Phase Equilibrium Engineering

Foreword

It is with pleasure that I introduce the third volume in the Elsevier Book Series on Supercritical Fluid Science and Technology, Phase Equilibrium Engineering, which has been authored by Drs. Esteban Brignole and Selva Pereda from Universidad National del Sur, Argentina, with one chapter also contributed by Drs. Martin Cismondi and Marcelo S. Zabaloy from Universidad National de Córdoba and Universidad National del Sur, Argentina, respectively. They are all well-recognized names in the supercritical fluids and phase equilibria community. The book reflects and benefits from their many years of accumulated knowledge and practical expertise.

Phase equilibrium is at the heart of chemical processes, and phase equilibrium at high pressures is a central theme in any application involving supercritical fluids. The topic becomes even more relevant when systems under consideration involve chemical transformations along a reaction coordinate which continually alter the compositional make up and thereby alter the phase equilibrium conditions.

This book starts out with a clear statement of the significance of phase equilibrium in process development where there is a critical need to fill the gap between reaction and separation stages by designing and controlling the phase conditions that are essential for the success of the process. The book emphasizes the importance and the need for effective information flow along the pathways connecting the chemical plant or process to the laboratory, to the thermodynamics and phase equilibria, and to modeling and simulations. This four-node grid and their interplay form the essence of Phase Equilibrium Engineering.

To provide a pedagogical development of the relevant engineering concepts, the authors start in Chapter 2 with a brief review of intermolecular forces (attractive and repulsive) and molecular interactions (dispersive, polar, electrostatic, induced dipole) that are important in phase equilibria and separation processes. Chapter 3 provides the background on thermodynamics of phase equilibrium and reviews the phase diagrams for pure substances and binary fluid mixtures within the framework of the van Konynenburg and Scott classification of the different types of phase behavior. The authors provide a clear and elegant graphical description of the changes in the binary mixture phase diagrams and the behavior of the critical lines from Type I to Type VI with changes in the size of the molecules and the nature of the molecular interactions and the energy asymmetries encountered. This chapter further provides a classification for ternary mixture phase diagrams that are based on the partial miscibility in one, two, or three of the binary pairs, which are graphically described in Gibb’s triangles. Multicomponent systems are also discussed in terms of pseudocomponents that are used to represent similar molecules.

Chapter 4 is devoted to thermodynamic models and provides guidelines for selecting the appropriate model from among the various options, ranging from cubic equations of state to SAFT (Statistical Associating Fluid Theory) for different scenarios which are accomplished by using real case studies for separations of different levels of complexity. A comprehensive treatment of a methodology for general phase equilibrium calculations and generation of phase diagrams is provided in Chapter 5.

Chapter 6 shifts the focus to engineering and provides a practical perspective on how the fundamental thermodynamics and phase equilibrium calculations and predictions are used in addressing complex separation processes using several case studies such as the supercritical biodiesel production process. These are continued in Chapter 7 by demonstrating how phase equilibrium engineering comes into play in distillation processes by an elegant description that makes the connections to the Type I to Type VI phase descriptions. The ethylene plant recovery section is used as a case study. In Chapter 8, discussions are extended to azeotropic mixtures and to the synthesis of solvents by computer-aided molecular design (MOLDES) to break up the azeotropes. As case studies, solvent design for recovery of aromatic fractions of reforming naphtha and high-pressure azeotropic separation of ethane + CO2 mixtures by extractive distillation using n-butane as solvent are presented.

Chapter 9 is devoted to green processes and high-pressure supercritical fluid solvents. Solvent tuning for systems displaying Type V (propane + vegetable oil) and Type III (carbon dioxide + natural oil) phase behavior are discussed in detail. Chapter 10 continues the discussions on the use of supercritical fluids in high-pressure fractionation and extraction of natural oils using orange oil deterpenation as a case study. Chapter 11 is devoted to reactive systems and supercritical reactors, and the phase behavior of reactive mixtures and solvents. Solvent selection strategies are discussed according to the reaction pathway using case studies such as selective hydrogenation of fatty acid methyl esters or hydrogenation of vegetable oils. Feasible or unfeasible operational regions are discussed in terms of the prevailing phase diagrams. Finally, Chapter 12 discusses how phase equilibrium engineering is used in the conceptual process design using production of biodiesel via transesterification of vegetable oil with methanol and alcohol extraction and dehydration as examples.

