Modeling of Fluid Phase Equilibria by PC-Saft EOS: Solubility of Gases/Vapor in Polythylene


Book Description

The prediction or correlation of thermodynamic properties and phase equilibria with equations of state remains an important goal in chemical and related industries. Although the use of equations of state has for a long time has been restricted to systems of simple fluids, there is an increasing demand for models that are also suitable for complex and macromolecular compounds. Due to its ability to describe the thermodynamics of symmetric as well as asymmetric systems, the most common approaches for modeling gas-polymer solubility have been based on the PC-SAFT EOS. It has wide applicability starting from low molecular weight organic compounds to highly non-ideal macro-molecular weight system such as polymer In the present work, PC-SAFT equation of state of Gross & Sadowski, 2001 has been used to model solubility of various gases /vapors in liquid polyethylene to demonstrate the suitability of PC-SAFT EOS for polymer-solvent system.




Working Guide to Vapor-Liquid Phase Equilibria Calculations


Book Description

Working Guide to Vapor-Liquid Phase Equilibria Calculations offers a practical guide for calculations of vapor-phase equilibria. The book begins by introducing basic concepts such as vapor pressure, vapor pressure charts, equilibrium ratios, and flash calculations. It then presents methods for predicting the equilibrium ratios of hydrocarbon mixtures: Wilson's correlation, Standing's correlation, convergence pressure method, and Whitson and Torp correlation. The book describes techniques to determine equilibrium ratios of the plus fraction, including Campbell's method, Winn's method, and Katz's method. The remaining chapters cover the solution of phase equilibrium problems in reservoir and process engineering; developments in the field of empirical cubic equations of state (EOS) and their applications in petroleum engineering; and the splitting of the plus fraction for EOS calculations. - Includes explanations of formulas - Step by step calculations - Provides examples and solutions




Modeling Vapor-Liquid Equilibria


Book Description

Reviews the latest developments in a subject relevant to professionals involved in the simulation and design of chemical processes - includes disk of computer programs.




Modeling of Solid-Liquid Equilibrium


Book Description

The knowledge of solid-liquid equilibrium (SLE) and availability of a validated computer based model is of great technical interest for developing and designing separation processes, such as crystallization and fractionation and solving industrial problems. The latest version of Statistical Associating Fluid Theory (SAFT), Perturbed Chain-SAFT (PC-SAFT), is very much successful for highly non-ideal macro-molecular weight system such as polymers. With the experimental SLE data available in literature for low molecular weight n-alkanes and aromatic compounds both at atmospheric and elevated pressure, the suitability of the developed SLE model based on PC-SAFT was tested. Subsequently sensitivity study was performed for polyethylene. The solubility of two different grade of polyethylene in mixed xylene was then determined using indigenously developed laser based technique. The viscosity average molecular weight, specific gravity, and melting point of the polyethylene samples were determined using standard technique. The validated model was then used to correlate the experimentally determined solubility of polyethylene in xylene.




CRC Handbook of Thermodynamic Data of Polymer Solutions at Elevated Pressures


Book Description

This handbook provides the only complete collection of high-pressure thermodynamic data that is essential for understanding polymer solutions. It contains data on vapor-liquid equilibria and gas solubilities, liquid-liquid equilibria, high-pressure fluid phase equilibria for polymer systems in supercritical fluids, enthalpic and volumetric data, as well as second virial coefficients all at elevated pressures. It covers all areas needed by researchers and engineers who handle polymer systems in supercritical fluids; materials science and technological applications such as computerized predictive packages; and chemical and biochemical processes, such as synthesis and characterization, fractionation, separation, purification, and finishing of polymers and related materials.




Vapor-Liquid Equilibria Using Unifac


Book Description

Vapor-Liquid Equilibria Using UNIFAC: A Group-Contribution Method focuses on the UNIFAC group-contribution method used in predicting quantitative information on the phase equilibria during separation by estimating activity coefficients. Drawing on tested vapor-liquid equilibrium data on which UNIFAC is based, it demonstrates through examples how the method may be used in practical engineering design calculations. Divided into nine chapters, this volume begins with a discussion of vapor and liquid phase nonidealities and how they are calculated in terms of fugacity and activity coefficients, respectively. It then introduces the reader to the UNIFAC method and how it works, the procedure used in establishing the parameters needed for the model, prediction of binary and multicomponent vapor-liquid equilibria for a large number of systems, the potential of UNIFAC for predicting liquid-liquid equilibria, and how UNIFAC can be used to solve practical distillation design problems. This book will benefit process design engineers who want to reliably predict phase equilibria for designing distillation columns and other separation processes.




