UNIQUAC参数的回归及其在汽液平衡中的应用
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摘要
本文首先介绍了在解决相平衡过程中状态方程法和活度系数法各自的优缺点及其发展状况。回顾了UNIQUAC模型的发展历程,并采用Extended -UNIQUAC模型对本文的实验数据进行了回归,本文选取了水(1)/乙酸(2)、甲醇(1)/水(2)、水(1)/甲酸(2)、乙醇(1)/水(2)、四氢呋喃(1)/环己烷(2)等5个二元体系进行了汽液平衡数据的测定,对它们进行了热力学一致性检验,作出了部分相图;并将这些汽液平衡数据用于UNIQUAC相互作用参数的回归,模型计算值与测量值的平均偏差为0.00619,最大偏差为0.01157。又用Extended -UNIQUAC模型对7组三元体系汽液平衡数据进行回归,得出了相应的相互作用参数以及组分的汽相组成平均偏差和总的平均偏差,结果表明对三元体系的关联结果偏差较小。
本文分别利用Extended -UNIQUAC、NRTL和WILSON模型对90个二元体系(共计1703个实验点)的汽相组成、泡点温度进行预测;通过这些预测并结合相关资料进行了二元体系汽液相平衡的研究。得出了活度系数关联式最优拟合频率,结果表明Extended -UNIQUAC模型的平均结果要占优,尤其对含水有机物和醇类的体系结果令人满意。在化学反应工程,分离工程,化工过程研究,开发和设计当中具有极强的实用价值。
In this paper, the merits and flaws and the development status of equation of state model and activity coefficient model used in solving the process of phase equilibria are introduced at first. The development history of UNIQUAC model is recalled in the paper, and Extended -UNIQUAC model is used to regress the experimental data of this work. The vapor-liquid phase equilibrium data of five binary systems include methanol/water, water/formicacid, ethanol/water, tetrahydrofuran/cyclohexane, water/aceticacid have been measured in this paper, and the thermodynamic consistency test have been made. And those binary vapor-liquid equilibrium data were applied to the regression of UNIQUAC interaction parameters. The average deviation between the model calculated and measured values is 0.00619, the maximum deviation is 0.01157.
Also seven ternary system VLE data have been regressed by Extended -UNIQUAC model and the corresponding interaction parameters have been gotten, as well as the average deviation of the vapour phase and the average deviation of the genental, the results show that the deviation of Correlation results for ternary system is small. In this work, Extended -UNIQUAC, NRTL and WILSON model have been applied to prodict the composition of the vapor phase, the bubble point temperature of vapor-liquid equilibria for 90 binary systems(1703 experimental data) .with the forecast and related informations,vapor-liquid binary system balance have been studied. Also the optimum fitting frequencies for activity coefficient of correlation have been gotten, results show that the Extended -UNIQUAC model is superior in the average results, especial for the aqueous-organic system and alcohols results are well. It is is highly practical value in the chemical reaction engineering, separation engineering, chemical process research, development and design.
本文分别利用Extended -UNIQUAC、NRTL和WILSON模型对90个二元体系(共计1703个实验点)的汽相组成、泡点温度进行预测;通过这些预测并结合相关资料进行了二元体系汽液相平衡的研究。得出了活度系数关联式最优拟合频率,结果表明Extended -UNIQUAC模型的平均结果要占优,尤其对含水有机物和醇类的体系结果令人满意。在化学反应工程,分离工程,化工过程研究,开发和设计当中具有极强的实用价值。
In this paper, the merits and flaws and the development status of equation of state model and activity coefficient model used in solving the process of phase equilibria are introduced at first. The development history of UNIQUAC model is recalled in the paper, and Extended -UNIQUAC model is used to regress the experimental data of this work. The vapor-liquid phase equilibrium data of five binary systems include methanol/water, water/formicacid, ethanol/water, tetrahydrofuran/cyclohexane, water/aceticacid have been measured in this paper, and the thermodynamic consistency test have been made. And those binary vapor-liquid equilibrium data were applied to the regression of UNIQUAC interaction parameters. The average deviation between the model calculated and measured values is 0.00619, the maximum deviation is 0.01157.