I trust you will find this volume with its application-oriented engineering approach to be of great value and interest.

Erdogan Kiran

Series Editor, Blacksburg, Virginia, December 2012

Preface

Phase design engineering has valuable applications in a variety of chemical processes as well as in many other fields such as metallurgy, geology, climatology, materials design, and oil reservoir engineering, to name only a few. In this book, we explore the phase design of fluid systems and we apply it to a number of separation processes and chemical reactors.

The design of the phase scenario that meets the process needs is what we have called a Phase Equilibrium Engineering (PEE) problem. We first used this terminology in a paper titled Phase Equilibrium Engineering of Supercritical Reactors published in 2002.¹ This discipline combines methods of phase equilibrium thermodynamics with process requirements in order to obtain desired phase scenarios. The challenges posed by the phase design of a reactor that works under homogeneous conditions have all the elements of a chemical engineering design problem. Indeed, the solvent properties of supercritical fluids, highly dependent on pressure, temperature, and composition, call for a systematic methodology for the design of the phase condition.

The development of a strategy for PEE starts with the analysis of the mixture components and their intermolecular forces. This volume thus begins with an introduction to the classification of industrial separation problems and explores the relationship between molecular interactions and separation technologies. The first part of the book also assesses the effect of molecular interactions on the general phase behavior and on the classification of binary and multicomponent mixtures.

The thermodynamic modeling of phase equilibria is reviewed starting with ideal mixtures and following with models for mixtures of increasing degree of nonideality. The most popular models are presented and a strategy of model selection is discussed, taking into account the class of mixtures and their molecular interactions. The classification of molecules, separation processes, and thermodynamic models confirms that the molecular nature of the mixture is the key to determine an adequate thermodynamic model and a suitable technology.

The above discussion is followed by the presentation of the GPEC program, a tool that proves useful to explore the effect of model parameters on the topological phase behavior of binary mixtures. The GPEC program is able to automatically compute the general phase diagrams of univariant lines of binary mixtures for the different types of phase behavior.

In the second part of the book, the principles of PEE are developed through the analysis of a series of case studies that look into the separation of heavy aromatic mixtures, the cryogenic processing of natural gas, and the separation of biodiesel mixtures obtained by supercritical alcoholysis. The use of material and energy balances, combined with the methodologies developed in the first part of the book, lead to the formulation of an efficient strategy for phase design. The principles of PEE are applied to the tuning of thermodynamic models and to the analysis of thermodynamic sensitivity in the context of fractional distillation of single columns and fractionation trains. Thereafter, we examine the question of solvent selection for the separation of highly nonideal mixtures as well as the computer-aided molecular design of solvents for liquid extraction and extractive distillation.

Finally, we study the phase design of both supercritical processing of natural products (extraction and fractionation) and of supercritical reactors. In these two cases, the selection of solvents and the identification of optimal operating conditions are carried out while taking into account green chemistry principles for sustainable development. These principles call for the use of new reactants and catalysts in order to achieve chemical synthesis that results in improved atom efficiency, higher yields and selectivities, and safer and environmentally friendly solvents. This discussion includes two more case studies where the phase design leads to the development of new technologies for biofuels production.

PEE is thus the road that takes us in a systematic way from the molecular level of the mixture to the art of process synthesis, through (i) the process goals, (ii) thermodynamic modeling, (iii) algorithms for phase equilibrium calculations, (iv) phase scenario and technology selection, (v) sensitivity analysis, and (vi) conceptual process design. Finally, this book highlights the fact that the answer to a successful phase design problem lies in the nature of the mixture we are working with.

The case studies presented in this book are based on the personal experiences of the authors and of many other colleagues. We would like to particularly thank and acknowledge the contributions of Susana Bottini, Soledad Díaz, Guillermo Mabe, Gloria Foco, Pablo Hegel, Susana Espinosa, Alberto Arcodaci, HernanGros, Ticiana Fornari, Marta Lacunza, Alberto Bandoni, Rubén Debeistegui, Marcelo Zabaloy, Martin Cismondi, Olga Ferreira, Laura Rovetto, Nicolás Gañan, Francisco Sánchez, Pedro Valle, and Alexis Vélez. Our recognition is also extended to Cor Peters, Peter Rasmussen, and the late LilianaUrlic, Noemi Petracci, and Aage Fredenslund. Most importantly, this book would never have been possible without the encouragement received from the Editor of this Series, Prof. Erdogan Kiran. We thank him deeply not only for supporting this book project but also for his insightful comments and invaluable editing help.

