烃-水体系互溶度预测模型的研究进展

doi:10.16085/j.issn.1000-6613.2017-0322

摘要/Abstract

摘要： 在化工、能源、环境、食品和药物等工业设计过程中，真实混合物的可靠溶解度数据非常重要，不仅能丰富相平衡数据库，还能指导工艺设备设计和产品质量控制。本文介绍了烃-水体系相互溶解度的模型化研究，包括状态方程法、活度系数法和经验关联式，以及近年来发展起来的真实溶剂似导体屏蔽模型法（conductor-like screening model for real solvents，COSMO-RS）。状态方程法和活度系数法主要是通过选择非对称的混合规则以及引进描述水分子极性作用的参数，来改善对烃-水体系相互溶解度的计算精度。经验关联式主要是对实验数据的拟合，每种烃的参数不同。COSMO-RS模型根据密度泛函理论（即建立极化电荷密度的简单经验式）计算单个分子嵌入虚拟导体产生的作用，通过准确描述界面统计相互作用获得体系的热力学性质。因此，该方法对各种体系具有普适性。分析表明，COSMO-RS模型对烃-水体系相互溶解度的预测值与实验值吻合良好，可以补充某些难以通过实验获得的烃-水体系互溶度数据。最后总结和展望了烃-水体系相互溶解度模型化的未来发展方向。

关键词: 烃-水体系, 溶解度, 真实溶剂似导体屏蔽模型, 模型

Abstract: In chemical engineering,energy,environment,food and medical industry,reliable solubility data for real mixture is very important for process design,which can not only enrich the database of phase equilibrium,but also be greatly helpful for the design of process device and the fine control of products quality. It introduces the model of the mutual solubility on hydrocarbon-water system,including state equation methods,activity coefficient methods,empirical correlations and COSMO-RS(conductor-like screening model for real solvents) model developed in recent years. The state equation methods and activity coefficient methods are usually employed to improve the accuracy of the mutual solubility on hydrocarbon-water system according to the asymmetric mixing rules and the adjustment of the parameters describing the polarity of water molecules. The empirical correlations are mainly used to fit the experimental data,where the parameters of the correlations are different with respect to particular hydrocarbon system. Furthermore,the COSMO-RS model calculates the single molecule embedded virtual conductor based on the density functional theory by which the simple empirical polarization charge density is established. It is efficient and accurate for describing the statistical thermodynamic interactions of interface,and thus the features of thermodynamic qualities can be grasped conveniently. The results indicate that the predicted data of COSMO-RS model agrees well with the experimental one,which show the universality of COSMO-RS model in various kinds of systems,and thus providing an easy method for complementing the unmeasurable experimental data of mutual solubility for hydrocarbon-water system. The future directions for prediction models of the mutual solubility on hydrocarbon-water system are proposed.

Key words: hydrocarbon-water system, solubility, COSMO-RS, model

中图分类号:

王敏, 曹睿, 刘艳升, 徐泓. 烃-水体系互溶度预测模型的研究进展[J]. 化工进展, 2017, 36(12): 4343-4349.

WANG Min, CAO Rui, LIU Yansheng, XU Hong. Progress on prediction models of mutual solubility of hydrocarbon-water system[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4343-4349.

