电解质NRTL模型研究与开发
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摘要
基于同种离子间相互排斥以及局部电中性这两种基本假设,根据Chen等1988年模型建立的可适用于混合溶剂电解质溶液体系热力学性质的计算模型,纯水性质采用IAPWS-97物性方法进行计算,对该电解质NRTL活度系数模型求解并开发,并采用工业中含电解质流程的相关实例进行验证,以及与Aspen plus软件在相同物性数据下的计算结果相比,开发的模型在计算单一电解质水溶液体系的活度系数、吉布斯自由能和焓值等数据方面的相对偏差低至0.0%,混合溶剂电解质溶液体系的计算结果偏差也都在0.1%以下,采用文献中的交互参数由于参数取值的差别导致相对偏差偏大,但也都在0.5%以下,从而表明该开发的模型可以应用于含电解质流程的模拟、计算和优化。
Based on the two basic hypothesis of mutual repulsion of the like-ion and the local electric neutrality, a computational model for thermodynamic properties of mixed-solvent electrolyte system was established according to the 1988 model revised by Chen et al. The properties of pure water were calculated by IAPWS-97 Property method,and the model was solved and developed. Using relevant examples of electrolyte process in industry verify the results. Compared with the calculation results of Aspen plus software under the same physical data, the relative deviations of the developed model are all low to 0.0% in calculating the activity coefficient, Gibbs energies and enthalpies for electrolyte system, and the deviation of calculation results of mixed-solvent electrolyte system is also less than 0.1%. The relative deviation is larger due to the difference of data values when used interaction parameters of the literature, but all of them are below 0.5%, which indicated that the developed activity coefficient model can be used for the process simulation, calculation and optimization of the of electrolyte system.
Based on the two basic hypothesis of mutual repulsion of the like-ion and the local electric neutrality, a computational model for thermodynamic properties of mixed-solvent electrolyte system was established according to the 1988 model revised by Chen et al. The properties of pure water were calculated by IAPWS-97 Property method,and the model was solved and developed. Using relevant examples of electrolyte process in industry verify the results. Compared with the calculation results of Aspen plus software under the same physical data, the relative deviations of the developed model are all low to 0.0% in calculating the activity coefficient, Gibbs energies and enthalpies for electrolyte system, and the deviation of calculation results of mixed-solvent electrolyte system is also less than 0.1%. The relative deviation is larger due to the difference of data values when used interaction parameters of the literature, but all of them are below 0.5%, which indicated that the developed activity coefficient model can be used for the process simulation, calculation and optimization of the of electrolyte system.
引文
1 Pitzer KS.Thermodynamics of electrolytes.I.Theoretical basis and general equations[J].J.Phys.Chem.,1973,77(2):268-277.
2 Zuo YX and Guo TM.Model of thermodynamic properties of electrolyte solution[J].Journal of Petroleum University(Natural Science Edition),1989,(04):107-115.
3 Meissner HP and Tester JW.Activity Coefficients of Strong Electrolytes in Aqueous Solutions[J].Aiche Journal,1972,18(3):661-662.
4 Bromley LA.Thermodynamic properties of strong electrolytes in aqueous solutions[J].Aiche Journal,1973,19(2):313-320.
5 Loehe JR and Donohue MD.Recent advances in modeling thermodynamic properties of aqueous strong electrolyte systems[J].AIChEJ.1997,43(1):180-195.
6陆小华,王延儒,时均.电解质溶液的热力学进展[J].化工进展,1988,7(3):13-17.
7张吕正,陆小华,王延儒等.电解质溶液相平衡预测系统的建立[J].计算机与应用化学,1995,(3):199-202.
8胡英,刘国杰,徐英年等.应用统计力学[M].北京:化学工业出版社,1990:335-403.
9左有祥,郭天民.电解质溶液的分子热力模型[J].化工学报,1990,41(1):1-9
10 Li YG.Electrolyte solution theory[M].Beijing:Tsinghua University Press,2005.
11 Chen CC,Britt HI,Boston JF,Evans LB.Local Compositions Model for Excess Gibbs Energy of Electrolyte Systems:Part I:Single Solvent,Single Completely Dissociated Electrolyte Systems[J].AIChEJ.,1982,28(4):588-596.
