修正的硬球三参数状态方程(Ⅱ)纯物质热力学性质的预测

对本文(I)报中MCSPT方程与物质有关的参数A_1、A_2、A_3、A_4和A_5给出了以偏心因子ω和临界压缩因子Z_c为关联因子的普遍化关联式,从而将MCSPT方程推广到极性、强极性物质热力学性质的预测.通过对72种物质饱和液体密度和151种物质液体蒸发焓的计算结果表明,MCSPT不仅能精确地预测物质的饱和性质,而且也能准确地计算焓差.     

修正的硬球三参数状态方程(Ⅱ)纯物质热力学性质的预测

对本文(I)报中MCSPT方程与物质有关的参数A_1、A_2、A_3、A_4和A_5给出了以偏心因子ω和临界压缩因子Z_c为关联因子的普遍化关联式,从而将MCSPT方程推广到极性、强极性物质热力学性质的预测.通过对72种物质饱和液体密度和151种物质液体蒸发焓的计算结果表明,MCSPT不仅能精确地预测物质的饱和性质,而且也能准确地计算焓差.     

煤液化油的基本热力学性质测定方法的分析

分析了煤液化油的一些基本热力学性质:比热、蒸汽压、气-液相平衡常数和蒸发焓等,并参考石油基本热力学性质的各种测定方法及关联式计算法,探索研究了煤液化油基本热力学性质的测定方法和关联式计算法,特别是对煤液化油比热、蒸汽压的测定、气-液相平衡常数的计算及蒸发焓的估算作了详尽的讨论.最后得出了测定煤液化油这些热力学性质的适宜方法.简要概括了煤液化油馏分临界性质参数的计算.     

用微扰理论建立水的分子热力学模型

提出1种水的分子热力学模型,从微扰理论出发,建立了自由能及其它热力学函数的关系式.水分子间作用包括硬球、色散、静电及诱导几个部分.通过同时关联0～300°C下饱和水蒸气压及液体密度数据获得分子参数,还预测了水的蒸发焓及饱和水蒸气的比容,比较了文献中处理水的几种理论方法.结果表明,本模型简单,且较接近实际.     

DMF的力场构建及乙腈-甲醇-DMF三元体系的汽液相平衡模拟

采用量子化学和Gibbs系综Monte Carlo模拟相结合的方法,对TraPPE-UA力场中缺失的N,N-二甲基甲酰胺（DMF）力场参数进行了补充,为含DMF多元体系的汽液相平衡模拟奠定了基础。采用新构建的力场参数,在NVT-Gibbs系综中计算了DMF的汽液相平衡性质,结果表明该力场能准确计算出DMF的饱和液相密度、蒸气压、沸点、临界值和蒸发焓。在NPT-Gibbs系综中,采用TraPPE-UA力场分别计算了乙腈-甲醇、DMF-甲醇、DMF-乙腈二元混合物的汽液相平衡性质,并与实验值进行了比较。模拟结果与实验值较为吻合,验证了力场模型的可靠性。最后在NPT-Gibbs系综中采用TraPPE-UA力场对乙腈-甲醇-DMF三元体系的汽液相平衡数据进行了预测,为设计和优化乙腈和甲醇的萃取分离过程提供了基础数据。     

DMF的力场构建及乙腈-甲醇-DMF三元体系的汽液相平衡模拟

采用量子化学和Gibbs系综Monte Carlo模拟相结合的方法,对Tra PPE-UA力场中缺失的N,N-二甲基甲酰胺(DMF)力场参数进行了补充,为含DMF多元体系的汽液相平衡模拟奠定了基础。采用新构建的力场参数,在NVT-Gibbs系综中计算了DMF的汽液相平衡性质,结果表明该力场能准确计算出DMF的饱和液相密度、蒸气压、沸点、临界值和蒸发焓。在NPT-Gibbs系综中,采用Tra PPE-UA力场分别计算了乙腈-甲醇、DMF-甲醇、DMF-乙腈二元混合物的汽液相平衡性质,并与实验值进行了比较。模拟结果与实验值较为吻合,验证了力场模型的可靠性。最后在NPT-Gibbs系综中采用Tra PPE-UA力场对乙腈-甲醇-DMF三元体系的汽液相平衡数据进行了预测,为设计和优化乙腈和甲醇的萃取分离过程提供了基础数据。     

LNG接收站蒸发计算状态方程选择

LNG物性参数是LNG接收站模型建立、工艺流程模拟计算及研究必不可少的基础数据。以国外实验数据为基础,采用Aspen HYSYS软件分析评价PR、SRK、LKP、BWRS状态方程对气液相组成、焓、密度等物性参数的预测结果,比选汽液相平衡和热力学参数的计算状态方程,建立了LNG接收站储罐蒸发模型,并比较了四种状态方程的准确度。结果表明：PR方程在汽液相平衡计算方面计算精度最高,相对误差为4.70%;LKP方程计算热力学参数最准确,预测误差为2.59%。综合考虑相平衡参数和热力学参数计算精度,PR方程精度最高,预测误差为3.77%。此外,PR方程对LNG储罐蒸发和储罐压力的模拟计算值与现场数据吻合度最好,因此LNG接收站蒸发计算推荐选用PR方程。研究结果对物性参数和LNG接收站蒸发计算状态方程的选择具有借鉴意义。     

