混合流体饱和汽相体积的测定与计算

用作者建立的实验装置测定了二氧化碳－丙酮、二氧化碳－乙醚、二氧化碳－二氯甲烷三个二元体系露点压力下的饱和汽相体积和Ｐ，Ｔ，ｙ数据，测定结果用修正的ＰＲ状态方程进行了关联。     

不同充汽方式下供汽系统动态特性仿真

以供汽系统为研究对象,采用集总参数法建立相应的数学模型,进行充汽阀自动控制充汽和旁通阀自动控制充汽两种充汽方式的动态仿真。结果表明:旁通阀自动控制充汽时完成3次充放汽时间为76.3s,充汽阀自动控制充汽时完成3次充放汽时间为62.9s,充汽阀自动控制充汽时平均每次充汽时间减少4.5s;两种充汽方式关键参数在充汽阶段均维持较为稳定,在阀门切换阶段存在较大波动,但压力波动均小于0.2 MPa;相同充汽方式下,汽包压力波动过热蒸汽压力波动供汽母管压力波动。     

不同充汽方式下供汽系统动态特性仿真

以供汽系统为研究对象,采用集总参数法建立相应的数学模型,进行充汽阀自动控制充汽和旁通阀自动控制充汽两种充汽方式的动态仿真。结果表明：旁通阀自动控制充汽时完成3次充放汽时间为76.3 s,充汽阀自动控制充汽时完成3次充放汽时间为62.9 s,充汽阀自动控制充汽时平均每次充汽时间减少4.5 s;两种充汽方式关键参数在充汽阶段均维持较为稳定,在阀门切换阶段存在较大波动,但压力波动均小于0.2 MPa;相同充汽方式下,汽包压力波动< 过热蒸汽压力波动< 供汽母管压力波动。     

交替充汽方式下双蒸汽蓄热器系统动态特性仿真

为了研究双蒸汽蓄热器系统的动态特性,采用集总参数法建立相应的数学模型,进行直接交替和间接交替两种充汽方式的动态仿真。仿真结果表明：直接交替充汽方式充汽时间减少2.6 s,压力波动更小;相同充汽方式下,汽包压力波动 < 过热蒸汽压力波动 < 供汽母管压力波动;直接交替充汽方式燃油量节省率为7.45%。通过数据对比分析可得：直接交替充汽方式具有充汽速度快、压力波动小、燃油经济性好的优点。     

交替充汽方式下双蒸汽蓄热器系统动态特性仿真

为了研究双蒸汽蓄热器系统的动态特性,采用集总参数法建立相应的数学模型,进行直接交替和间接交替两种充汽方式的动态仿真。仿真结果表明:直接交替充汽方式充汽时间减少2.6s,压力波动更小;相同充汽方式下,汽包压力波动过热蒸汽压力波动供汽母管压力波动;直接交替充汽方式燃油量节省率为7.45%。通过数据对比分析可得:直接交替充汽方式具有充汽速度快、压力波动小、燃油经济性好的优点。     

立方型状态方程含过量自由焓模型的新混合规则

提出了在参考压力下将过量自由焓(g~E)模型引入状态方程的修正Huron-Vidal混合规则,由g~E模型确定状态方程中混合物的参数,以SRK方程和Wilson模型为例,取大气压为参考压力,计算了16个体系50组汽液平衡,结果表明本文建议的混合规则可直接使用现有文献报道的常压g~E模型参数由立方型状态方程预测常压汽液平衡,并对直接外推预测高压汽液平衡作了尝试.     

汽相循环法加压汽液平衡装置

本装置具有汽相强制循环、体积自动补偿、汽相液相同时采样、用一台色谱仪在线连续分析等特点。目前可达到压力为25公斤/厘米~2、温度在-28℃到 10℃。用于测定氟氯烃类的汽液平衡,得到了比较满意的数据。一般,每昼夜可测取一条具有24个以上数据点的汽液平衡等温线。     

甲醇-甲醛-聚甲氧基二甲醚三元体系汽液平衡

聚甲氧基二甲醚(PODE_n)是一种含氧量较高的化合物,近年来更是发展为一种优质的柴油添加剂。在101.3 kPa恒定压力下,使用改进的汽液平衡双循环Rose釜测定了甲醇-甲醛-PODE₂三元体系汽液平衡数据。运用最大似然原理,在Aspen Plus软件中,分别采用NRTL、Wilson以及UNIQUAC三种活度系数模型对测定的三元汽液平衡数据进行回归,分别得到三个模型所对应的二元交互参数以及模拟计算值。通过对比模拟值与实验值,得到温度和气相组成的平均绝对偏差,分别小于1.10 K、0.0250和0.0240。三个模型的关联结果均适用于此体系,得到的二元交互参数能够应用于甲醇-甲醛-PODE₂三元体系的精馏设计,为相关物系的工业分离优化奠定了数据基础。     

