Progress in study on thermodynamic properties of phase equilibria using molecular simulation

doi:10.16085/j.issn.1000-6613.2017-0205

Abstract

Abstract: Chemical unit operation for separation and phase equilibria are inextricably linked, and the phase equilibrium phenomenon has drawn great attentions of chemical engineers and researchers. With the rapid development of computing technology and statistical mechanics, the study of phase equilibria using molecular simulation method has been a hot topic in recent years. In this paper, the research progress in this filed over the past two decades was summarized, and the molecular simulation methods of phase equilibria and the development of force fields were discussed in detail. The applications of phase equilibria by molecular simulation to calculate the macroscopic thermodynamic data, to select the extractant and to analyze the thermodynamic mechanism were introduced systematically. The analysis showed that the molecular simulation method was well developed for the calculation of macroscopic thermodynamics data and the phase equilibrium data of various systems can be accurately calculated. The advantage of the molecular simulation method in the selection of the extractant was elucidated. Meanwhile, the lack of research in the microscopic analysis of thermodynamic mechanism was pointed out. Moreover,the development of molecular simulation method in the field of phase equilibria was analyzed and forecasted.

Key words: molecular simulation, force field, phase equilibria, microstructure

摘要： 化工单元操作与相平衡有着密不可分的联系，相平衡现象一直是化工工程师以及广大科研工作者们研究的热门课题。近年来随着计算机技术和统计力学的快速发展，应用分子模拟方法研究相平衡已成为热点。本文综述了近二十年来该领域的研究进展，归纳总结了分子模拟计算相平衡的多种方法以及4种常用的模拟力场。系统介绍并分析了相平衡分子模拟在宏观热力学数据计算、萃取剂筛选以及热力学机理分析等方面的应用情况，表明分子模拟方法在宏观热力学数据计算方面趋于成熟，能够准确模拟较多物系的相平衡数据，阐明了分子模拟方法在萃取剂筛选方面的优势，同时指出了分子模拟在热力学性质微观机理分析方面的不足和局限性，最后对分子模拟方法在相平衡领域的发展进行了展望。

关键词: 分子模拟, 力场, 相平衡, 微观结构

CLC Number:

LI Hong, ZHANG Ji, LI Xingang, GAO Xin. Progress in study on thermodynamic properties of phase equilibria using molecular simulation[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 2731-2741.

李洪, 张季, 李鑫钢, 高鑫. 分子模拟方法计算相平衡热力学性质的研究进展[J]. 化工进展, 2017, 36(08): 2731-2741.