Esteban Brignole and Selva Pereda

Bahía Blanca, Argentina December, 2012

¹S. Pereda, S.B. Bottini, E. Brignole, Am. Inst. Chem. Eng. J. 48 (2002) 2635–2645.

Chapter 1

Phase Equilibrium and Process Development

Esteban Brignole

Selva Pereda

Abstract

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.

Keywords

Process development; Phase design; Thermodynamic modeling; Process simulator; Phase equilibrium engineering

With this volume, we aim to fill the gap between the books on reactors and separations process design, and the chemical engineering thermodynamics. Our goal is to change 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. In this way, we can say that we put phase equilibrium thermodynamics to work. Phase equilibrium from a theoretical and experimental point of view belongs to the realm of thermodynamics. The ties to the fundamental laws of thermodynamics are so strong that the teaching of phase equilibria emphasizes more the relationships between the thermodynamic variables of each phase in equilibrium than its engineering applications.

The main goal of phase equilibrium engineering is the design of the system conditions to achieve the desired phase equilibrium scenario that the process at hand requires. The mixture under consideration and the process to be accomplished illuminate the search for the thermodynamic and process variables that give the required phase conditions. The synthesis of new processes based on the phase behavior is also discussed in this book. Dealing with these types of problems, the engineer could make use of several design variables: pressure and temperature, feed composition, entrainers, solvents, supercritical condition, etc. to modify the phase scenario.

1.1 The World of Phase Equilibria in Chemical Processes

The world of applied phase equilibrium thermodynamics has four cardinal points: (1) the chemical plant or process, (2) the laboratory, (3) the thermodynamic modeling of phase equilibria, and (4) the simulator. How all these components can be focused and tuned in harmony to get the better design or operation is the ultimate goal of phase equilibrium engineering.

Figure 1.1 illustrates the world of phase equilibrium and the flow of information between the main players and how each pair defines different realms. The exchange of information between the chemical plant and the laboratory is commonplace, as well as the interaction between the thermodynamic modeling and the lab; however, the information on the chemical plant process is seldom used in the modeling of phase equilibria. The parameterization of the thermodynamic models for phase equilibria is usually based on experimental binary information. These models and their parameters are available in the modern process simulators. On the other hand, the process simulator is normally used in the industrial plant without proper tuning of the thermodynamic models to the process needs. In the industrial world, the virtual plant (the simulator) and the real process or chemical plant coexists, and often rather crude assumptions are made to match the simulator results with the plant data which could lead to serious errors in parameter estimation of plant units, revamping projects, process optimization, and new designs. Going back to Fig. 1.1, if we keep the game only on the sides, it will be a boring match and our main goal will not be achieved. On the contrary, if the information flows from the plant or the actual process to the other players, that also exchange information among them, very fruitful results in the design and optimization of the process will be obtained. The development of modern process simulators with a large collection of thermodynamic models and parameters makes more critical the wise use of information from the real system to get the most from the process simulators, and to avoid critical errors in design, operation, and plant parameters estimation.

Figure 1.1 Phase equilibrium worlds: industry and academy in the real and engineering world.

1.2 Thermodynamic Modeling in Process Development

The need of information on physicochemical properties of pure compounds and their mixtures is always present in the synthesis, design, simulation, debottlenecking, control, and optimization of chemical plants. From the point of view of the modern chemical industry and their sustainable development, the properties associated with the equilibrium between phases, that is, vapor–liquid (VL), liquid–liquid (LL), gas–liquid (GL), and solid–liquid, play a dominant role. Other properties of interest are related to the thermodynamic energy functions, transport, and volumetric properties.