变阱宽方阱链流体状态方程模拟制冷剂的汽液平衡

应用作者先前基于二阶微扰理论和PY2近似积分方程建立的可变阱宽方阱链流体状态方程模拟了纯制冷剂及其混合体系的汽液平衡。通过关联不同温度下制冷剂的饱和蒸气压和液体体积得到了18种纯制冷剂的分子参数,新方程计算的饱和蒸气压和液体体积总的平均偏差分别为1.11％和0.92％。结合简单混合规则,将此方程扩展到混合体系。研究发现,建立的方程可满意预测制冷剂二元混合体系除临界区附近外的汽液平衡,对两个三元体系汽液平衡的预测也取得了满意的效果,当引入一个与温度无关的可调参数时,关联精度大为提高,预示着新的方程可模拟制冷剂的汽液平衡。     

蒸汽分级供应流程的特点

自备电厂、小锅炉、合成氨副产蒸汽联网外供蒸汽、受小锅炉压力的限制，不能满足用汽工段的要求，因此将蒸汽分为三个压力等级分别供给用汽工段，优化了蒸汽管网流程。     

A modified Peng–Robinson equation of state for phase equilibrium calculation of liquefied,synthetic natural gas,and gas condensate mixtures

A modified Peng–Robinson equation of state, MPR2 EOS, is introduced by incorporating a new alpha function and a temperature dependent function for covolume, b. The modified cubic EOS has three input per each substance: critical temperature, critical pressure, and acentric factor. The coefficients of temperature dependence of the alpha and beta functions, relating to the parameters a and b of the new cubic EOS, are obtained by simultaneous fitting of saturated experimental vapour pressure and liquid density data for several pure components. The percent absolute average deviation (AAD%) of 1.38, 4.80 and 2.89 are obtained to correlation of the saturation vapour pressure, liquid density and vapour volume, respectively. Also the ADD% of 2.575 is computed for prediction of saturation enthalpy of vapourisation of the pure compounds. For calculation of phase equilibrium of mixture, the modified PR EOS is used for prediction of liquid density of the LNG mixtures. Also the new EOS is applied for construction of the phase envelop of synthetic natural gas, SNG, mixtures and calculation vapour–liquid equilibria of gas condensates. The results demonstrate that the new MPR2 EOS can be used for calculation of vapour–liquid equilibrium of pure components and mixtures with good accuracy.     

VAPOUR LIQUID EQUILIBRIA IN STRONG ELECTROLYTE SOLUTIONS BY THE CORGC EQUATION OF STATE

The capability of chain-of-rotalor group contribution equation of state (CORGC EOS) in prediction of vapour-liquid equilibria for electrolyte solutions is discussed. A new approach is considered in which salt is considered as a single component and therefore, there is no ion in the solution. The interaction parameters between water and 50 salts are determined and reported. The parameters are temperature dependent and thus, vapour-liquid equilibria calculations can be achieved at moderate temperature. The percent average absolute deviation for prediction of vapour pressure and osmotic coefficient for 50 aqueous solutions are equal to 0.89 and 16.7, respectively. Comparison between the calculated results and experimental data has been performed.     

Modeling aspirin and naproxen ternary solubility in supercritical CO2/alcohol with a new Peng–Robinson EOS plus association model

A new version of the Peng–Robinson equation of state (PR EOS) is developed through the use of Wertheim's thermodynamic perturbation theory of associating fluids and statistical associating fluid theory (SAFT). The new equation is characterized by two temperature-independent parameters, namely, association strength and association volume, which account for the association interactions between associating molecules. In this work, we employed the equation to model aspirin and naproxen solubility enhancement obtained in the ternary supercritical CO₂/alcohol systems, where the original PR EOS has resulted in large and negative binary interaction parameters between the polar solute and polar cosolvent. Calculated results show that the Peng–Robinson EOS plus association model gives better performance to correlate these ternary solubility data over the ranges of temperature, pressure and cosolvent concentration investigated than its conventional form that uses temperature-dependent parameters.     

EOS状态下基于多相流有规栅格理论的水-碳氢化合物两相体系的临界轨迹关系

Quantitative representation of complicated behavior of fluid mixtures in the critical region by any of equation-of-state theories remains as a difficults thermodynamic topics to date.In the present work,a computational efforts were made for representing various types of critical loci of binary water with hydrocarbon systems showing Type Ⅱ and Type Ⅲ phase behavior by an elementary equation of state[called multi-fluid nonrandom lattice fluid EOS(MF-NLF EOS)]based on the lattice statistical mechanical theory.The model EOS requires two molecular parameters which representing molecular size and interaction energy for a pure component and single adjustable interaction energy parameter for binary mixtures.Critical temperature and pressure data were used to obtain molecular size parameter and vapor pressure data were used to obtain interaction energy parameter.The MF-NLF EOS model adapted in the present study correlated quantitatively well the critical loci of various binary water with hydrocarbon systems.     