参考文献

[1] PRAUSNITZ J M,LICHTENTNALER R N,AZEVEDO E G,et al.Molecular thermodynamics of fluid phase equilibria[M].5th ed. State of New Jersey:Prentice Hall,1999.
[2] TSONOPOULOS C.Thermodynamic analysis of the mutual solubilities of normal alkanes and water[J].Fluid Phase Equilibria,1999,156:21-33.
[3] ZHANG W,WILDER J W,SMITH D H.Interpretation of ethane hydrate equilibrium data for porous media involving hydrate-ice equilibria[J].AIChE J.,2002,48:2324-2331.
[4] AVLONITIS D.An investigation of gas hydrates formation energetics[J].AIChE J.,2005,51:1258-1273.
[5] POLAK J,LU B C Y.Mutual solubilities of hydrocarbons and water at 0 and 25℃[J].Chem.,1973,51(24):4018-4023.
[6] 牟天成,JÜRGEN G.真实溶剂似导体屏蔽模型(COSMO-RS)[J]. 化学进展,2008,20(10):1487-1494. MU T C,JÜRGEN G.Conductor-like screening model for real solvents (COSMO-RS)[J]. Progress in Chemistry,2008,20(10):1487-1494.
[7] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 2. Benzene with water and heavy water[J].Phys. Chem. Ref. Data,2005,34:477-552.
[8] TSONOPOULOS C.Thermodynamic analysis of the mutual solubilities of hydrocarbons and water[J]. Fluid Phase Equilibria,2001,186:185-206.
[9] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 1. C₅ hydrocarbons with water[J].Phys. Chem. Ref. Data,2005,34:441-476.
[10] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated.Part 3. C₆H₈-C₆H₁₂ hydrocarbons with water and heavy water[J].Phys. Chem. Ref. Data,2005,34:657-708.
[11] MACZYNSKI A,SHAW D G,GORAL M,et al.IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 4. C₆H₁₄ hydrocarbons with water[J]. Phys. Chem. Ref. Data,2005,34:709-53.
[12] MACZYNSKI A,SHAW D G,GORAL M,et al.IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 5. C₇ hydrocarbons with water and heavy water[J].Phys. Chem. Ref. Data,2005,34:1399-487.
[13] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 6. C₈H₈-C₈H₁₀ hydrocarbons with water[J].Phys. Chem. Ref. Data,2005,34:1489-553.
[14] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater revised and updated. Part 7. C₈H₁₂-C₈H₁₈ hydrocarbons with water[J].Phys. Chem. Ref. Data,2005,34:2261-2298.
[15] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 8. C₉ hydrocarbons with water[J].Phys. Chem. Ref. Data,2005,34:2299-345.
[16] MACZYNSKI A,SHAW D G,GORAL M,et al. IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 9. C₁₀ hydrocarbons with water[J].Phys. Chem. Ref. Data,2006,35:93-151.
[17] MACZYNSKI A,SHAW D G,GORAL M,et al.IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 10. C₁₁ and C₁₂ hydrocarbons with water[J].Phys. Chem. Ref. Data,2006,35:153-203.
[18] SHAW DG,MACAYNSKI A,GORAL M,et al.IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 11. C₁₃-C₃₆ hydrocarbons with water[J].Phys. Chem. Ref. Data,2006,35:687-784.
[19] SHAW D G,MACAYNSKI A,HEFTER G T,et al.IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 12. C₅-C₂₆ hydrocarbons with seawater[J].Phys. Chem. Ref. Data,2006,35:785-838.
[20] KABADI V N,DANNER R P.A modified Soave-Redlich-Kwong equation of state for water hydrocarbon phase equilibria[J].Ind. Eng. Chem. Process Des. Dev.,1985,24:537-541.
[21] ECONOMOU I G,TSONOPOULOS C.Associating models and mixing rules in equations of state for water/hydrocarbon mixtures[J].Chem. Eng. Sci.,1997,52:511-525.
[22] SHIN H Y,HARUKI M,YOO K P,et al.Phase behavior of water + hydrocarbon binary systems by using multi-fluid nonrandom lattice hydrogen bonding theory[J].Fluid Phase Equilibria,2001,189:49-61.
[23] HARUKI M,IWAI Y,ARAI Y.Prediction of phase equilibria for the mixtures containing polar substances at high temperatures and pressures by group contribution equation of state[J].Fluid Phase Equilibria,2001,189:13-30.