References

[1] American Chemical Society,American Institute of Chemical Engineers,Chemical Manufacturers Association.Council for chemical research and synthetic organic chemical manufacturers association ACS technology vision 2020:the US chemical industry[M].Washington D C:American Chemical Society,1996.
[2] 朱宇,陆小华,丁皓,等.分子模拟在化工应用中的若干问题及思考[J].化工学报,2004,55(8):1213-1223. ZHU Y,LU X H,DING H,et al.Molecular simulation in chemical engineering[J]. Journal of Chemical Industry and Engineering(China),2004,55(8):1213-1223.
[3] CASE F H,CHAKA A,MOORE J D,et al.The sixth industrial fluid properties simulation challenge[J]. Fluid Phase Equilibria,2011,310:1-3.
[4] DONATE F A,HASEGAWA K,MOORE J D.Benchmarks for the sixth industrial fluid properties simulation challenge[J].Fluid Phase Equilibria,2011,310:4-6.
[5] IFPSC is an open international competition organized and sponsored by ACS,AIChE,NIST,and industrial partners[EB/OL].
[2016] . http://fluidproperties.org/.
[6] 惠丰,张敏华,马静.Gibbs系综蒙特卡罗方法模拟相平衡研究进展[J].化工进展,2012,31(8):1677-1684. HUI F,ZHANG M H,MA J.Advancement on Gibbs ensemble Monte Carlo simulation on fluid phase equilibrium[J].Chemical Industry and Engineering Progress,2012,31(8):1677-1684.
[7] 李春艳,刘华,刘波涛.分子模拟的方法及其应用[J].当代化工,2011,40(5):494-497. LI C Y,LIU H,LIU B T.Method of molecular simulation and its application[J].Contemporary Chemical Industry,2011,40(5):494-497.
[8] 程涛,孙淮.用分子模拟法预测环氧乙烷液体的热力学性质[J].计算机与应用化学,2010,27(2):183-186. CHENG T,SUN H.Prediction of the ethylene oxide (EO)properties by computer simulation[J].Computers and Applied Chemistry,2010,27(2):183-186.
[9] YANG Z,GONG M,DONG X,et al.Molecular modeling and simulation of vapor-liquid equilibrium of the refrigerant R152a and its mixture R152a+R32[J].Fluid Phase Equilibria,2015,394:93-100.
[10] 赵胜喜,祁影霞,喻志广,等. R32热力学性质的蒙特卡罗模拟[J].制冷技术,2012,40(11):37-40. ZHAO S X,QI Y X,YU Z G,et al.Monte Carlo simulation of the thermodynamic properties of R32[J].Refrigeration,2012,40(11):37-40.
[11] MUÑOZ-MUÑOZ Y M,LLANO-RESTREPO M.Vapor-liquid equilibria for the binary systems ethylene + water,ethylene + ethanol,and ethanol + water,and the ternary system ethylene + water+ ethanol from Gibbs-ensemble molecular simulation[J].Fluid Phase Equilibria,2015,394:1-11.
[12] MOODLEY S,JOHANSSON E,BOLTON K,et al.Gibbs ensemble Monte Carlo simulations of binary vapour-liquid-liquid equilibrium:application ton-hexane-water and ethane-ethanol systems[J]. Molecular Simulation,2010,36(10):758-762.
[13] ROSENBLUTH M N,ROSENBLUTH A W.Monte Carlo calculation of the average extension of molecular chains[J].The Journal of Chemical Physics,1955,23:356-359.
[14] 赵艳斌.加氢焦化甲苯精制与分子模拟对气液相平衡的研究[D].天津:天津大学,2012. ZHAO Y B.Purification of hydrogenated toluene and the research on vapor-liquid equilibria by molecular simulation[D].Tianjin:Tianjin University,2012.
[15] 李洪,李东洋,李鑫钢,等.二元醇混合物汽液相平衡的GEMC模拟与微观结构分析[J].化工进展,2016,35(9):2670-2677. LI H,LI D Y,LI X G,et al.GEMC simulation and microstructure analysis of vapor-liquid equilibrium for diol mixtures[J].Chemical Industry and Engineering Progress,2016,35(9):2670-2677.
[16] LÍSAL M,SMITH W R,NEZBEDA I.Accurate vapour-liquid equilibrium calculations for complex systems using the reaction Gibbs ensemble Monte Carlo simulation method[J].Fluid Phase Equilibria,2001,181:127-146.
