In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene p...In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.展开更多
High-pressure vapor-liquid equilibrium data for the binary systems of methyl propionate＋carbon dioxide and propyl propionate＋carbon dioxide were measured at pressure from 1.00 MPa to 12.00 MPa and temperature in the...High-pressure vapor-liquid equilibrium data for the binary systems of methyl propionate＋carbon dioxide and propyl propionate＋carbon dioxide were measured at pressure from 1.00 MPa to 12.00 MPa and temperature in the range from 313 K to 373 K. Experimental results were correlated with the Peng-Robinson equation of state with the two-parameter van der Waals mixing rule. At the same time, the Henry＇s coefficient, partial molar enthalpy change and partial molar entropy change of CO2 during dissolution at different temperature were also calculated.展开更多
Four empirical models are tested for fitting the T-y-x equilibrium data of ethanol-water mixture by minimizing the Root Mean Square （RMS） between equilibrium data and theoretical points. The total pressure of the co...Four empirical models are tested for fitting the T-y-x equilibrium data of ethanol-water mixture by minimizing the Root Mean Square （RMS） between equilibrium data and theoretical points. The total pressure of the correspondent data is 101.3 kPa. All models parameters are also identified. The study suggests that NRTL model fits the equilibrium data best with RMS = 0.4 %.展开更多
New liquid-liquid equilibrium data for polyethylene glycol （PEG） 3000 ＋ CHO2K ＋ H20 systems were measured at 298.15 K and pH values of 7.95, 8.40 and 9.98. It was found that an increase in pH caused the binodal cu...New liquid-liquid equilibrium data for polyethylene glycol （PEG） 3000 ＋ CHO2K ＋ H20 systems were measured at 298.15 K and pH values of 7.95, 8.40 and 9.98. It was found that an increase in pH caused the binodal curve to be displaced downward and the two-phase region to expand. Accordingly, the binodal curve was adjusted to the Pirdashti equation and the tie-line compositions were correlated using the Othmer-Tobias, Bancroft and Hand equations. The study measured the refractive index and densities of several homogeneous binary and ternary solutions. The solutions were used for calibration within a range of 0% to 30% of the mass of the PEG and potassium formate. The density and refractive index data show a linear variation with the mass fraction of the polymer and the salt. The effect of pH on the binodal, tie-line lengths （TLL） and slope of the tie-line （STL） in the systems was exam- ined. It was found that an increase in pH increased the TLL and decreased the STL It was observed that the density of the aqueous two-phase system was influenced by the TLL The difference in density between phases （△p） increased as the TLL and pH increased. It was found that the TLL and Ap showed a linear relationship. The effective excluded volume （EEV） of the PEG was obtained and it was found that EEV also increased as the pH increased.展开更多
Although coal swelling/shrinking during coal seam gas extraction has been studied for decades,its impacts on the evolution of permeability are still not well understood.This has long been recognized,but no satisfactor...Although coal swelling/shrinking during coal seam gas extraction has been studied for decades,its impacts on the evolution of permeability are still not well understood.This has long been recognized,but no satisfactory solutions have been found.In previous studies,it is normally assumed that the matrix swelling/shrinking strain can be split between the fracture and the bulk coal and that the splitting coefficient remains unchanged during gas sorption.In this study,we defined the fracture strain as a function of permeability change ratio and back-calculated the fracture strains at different states.In the equilibrium state,the gas pressure is steady within the coal;in the non-equilibrium state,the gas pressure changes with time.For equilibrium states,the back-calculated fracture strains are extremely large and may be physically impossible in some case.For non-equilibrium states,two experiments were conducted:one for a natural coal sample and the other for a reconstructed one.For the fractured coal,the evolution of permeability is primarily controlled by the transition of coal fracture strain or permeability from local matrix swelling effect to global effect.For the reconstituted coal,the evolution of pore strain or permeability is primarily controlled by the global effect.展开更多
Vapor-liquid equilibrium data for the binary systems of ethyl acetate + methanol,ethyl acetate + ethanol and ethyl acetate + 1-propanol at 0.3 MPa were determined.The experimental data were verified with the point-to-...Vapor-liquid equilibrium data for the binary systems of ethyl acetate + methanol,ethyl acetate + ethanol and ethyl acetate + 1-propanol at 0.3 MPa were determined.The experimental data were verified with the point-to-point test of van Ness(1973).All these systems present an azeotropic point at 0.3 MPa that increases in ester composition for longer alcohol chains.The UNIFAC in different versions and ASOG prediction models were applied.展开更多
基金supported by the National Natural Science Foundation of China(22178190)。
文摘In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.
