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
In an equilibrium vessel,the solid-liquid equilibria(SLE) for three binary mixtures of phenyl salicylate with 1-butanol,2-butanol,and 2-methyl-1-propanol,respectively,have been measured from 283.15 K to the melting te...In an equilibrium vessel,the solid-liquid equilibria(SLE) for three binary mixtures of phenyl salicylate with 1-butanol,2-butanol,and 2-methyl-1-propanol,respectively,have been measured from 283.15 K to the melting temperature of the solute using a method in which an excess amount of solute was equilibrated with the alcohol solution.The liquid concentrations of the investigated phenyl salicylate in the saturated solution were analyzed by UV spectrometry.Activity coefficients for phenyl salicylate have been calculated by means of the Wilson,NRTL,and UNIQUAC equations and with them were correlated solubility data that were compared with the experimental ones.The best correlation of the solubility data has been obtained by the Wilson equation by which the average root-mean-square deviation of temperature for the three systems is 1.03 K.展开更多
The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robi...The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robinson equation, a traditional cubic equation of state widely employed in chemical industries, as well as with the perturbed-chain statistical associating fluid PC-SAFT theory of Gross-Sadowski. By correlation of the binary inter- action parameters of these equations, the measured vapor-liquid equilibrium data can be accurately predicted. Thus, this work shows that these models are able to represent the experimental data for systems with associating comoounds via hydrogen bonding.展开更多
Isobaric vapor-liquid equilibrium(VLE) data for acetic acid + sec-butyl acetate and water+acetic acid + sec-butyl acetate systems were determined at 101.3 kPa using a modified Rose type.The nonideality of the vapor ph...Isobaric vapor-liquid equilibrium(VLE) data for acetic acid + sec-butyl acetate and water+acetic acid + sec-butyl acetate systems were determined at 101.3 kPa using a modified Rose type.The nonideality of the vapor phase caused by the association of the acetic acid was corrected by the chemical theory and Hayden-O'Connell method.Thermodynamic consistency was tested for the binary VLE data.The experimental data were correlated successfully with the Non-Random Two Liquids(NRTL) model.The Root Mean Square Deviation(RMSD) of the ternary system was 0.0038.The saturation vapor pressure of sec-butyl acetate at 329 to 385 K was measured by means of two connected equilibrium cells.The vapor pressures of water and sec-butyl acetate were correlated with the Antoine equation.The binary interaction parameters and the ternary VLE data were obtained from this work.展开更多
In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model f...In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.展开更多
Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance....Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance. Firstly, thermodynamic analysis shows that the reaction is exothermic and a high equilibrium conversion of TDA is expected due to its large reaction equilibrium constant. Secondly, under the suitable reaction conditions, 130 °C, 7 h, and molar ratio of TDA/zinc acetate/urea/sulfolane 1/0.05/3.5/10, TDA conversion is 54.3%, and TBU yield and selectivity are 39.8% and 73.3% respectively. Lastly, the synthesis of TBU is a 1st order reaction with respect to TDA and the reaction kinetics model is established. This work will provide useful information for commercializing the urea route to toluene-2,4-dicarbamate (TDC).展开更多
A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage efficiencies or height equivalent to a theoretical ...A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage efficiencies or height equivalent to a theoretical plate (HETP) were entirely avoided by this model. The consistency of simulated results and experimental data in conversions and concentration of each component along a column indicates that the model predicts the actual process well. The influences of operating parameters on hydrolytic conversions, such as feed molar ratios, feed locations, feed and reflux rates, heights of reactive and stripping sections, were analyzed adequately by simulating calculations. A good operating mode was then obtained, which is helpful to the development of a new process.展开更多
Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure...Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure.It is shown that the solubilities of trans-1,2-cyclohexanediol in butyl acetate+water were affected greatly by the proportion of butyl acetate and water,and presented maximum value at given temperature.The UNIFAC model was used to correlate the experimental data.The average relative deviation(ARD)between experimental and calculated values is 3.03%.展开更多