[17] ROSCH T W,MAGINN E J.Reaction ensemble Monte Carlo simulation of complex molecular systems[J].Journal of Chemical Theory and Computation,2011,7:269-279.
[18] 吕程.用分子模拟的方法研究多组元系统的汽液相平衡[D].天津:天津大学,2014. LV C.Research on vapor-liquid equilibrium properties of multi-components system using molecular simulation[D].Tianjin:Tianjin University,2014.
[19] 王秀丽.Gibbs系综Monte Carlo方法研究流体相平衡[D].天津:天津大学,2003. WANG X L.Gibbs ensemble Monte Carlo method to study fluid phase equilibrium[D].Tianjin:Tianjin University,2003.
[20] 李晓锋,赵立峰,孙淮.GEMC和GDI方法计算流体气液相平衡的比较[J].物理化学学报,2008,24(10):1824-1830. LI X F,ZHAO L F,SUN H.Comparison of GEMC and GDI methods in prediction of the fluid vapor-liquid equilibrium[J].Acta Physico-Chimica Sinica,2008,24(10):1824-1830.
[21] 冯玉军.分子模拟在油田化学及相关领域的应用[J].油田化学,1998,15(1):70-75. FENG Y J.Molecular simulation and its applications in the oilfield chemistry and related fields[J].Oilfield Chemistry,1998,15(1):70-75.
[22] PANAGIOTOPOULOS A Z,WONG V.Phase equilibria of lattice polymers from histogram reweighting Monte Carlo simulations[J].Macromolecules, 1998,31:912-918.
[23] BOULOUGOURIS G C,PERISTERAS L D,ECONOMOU I G,et al.Predicting fluid phase equilibrium via histogram reweighting with Gibbs ensemble Monte Carlo simulations[J].The Journal of Supercritical Fluids,2010,55:503-509.
[24] USTINOV E A,DO D D.Application of kinetic Monte Carlo method to equilibrium systems:vapour-liquid equilibria[J].Journal of Colloid and Interface Science,2012,366:216-223.
[25] NGUYEN V T,TAN S J,DO D D,et al.Application of kinetic Monte Carlo method to the vapour-liquid equilibria of associating fluids and their mixtures[J].Molecular Simulation,2015,42:642-654.
[26] FAN C,DO D D,NICHOLSON D.New Monte Carlo simulation of adsorption of gases on surfaces and in pores:a concept of multibins[J].The Journal of Physical Chemistry B,2011,115:10509-10517.
[27] FAN C,DO D D,NICHOLSON D.A new and effective Bin-Monte Carlo scheme to study vapour-liquid equilibria and vapour-solid equilibria[J].Fluid Phase Equilibria,2012,325:53-65.
[28] 侯延军,章威,徐筱杰,等.计算机辅助药物分子设计[M].北京:化学工业出版社,2004:221. HOU Y J,ZHANG W,XU X J,et al.Computer aided drug molecular design[M].Beijing:Chemical Industry Press,2004:221.
[29] BAI P,TSAPATSIS M,SIEPMANN J I.Trappe-Zeo:transferable potentials for phase equilibria force field for all-silica zeolites[J].The Journal of Physical Chemistry C,2013,117:24375-24387.
[30] DONG X Q,GUAN X X,JIANG Y,et al.Extension of the TraPPE-UA force field to the simulation of vapor-liquid phase equilibria of vinyl acetate system[J].Journal of Molecular Liquids,2015,209:520-525.
[31] FETISOV E O,SIEPMANN J I.Prediction of vapor-liquid coexistence properties and critical points of polychlorinated biphenyls from Monte Carlo simulations with the TraPPE-EH force field[J].Journal of Chemical & Engineering Data,2014,59:3301-3306.
[32] KAMATH G,ROBINSON J,POTOFF J J.Application of TraPPE-UA force field for determination of vapor-liquid equilibria of carboxylate esters[J].Fluid Phase Equilibria,2006,240:46-55.
[33] KEASLER S J,CHARAN S M,WICK C D,et al.Transferable potentials for phase equilibria-united atom description of five-and six-membered cyclic alkanes and ethers[J].The Journal of Physical Chemistry B,2012,116:11234-11246.