12 Bill M,Evans LB and Chen CC.Thermodynamic representation ofphase equilibria of mixed-solvent electrolyte system[J].AIChEJ.,1986,32(10):1655-1664.
13 Chen CC and AND Evans LB.A Local Composition Model for the Excess Gibbs Energy of Aqueous Electrolyte Systems[J].AIChE J.,1986,32(3):444-459.
14 Chen CC,Mathias PM and Orbey H.Use of hydration and dissociation chemistries with the electrolyte-NRTLmodel[J].AICHE J.,1999,45(7):1576-1586.
15 Chen CC,Bokis CP and Mathias P.Segment-Based Excess Gibbs Energy Model for Aqueous Organic Electrolytes[J].AIChEJ.,2001,47(11):2593-2602.
16 Chen CC,Song YH.Generalized Electrolyte-NRTLModel for Mixed-Solvent Electrolyte Systems[J].AICh E J.,2004,50(8):1928-1941.
17 Chen CC,Song YH and Bollas GM.Formulation and Behavior of a Symmetric Electrolyte Nrtl Model for Gibbs Energy of Electrolyte Systems[C]//Aiche Meeting.2008.
18 Liu YD and SUPHATWATASASIRI.Representation of liquid-liquid equilibrium of mixed-solvent electrolyte systems using the extendedelectrolyte NRTL model[J].Fluid Phase Equilibria,1996,116:193-200.
19 Zerres H and Prausnitz JM.Thermodynamics of phase equilibria in aqueous-organic systems with salt[J].AICh EJ.,1994,40(4):676-691.
20 Jaretun A and ALY G.New local composition model for electrolyte solutions:single solvent,single electrolyte systems[J].Fluid Phase Equilibria,1999,163:175-193.
21 Jaretun A and ALY G.New local composition model for electrolyte solutions:Multi-component systems[J].Fluid Phase Equilibria,2000,175:213-228.
22 Bochove GHV,Krooshof GJP and Loos TWD.Modelling of liquid-liquid equilibria of mixed solvent electrolyte systems using the extended electrolyte NRTL[J].Fluid Phase Equilibria,2000,171(1):45-58.
23 Song YH and Chen CC.Symmetric Nonrandom TwoLiquid Segment Activity Coefficient Model for Electrolytes[J].Industrial&Engineering Chemistry Research,2009,48(11):5522-5529.
24 Song YH and Chen CC.Symmetric electrolyte nonrandom two-liquid activity coefficient model[J].Ind.Eng.Chem.Res.,2009,48:7788-7797.
25 Bollas GM,Chen CC and Barton PI.refined electrolytenrtl model:activity coefficient expressions for application to multi-electrolyte systems[J].AIChE J.,2010,54(6):1608-1624.
26 Zemanitis JF,Clark DM,Rafal M,et al.Handbook of Aqueous Electrolyte Thermodynamics:Theory&Application[M].The American Institute of Chemical Engineers,1986.
27 ASPEN TECHNOLOGY INC,Aspen Plus Electrolytes Manual[M].Cambridge,Masschusetts Aspen,1988:495-519.
28 Haynes WM,Lide DR and Bruno TJ.CRC Handbook of Chemistry and Physics,96th.Edition,2015-2016.
2 Zuo YX and Guo TM.Model of thermodynamic properties of electrolyte solution[J].Journal of Petroleum University(Natural Science Edition),1989,(04):107-115.
3 Meissner HP and Tester JW.Activity Coefficients of Strong Electrolytes in Aqueous Solutions[J].Aiche Journal,1972,18(3):661-662.
4 Bromley LA.Thermodynamic properties of strong electrolytes in aqueous solutions[J].Aiche Journal,1973,19(2):313-320.
5 Loehe JR and Donohue MD.Recent advances in modeling thermodynamic properties of aqueous strong electrolyte systems[J].AIChEJ.1997,43(1):180-195.
