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Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Alberto Brignole
Publisher: Newnes
Total Pages: 347
Release: 2013-04-02
Genre: Technology & Engineering
ISBN: 044459471X

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Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and optimization is analyzed. The relation between the mixture molecular properties, the selection of the thermodynamic model and the process technology that could be applied are discussed. A classification of mixtures, separation process, thermodynamic models and technologies is presented to guide the engineer in the world of separation processes. The phase condition required for a given reacting system is studied at subcritical and supercritical conditions. The four cardinal points of phase equilibrium engineering are: the chemical plant or process, the laboratory, the modeling of phase equilibria and the simulator. The harmonization of all these components to obtain a better design or operation is the ultimate goal of phase equilibrium engineering. Methodologies are discussed using relevant industrial examples The molecular nature and composition of the process mixture is given a key role in process decisions Phase equilibrium diagrams are used as a drawing board for process implementation


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 43
Release: 2013-04-02
Genre: Science
ISBN: 0128082577

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Phase equilibrium knowledge is required for the design of all sorts of chemical processes that may involve separations, reactions, fluids flow, particle micronization, etc. Indeed, different phase behavior scenarios are required for a rational conceptual process design. The aim of this chapter is to present the possible fluid mixture phase behavior that can be found in binary, ternary, and multicomponent systems. Moreover, representation of phase behavior in terms of phase diagrams is discussed. Dealing with phase diagrams of complex mixtures is not an easy task for beginners; however, very simple concepts are behind the rules for their construction. Phase diagrams are essential tools for phase equilibrium engineering as they provide valuable hints to understand the process and to assess the feasible and optimum operating regions. In this chapter, the “phenomenological” meaning of each phase behavior and its relation with molecular properties is discussed. A special attention is given to binary system phase behavior. Even though, in practice we rarely found such simple mixtures, they furnish a great deal of information for the understanding of multicomponent systems.


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 42
Release: 2013-04-02
Genre: Science
ISBN: 0128082607

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In this chapter, the basic methodologies of phase equilibrium engineering are introduced through the systematic analysis of several case studies. Some of the thermodynamic tools that have been presented in the previous chapters are applied to illustrate how the phase and conceptual process design of complex engineering problems can be tackled from a phase equilibrium engineering approach. In all the case studies, the first step is to consider in great detail the properties of the process feed, the components, their physical properties, concentrations, and molecular interactions. This information is then used for the selection of thermodynamic models, a suitable technology, pressure, temperature, and compositional operating boundaries. It is shown how the mixture composition and the process goals and specifications determine the process scheme and the unit thermodynamic sensitivity. In addition, the importance of the mixture composition is highlighted in combination with the energy and material balance in the case study for the selection of the desirable natural gas cryogenic technologies. The use of a pressure versus temperature drawing board is used to plot the process trajectory and the mixture phase envelopes from the initial conditions to the key phase engineering design problem. Moreover, the phase design provides also a sound basis for the process initial specification and computer simulation. As another example of phase equilibrium engineering, the heat integration in a complex process is solved by the application of the Gibbs phase rule to the LLV equilibria of a ternary mixture.


Phase Equilibria in Chemical Engineering

Phase Equilibria in Chemical Engineering
Author: Stanley M. Walas
Publisher: Butterworth-Heinemann
Total Pages: 689
Release: 2013-10-22
Genre: Science
ISBN: 1483145085

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Phase Equilibria in Chemical Engineering is devoted to the thermodynamic basis and practical aspects of the calculation of equilibrium conditions of multiple phases that are pertinent to chemical engineering processes. Efforts have been made throughout the book to provide guidance to adequate theory and practice. The book begins with a long chapter on equations of state, since it is intimately bound up with the development of thermodynamics. Following material on basic thermodynamics and nonidealities in terms of fugacities and activities, individual chapters are devoted to equilibria primarily between pairs of phases. A few topics that do not fit into these categories and for which the state of the art is not yet developed quantitatively have been relegated to a separate chapter. The chapter on chemical equilibria is pertinent since many processes involve simultaneous chemical and phase equilibria. Also included are chapters on the evaluation of enthalpy and entropy changes of nonideal substances and mixtures, and on experimental methods. This book is intended as a reference and self-study as well as a textbook either for full courses in phase equilibria or as a supplement to related courses in the chemical engineering curriculum. Practicing engineers concerned with separation technology and process design also may find the book useful.


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 19
Release: 2013-04-02
Genre: Science
ISBN: 0128082550

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This volume on phase equilibrium engineering (PEE) aims to fill the gap between the books on reactors and separation process design and the textbooks on chemical engineering thermodynamics. The goal is to change the focus from the use of thermodynamic relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. In this way, phase equilibrium thermodynamics is put to work. The main goal of PEE is the design of the system conditions to achieve the desired phase equilibrium scenario that the process at hand requires. In this chapter, the philosophy of phase equilibrium thermodynamic modeling is discussed in the context of process development and chemical plant operation. Typical phase scenarios that are encountered in separation, materials, and chemical process are presented as well as the problem of phase design and the PEE tools.


