CALCULATION OF THE VAPORIZATION ENTHALPY OF NONPOLAR FLUIDS AT THE STANDARD TEMPERATURE

Different analytical models were used to calculate the enthalpy of vaporization of nonpolar fluids at the standard temperature of 298.15 K. The models considered were some general classical expressions, three group contribution models that allow the property to be calculated at any temperature, another group contribution model specifically designed for calculations at the standard temperature, and finally a molecular model proposed by our research group. The results for 42 nonpolar fluids are compared with the value obtained in the correlation proposed in the DIPPR project.     

COMPARISON OF PREDICTIVE CORRELATIONS FOR THE NORMAL BOILING DENSITY OF NONPOLAR FLUIDS

Seven empirical correlations for the calculation of the normal boiling density of non polar pure fluids are studied for their accuracy and applicability. One of the correlations is specific only for the normal boiling density, five are based on the corresponding states method (these need the critical parameters and acentric factor as inputs), and the other is a new kind of correlation that uses the Lennard-Jones molecular parameters and the acentric factor as input data. As reference, we take the value for the normal boiling density given by the specific correlation functions proposed in the DIPPR project for 252 nonpolar fluids, grouped into 17 families. In view of the results, we recommend the use of the Yamada-Gunn expression because of its simplicity and because other, less simple, models represent no clear improvement over its accuracy. We also recommend the use of the molecular-parameter model because it gives very good results for some families of fluids.     

COMPARISON OF PREDICTIVE CORRELATIONS FOR THE NORMAL BOILING DENSITY OF NONPOLAR FLUIDS

Seven empirical correlations for the calculation of the normal boiling density of non polar pure fluids are studied for their accuracy and applicability. One of the correlations is specific only for the normal boiling density, five are based on the corresponding states method (these need the critical parameters and acentric factor as inputs), and the other is a new kind of correlation that uses the Lennard-Jones molecular parameters and the acentric factor as input data. As reference, we take the value for the normal boiling density given by the specific correlation functions proposed in the DIPPR project for 252 nonpolar fluids, grouped into 17 families. In view of the results, we recommend the use of the Yamada-Gunn expression because of its simplicity and because other, less simple, models represent no clear improvement over its accuracy. We also recommend the use of the molecular-parameter model because it gives very good results for some families of fluids.     

ESTIMATION OF CRITICAL PROPERTIES OF BINARY MIXTURES USING GROUP CONTRIBUTION METHODS

A new method for estimating critical temperature (T_c), critical pressure (P_c), and critical volume (V_c), of both nonpolar and polar binary mixtures displaying continuous critical loci is proposed. The methodology is based on the group contribution concept for estimation of critical constants of pure compounds, and the combining rule concept for estimation of mixture properties. Lydersen group contribution method is used to demonstrate the application of this methodology. The combining rules are formulated and their adjustable parameters are determined using 43 nonpolar and polar binary mixtures including 417 data points for (T_c), 390 data points for (P_c), and 219 data points for (V_c), respectively. The method is then evaluated with 15 independently selected binary mixtures containing hydrocarbons, alcohols, ethers, amine, carbon dioxide, nitrous oxide, sulfur dioxide, chloroform, and hydrogen sulfide. The average deviations of the estimated (T_c), (P_c), (V_c) are 1.60%, 7.26%, and 3.64%, respectively. The present procedure does not require experimentally adjusted interaction parameters for estimation of the critical properties of a given binary mixture.     

RECENT PROGRESS IN THE COMPUTATION OF EQUILIBRIUM RATIOS

The computation of equilibrium ratios plays an important role in any distillation design calculation. Three different types of models are used for generating equilibrium ratios in non-ideal mixtures:(1)Equations of state (2)Activity coefficient models (3)Group contribution methods Significant developments have taken place for all three types of models in recent years. New models have appeared, many model parameters have become available, and efficient and safe algorithms for implementing the models in distillation calculations have been proposed. The purpose of this contribution is to review these developments.     

RECENT PROGRESS IN THE COMPUTATION OF EQUILIBRIUM RATIOS

The computation of equilibrium ratios plays an important role in any distillation design calculation. Three different types of models are used for generating equilibrium ratios in non-ideal mixtures:(1)Equations of state (2)Activity coefficient models (3)Group contribution methods Significant developments have taken place for all three types of models in recent years. New models have appeared, many model parameters have become available, and efficient and safe algorithms for implementing the models in distillation calculations have been proposed. The purpose of this contribution is to review these developments.     