A new dynamic ebulliometer is used to determine vapor-liquid equilibrium(VLE) data experimentally. In the equipment,both phases are recirculated. Its operation is a consequence of the Cotrell pump effect produced when...A new dynamic ebulliometer is used to determine vapor-liquid equilibrium(VLE) data experimentally. In the equipment,both phases are recirculated. Its operation is a consequence of the Cotrell pump effect produced when the mixture is heated in a double-walled inverted vessel. The reliability of the apparatus is tested with the mixtures studied previously by various authors. VLE data for the binary systems of methyl acetate + methanol and the methyl acetate + ethanol at 0.5 MPa are determined. The experimental data are confirmed with the point-to-point test of van Ness,applying the Fortran program of Frendslund et al. In addition,the experimental results are com-pared with the UNIFAC(including different versions) and ASOG prediction models.展开更多
The vapor-liquid equilibrium data of four binary systems (acetic acid +p-xylene, methyl acetate +n-propyl acetate, n-propyl acetate +p-xylene and methyl acetate +p-xylene) are measured at 101.33 kPa with Ellis equilib...The vapor-liquid equilibrium data of four binary systems (acetic acid +p-xylene, methyl acetate +n-propyl acetate, n-propyl acetate +p-xylene and methyl acetate +p-xylene) are measured at 101.33 kPa with Ellis equilibrium still, and then both the NRTL and UNIQUAC models are used in combination with the HOC model for correlating and estimating the vapor-liquid equilibrium of these four binary systems. The estimated binary VLE results using correlated parameters agree well with the measured data except the methyl acetate +p-xylene system which easily causes bumping and liquid rushing out of the sampling tap due to their dramatically different boiling points. The correlation results by NRTL and UNIQUAC models have little difference on the average absolute deviations of temperature and composition of vapor phase, and the results by NRTL model are slightly better than those by UNIQUAC model except for the methyl acetate +n-propyl acetate system, for which the latter gives more accurate correlations.展开更多
Liquid-liquid equilibrium (LLE) data for the ternary systemwater-ethanol-dimethyl succinate have been determined experimentallyat temperatures ranging from 298.15 to 318.15 K at 5 K intervals.Complete phase diagrams w...Liquid-liquid equilibrium (LLE) data for the ternary systemwater-ethanol-dimethyl succinate have been determined experimentallyat temperatures ranging from 298.15 to 318.15 K at 5 K intervals.Complete phase diagrams were obtained by determining solubility andthe tie-line data. Tie-line compositions were correlated byOthmer-Tobias method. The universal quasichemical functional groupactivity coefficient (UNIFAC) and modified UNIFAC methods were usedto predict the phase equilibrium in the system using the interactionparameters deter- Mined from experimental data between groups CH_3,CH_2, OH, CH_3 COO and H_2O.展开更多
The organic dissolvent (di-n-butyl phthalate) needs to be washed by water to recycle itself in the process of recovering maleic anhydride by organic dissolvent. The design and optimization of the extraction process ...The organic dissolvent (di-n-butyl phthalate) needs to be washed by water to recycle itself in the process of recovering maleic anhydride by organic dissolvent. The design and optimization of the extraction process require the distribution coefficients of the organic solutes, o-phthalic acid and trans-butenedioic in water and di-n-butyl phthalate, on which the extraction efficiency depends. In this study, the distribution coefficients of o-phthalic acid and trans-butenedioic in water and all-n-butyl phthalate(DBP) at 298.15 K, 318.15 K and 333.15 K were determined respectively by acid-alkali titration. The dissociation constants of o-phthalic acid and trans-butenedioic at those temperatures were obtained by fitting the measured hydrogen-ion concentrations and the known solute concentrations in the aqueous solution containing the two organic solutes. Then the distribution constants were calculated. Both the distribution coefficients and the distribution constants increase along with the temperature increasing. And the distribution coefficients at 333. 15 K are large enough to ensure the efficiency of extraction process. In addition, the mutual solubility of water and all-n-butyl phthalate at 298.1.5 K, 318. 1.5 K and 333. 15 K was also measured respectively by High Performance Liquid Chromatography and Karl Fischer Watertitration, which was not more than 0. 5%( mass fraction ).展开更多
