Benzene(BEN)and cyclohexane(CYH),which have very close boiling points and a binary azeotrope,are the most difficult binary components in the separation of aromatic and non-aromatic hydrocarbons.This study further expl...Benzene(BEN)and cyclohexane(CYH),which have very close boiling points and a binary azeotrope,are the most difficult binary components in the separation of aromatic and non-aromatic hydrocarbons.This study further explored the separation mechanism and industrial application prospects of BEN+CYH mixtures separated by a dicationic ionic liquid(DIL)[C_(5)(MIM)_(2)][NTf_(2)]_(2) based on experimental research.The calculation results of the Conductor-like Screening model Segment Activity Coefficient(COSMO-SAC)model show that selectivity and solvent capacity of the DIL are significantly improved.The effects of different anions and cations on the micro-structure distribution and diffusion behavior of BEN+CYH system were investigated by quantum chemistry(QC)calculations and molecular dynamics(MD)simulations.The results indicate that the anion[NTf_(2)]_(2)has low polarity,uniform charge distribution,and a dual role of hydrogen bonding andπ-πbonding,and the cation[C_(5)(MIM)_(2)]^(2+) has stronger interaction with BEN and higher selectivity than conventional cations.The liquid-liquid extraction and extractive distillation(LLE-ED)process using an optimized 65 mol/mol DIL+35 mol/mol H_(2)O mixed solution as the extractant was proposed,which solved the problem of low product purity in the LLE process and high energy consumption in the ED process.Under the best operating conditions,the purity of CYH product was 99.9%,the purity of BEN product was 99.6%,the recovery rate of BEN reached 99.9%,and the recovery rate of DIL reached 99.9%.The heat-integrated LLE-ED process reduced total annual cost by 21.6%,and reduced CO_(2) emissions by 48.0%,which has broad industrial application prospects.展开更多
P(AA-MA) copolymers composed of acrylic acid and methyl acrylate with different molecular weights and sequence structures were synthesized by combination of ATRP and selective hydrolysis. These copolymers were used ...P(AA-MA) copolymers composed of acrylic acid and methyl acrylate with different molecular weights and sequence structures were synthesized by combination of ATRP and selective hydrolysis. These copolymers were used as membrane materials to separate benzene/cyclohexane mixture by pervaporation. The effects of molecular weight and sequence structure of the copolymers on the pervaporation performance were investigated in detail. For the random copolymers, the permeate flux decreased rapidly with the increasing of molecular weight. The separation factor was also influenced by the molecular weight, which was changed from no selectivity to cyclohexane selectivity with increasing the molecular weight. Contrarily, the block copolymer membrane showed good benzene selectivity with separation factor of 4.3 and permeate flux of 157 g/(m2h) to 50 wt% benzene/cyclohexane mixture.展开更多
The viscosities, η, and ultrasonic speeds, u, of pure benzene, triethylamine, (TEA) tributylamine, (TBA), and those of their binary mixtures, with benzene as common component, covering the whole composition range...The viscosities, η, and ultrasonic speeds, u, of pure benzene, triethylamine, (TEA) tributylamine, (TBA), and those of their binary mixtures, with benzene as common component, covering the whole composition range have been measured at 278.15 K, 283.15 K, 288.15 K, 293.15 K, 298.15 K, 303.15 K, 308.15 K, 313.15 K, and 318.15 K. From the experimental data the deviations in viscosity, △η, deviations in Gibbs free energy, AG, deviations in ultrasonic speed, △u, deviations in entropies, △S^*, and deviations in enthalpies, △H^*, of activation of viscous flow have been determined. The sign and magnitude of these parameters were found to be sensitive towards interactions prevailing in the studied systems. Further, the excess molar volumes, VE, were calculated using data for the binary mixtures. Moreover, theoretical values of viscosities and ultrasonic speeds of the binary mixtures were calculated using different empirical relations and theories. The results were in experimental and theoretical values. discussed in terms of average deviations (AD)展开更多
基金This work is financially supported by the National Key R&D Program of China(2017YFB0602401).
文摘Benzene(BEN)and cyclohexane(CYH),which have very close boiling points and a binary azeotrope,are the most difficult binary components in the separation of aromatic and non-aromatic hydrocarbons.This study further explored the separation mechanism and industrial application prospects of BEN+CYH mixtures separated by a dicationic ionic liquid(DIL)[C_(5)(MIM)_(2)][NTf_(2)]_(2) based on experimental research.The calculation results of the Conductor-like Screening model Segment Activity Coefficient(COSMO-SAC)model show that selectivity and solvent capacity of the DIL are significantly improved.The effects of different anions and cations on the micro-structure distribution and diffusion behavior of BEN+CYH system were investigated by quantum chemistry(QC)calculations and molecular dynamics(MD)simulations.The results indicate that the anion[NTf_(2)]_(2)has low polarity,uniform charge distribution,and a dual role of hydrogen bonding andπ-πbonding,and the cation[C_(5)(MIM)_(2)]^(2+) has stronger interaction with BEN and higher selectivity than conventional cations.The liquid-liquid extraction and extractive distillation(LLE-ED)process using an optimized 65 mol/mol DIL+35 mol/mol H_(2)O mixed solution as the extractant was proposed,which solved the problem of low product purity in the LLE process and high energy consumption in the ED process.Under the best operating conditions,the purity of CYH product was 99.9%,the purity of BEN product was 99.6%,the recovery rate of BEN reached 99.9%,and the recovery rate of DIL reached 99.9%.The heat-integrated LLE-ED process reduced total annual cost by 21.6%,and reduced CO_(2) emissions by 48.0%,which has broad industrial application prospects.
基金supported by the National Natural Science Foundation of China(No.20704036)
文摘P(AA-MA) copolymers composed of acrylic acid and methyl acrylate with different molecular weights and sequence structures were synthesized by combination of ATRP and selective hydrolysis. These copolymers were used as membrane materials to separate benzene/cyclohexane mixture by pervaporation. The effects of molecular weight and sequence structure of the copolymers on the pervaporation performance were investigated in detail. For the random copolymers, the permeate flux decreased rapidly with the increasing of molecular weight. The separation factor was also influenced by the molecular weight, which was changed from no selectivity to cyclohexane selectivity with increasing the molecular weight. Contrarily, the block copolymer membrane showed good benzene selectivity with separation factor of 4.3 and permeate flux of 157 g/(m2h) to 50 wt% benzene/cyclohexane mixture.
文摘The viscosities, η, and ultrasonic speeds, u, of pure benzene, triethylamine, (TEA) tributylamine, (TBA), and those of their binary mixtures, with benzene as common component, covering the whole composition range have been measured at 278.15 K, 283.15 K, 288.15 K, 293.15 K, 298.15 K, 303.15 K, 308.15 K, 313.15 K, and 318.15 K. From the experimental data the deviations in viscosity, △η, deviations in Gibbs free energy, AG, deviations in ultrasonic speed, △u, deviations in entropies, △S^*, and deviations in enthalpies, △H^*, of activation of viscous flow have been determined. The sign and magnitude of these parameters were found to be sensitive towards interactions prevailing in the studied systems. Further, the excess molar volumes, VE, were calculated using data for the binary mixtures. Moreover, theoretical values of viscosities and ultrasonic speeds of the binary mixtures were calculated using different empirical relations and theories. The results were in experimental and theoretical values. discussed in terms of average deviations (AD)