[34] KELKAR M S,RAFFERTY J L,MAGINN E J,et al.Prediction of viscosities and vapor-liquid equilibria for five polyhydric alcohols by molecular simulation[J].Fluid Phase Equilibria,2007,260:218-231.
[35] KETKO M H,RAFFERTY,SIEPMANN J I,et al.Development of the TraPPE-UA force field for ethylene oxide[J].Fluid Phase Equilibria,2008,274:44-49.
[36] MAERZKE K A,SCHULTZ N E,ROSS R B,et al.TraPPE-UA force field for acrylates and Monte Carlo simulations for their mixtures with alkanes and alcohols[J].The Journal of Physical Chemistry B,2009,113:6415-6425.
[37] RAI N,SIEPMANN J I.Transferable potentials for phase equilibria. 10. explicit-hydrogen description of substituted benzenes and polycyclic aromatic compounds[J]. The Journal of Physical Chemistry B,2013,117:273-288.
[38] ZHANG J,LI H,LI X G,et al.Application of molecular simulations to ethyl acetate-ethanol:phase equilibria and azeotropic phenomenon[M]. Shanghai:Shanghai Jiao Tong University,2016:https://www.icms2016.org/.
[39] FERRANDO N,GEDIK I,LACHET V,et al.Prediction of phase equilibrium and hydration free energy of carboxylic acids by Monte Carlo simulations[J].The Journal of Physical Chemistry B,2013,117:7123-7132.
[40] FERRANDO N,LACHET V,BOUTIN A.Monte Carlo simulations of mixtures involving ketones and aldehydes by a direct bubble pressure calculation[J].The Journal of Physical Chemistry B,2010,114:8680-8688.
[41] FERRANDO N,LACHET V,BOUTIN A.Transferable force field for carboxylate esters:application to fatty acid methylic ester phase equilibria prediction[J].The Journal of Physical Chemistry B,2012,116:3239-3248.
[42] FERRANDO N,LACHET V,PEREZ-PELLITERO,et al.A transferable force field to predict phase equilibria and surface tension of ethers and glycol ethers[J].The Journal of Physical Chemistry B,2011,115:10654-10664.
[43] FERRANDO N,LACHET V,TEULER J M,et al.Transferable force field for alcohols and polyalcohols[J].The Journal of Physical Chemistry B,2009,113:5985-5995.
[44] OROZCO G A,NIETO-DRAGHI C,MACHIE A D,et al.Transferable force field for equilibrium and transport properties in linear,branched,and bifunctional amines Ⅰ. primary amines[J].The Journal of Physical Chemistry B,2011,115:14617-14625.
[45] OROZCO G A,NIETO-DRAGHI C,MACHIE A D,et al.Transferable force field for equilibrium and transport properties in linear and branched monofunctional and multifunctional amines. Ⅱ. secondary and tertiary amines[J].The Journal of Physical Chemistry B,2012,116:6193-6202.
[46] 程涛.用分子力学力场方法计算热力学性质以及预测极端状态下的状态函数[D].上海:上海交通大学,2009. CHENG T.Using molecular mechanics force field method to predict thermodynamic properties and state function under extreme condition[D].Shanghai:Shanghai Jiao Tong University,2009.
[47] 李晓锋.分子力场方法及热力学性质的预测[D].上海:上海交通大学,2009. LI X F.Force field method and thermodynamic properties prediction[D].Shanghai:Shanghai Jiao Tong University,2009.
[48] 赵立峰.分子力场方法及其在材料科学中的若干应用问题[D].上海:上海交通大学,2008. ZHAO L F.Force field methods and representative applications in material science[D].Shanghai:Shanghai Jiao Tong University,2008.
[49] 付嘉.分子模拟方法预测MOFs材料储氢能力[D].上海:上海交通大学,2009. FU J.Prediction of hydrogen storage capacity of MOFs by molecular simulation[D].Shanghai:Shanghai Jiao Tong University,2009.