Vapor-liquid Phase Equilibria of Nonideal Fluids with a Ge-EoS Model


Book Description

This study dealt with the prediction and correlation of vapor-liquid equilibria behavior of nonideal fluids. The thermodynamic formalism of the GE-EoS models, which combines the two traditional methods gamma-phi and phi-phi used so far for low and high pressure phase equilibria correlations respectively, has been combined with the 1FGE model, based on one-fluid theory, to produce a more consistent approach to the phase equilibrium problem. In the first part of our study we examine the predictive abilities of our model for vapor-liquid equilibria of highly nonideal fluids. The results establish the fact that the Huron-Vidal mixing rule with a one parameter version of the lFGE model, is able to successfully utilize available experimental information at low pressures for phase equilibria predictions of multicomponent mixtures over an extended range of pressures and temperatures. In the second part of the study we perform an analysis of the correlative abilities of the 1FGE model, as applied to hydrogen-hydrocarbon mixtures. The results of this part suggest that the unique local composition character of the 1FGE model, along with its one size and one temperature-dependent energy parameter, make it able to adequately describe vapor-liquid equilibria behavior of multicomponent mixtures for this highly asymmetric class of mixtures. Moreover, it is shown that the model parameters for binary hydrogen-hydrocarbon mixtures can be correlated to the acentric factor of the hydrocarbon. The important class of the refrigerant mixtures was modeled in the third part of this study. The lFGE model was introduced into the Wong-Sandler mixing rule, based on the infinite pressure state thermodynamic formalism. The results for these systems showed that a limited amount of experimental data, either at low or high pressures can be utilized to provide a parameter which is practically independent of the temperature set used. As shown from the results, this single parameter can be used to extend vapor-liquid equilibria predictions over a range of conditions for this difficult class of systems. More importantly, we set a heuristic rule able to screen multiparameter and one parameter models. A coordination temperature-parameter planet can be used as a predictive tool from a limited amount of information. Our model comes in lieu of the GE models based on two-fluid theory, which are inconsistent with the one fluid character of an EoS. The 1FGE-EoS framework proposed in this work meets current needs in the area of Applied Thermodynamics, which require that the model's parameters can be obtained from a limited information of experimental data and can give for accurate phase equilibria predictions of nonideal mixtures from low to high pressures.




Phase Behavior


Book Description

Phase Behavior provides the reader with the tools needed to solve problems requiring a description of phase behavior and specific pressure/volume/temperature (PVT) properties.




High-pressure Gases in Amorphous Polymers


Book Description

In this work, a parameterization strategy that allows the calculation of polymer molecular parameters from macroscopic properties of binary polymer solutions is presented. The proposed parameterization is demonstrated by reference to the PC-SAFT equation of state, but can be applied to any molecular-based model. The parameterization scheme has been developed in terms of the polymer-solvent interaction parameter and the Hildebrand parameter, which describe the molecular nature and extent of the polymersolvent interactions. The specification of these macroscopic properties yields a set of polymer parameters that are suitable for the description of thermodynamic properties and phase behavior of polymer solutions. In this way neither extensive experimental data nor complex minimization techniques are necessary, as is required for the current approaches for the estimation of pure-polymer parameters for SAFT-type equations. Using polymer parameters calculated from the proposed parameterization strategy, the PC-SAFT model could satisfactorily predict the phase equilibria, gas solubility and polymer swelling behavior of binary and ternary polymer solutions with different solvents, including nonassociating compounds such as n-alkanes, polar compounds such as ethers, esters and ketones, and associating compounds such as alcohols. A computational approach for building atomistic models for amorphous polymer networks in order to simulate their pore structure and gas adsorption properties is also presented. The computational approach replicates the basic reactivity rules of the selfcondensation reaction of dichloroxylene (DCX) via Friedel-Crafts chemistry and allows the formation of amorphous polymer networks, which are not possible to generate by structural X-ray crystallography/diffraction as is usually done for crystalline materials. The method is discussed for poly(dichloroxylene) networks, but can be extended to other polymer networks. Atomistic models were further refined by fitting to characterization data (i.e., bulk density, absolute density, micropore volume and elemental composition). These models were characterized by specific surface area and pore size distribution. A sensitivity analysis was performed to determine the minimum box size that should be used in adsorption simulations. Simulated adsorption isotherms and isosteric heats for methane and hydrogen were found to be in reasonable agreement with the experimental data.