The binary liquid-liquid equilibrium(LLE) data for salt-containing systems of 1-butanol+water+CaCl2, n-butyl acetate+water+CaCl2 and ethyl acetate+acetic acid+water+CaCl2 were determined and the salt effect was analyz...The binary liquid-liquid equilibrium(LLE) data for salt-containing systems of 1-butanol+water+CaCl2, n-butyl acetate+water+CaCl2 and ethyl acetate+acetic acid+water+CaCl2 were determined and the salt effect was analyzed. The results showed that an obvious salt effect could be identified for the systems of 1-butanol+water+CaCl2 and ethyl acetate+acetic acid+water.展开更多
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In an equilibrium vessel,the solid-liquid equilibria(SLE) for three binary mixtures of phenyl salicylate with 1-butanol,2-butanol,and 2-methyl-1-propanol,respectively,have been measured from 283.15 K to the melting temperature of the solute using a method in which an excess amount of solute was equilibrated with the alcohol solution.The liquid concentrations of the investigated phenyl salicylate in the saturated solution were analyzed by UV spectrometry.Activity coefficients for phenyl salicylate have been calculated by means of the Wilson,NRTL,and UNIQUAC equations and with them were correlated solubility data that were compared with the experimental ones.The best correlation of the solubility data has been obtained by the Wilson equation by which the average root-mean-square deviation of temperature for the three systems is 1.03 K.
文摘The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robinson equation, a traditional cubic equation of state widely employed in chemical industries, as well as with the perturbed-chain statistical associating fluid PC-SAFT theory of Gross-Sadowski. By correlation of the binary inter- action parameters of these equations, the measured vapor-liquid equilibrium data can be accurately predicted. Thus, this work shows that these models are able to represent the experimental data for systems with associating comoounds via hydrogen bonding.
基金Supported by the National Natural Science Foundation of China (21176049) and the Natural Science Foundation of Fujian Province (2012J01034).
文摘Isobaric vapor-liquid equilibrium(VLE) data for acetic acid + sec-butyl acetate and water+acetic acid + sec-butyl acetate systems were determined at 101.3 kPa using a modified Rose type.The nonideality of the vapor phase caused by the association of the acetic acid was corrected by the chemical theory and Hayden-O'Connell method.Thermodynamic consistency was tested for the binary VLE data.The experimental data were correlated successfully with the Non-Random Two Liquids(NRTL) model.The Root Mean Square Deviation(RMSD) of the ternary system was 0.0038.The saturation vapor pressure of sec-butyl acetate at 329 to 385 K was measured by means of two connected equilibrium cells.The vapor pressures of water and sec-butyl acetate were correlated with the Antoine equation.The binary interaction parameters and the ternary VLE data were obtained from this work.
文摘In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.
基金Supported by the National Natural Science Foundation of China (20976035, 21076059) the Natural Science Foundation of Hebei Province (B2010000019)
文摘Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance. Firstly, thermodynamic analysis shows that the reaction is exothermic and a high equilibrium conversion of TDA is expected due to its large reaction equilibrium constant. Secondly, under the suitable reaction conditions, 130 °C, 7 h, and molar ratio of TDA/zinc acetate/urea/sulfolane 1/0.05/3.5/10, TDA conversion is 54.3%, and TBU yield and selectivity are 39.8% and 73.3% respectively. Lastly, the synthesis of TBU is a 1st order reaction with respect to TDA and the reaction kinetics model is established. This work will provide useful information for commercializing the urea route to toluene-2,4-dicarbamate (TDC).
文摘A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage efficiencies or height equivalent to a theoretical plate (HETP) were entirely avoided by this model. The consistency of simulated results and experimental data in conversions and concentration of each component along a column indicates that the model predicts the actual process well. The influences of operating parameters on hydrolytic conversions, such as feed molar ratios, feed locations, feed and reflux rates, heights of reactive and stripping sections, were analyzed adequately by simulating calculations. A good operating mode was then obtained, which is helpful to the development of a new process.
基金Supported by the Natural Science Foundation of Henan Province (No.0211020800).
文摘Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure.It is shown that the solubilities of trans-1,2-cyclohexanediol in butyl acetate+water were affected greatly by the proportion of butyl acetate and water,and presented maximum value at given temperature.The UNIFAC model was used to correlate the experimental data.The average relative deviation(ARD)between experimental and calculated values is 3.03%.