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 43
Release: 2013-04-02
Genre: Science
ISBN: 0128082615

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This chapter starts with the analysis of the distillation path of binary mixtures on the general phase behavior P–T diagram of binary mixtures. The univariant lines of these diagrams limit the region of vapor–liquid equilibria where binary distillation can be applied. On this basis, the conditions under which distillation is possible for types I, II, IV, and V of binary mixtures are discussed. Furthermore, in this chapter, the principles of fractional distillation, as well as the computational procedures, are discussed. The thermodynamic modeling of a train of distillation columns to separate the components of an ethane-cracked gas mixture is used to develop a strategy for an equation of state parameter tuning. This strategy is based on the analysis of the distillation column phase equilibrium sensitivity and leads to an unique matrix of equation of state dominant binary parameters for the whole fractionation train. The chapter ends with a list of phase equilibrium engineering guidelines to make a realistic design/simulation of distillation columns.


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 41
Release: 2013-04-02
Genre: Science
ISBN: 0128082666

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The application of the principles of phase equilibrium engineering to the development of two innovative technologies for the production of biofuels is discussed in this chapter. The first technology is the production of biodiesel by transesterification of vegetable oils with supercritical methanol; the second, the extraction and dehydration of alcohols by near-critical dual effect solvents that exhibit good solvent power to extract alcohols and water entrainment effect to dehydrate the extracted alcohol. In the first case, the complexity of the reacting system, the large size asymmetry, and strong molecular interactions of the mixture components: methanol, vegetable oils, fatty esters, and glycerin precluded the design and analysis of the process conditions based on thermodynamic model predictions. Therefore, in this case, a systematic approach based on experimental studies was used to unveil the phase scenario and the physical properties required for the design and optimization of this technology. The conceptual design of extraction and dehydration of alcohols by near-critical solvents followed a different path. The process development was initially based on very limited experimental information. In this case, an equation of state for highly nonideal systems was the main tool for exploration of the process conditions over a wide range of pressures, temperatures, and compositions. This equation of state was based on a group contribution approach (GC-EOS) that allowed extrapolating the scarce experimental information available not only in pressure, temperature, and composition but also in molecular structure. The basic conceptual design was later confirmed by experimental information and pilot plant studies. In this case, the design of the experimental studies was guided by the process conceptual design. The experimental results provided key information for the upgrading of the thermodynamic model.


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 50
Release: 2013-04-02
Genre: Science
ISBN: 0128082585

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In previous chapters, we have seen the fundamental criteria for phase equilibria and how the phenomenological phase behavior and separation technology of real mixtures are determined by their constituent molecular interactions. Our purpose in this chapter is to present the properties of fluids and the models for the prediction of thermodynamic properties and phase equilibria. These models are classified as predictive models using only pure component properties and semiempirical models based on a molecular thermodynamic approach. Finally, the chapter highlights the importance of the class of mixture and molecular interactions of its components in the selection of thermodynamic models for phase equilibrium calculations.


Phase Equilibrium Engineering

Phase Equilibrium Engineering
Author: Esteban Brignole
Publisher: Elsevier Inc. Chapters
Total Pages: 57
Release: 2013-04-02
Genre: Science
ISBN: 0128082658

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The benefits of using SCF as reaction media have promoted an intense research and development activity in this field. In this chapter, several case studies demonstrate the advantages of working under supercritical conditions. In particular, gas–liquid catalyzed reactions are one of the areas where the use of supercritical fluids is very attractive. In general, these reactions are diffusion-controlled and the use of supercritical fluids increases the reaction rate by eliminating the gas–liquid interface. In this chapter also, the interesting properties of operation under near-critical conditions are analyzed: higher solubility of reactants and products in the supercritical phase, reduced deposition of reacting components on the catalyst pores, diffusion coefficients higher than in liquids, independent control of the concentration of permanent gases like H2, O2, or CO in the reaction mixture, higher thermal capacity, and low interfacial tension The hydrogenation of low volatile liquids, using solid–fluid heterogeneous catalysts, is presented to show the advantages of working under supercritical conditions. In this case study, the selection of the process conditions that guarantees operation under a supercritical single-phase state is discussed as a typical phase equilibrium engineering problem. Finally, for reactions in which the SCF plays a role not only as solvent but also as a reactant, the problem of phase condition design and cosolvent selection is addressed.


Phase Equilibrium in Mixtures

Phase Equilibrium in Mixtures
Author: M. B. King
Publisher: Elsevier
Total Pages: 604
Release: 2013-10-22
Genre: Technology & Engineering
ISBN: 1483152413

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Phase Equilibrium in Mixtures deals with phase equilibrium and the methods of correlating, checking, and predicting phase data. Topics covered range from latent heat and vapor pressure to dilute solutions, ideal and near-ideal solutions, and consistency tests. Molecular considerations and their use for the prediction and correlation of data are also discussed. Comprised of nine chapters, this volume begins with an introduction to the role of thermodynamics and the criteria for equilibrium between phases, along with fugacity and the thermodynamic functions of mixing. The discussion then turns to some of the phase phenomena which may be encountered in chemical engineering practice; methods of correlating and extending vapor pressure data and practical techniques for calculating latent heats from these data; the behavior of dilute solutions both at low and high pressures for reacting and non-reacting systems; and the behavior of ideal and near-ideal solutions. The remaining chapters explore non-ideal solutions at normal pressures; practical methods for testing the thermodynamic consistency of phase data; and the extent to which the broad aspects of phase behavior may be interpreted in the light of simple molecular considerations. This book is intended primarily for graduate chemical engineers but should also be of interest to those graduates in physics or chemistry who need to use phase equilibrium data.