文摘High-pressure vapor-liquid equilibrium data for the binary systems of methyl propionate＋carbon dioxide and propyl propionate＋carbon dioxide were measured at pressure from 1.00 MPa to 12.00 MPa and temperature in the range from 313 K to 373 K. Experimental results were correlated with the Peng-Robinson equation of state with the two-parameter van der Waals mixing rule. At the same time, the Henry＇s coefficient, partial molar enthalpy change and partial molar entropy change of CO2 during dissolution at different temperature were also calculated.
文摘Four empirical models are tested for fitting the T-y-x equilibrium data of ethanol-water mixture by minimizing the Root Mean Square （RMS） between equilibrium data and theoretical points. The total pressure of the correspondent data is 101.3 kPa. All models parameters are also identified. The study suggests that NRTL model fits the equilibrium data best with RMS = 0.4 %.
文摘New liquid-liquid equilibrium data for polyethylene glycol （PEG） 3000 ＋ CHO2K ＋ H20 systems were measured at 298.15 K and pH values of 7.95, 8.40 and 9.98. It was found that an increase in pH caused the binodal curve to be displaced downward and the two-phase region to expand. Accordingly, the binodal curve was adjusted to the Pirdashti equation and the tie-line compositions were correlated using the Othmer-Tobias, Bancroft and Hand equations. The study measured the refractive index and densities of several homogeneous binary and ternary solutions. The solutions were used for calibration within a range of 0% to 30% of the mass of the PEG and potassium formate. The density and refractive index data show a linear variation with the mass fraction of the polymer and the salt. The effect of pH on the binodal, tie-line lengths （TLL） and slope of the tie-line （STL） in the systems was exam- ined. It was found that an increase in pH increased the TLL and decreased the STL It was observed that the density of the aqueous two-phase system was influenced by the TLL The difference in density between phases （△p） increased as the TLL and pH increased. It was found that the TLL and Ap showed a linear relationship. The effective excluded volume （EEV） of the PEG was obtained and it was found that EEV also increased as the pH increased.
基金supported by the State Key Research Development Program of China(Grant No.2017YFC0804203)Key Research Program of Frontier Sciences,Chinese Academy of Sciences(Grant No.QYZDB-SSW-DQC029)the Australian Research Council under Grant DP200101293.
文摘Although coal swelling/shrinking during coal seam gas extraction has been studied for decades,its impacts on the evolution of permeability are still not well understood.This has long been recognized,but no satisfactory solutions have been found.In previous studies,it is normally assumed that the matrix swelling/shrinking strain can be split between the fracture and the bulk coal and that the splitting coefficient remains unchanged during gas sorption.In this study,we defined the fracture strain as a function of permeability change ratio and back-calculated the fracture strains at different states.In the equilibrium state,the gas pressure is steady within the coal;in the non-equilibrium state,the gas pressure changes with time.For equilibrium states,the back-calculated fracture strains are extremely large and may be physically impossible in some case.For non-equilibrium states,two experiments were conducted:one for a natural coal sample and the other for a reconstructed one.For the fractured coal,the evolution of permeability is primarily controlled by the transition of coal fracture strain or permeability from local matrix swelling effect to global effect.For the reconstituted coal,the evolution of pore strain or permeability is primarily controlled by the global effect.
文摘Vapor-liquid equilibrium data for the binary systems of ethyl acetate + methanol,ethyl acetate + ethanol and ethyl acetate + 1-propanol at 0.3 MPa were determined.The experimental data were verified with the point-to-point test of van Ness(1973).All these systems present an azeotropic point at 0.3 MPa that increases in ester composition for longer alcohol chains.The UNIFAC in different versions and ASOG prediction models were applied.