6陆小华,王延儒,时均.电解质溶液的热力学进展[J].化工进展,1988,7(3):13-17.
7张吕正,陆小华,王延儒等.电解质溶液相平衡预测系统的建立[J].计算机与应用化学,1995,(3):199-202.
8胡英,刘国杰,徐英年等.应用统计力学[M].北京:化学工业出版社,1990:335-403.
9左有祥,郭天民.电解质溶液的分子热力模型[J].化工学报,1990,41(1):1-9
10 Li YG.Electrolyte solution theory[M].Beijing:Tsinghua University Press,2005.
11 Chen CC,Britt HI,Boston JF,Evans LB.Local Compositions Model for Excess Gibbs Energy of Electrolyte Systems:Part I:Single Solvent,Single Completely Dissociated Electrolyte Systems[J].AIChEJ.,1982,28(4):588-596.
12 Bill M,Evans LB and Chen CC.Thermodynamic representation ofphase equilibria of mixed-solvent electrolyte system[J].AIChEJ.,1986,32(10):1655-1664.
13 Chen CC and AND Evans LB.A Local Composition Model for the Excess Gibbs Energy of Aqueous Electrolyte Systems[J].AIChE J.,1986,32(3):444-459.
14 Chen CC,Mathias PM and Orbey H.Use of hydration and dissociation chemistries with the electrolyte-NRTLmodel[J].AICHE J.,1999,45(7):1576-1586.
15 Chen CC,Bokis CP and Mathias P.Segment-Based Excess Gibbs Energy Model for Aqueous Organic Electrolytes[J].AIChEJ.,2001,47(11):2593-2602.
16 Chen CC,Song YH.Generalized Electrolyte-NRTLModel for Mixed-Solvent Electrolyte Systems[J].AICh E J.,2004,50(8):1928-1941.
17 Chen CC,Song YH and Bollas GM.Formulation and Behavior of a Symmetric Electrolyte Nrtl Model for Gibbs Energy of Electrolyte Systems[C]//Aiche Meeting.2008.
18 Liu YD and SUPHATWATASASIRI.Representation of liquid-liquid equilibrium of mixed-solvent electrolyte systems using the extendedelectrolyte NRTL model[J].Fluid Phase Equilibria,1996,116:193-200.
19 Zerres H and Prausnitz JM.Thermodynamics of phase equilibria in aqueous-organic systems with salt[J].AICh EJ.,1994,40(4):676-691.
20 Jaretun A and ALY G.New local composition model for electrolyte solutions:single solvent,single electrolyte systems[J].Fluid Phase Equilibria,1999,163:175-193.
21 Jaretun A and ALY G.New local composition model for electrolyte solutions:Multi-component systems[J].Fluid Phase Equilibria,2000,175:213-228.
22 Bochove GHV,Krooshof GJP and Loos TWD.Modelling of liquid-liquid equilibria of mixed solvent electrolyte systems using the extended electrolyte NRTL[J].Fluid Phase Equilibria,2000,171(1):45-58.
23 Song YH and Chen CC.Symmetric Nonrandom TwoLiquid Segment Activity Coefficient Model for Electrolytes[J].Industrial&Engineering Chemistry Research,2009,48(11):5522-5529.
24 Song YH and Chen CC.Symmetric electrolyte nonrandom two-liquid activity coefficient model[J].Ind.Eng.Chem.Res.,2009,48:7788-7797.
25 Bollas GM,Chen CC and Barton PI.refined electrolytenrtl model:activity coefficient expressions for application to multi-electrolyte systems[J].AIChE J.,2010,54(6):1608-1624.
26 Zemanitis JF,Clark DM,Rafal M,et al.Handbook of Aqueous Electrolyte Thermodynamics:Theory&Application[M].The American Institute of Chemical Engineers,1986.
27 ASPEN TECHNOLOGY INC,Aspen Plus Electrolytes Manual[M].Cambridge,Masschusetts Aspen,1988:495-519.
28 Haynes WM,Lide DR and Bruno TJ.CRC Handbook of Chemistry and Physics,96th.Edition,2015-2016.