[24] HARUKI M,IWAI Y,NAGAO S,et al.Measurement and correlation of liquid-liquid equilibria for water + aromatic hydrocarbon binary systems at high temperatures and pressures[J].Chem. Eng. Data,2001,46:950-953.
[25] 李进龙,何昌春,彭昌军,等.基于化学缔合统计理论的链状流体状态方程[J].中国科学(化学),2010(9):1198-1209. LI J L,HE C C,PENG C J,et al.A chain of fluid state equation based on the theory of chemical association statistics[J].Chinese Science(Chemistry),2010(9):1198-1209.
[26] HEMPTINNE DE J C,MOUGIN P,BARREAU A,et al.Application to petroleum engineering of statistical thermodynamics-based equations of state[J].Oil & Gas Science and Technology-Rev. IFP,2006,61(3):363-386.
[27] KONTOGEORGIS G M,MICHELSENM L,FOLAS G K,et al.Ten years with the CPA (cubic-plus-association) equation of state. part 1. Pure compounds and self-associating systems[J].Ind. Eng. Chem. Res.,2006,45:4855-4868.
[28] KONTOGEORGIS G M,MICHELSEN M L,FOLAS G K,et al.Ten years with the CPA (cubic-plus-association) equation of state.part 2. Cross-associating and multicomponent systems[J].Ind. Eng. Chem. Res.,2006,45:4869-4878.
[29] KRASKA T,GUBBINS K E. Phase equilibria calculations with a modified SAFT equation of state. 1. Pure alkanes,alkanols,and water[J].Ind. Eng. Chem. Res.,1996,35:4738-4746.
[30] GROSS J,SADOWSJI G.. Application of the perturbed-chain SAFT equation of state to associating systems[J]. Ind. Eng. Chem. Res.,2002,41:5510-5515.
[31] GRENNER A,SCHMELZER J,SOLMS N V,et al.Comparison of two association models (elliott-suresh-donohue and simplified PC-SAFT) for complex phase equilibria of hydrocarbon-water and amine-containing mixtures[J].Ind. Eng. Chem. Res.,2006,45:8170-8179.
[32] KARAKATSANI E K,KONTOGEORGIS G M,ECONOMOU I G,et al.Evaluation of the truncated perturbed chain-polar statistical associating fluid theory for complex mixture fluid phase equilibria[J].Ind. Eng. Chem. Res.,2006,45:6063-6074.
[33] KONTOGEORGIS G M,VOUTSAS E C,YAKOUMIS I V,et al.An equation of state for associating fluids[J].Ind. Eng. Chem. Res.,1996,35:4310-4318.
[34] KONTOGEORGIS G M,YAKOUMIS I V,MEIJER H,et al. Multicomponent phase equilibrium calculations for water-methanol-alkane mixtures[J].Fluid Phase Equilibria,1999,158/159/160:201-209.
[35] YAN W,GEORGIOS M,KONTOGEORGIS G M,et al.Application of the CPA equation of state to reservoir fluids in presence of water and polar chemicals[J].Fluid Phase Equilibria,2009,276:75-85.
[36] OLIVEIRA M B,COUTINHO J A P,QUEIMADA A J.Mutual solubilities of hydrocarbons and water with the CPA EoS[J].Fluid Phase Equilibria,2007,258(1):58-66.
[37] MEDEIROS M.Mutual solubilities of water and hydrocarbons from the cubic plus association equation of state:a new mixing rule for the correlation of observed minimum hydrocarbon solubilities[J]. Fluid Phase Equilibria,2014,368:5-13.
[38] KABADI V N,DANNER R P,A modified Soave-Redlich-Kwong equation of state for water-hydrocarbon phase equilibria[J].Ind. Eng. Chem. Process Des. Dev.,1985,24:537-541.
[39] FREDENSLUND A,GMEHLING J,RASMUSSEN P.Vapor-liquid equilibria using UNIFAC[R].Amsterdam:Elsevier,1977.
[40] 刘洪勤,高崇侠,赵新亮.无限稀释活度系数的预测模型[J].高校化学工程学报,1996(1):9-16. LIU HQ,GAO C X,ZHAO X L.Prediction model of infinite dilution activity coefficient[J].Journal of Chemical Engineering,1996(1):9-16.
[41] GMEHLING J,LI J D,SCHILLER M A.A modified UNIFAC model. 2. Present parameter matrix and results for different thermodynamic properties[J].Ind. Eng. Chem. Res.,1993,32(1):178-193.