Unified equation of state based on the lattice fluid theory for phase equilibria of complex mixtures part II. Application to complex mixtures

In part I of the present article [Yoo et al., 1995], new rigorous and simplified lattice-fluid equations of state (EOS) were derived and their characteristic features of the molecular thermodynamic foundation were discussed by applying to pure fluids. In this part II, both EOSs were extended to various phase equilibrium properties of mixtures. Comparison of the models with experimental mixture data ranges from density, to equilibria of vaporliquid, vapor-solid and liquid-liquid phases for nonpolar/nonpolar, nonpolar/polar, polar/polar mixtures. Both models were also applied to supercritical fluid phase equilibria and activities of solvents in polymer solutions. With two temperature dependent parameters for pure compounds and one temperature-independent binary interaction energy parameter for a binary mixtures, results obtained to date illustrated that both EOSs are quantitatively applicable to versatile phase equilibria of mixtures over a wide range of temperatures, pressures and compositions.     

A SIMPLE CALCULATION OF THE PRESSURE AND LIQUID MOLE FRACTION AT THE VLE OF ETHANE/LIGHT HYDROCARBON BINARY MIXTURES

An analytical expression for the calculation of the pressure and liquid mole fraction at the VLE of ethane/light hydrocarbon binary mixtures is proposed. The model is based on a simple analytical expression for the vapor pressure of pure non-polar fluids, which, for a given temperature, only requires as input the values of the Lennard-Jones molecular parameters and the acentric factor. A properly modified Lorentz-Berthelot mixing rule is used, the interaction parameters being given as simple functions of the temperature and composition with eight constants for each binary mixture. The model is shown to reproduce accurately and simply the pressure (for a given liquid mole fraction) or the liquid composition (for a given pressure) of six ethane + hydrocarbon systems at different temperatures.     

AN IMPROVED PENG-ROBINSON EQUATION OF STATE WITH A NEW TEMPERATURE DEPENDENT ATTRACTIVE TERM

An improved form of the Peng-Robinson cubic equation of state has been proposed. The temperature dependence of the attractive term has been modified so as to accurately represent vapor pressures of several fluids with large acentric factors from triple point to close to the critical point. The prediction of saturated liquid volume is also improved by introducing volume translation term in the equation of state. Comparisons of theoretical results with experimental data are made for the vapor/liquid phase equilibria of 44 pure fluids including nonpolar, polar and associating fluids. Our results show that the modified Peng-Robinson equation of state can represent accurately saturated vapor pressures of the fluids investigated in this paper, and it is more accurate than the Peng-Robinson equation of state and its earlier modifications due to Stryjek and Vera (1986) and Twu et al. (1995rpar;. Incorporation of the volume translation term in the equation of state has been found to improve the accuracy of saturated liquid volume significantly.     

A new generalized corresponding-states equation of state for the extension of the Lee-Kesler equation to fluids consisting of polar and larger nonpolar molecules

The Lee-Kesler equation of state for the thermodynamic properties of small nonpolar fluids is extended to all fluids consisting of polar and larger nonpolar molecules, based on the general corresponding-states theory for highly nonspherical fluids. The thermodynamic functions are represented by an analytical equation of state. The results for polar fluids are substantially better than those obtainable from other currently available methods, while the results for nonpolar fluids are equivalent to and mostly better than those obtained by the Lee-Kesler method. The input data required are the critical temperature, the critical volume, the acentric factor and the aspherical factor, which is related to the critical compression factor; the critical volume is therefore required in the present method. The method developed in this work shows good accuracy for 15 representative nonpolar, polar, hydrogen bonding and associating fluids and provides a simple method for industrial applications. Average deviations for the compressibility factor, the heat capacity and the speed of sound for six nonpolar and nine polar fluids from the new equation of state are 0.74%, 2.1% and 2.3%, which are about 8 times smaller than those obtained from the Lee-Kesler equation (about 5.6%, 17% and 29%, respectively).     