[50] SUN H.Prediction of fluid densities using automatically derived VDW parameters[J].Fluid Phase Equilibria,2004,217:59-76.
[51] LI X F, ZHAO L F,CHENG T,et al.One force field for predicting multiple thermodynamic properties of liquid and vapor tthylene oxide[J].Fluid Phase Equilibria,2008,274:36-43.
[52] 王琳琳.烯烃类分子第一性原理分子力学力场[D].上海:上海交通大学,2009. WANG L L.Development and application of a first-principle force field for alkenes[D]. Shanghai:Shanghai Jiao Tong University,2009.
[53] 熊振海.大环芳香平面配体过渡金属配合物的密度泛函研究及其分子力场开发[D].上海:上海交通大学,2006. XIONG Z H.Study on density function and molecular force field development of transition metal complexes of macrocyclic aromatic flat ligands[D].Shanghai:Shanghai Jiao Tong University,2006.
[54] 陈清.分子模拟方法在高分子质子交换膜和表面活性剂中的若干应用研究[D].上海:上海交通大学,2011. CHEN Q.Study on polymer proton exchange membrane and surfactant using molecular simulation method[D].Shanghai:Shanghai Jiao Tong University,2011.
[55] 孙迎新.微孔-介孔材料中气体吸附、扩散及催化转化过程的分子模拟研究[D].上海:上海交通大学,2010. SUN Y X.Molecular simulation of gas adsorption,diffusion and catalytic conversion in microporous-mesoporous materials[D]. Shanghai:Shanghai Jiao Tong University,2010.
[56] HAJIPOUR M,AGHAMIRI S F,SABZYAN H,et al.Extension of the exp-6 model to the simulation of vapor-liquid equilibria of primary alcohols and their mixtures[J].Fluid Phase Equilibria,2011,301:73-79.
[57] ZHANG M H,CHEN L H,YANG H M,et al.Gibbs ensemble Monte Carlo simulation using an optimized potential model:pure acetic acid and a mixture of it with ethylene[J].Journal of Molecular Modeling,2016,22:162.
[58] MOU?KA F,NEZBEDA I.Gibbs ensemble simulation on polarizable models:vapor-liquid equilibrium in Baranyai-Kiss models of water[J].Fluid Phase Equilibria,2013,360:472-476.
[59] MARTIN M G.MCCCS Towhee:a tool for Monte Carlo molecular simulation[J].Molecular Simulation,2013,39(14/15):1212-1222.
[60] 董秀芹,管肖肖,马静.二氧化碳-醋酸乙烯体系相平衡的GEMC模拟[J].计算机与应用化学,2015,32(10):1182-1186. DONG X Q,GUAN X X,MA J.Gibbs ensemble Monte Carlo simulations of binary mixture of CO₂ and vinyl acetate[J].Computers and Applied Chemistry,2015,32(10):1182-1186.
[61] 董秀芹,姚玲,张敏华.乙烯-醋酸乙烯酯体系的汽液相平衡分子模拟[J].计算机与应用化学,2013,30(6):625-628. DONG X Q,YAO L,ZHANG M H.Vapor-liquid equilibrium of ethylene and vinyl acetate by molecular simulation[J].Computers and Applied Chemistry,2013,30(6):625-628.
[62] 董秀芹,姚玲,张敏华.醋酸乙烯的NVT-GEMC模拟研究[J].计算机与应用化学,2013,30(5):550-552. DONG X Q,YAO L,ZHANG M H.NVT-GEMC simulation on vinyl acetate[J].Computers and Applied Chemistry,2013,30(5):550-552.
[63] 惠丰.乙烯-醋酸体系汽液相平衡的Gibbs系综蒙特卡罗模拟研究[D].天津:天津大学,2012. HUI F.Study on vapor-liquid equilibrium of ethylene-acetic acid system with Gibbs ensemble Monte Carlo simulation[D].Tianjin:Tianjin University,2012.
[64] 惠丰,张敏华,马静.乙烯在醋酸中溶解度的Gibbs系综蒙特卡罗模拟[J].计算机与应用化学,2012,29(5):629-633. HUI F,ZHANG M H,MA J.Vapor-liquid equilibrium of ethylene and acetic acid system by Gibbs ensemble Monte Carlo simulation[J].Computers and Applied Chemistry,2012,29(5):629-633.
[65] 杨华明.醋酸缔合及醋酸-丁烯醛体系汽液相平衡的分子模拟研究[D].天津:天津大学,2015. YANG H M.The molecular simulation on the association of acetic acid and vapor-liquid phase equilibrium for acetic acid-crotonaldehyde[D].Tianjin:Tianjin University,2015.
[66] 姚玲.Gibbs系综蒙特卡罗方法乙烯-醋酸乙烯汽液相平衡研究[D].天津:天津大学,2012. YAO L.Vapor-liquid equilibrium of ethylene and vinyl acetate by Gibbs ensemble Monte Carlo simulation[D].Tianjin:Tianjin University,2012.