A002 N2在丙醇中亨利常数的分子模拟计算中有关问题

亨利常数是化工中的一个重要热力学参数,但在实验测定比较困难.分子模拟法计算该参数不依赖于任何经验参数,相对于实验有很大的优势.本文探讨了在正则系综下用Widom方法计算亨利常数中的一些影响因素.结果发现,用立方格子法插入、插入时粒子不需要旋转.在格子密度在0.5格子/A3时,计算结果一般可以收敛到较高的准确度.计算结果对溶剂密度非常敏感.     

优化温度相关力场预测正构烷烃热力学性质

为了实现不同温度下正构烷烃及其混合物热力学性质的准确预测,以正构烷烃(n-C4~C10)为训练集,通过对全原子OPLS-AA力场中非键相互作用参数(ε)的模拟优化,得到了ε与对比温度(Tr)以及正构烷烃碳原子个数(NC)的经验关系式。利用该关系式计算出不同温度不同种类的正构烷烃的ε值,预测了正构烷烃纯物质及其混合物的黏度、密度、扩散系数等物性,并将新力场模拟计算值与理论估算值以及实验值进行比较。结果表明,采用优化温度相关力场预测烷烃及其混合物的物性与实验值最为吻合。密度、黏度和扩散系数的预测值与实验值的相对偏差分别小于2%、5%和10%,显著优于目前的理论方法和原OPLS-AA力场模拟计算的预测值。上述温度相关力场参数的确立,对于利用分子动力学模拟方法准确地预测正构烷烃及其混合物的热力学性质具有重要的实际应用价值。     

R1234ze(E)制冷剂PC-SAFT状态方程

R1234ze(E)属于氢氟烯烃类（HFOs）物质,是一种新型替代制冷工质。为了更加精确地描述其热力学性质,以PC-SAFT状态方程为基础,利用文献公开报道的R1234ze(E)的饱和液相密度及饱和蒸气压测量数据,拟合获取到PC-SAFT状态方程的3个参数。基于MATLAB软件,实现了利用PC-SAFT状态方程计算工质的热力学性质。研究结果表明：与CPA状态方程相比,PC-SAFT状态方程在计算饱和气相密度时偏差有所增大,但是在计算饱和液体密度和单相液体密度时的精度显著提升。     

Extension of EOS non-iterative methods to density calculations: Correlation of saturated molar volumes and heats of vaporization

Soave's direct calculation procedures for the vapor pressure of pure compounds with cubic equations of state (EOSs), have been extended to the calculation of phase densities at saturation for Peng-Robinson (PR) type EOSs. These universal relations have been used to propose EOS-based correlation methods for the pure compound saturated liquid and vapor molar volumes, at temperatures higher than the normal boiling point. The methods yield satisfactory results independently of the molecular nature of the chemical under consideration. The results for phase densities are used to correct the heats of vaporization predicted by the ZVPR-EOS. Complete relative error information is provided for calculated heats of vaporization and correlated vapor and liquid phase molar volumes for more than one hundred compounds of industrial interest.     

COMPARISON OF A PAIR OF THREE PARAMETER EQUATIONS OF STATE

The lattice fluid (LF) equation of state derived by Sanchez and Lacombe from a lattice model is compared to the empirical Peng-Robinson (PR) equation for normal alkane fluids ranging from methane to heptadecane in molecular weight. With respect to vapor pressure predictions, the equations are both good. The LF equation is superior, especially for higher molecular weight fluids, to the Peng-Robinson equation in predicting saturated liquid densities. For carbon numbers less than 6, the PR equation predicts heats of vaporization more accurately, whereas for carbon numbers greater than 9 the LF equation is more accurate than the PR one for temperatures lower than about 95% of critical.     

Use of velocity of sound in predicting thermodynamic properties of dense fluids from cubic equations of state

In this paper it has been shown that velocity of sound data may be used to obtain constants of a cubic equation of state and then thermodynamic properties can be accurately calculated through the constants extracted from sonic velocity data. Results are presented for estimation of heat capacities, enthalpies, vapor pressures and compressibility factors of some pure vapor and liquid compounds as well as some binary mixtures for pressures up to 100 MPa and temperatures up to 600 K for hydrocarbons from methane to hexadecane. The method will be useful for those mixtures containing heavy compounds for which accurate data on critical constants are not available, but for which the sonic velocity can be measured.     