基团对应状态法(CSGC)用于纯物质饱和蒸气压的估算

将对应态原理与基团贡献法相结合,引入拟临界性质的概念,提出基团对应状态法(Correspounding State with Group Contribution,简称CSGC)。并将其与Riedel方程相结合用于饱和蒸气压的估算,提出新的蒸气压估算方程(CSGC-PR方程)。88种基团的参数由包括饱和烃、不饱和烃、环烃、芳烃、含氧化合物、含硫化合物、含氮化合物、含卤化合物等350种物质5255个饱和蒸气压实验数据关联获得。新模型的估算精度优于现有的对应状态法,不仅对于高碳数分子有良好的估算精度,并对非极性物质能较好地外推高压下的饱和蒸气压。     

UCKRON II TEST PROBLEM THE EFFECTS OF PORE DIFFUSION

The UCKRON I test problem was reworked with the inclusion of diffusional limitations to the kinetics. For this purpose, the rate expressions, i.e. the full kinetic model and the Langmuir-Hinshelwood model, proposed in the previous workshop, were assumed to represent the true kinetics.

A simple mathematical model based on simplified effective diffusivities and the “Dusty-Gas” model were used to take account of pore diffusion resistance within the catalyst particle. These models predicted effectiveness factors based on the reaction at the bulk conditions. The effectiveness factors were then correlated against temperature and the partial pressure of reacting species.

These correlations were then used to predict the temperature profiles within the water cooled plug flow reactor for various values of cooling media temperature.     

基于黏滞球模型的CPA状态方程应用于醇胺系统相平衡的计算

考虑到醇胺及其混合物中分子间存在缔合作用的事实,结合立方型PR状态方程,通过引入基于黏滞球模型(SSM)发展起来的缔合流体的分子热力学模型,建立了一个新的CPA(cubic-plus-association)状态方程,即CPA-SSM,并将方程应用到醇胺系统相平衡的计算中。通过关联对比温度0.55～0.90范围下醇胺流体的实验饱和蒸气压和液相体积得到了8种醇胺流体的分子参数。结果表明,CPA-SSM方程可满意地计算出醇胺饱和蒸气压和液体密度,总平均误差分别只有0.57%和1.80%。对醇胺混合物,无论是恒压还是恒温系统,只需引入一个与温度无关的可调参数,CPA-SSM方程即可满意关联二元系统的汽液平衡数据,并可进一步预测多元混合物的汽液平衡。     

A CRITICAL REVIEW: SURFACE AND INTERFACIAL TENSION MEASUREMENT BY THE DROP WEIGHT METHOD

The drop weight method has been used as a standard method for surface and interfacial tension measurement. However, lack of appropriate guidelines in using this method has resulted in errors. The specific objective of this critical review is to present the experimental setup, the limitations on the correction factors, and the principle of the drop weight method. Mathematical models of correction factors were evaluated by using a proposed error analysis. The use of the proposed Lee-Chan-Pogaku model and HG-Equation 2 for correction factor determination is suggested. However, further investigations would be required to justify the validity of the correction factors at low r/V^1/3 range and their use for viscous fluids. The physics of drop detachment is complicated; more investigations would be required to form a rigid theory of this method.     

一个新的基团贡献型状态方程——GC-MCSPT方程

将超额Gibbs函数模型与修正的硬球三参数状态方程(MCSPT方程)相结合,导出由基团贡献模型定义的状态方程参数混合规则.直接利用低温下的基团贡献模型参数,如UNIFAC模型、修正的UNIFAC模型(简称MUNIFAC)的交互作用参数,分别预测了二元强极性物系的低压和高压相平衡以及三元强极性物系的汽液相平衡.结果表明,新模型具有广泛的预测能力和满意的预测精度.     

