial feed having different compositions of ethylbenzene and xylene isomers was used for the experimentation. Hence, they were expected to hinder the movement of reactant molecules both on the external surface and within the zeolite channels. It was observed that irrespective of the different feed compositions the concentration of the xylene isomers was intact in the product. There is no other byproducts formation like para-ethylmethyl benzene. The effects of varying the concentration of aromatic compounds in the feed on ethylbenzene conversion and product distribution over the parent and modified H-ZSM-5 catalyst have been discussed. Ethylbenzene disproportionation reaction follows the pseudo first order reaction with an activation energy of 8.6 kcal/mol.
基金supported by the National Natural Science Foundation of China(No.20172034)Foundation for Univemity Key Teacher by Ministry of Educationthe grant for the State Key Program of China.
文摘A new method of synthesizing single-component molecular conductor [Ni(dmit)2] by the reaction 2(Me4N)[Ni(dmit)2]2 [Ni(dmit)2] + (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2] exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.
基金Supported by the National＇Creative Research Groups Science Foundation of China （No.60421002） and priority supported financially by ＂the New Century 151 Talent Project＂ of Zhejiang Province.
文摘A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourly space velocity(WHSV)into account is incorporated into the model,which reasonably accounts for the loss in activity because of coke deposition on the surface of catalyst during long-term operation.The kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza- tion method.Sets of plant data at different operating conditions are applied to make sure validation of the model and the results show a good agreement between the model predictions and plant observations.The simulation analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail,giv- ing the guidance to select suitable operating conditions.
文摘Mechanically activated disproportionation of Nd 12 Fe 82 B 6 alloy by ball milling in hydrogen atmosphere was experimentally investigated. The aspects of thermodynamics and kinetics for the mechanically activated disproportionation of the NdFeB alloy were discussed. Both the evolution of the disproportionation reaction and the corresponding microstructure change of the alloy during milling were characterized by X ray diffraction (XRD) analysis. The results show that the matrix phase Nd 2Fe 14 B of the as cast Nd 12 Fe 82 B 6 alloy can be disproportionated into a mixture of Nd hydride (H 5Nd 2), FeB/Fe 2B, and α Fe, by ball milling under hydrogen pressure of 0.2 MPa. The as disproportionated phases are of the size about 20 nm, suggesting that ball milling in hydrogen is an effective route for low temperature disproportionation processing of the NdFeB alloy to ensure a full nano structured as disproportionated microstructure. This is the basis for synthesizing Nd 2Fe 14 B/ α Fe nano composites with magnetic exchange coupling effect by subsequent desorption recombination processing.