[67] 杨华明,张敏华,马静.丁烯醛及丁烯醛-乙醛二元体系汽液相平衡模拟[J].化工学报,2015,66(5):1627-1632. YANG H M,ZHANG M H,MA J.Vapor-liquid equilibrium simulation for crotonaldehyde and its mixture with ethanal[J].CIESC Journal,2015,66(5):1627-1632.
[68] 蒋国柱.吉布斯系综模拟流体汽液相平衡[D].重庆:重庆大学,2003. JIANG G Z.Gibbs ensemble simulates vapor-liquid equilibria of fluids[D].Chongqing:Chongqing University,2003.
[69] 蒋国柱,薛荣书,魏顺安.吉布斯系综Monte Carlo技术模拟L-J流体汽液相平衡[J].重庆大学学报,2003,26(8):64-67. JIANG G Z,XUE R S,WEI S A.Computer simulation for liquid-vapor phase equilibrium of L-J fluid by the GEMC method[J].Journal of Chongqing University,2003,26(8):64-67.
[70] 李艳姣.吉布斯系综蒙特卡洛法模拟研究链状流体的汽液相平衡[D].重庆:重庆大学,2007. LI Y J.Study on the vapor-liquid phase equilibrium of chain-fluids with Gibbs Ensemble Monte Carlo simulation[D].Chongqing:Chongqing University,2007.
[71] 施恩明.GEMC模拟流体气液相平衡[D].重庆:重庆大学,2006. SHI E M.GEMC simulation of the vapor liquild phase equilibrium[D].Chongqing:Chongqing University,2006.
[72] 肖勇.流体汽液相平衡的分子模拟[D].重庆:重庆大学,2005. XIAO Y.Study the vapor-liquid equilibria of fluids through molecular simulation[D].Chongqing:Chongqing University,2005.
[73] 肖勇,薛荣书,施晓明,等.水的汽液相平衡及径向分布的分子模拟研究[J].计算机与应用化学,2005,22(10):871-873. XIAO Y,XUE R S,SHI X M,et al.Study the vapor-liquid equilibrium and radial distribution of water by molecular simulation[J].Computers and Applied Chemistry,2005,22(10):871-873.
[74] 袁健芳.二元混合物流体相平衡吉布斯系综模拟[D].重庆:重庆大学,2004. YUAN J F.Gibbs ensemble simulates for vapor-liquid equilibria of binary mixture fluids[D].Chongqing:Chongqing University,2004.
[75] MUÑOZ-MUÑOZ Y M,VRABEC J,LLANO-RESTREPO M.Vapor-phase chemical equilibrium and combined chemical and vapor-liquid equilibrium for the ternary system ethylene+water+ethanol from reaction-ensemble and reactive Gibbs-ensemble molecular simulations[J]. Fluid Phase Equilibria,2015,403:104-113.
[76] ZENG Y P,WANG C F,HU J M,et al.Phase equilibria and structural properties of thiophene/[BMIM] [BF₄]:a molecular insight from Monte Carlo simulations[J]. AIChE Journal,2014,60:3916-3924.
[77] XU W H,YANG J C.Computer simulations on aggregation of acetic acid in the gas phase,liquid phase,and supercritical carbon dioxide[J].The Journal of Physical Chemistry A,2010,114:5377-5388.
[78] 蒲亮,缪强,张志炳,等.醋酸水溶液汽液非接触相平衡的蒙特卡罗模拟研究[J].计算机与应用化学,2008,25(2):185-188. PU L,MIU Q,ZHANG Z B,et al.Monte Carlo simulation of non-contact vapor-liquid phase equilibrium in acetic acid aqueous solution[J].Computers and Applied Chemistry,2008,25(2):185-188.
[79] 刘志平,黄世萍,汪文川.分子计算科学-化学工程新的生长点[J].化工学报,2003,54(4):464-476. LIU Z P,HUANG S P,WANG W C.Molecular computational science new paradigm of chemical engineering[J].CIESC Journal,2003,54(4):464-476.
[80] 吕程,曾爱武.应用分子模拟研究苯-噻吩二元体系的汽液相平衡[J].计算机与应用化学,2016,33(4):425-428. LV C,ZENG A W.Research on vapor-liquid equilibrium for benzene/thiophene binary system by molecular simulation[J]. Computers and Applied Chemistry,2016,33(4):425-428.
[81] 吕程,鞠吉,曾爱武.苯-噻吩-NMP三元体系汽液平衡的GEMC模拟[J].计算机与应用化学,2016,33(3):309-312. LV C,JU J,ZENG A W.GEMC simulation for benzene/thiophene/NMP ternary system[J].Computers and Applied Chemistry,2016,33(3):309-312.
[82] WU X W,LI Y G,LU J F,et al.Monte Carlo simulation of the water-methanol system[J].Fluid Phase Equilibria,1992,77:139-156.