文摘A new dynamic ebulliometer is used to determine vapor-liquid equilibrium(VLE) data experimentally. In the equipment,both phases are recirculated. Its operation is a consequence of the Cotrell pump effect produced when the mixture is heated in a double-walled inverted vessel. The reliability of the apparatus is tested with the mixtures studied previously by various authors. VLE data for the binary systems of methyl acetate + methanol and the methyl acetate + ethanol at 0.5 MPa are determined. The experimental data are confirmed with the point-to-point test of van Ness,applying the Fortran program of Frendslund et al. In addition,the experimental results are com-pared with the UNIFAC(including different versions) and ASOG prediction models.
基金Supported by the Major State Basic Research Development Program of China (2012CB720500), the National Natural Science Foundation of China (U1162202, 61174118) and the Shanghai Leading Academic Discipline Project (B504).
文摘The vapor-liquid equilibrium data of four binary systems (acetic acid +p-xylene, methyl acetate +n-propyl acetate, n-propyl acetate +p-xylene and methyl acetate +p-xylene) are measured at 101.33 kPa with Ellis equilibrium still, and then both the NRTL and UNIQUAC models are used in combination with the HOC model for correlating and estimating the vapor-liquid equilibrium of these four binary systems. The estimated binary VLE results using correlated parameters agree well with the measured data except the methyl acetate +p-xylene system which easily causes bumping and liquid rushing out of the sampling tap due to their dramatically different boiling points. The correlation results by NRTL and UNIQUAC models have little difference on the average absolute deviations of temperature and composition of vapor phase, and the results by NRTL model are slightly better than those by UNIQUAC model except for the methyl acetate +n-propyl acetate system, for which the latter gives more accurate correlations.
文摘Liquid-liquid equilibrium (LLE) data for the ternary systemwater-ethanol-dimethyl succinate have been determined experimentallyat temperatures ranging from 298.15 to 318.15 K at 5 K intervals.Complete phase diagrams were obtained by determining solubility andthe tie-line data. Tie-line compositions were correlated byOthmer-Tobias method. The universal quasichemical functional groupactivity coefficient (UNIFAC) and modified UNIFAC methods were usedto predict the phase equilibrium in the system using the interactionparameters deter- Mined from experimental data between groups CH_3,CH_2, OH, CH_3 COO and H_2O.
基金Supported by Tianjin Chemical Engineering Design Institute (No.G203051).
文摘The organic dissolvent (di-n-butyl phthalate) needs to be washed by water to recycle itself in the process of recovering maleic anhydride by organic dissolvent. The design and optimization of the extraction process require the distribution coefficients of the organic solutes, o-phthalic acid and trans-butenedioic in water and di-n-butyl phthalate, on which the extraction efficiency depends. In this study, the distribution coefficients of o-phthalic acid and trans-butenedioic in water and all-n-butyl phthalate(DBP) at 298.15 K, 318.15 K and 333.15 K were determined respectively by acid-alkali titration. The dissociation constants of o-phthalic acid and trans-butenedioic at those temperatures were obtained by fitting the measured hydrogen-ion concentrations and the known solute concentrations in the aqueous solution containing the two organic solutes. Then the distribution constants were calculated. Both the distribution coefficients and the distribution constants increase along with the temperature increasing. And the distribution coefficients at 333. 15 K are large enough to ensure the efficiency of extraction process. In addition, the mutual solubility of water and all-n-butyl phthalate at 298.1.5 K, 318. 1.5 K and 333. 15 K was also measured respectively by High Performance Liquid Chromatography and Karl Fischer Watertitration, which was not more than 0. 5%( mass fraction ).
文摘The binary liquid-liquid equilibrium(LLE) data for salt-containing systems of 1-butanol+water+CaCl2, n-butyl acetate+water+CaCl2 and ethyl acetate+acetic acid+water+CaCl2 were determined and the salt effect was analyzed. The results showed that an obvious salt effect could be identified for the systems of 1-butanol+water+CaCl2 and ethyl acetate+acetic acid+water.