Also seven ternary system VLE data have been regressed by Extended -UNIQUAC model and the corresponding interaction parameters have been gotten, as well as the average deviation of the vapour phase and the average deviation of the genental, the results show that the deviation of Correlation results for ternary system is small. In this work, Extended -UNIQUAC, NRTL and WILSON model have been applied to prodict the composition of the vapor phase, the bubble point temperature of vapor-liquid equilibria for 90 binary systems(1703 experimental data) .with the forecast and related informations,vapor-liquid binary system balance have been studied. Also the optimum fitting frequencies for activity coefficient of correlation have been gotten, results show that the Extended -UNIQUAC model is superior in the average results, especial for the aqueous-organic system and alcohols results are well. It is is highly practical value in the chemical reaction engineering, separation engineering, chemical process research, development and design.
引文
[1] Gmehling J,Onken U,Vapor-liquid equilibrium data collection[M]. Frankfurt: DECHEMA, 1977~1995.
[2] Wichterle I, Linke T, Hala E, Vapor-liquid equilibrium data bibliography[M].1973, Supple. 1, 1976, Supple. 2, 1979, Supple. 4, 1982, Supple. 4, 1985. [3 Maczynski A, Verified vapor-liquid equilibrium data[M]. vol. 1~7, Warszawa: PMN, 1976~1983.
[4] Ohe S, Vapor-liquid equilibrium data-salt effect[J]. Amsterdam: Elsevier, 1991.
[5]姚加.缔合体系分子热力学:(博士后学位论文)[D].杭州:浙江大学.
[6] Redlich O,Kwong JNS.On the Thermodynamics of Solutions.V.An Equation of State.Fugacities of Gaseous Solutions[J]. Chem Rev,1949,44(1):233-244.
[7] Soave G.Equilibrium conslant form a modified Redlick-Kwong equation of state[J]. Chem Eng Sci,1972,37:1197-1211.
[8] Peng DY,Robinson DB.A New Tow-Constant Equation of State[J]. Ind Eng Chem Fundam,1976,15(1):59-64.
[9]陈新志,蔡振云,胡望明.化工热力学[M].北京:化学工业出版社,2005.
[10]物性定数[M].东京:丸善,1-10集,1963-1972.
[11] Knapp H, Doring R, Oeirch L, et al., Vapor-liquid equilibria for mixtures of low boiling substances[J]. Frankfurt: DECHEMA, 1982, 1989.
[12] Abrams, D. S. and Prauznitz, J. M. Statistical Thermodynamics of Liquid Mixtures: A new Expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems[J]. AIChE J., 21 , No 6, (1975) pp 116-128.
[13] Marsh N Kenneth, Niamskul Prin, Gmehling Jurgen, et al., Review of thermophysical property measurements on mixture containing MTBE, TAME,and other ethers with non-polar solvents[J]. Fluid phase equilibria, 1999,156:207~227.
[14]朱自强,徐迅.化工热力学[M] .北京:化学工业出版社,1991.
[15]董艳辉.含醚类汽油添加剂多组分液液相平衡[D].暨南大学硕士论文. 2006.
[16]马沛生.化工数据[M].北京:中国石化出版社.2003.7.81-82.
[17]《化学工程手册》编辑委员会.《化学工程手册》[M].北京:化学工业出版社,1989,10.
[18]周浩,刘洪来,胡英.基团贡献法预测高分子溶液汽液平衡[J].高校化学工程学报. 1997.11(3).231-237.
[19] .M.普劳斯尼茨.用计算机计算多元汽-液和液-液平衡[M].北京:化学工业出版社,1980.
[20] T. Oishi, J. M. Prausnitz. Estimation of solvent Activities in Polymer Solutions Using a Group-Contribution Method [J]. Ind.Eng. Chem. Proc. Des. Dev. 1978. 17. 333-339
[21] Fredenslund, As., Gmehling, J. Rasmussen, P. Vapor-Liquid Equilibra Using UNIFAC-A Group Contribution [M]. Elsevier. Amsterdam. 1977.
[22] Suojiang Zhang, Toshihiko Hiaki, Kazuo Kojima. Prediction of infinite dilution activity coefficients for systems including water based on the group contribution model with mixture-type groupsⅠ. Alkane-H2O and alkanol - H2O mixtures [J]. Fluid Phase Equilibria. 1998. 149. 27-40.
[23] H. S. Elbro, A. Fredenslund, P. Rasmussen. A new simple equation for the prediction of solvent activities in polymer solutions [J]. Macromolecules. 1990. 23. 4707-4714.
[24] Kikic. I, Fredenslund. On the combinatorial part of the UNIFAC and UNIQUAC models [J]. The Candian Journal of chemical Engineering. 1980. 58. 253-258.