Thermodynamic properties of the system toluene — 1, 1, 1-trichloroethane

Data on molar excess enthalpy on mixing at 298.15 K and 308.15 K, vapor-liquid equilibrium, latent heats of vaporization at 91.444 kPa and vapor pressures for the system toluene – 1, 1, 1-trichloroethane are presented. A simple adiabatic calorimeter designed for molar excess enthalpy measurements is described, tested and used.     

THE MODIFIED PGR EQUATION OF STATE: PURE-FLUID PREDICTIONS

The Park-Gasem-Robinson (PGR) equation of state (EOS) has been modified to improve its volumetric and equilibrium predictions. Specifically, the attractive term of the PGR equation was modified to enhance the flexibility of the model, and a new expression was developed for the temperature dependence of the attractive term in this segment-segment interaction model.

The predictive capability of the modified PGR EOS for vapor pressure and saturated liquid and vapor densities was evaluated for selected normal paraffins, normal alkenes, cyclo-paraffins, light aromatics, argon, carbon dioxide, and water. The generalized EOS constants and substance-specific characteristic parameters in the modified PGR EOS were obtained from pure component vapor pressures and saturated liquid and vapor molar volumes. The calculated phase properties were compared with those of the Peng-Robinson (PR), the simplified-perturbed-hard-chain theory (SPHCT), and the original PGR equations. Generally, the performance of the proposed EOS (%AAD of 1.3, 2.8, and 3.7 for vapor pressure, saturated liquid, and vapor densities, respectively) was better than the SPHCT and original PGR equations in predicting the pure fluid properties.     

COMPARISON OF A PAIR OF THREE PARAMETER EQUATIONS OF STATE

The lattice fluid (LF) equation of state derived by Sanchez and Lacombe from a lattice model is compared to the empirical Peng-Robinson (PR) equation for normal alkane fluids ranging from methane to heptadecane in molecular weight. With respect to vapor pressure predictions, the equations are both good. The LF equation is superior, especially for higher molecular weight fluids, to the Peng-Robinson equation in predicting saturated liquid densities. For carbon numbers less than 6, the PR equation predicts heats of vaporization more accurately, whereas for carbon numbers greater than 9 the LF equation is more accurate than the PR one for temperatures lower than about 95% of critical.     

The excess enthalpy of gaseous mixtures of carbon dioxide with methane

Excess enthalpies (heats of mixing) of mixtures of methane and carbon dioxide have been measured in a flow calorimeter at temperatures between 10°C and 80°C and pressures up to 100 atmospheres. All measurements were for the mixing of two gas phases. The results were compared with various predictions based on equations of state and the principle of corresponding states.     

THERMOPHYSICAL PROPERTIES OF ASSOCIATING FLUIDS IN NATURAL GAS INDUSTRY USING PC-SAFT EQUATION OF STATE

The perturbed-chain statistical associating fluid theory (PC-SAFT) is employed to calculate the thermophysical properties of some associating fluids that are widely used in the natural gas industry. Methanol, alkanolamines, and glycols are considered in this work. The alkanolamines include monoethanolamine (MEA), diethanolamine (DEA), and methyldiethanolamine (MDEA). Two new modified associating schemes are introduced to describe the alkanolamine associating behavior. The glycols considered in this work are monoethylene glycol (MEG), diethylene glycol (DEG), and triethylene glycol (TEG). The pure component parameters of these associating fluids are determined using vapor pressure and saturated liquid density data. The heats of vaporization and heat capacities of these compounds are then predicted. Sound velocities and Joule-Thomson coefficients are additionally predicted for methanol. The results indicate that PC-SAFT is accurate for correlating the vapor pressure and liquid density of methanol, the glycols, and alkanolamines. PC-SAFT is also accurate in predicting the Joule-Thomson coefficients and sound velocities of methanol. Although PC-SAFT is not accurate enough for predicting the thermal properties (heat capacities and heats of vaporization) of MEG and TEG, it reasonably describes the thermal properties of MEA, DEA, MDEA, and DEG.     

OPTIMIZATION OF THE COMPOSITIONS FOR CFC ALTERNATIVE MIXTURE REFRIGERANTS

In this work,eight commonly used and recently developed cubic EOSs have beenextensively tested for the calculation of thermodynamic properties,including vapor pressure,vaporand liquid densities and heat of vaporization for 26 pure CFCs and their alternatives.The modifiedDu-Guo EOS is recommended for the vapor-liquid equilibria calculations of mixtures for its goodaccuracy.A method for the development of the optimized mixture compositions of CFC alternativeshas been proposed by using minimization of deviations between the vapor pressures of CFC and thealternative mixtures of interest.As examples,two binary mixtures R22-R142b and R22-R152a,and aternary R22-R142b-R152a have been tested.The results show that the vapor pressure of R12 can bewell duplicated by a mixture refrigerant with the optimized composition.On the other hand,thedeviations between the heat of vaporization are somewhat apparent within 10 percent.Moreover,allthe mixtures discussed here are of the characteristics of being near azeotropic,and