Artificial neural network for the prediction of physical properties of organic compounds based on the group contribution method

In the development and optimization of chemical processes involving the selection of organic fluids, knowledge of the physical properties of compounds is vital. In many cases, it is complex to find experimental measurements for all substances, so it becomes necessary to have a tool to predict properties based on the characteristics of the molecule. One of the most extensively used methods in the literature is the estimation by contribution of functional groups, where properties are calculated using the constituent elements of the molecule. There are several models published in the literature, but they fail to represent a wide variety of compounds with high accuracy and simultaneously maintain a low computational complexity. The aim of this work is to develop a prediction model for eight thermodynamic properties (melting temperature, boiling temperature, critical pressure, critical temperature, critical volume, enthalpy of vaporization, enthalpy of fusion, and enthalpy of gas formation) based on the group contribution methodology by implementing a multilayer perceptron. Here, 2736 substances were used to train the neural network, whose prediction capacity was compared with other reference models available in the literature. The proposed model presents errors ranging from 1% to 5% for the different properties (except for the melting point), which improves the reference models with errors in the range of 3%–30%. Nevertheless, a difficulty in the prediction of the melting point is detected, which could represent an inherent hindrance to this methodology.     

A new cubic equation of state for fluids and fluid mixtures

A new cubic equation of state for pure fluids is presented in this work. The new equation requires the critical temperature and pressure, as well as two additional parameters to characterize each particular fluid. These parameters have been evaluated by minimizing deviations in saturated liquid densities while simultaneously satisfying the equality of fugacities along the saturation curve. Thus, good predictions of volumetric properties in the liquid region are obtained, while accuracy in vapour—liquid equilibrium calculations is maintained. Parameters for polar as well as nonpolar fluids are presented in this paper. In the case of nonpolar fluids, the two parameters required can be correlated with the acentric factor. No such relationship with independently measured quantities could be found for polar fluids. It is shown that the new equation reproduces many of the good features of the Soave and Peng—Robinson equations of state for nonpolar fluids, whilst overcoming some of the limitations of these equations for polar fluids. Applications of the equation of state to the correlation of phase equilibria are demonstrated.     

Mathematical Modeling of Coke Formation and Deposition due to Thermal Cracking of Petroleum Fluids

A two‐dimensional mathematical dynamics model is presented to predict coke formation due to thermal cracking inside the tubes of fired heaters on two types of petroleum fluid. The laminar and turbulent flows are analyzed for both petroleum fluids. The second‐order k‐? standard model is adopted to make this mathematical model more accurate than previous models of coke formation. The radial and axial variations for temperature, velocity, and concentration due to the high temperature gradients inside the tubes are considered in the model equations. The finite volume method is the numerical model used to discretize the conservation equations. The proposed model is suitable to predict coke formation inside heater tubes since it indicates operational conditions where coke formation is minimized.     

MODELLING THE DEACTIVATION KINETICS OF CYCLOHEXANE DEHYDROGENATION ON PLATINUM/ALUMINA CATALYST

Two reaction deactivation kinetic models of the deactivation of cyclohexane on platinum/alumina catalyst have been proposed based on the coking mechanism of Corella and Asua and the reaction mechanism of Susu el al. The difference in the models was in the number of active sites participating in the coking reaction represented by h with h = 1 in model 1 and h ≠ 1 in model 2. The models were dynamic models and parameter estimates were carried out by a method that did not require decoupling of the main from the coking reaction. The model formulation has made possible the estimation of the level of residual activity by the incorporation of a factor, ƒ, that represents incomplete deactivation. For the deactivation kinetic data studied, a high value of ƒ; was obtained indicating a low residual activity. The models were found to give a good fit with the data. The standard deviation of the models from experimental were 10.21 % for model 1 (h ≠ 1) and 12.63% for model 2 (h ≠ 1), None of the models is superior to the other, though for having a lower standard deviation model I is better. It is therefore appropriate to propose that deactivation by coking in this work occurred preferably by a single site mechanism of the rate controlling step of the coking reaction.     

A CRITICAL REVIEW: SURFACE AND INTERFACIAL TENSION MEASUREMENT BY THE DROP WEIGHT METHOD

The drop weight method has been used as a standard method for surface and interfacial tension measurement. However, lack of appropriate guidelines in using this method has resulted in errors. The specific objective of this critical review is to present the experimental setup, the limitations on the correction factors, and the principle of the drop weight method. Mathematical models of correction factors were evaluated by using a proposed error analysis. The use of the proposed Lee-Chan-Pogaku model and HG-Equation 2 for correction factor determination is suggested. However, further investigations would be required to justify the validity of the correction factors at low r/V ^1/3 range and their use for viscous fluids. The physics of drop detachment is complicated; more investigations would be required to form a rigid theory of this method.