[25]胡昌彬.用HVOS-PR/MDUNIFAC状态方程活度系数法预测汽液相平衡[D].重庆大学.硕士论文.2007.
[26] Rgen Gmehling, Jiding Li, Martin Schiller.A Modified UNIFAC Model.2.Present Parameter Matrix and Results for Different Thermodynamic Properties[J]. Ind. Eng. Chem. Res. 1993. 32. 178-193.
[27] Malanowski S, Experimental methods for vapor-liquid equilibria, Part ICirculaiton methods[J]. Fluid Phase Equilibria, 1982, 8: 197~219.
[28] http://mole.ipe.ac.cn/nedb/Binary.htm.
[29] http://mole.ipe.ac.cn/phase_transition/phase_transition_query.aspx.
[30] http://db.membrane.org.cn/data_view.asp?data_type=t13.
[31] Michelsen, Michael L. Modified huron-vidal mixing rule for cubic equations of state [J]. Fluid Phase Equilibria. 1990. 60. 213-219.
[32] Orbey, H., Sandler, S. I. On the combination of equation of state and excess free energy models [J]. Fluid Phase Equilibria. 1995. 111. 53-70.
[33] Dahl Soren, Michelsen, Michael L. High-pressure vapor-liquid equilibrium with a UNIFAC-based equation of state [J]. AIChE J. 1990. 36. 1829-1836.
[34] Boukouvalas, C., Spiliotis, N., Coutsikos, P., Tzouvaras, N., Tassios, D. Prediction of vapor-liquid equilibrium with the LCVM model: a linear combination of the Vidal and Michelsen mixing rules coupled with the original UNIFAC and the t-mPR equation of state[J]. Fluid Phase Equilibria. 1994. 92. 75-106.
[35] Wong, D. S. H., Sandler, Stanley I. Theoretically correct mixing rule for cubic equations of state [J]. AIChE J. 1992. 38. 671-680.
[36] Hala E, Pick J, Fried V, Vapour-liquid equilibrium, London: Pergamon Press,1967, 7~14.
[37] Jiding Li, Magnus Topphoff, Kai Fischer, Jürgen Gmehling. Prediction of Gas Solubilities in Aqueous Electrolyte Systems Using the Predictive Soave-Redlich-Kwong Model [J]. Ind. Eng. Chem. Res. 2001. 40. 3703-3710.
[38] Malanowski S, Experimental methods for vapor-liquid equilibria, Part ICirculaiton methods, Fluid Phase Equilibria, 1982, 8: 197~219.
[2] Wichterle I, Linke T, Hala E, Vapor-liquid equilibrium data bibliography[M].1973, Supple. 1, 1976, Supple. 2, 1979, Supple. 4, 1982, Supple. 4, 1985. [3 Maczynski A, Verified vapor-liquid equilibrium data[M]. vol. 1~7, Warszawa: PMN, 1976~1983.
[4] Ohe S, Vapor-liquid equilibrium data-salt effect[J]. Amsterdam: Elsevier, 1991.
[5]姚加.缔合体系分子热力学:(博士后学位论文)[D].杭州:浙江大学.
[6] Redlich O,Kwong JNS.On the Thermodynamics of Solutions.V.An Equation of State.Fugacities of Gaseous Solutions[J]. Chem Rev,1949,44(1):233-244.
[7] Soave G.Equilibrium conslant form a modified Redlick-Kwong equation of state[J]. Chem Eng Sci,1972,37:1197-1211.
[8] Peng DY,Robinson DB.A New Tow-Constant Equation of State[J]. Ind Eng Chem Fundam,1976,15(1):59-64.
[9]陈新志,蔡振云,胡望明.化工热力学[M].北京:化学工业出版社,2005.
[10]物性定数[M].东京:丸善,1-10集,1963-1972.
[11] Knapp H, Doring R, Oeirch L, et al., Vapor-liquid equilibria for mixtures of low boiling substances[J]. Frankfurt: DECHEMA, 1982, 1989.
[12] Abrams, D. S. and Prauznitz, J. M. Statistical Thermodynamics of Liquid Mixtures: A new Expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems[J]. AIChE J., 21 , No 6, (1975) pp 116-128.
[13] Marsh N Kenneth, Niamskul Prin, Gmehling Jurgen, et al., Review of thermophysical property measurements on mixture containing MTBE, TAME,and other ethers with non-polar solvents[J]. Fluid phase equilibria, 1999,156:207~227.