A simplified equation of state for polymer melts from perturbed Yukawa hard-sphere chain

This paper addresses the modeling of the pressure?Cvolume?Ctemperature (PVT) properties of 14 polymer melts using simplified Yukawa hard-sphere-chain equation of sate (EOS) plus first-order perturbation theory. Three pure-component parameters appeared in the EOS have been determined via the volumetric data. These parameters reflect the segment number, non-bonded segment?Csegment interaction energy, and segment size. Likewise, this study considered chains that interact through a range-parameter of Yukawa potential with l.8. The reliability of the proposed model has been assessed by comparing the results with 1,315 experimental data points over a broad range of pressures and temperatures for which, their measured values were available in the literature. Our calculations on the specific volume of studied liquid polymers reproduce very accurately the experimental PVT data. The overall average absolute deviation of the calculated specific volumes from literature data was found to be 0.89?%.     

Solubility of propylene in semicrystalline polypropylene

Gas solubilities and polymer swelling in propylene and semicrystalline polypropylene system at temperatures of 323.2 and 348.2 K and pressures up to propylene's vapor pressure were measured. Pressure, specific volume, and temperature (PVT) measurements of polypropylene were carried out at temperatures from 313 to 573 K and pressures up 200 MPa. Two kinds of polypropylenes, which had different stereoregularities, were used for both solubility and PVT measurements. The solubilities were correlated with the Sanchez–Lacombe equation of state (EOS) with temperature‐dependent binary interaction parameters to within 5% average relative percentage deviation. Swelling ratios estimated with Sanchez–Lacombe EOS coupled with optimized interaction parameters were 20% lower than the experimental values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1134–1143, 2001     

On the Jones-Wilkins-Lee equation of state for high explosive products

The Jones-Wilkins-Lee (JWL) model is a widely used Equation Of State (EOS) in the literature to model high explosive products. It is based on exponentially decaying isentropes in the pressure-volume diagram, completed by an additional term meant to recover an ideal-gas behavior for large expansions where exponential terms are negligible. A step-by-step analysis of the EOS is proposed. Starting from the main isentrope, the constant Grüneisen, and constant isochoric heat capacity, the JWL expressions of pressure, temperature, sound speed, specific internal energy, specific entropy and specific enthalpy are derived. For a specific set of JWL parameters meant to model HMX products, various thermodynamic fields are investigated in pressure–volume and temperature–volume planes. The positivity of pressure and temperature, the convexity, the thermodynamic stability, and the monotonicity along an Hugoniot are investigated in order to characterize the JWL domain of validity. For each of these constraints, different regions of validity are found. Besides presenting a study of the JWL model and its limits, this work also provides a standalone presentation and derivation containing the necessary materials for the understanding and for the use of the JWL EOS in reactive hydrodynamic simulations of condensed phase explosives.     

Calculation of Vapor‐Liquid Equilibrium Data of Binary Mixtures Using Vapor Pressure Data

The design of plants or unit operations requires the knowledge of data for multicomponent systems. An approach is presented for the regression of binary interaction parameters required for the calculation of activity coefficients. Binary vapor pressure data are used to correlate these parameters for calculation of vapour/liquid equilibrium data. The advantage of the approach is the fact that only easily measured vapor pressure data are required. The procedure is demonstrated by means of two binary mixtures. Parameter regression, prediction of vapour/liquid equilibrium data as well as their experimental verification are demonstrated.     

Improved vapor pressure prediction from PR + COSMOSAC EOS using normal boiling temperature

We evaluate the predictive power of the PR + COSMOSAC Equation of State (EOS) for vapor pressure using a large dataset of 19,081 compounds. The PR + COSMOSAC EOS uses results of quantum mechanical solvation calculations to determine the energy and molecular volume parameters in the Peng-Robinson EOS and thus does not require experimental critical temperature (T_c), pressure (P_c), and acentric factor (ω) as in the conventional approach. The prediction accuracy (average absolute relative deviation) is 141%, about seven times that of the PR EOS. A new approach is developed to improve the prediction accuracy from PR + COSMOSAC EOS by incorporating experimental normal boiling temperature. The prediction accuracy improves to 58%, about three times that of the PR EOS. The PR + COSMOSAC EOS is an effective method for vapor pressure prediction when no or just some experimental data is available.     

Measurement of excess enthalpies using a high-pressure flow microcalorimeter and determination of binary interaction parameters for thermodynamic models

While an equation of state (EOS) plays a critical role in estimating thermodynamic properties, employing it in the determination of binary interaction parameters is extremely important. In general, these parameters can be determined from phase equilibrium data. However, data collection from experiments is a time-consuming and tedious process. In this study, after measuring the excess enthalpies of binary systems containing CO₂ by high-pressure flow isothermal microcalorimetry (IMC), we determined the EOS binary interaction parameters, specifically, the Peng-Robinson EOS binary interaction parameters. These binary interaction parameters obtained by IMC were compared with those obtained by vapor-liquid equilibrium (VLE) experiments. Hence, high-pressure flow IMC appears to be an effective method for the determination of interaction parameters that are used in the estimation of thermodynamic properties. Further, the Flory-Huggins interaction parameters of a binary mixture CO₂ containing with various mole compositions were also estimated by employing high-pressure IMC.