[42] LARSEN B L,RASMUSSEN P,FREDENSLUND A.A modified UNIFAC group-contribution model for prediction of phase equilibria and heats of mixing[J].Ind. Eng. Chem. Res.,1987,26(11):2274-2286.
[43] JAKOB A,GRENSEMANN H,LOHMANN J,et al.Further development of modified UNIFAC(Dortmund):revision and extension 5[J].Ind. Eng. Chem. Res.2006,45(23):7924-7933.
[44] MAGNUSSEN T,RASMUSSEN P.UNIFAC parameter table for prediction of liquid-liquid equilibriums[J].Industrial & Engineering,1981,20(2):331-339.
[45] SATYRO M A,SHAW J M,YARRANTON H W.A practical method for the estimation of oil and water mutual solubilities[J]. Fluid Phase Equilibria,2013,355:12-25.
[46] LORIA H,HAY G,SATYRO M A.Thermodynamic modeling and process simulation through PIONA characterization[J]. Energy & Fuels,2013,27(6):3578-3584.
[47] YARRANTON H W,SATYRO M A.Expanded fluid based viscosity correlation for hydrocarbons[J].Ind. Eng. Chem. Res.,2009,48(7):3640-3648.
[48] POSSANI L F K,STAUDT P B,SOARES R D P.Prediction of water solubilities in hydrocarbons and oils using F-SAC coupled with SRK-EoS[J].Fluid Phase Equilibria,2016,427:394-405.
[49] STAUDT P B,SOARES R D P. A self-consistent Gibbs excess mixing rule for cubic equations of state[J].Fluid Phase Equilibria,2012,334:76-88.
[50] API Technical data book:petroleum refining[M].9th ed.Washington (DC):American Petroleum Institute,2013.
[51] HEMPTINNE DE J C,LEDANOIS J M,MOUGIN P,et al.Select thermodynamic models for process simulation——A practical guide using a three steps methodology[M].Editions Technip,2012.
[52] BRADY C J,CUNNINGHAM J R,WILSON G M. Water-hydrocarbon liquid-liquid-vapor equilibrium measurements to 530 F?[R]. Gas Processors Association Research Report,1982.
[53] KLAMT A.Conductor-like screening model for real solvents:a new approach to the quantitative calculation of solvation phenomena[J]. The Journal of Physical Chemistry,1995,99(7):2224-2235.
[54] KLAMT A.Refinement and parametrization of COSMO-RS[J].The Journal of Physical Chemistry A,1998,102(26):5074-5085.
[55] KLAMT A,ECKERT F.COSMO-RS:a novel and efficient method for the a priori prediction of thermophysical data of liquids[J].Fluid Phase Equilibria,2000,172(1):43-72.
[56] ECKERT F,KLAMT A.Fast solvent screening via quantum chemistry:COSMO-RS approach[J].AIChE Journal,2002,48(2):369-385.
[57] KLAMT A.Prediction of the mutual solubilities of hydrocarbons and water with COSMO-RS[J].Fluid Phase Equilibria,2003,206:223-235.
[58] FREIRE M G,CARVALHO P J,SANTOS L M N B F,et al.Solubility of water in fluorocarbons:experimental and COSMO-RS prediction results[J]. Journal of Chemical Thermodynamics,2010,42(2):213-219.
[59] KAHLEN J,MASUCH K,LEONHARD K. Modelling cellulose solubilities in ionic liquids using COSMO-RS[J]. Green Chemistry,2010,12(12):2172-2181.
[60] JAAPAR S Z S,IWAI Y,MORAD N A.Effect of co-solvent on the solubility of ginger bioactive compounds in water using COSMO-RS calculations[J].Applied Mechanics and Materials,2014(624):174-178.
[61] JAAPAR S Z S,MORAD N A,IWAI Y.Solubilities prediction of ginger bioactive compounds in liquid phase of water by the COSMO-RS method[M]//Recent trends in physics of material science and technology,Springer Singapore,2015:337-352.
[62] SCHRODER B,SANTOS L M N B F,MARRUCHO I M.Prediction of aqueous solubilities of solid carboxylic acids with COSMO-RS[J]. Fluid Phase Equilibria,2010(289):140-147.
[63] VIDAL J.Thermodynamics-applications in chemical engineering and the petroleum industry[M].Paris:Editions Technip,2003.
[64] SATYRO M A.The role of thermodynamic modeling consistency in process simulation[C]//8th World Congress of Chemical Engineering,Palais des Congres,Montreal,2009.