[14]朱自强,徐迅.化工热力学[M] .北京:化学工业出版社,1991.
[15]董艳辉.含醚类汽油添加剂多组分液液相平衡[D].暨南大学硕士论文. 2006.
[16]马沛生.化工数据[M].北京:中国石化出版社.2003.7.81-82.
[17]《化学工程手册》编辑委员会.《化学工程手册》[M].北京:化学工业出版社,1989,10.
[18]周浩,刘洪来,胡英.基团贡献法预测高分子溶液汽液平衡[J].高校化学工程学报. 1997.11(3).231-237.
[19] .M.普劳斯尼茨.用计算机计算多元汽-液和液-液平衡[M].北京:化学工业出版社,1980.
[20] T. Oishi, J. M. Prausnitz. Estimation of solvent Activities in Polymer Solutions Using a Group-Contribution Method [J]. Ind.Eng. Chem. Proc. Des. Dev. 1978. 17. 333-339
[21] Fredenslund, As., Gmehling, J. Rasmussen, P. Vapor-Liquid Equilibra Using UNIFAC-A Group Contribution [M]. Elsevier. Amsterdam. 1977.
[22] Suojiang Zhang, Toshihiko Hiaki, Kazuo Kojima. Prediction of infinite dilution activity coefficients for systems including water based on the group contribution model with mixture-type groupsⅠ. Alkane-H2O and alkanol - H2O mixtures [J]. Fluid Phase Equilibria. 1998. 149. 27-40.
[23] H. S. Elbro, A. Fredenslund, P. Rasmussen. A new simple equation for the prediction of solvent activities in polymer solutions [J]. Macromolecules. 1990. 23. 4707-4714.
[24] Kikic. I, Fredenslund. On the combinatorial part of the UNIFAC and UNIQUAC models [J]. The Candian Journal of chemical Engineering. 1980. 58. 253-258.
[25]胡昌彬.用HVOS-PR/MDUNIFAC状态方程活度系数法预测汽液相平衡[D].重庆大学.硕士论文.2007.
[26] Rgen Gmehling, Jiding Li, Martin Schiller.A Modified UNIFAC Model.2.Present Parameter Matrix and Results for Different Thermodynamic Properties[J]. Ind. Eng. Chem. Res. 1993. 32. 178-193.
[27] Malanowski S, Experimental methods for vapor-liquid equilibria, Part ICirculaiton methods[J]. Fluid Phase Equilibria, 1982, 8: 197~219.
[28] http://mole.ipe.ac.cn/nedb/Binary.htm.
[29] http://mole.ipe.ac.cn/phase_transition/phase_transition_query.aspx.
[30] http://db.membrane.org.cn/data_view.asp?data_type=t13.
[31] Michelsen, Michael L. Modified huron-vidal mixing rule for cubic equations of state [J]. Fluid Phase Equilibria. 1990. 60. 213-219.
[32] Orbey, H., Sandler, S. I. On the combination of equation of state and excess free energy models [J]. Fluid Phase Equilibria. 1995. 111. 53-70.
[33] Dahl Soren, Michelsen, Michael L. High-pressure vapor-liquid equilibrium with a UNIFAC-based equation of state [J]. AIChE J. 1990. 36. 1829-1836.
[34] Boukouvalas, C., Spiliotis, N., Coutsikos, P., Tzouvaras, N., Tassios, D. Prediction of vapor-liquid equilibrium with the LCVM model: a linear combination of the Vidal and Michelsen mixing rules coupled with the original UNIFAC and the t-mPR equation of state[J]. Fluid Phase Equilibria. 1994. 92. 75-106.
[35] Wong, D. S. H., Sandler, Stanley I. Theoretically correct mixing rule for cubic equations of state [J]. AIChE J. 1992. 38. 671-680.
[36] Hala E, Pick J, Fried V, Vapour-liquid equilibrium, London: Pergamon Press,1967, 7~14.
[37] Jiding Li, Magnus Topphoff, Kai Fischer, Jürgen Gmehling. Prediction of Gas Solubilities in Aqueous Electrolyte Systems Using the Predictive Soave-Redlich-Kwong Model [J]. Ind. Eng. Chem. Res. 2001. 40. 3703-3710.
[38] Malanowski S, Experimental methods for vapor-liquid equilibria, Part ICirculaiton methods, Fluid Phase Equilibria, 1982, 8: 197~219.