In the design or conception of a new process, a wealth of experimental information is required. This information comes from laboratory and bench scale studies, pilot plant, and industrial units. Even when a large amount of phase equilibrium and physical properties data is available, the need for thermodynamic model predictions is always present. The scenario of phase conditions in a plant is infinitely varied, and the experimental data will cover only some regions, hopefully the most critical, of the information required. The experimental data available are like a scaffolding that supports the thermodynamic predictions of the volumetric properties, phase equilibrium, and energy functions required for the design and simulation of all the process units. When more abundant and reliable are the experimental data, better predictions of the physical and thermodynamic properties will be obtained from the selected thermodynamic model.

Therefore, a well-tuned thermodynamic model for the mixture under the process conditions is a key engineering tool for the design and optimization of the plant units. The process thermodynamic sensitivity will provide a strategy for parameter estimation of thermodynamic models, tailored to the process needs. On the other hand, models with qualitative predictive capacity are needed in development studies. A well-tuned thermodynamic model allows studying different pressure and temperature conditions of operation, exploring new phase scenarios to carry out the reactions, as well as, testing new separation techniques.

The likelihood of finding the required information generally is limited to pure compounds or binary mixtures. Modern equations of state, on the basis of pure component physical constants and a few empirical parameters, are used to obtain PVT relations for pure compounds and their mixtures. In general, the mixture phase equilibria can be estimated on the basis of limited experimental information using the tools of classical thermodynamics, combined with the predictions of PVT properties from equations of state. Also, group contribution models can be applied to extend the scarce information available, to systems for which no experimental information has been measured.

1.3 Definition of Phase Equilibrium Engineering

The chemical and pharmaceutical industry is blamed for its negative environmental impact. The Green Chemistry principles for a sustainable development of the chemical industry claim for new reactants and catalyst for chemical synthesis with improved atom efficiency, higher yields and selectivities, process intensification and simplification, less waste, and safe and environmentally friendly solvents. Among the benign solvents, the supercritical fluids (SCFs) have an increasing role. SCFs are classified as low or high critical temperature (Tc) solvents. Low Tc SCFs, like CO2 and ethane, offer in general low solvent power, unless very high pressures are applied. In addition, these solvents are selective for compounds of low to moderate polarity and low molecular weight. High Tc SCFs have high solvent power but low selectivity. Typical examples of high Tc solvents are supercritical water or toluene.

The SCFs have very attractive physical properties and exceptionally tuneable solvent power. SCFs add a new dimension to conventional solvents, that is, the density-dependent solvent power, as the density of SCFs is very sensitive to changes in pressure, temperature, and composition.

The design of the phase scenario that meets the process needs is what we call a phase equilibrium engineering problem. This discipline combines the methods of phase equilibrium thermodynamics with the process requirements to obtain the desired phase scenario and thermodynamic properties.

We may look for homogeneous conditions in a supercritical reactor, for phase split and selectivity in a separation process, or a tuneable phase condition to achieve both reaction and separation process in a single step. For each problem, there will be a set of specifications which represent the process restrictions. For instance, if we need to operate a reactor under homogeneous conditions, we specify the reactants, degree of conversion, and the operating temperature. Phase equilibrium engineering, by systematic analysis, develops criteria for selecting the right solvent, the solvent-to-feed ratio, and the pressure of operation, to keep the whole reaction trajectory in a single phase region [1].

A multicomponent fluid mixture can be in a homogenous phase at supercritical conditions or as a subcooled liquid or superheated vapor, or in a heterogeneous VL or LL phase condition. The phase envelope or pressure–temperature diagram is a useful plot for a given mixture composition; it presents the bubble and dew point phase transition curves as well as the mixture critical point. The region under the curve is heterogeneous. Above the maximum pressure at any temperature, we will have a single phase.

Figure 1.2 presents a phase envelope sketch for a given mixture where three typical phase scenario requirements are indicated. Of course, during the course of a reaction or a separation process, with the change in compositions, different phase envelopes will be obtained, and the process trajectory should be always in the specified phase scenario: homogeneous or heterogeneous.

Figure 1.2 Process potential phase scenario. •, critical point; dashed line, bubble points; solid line, dew points.

1.4 Phase Scenarios in Separation, Materials, and Chemical Processes

All sorts of phase scenarios are present in nature, in living or inert bodies: the exchange of oxygen and carbon dioxide in our lungs (GL), the formation of clouds and ice in the atmosphere, the evaporation of water from oceans and rivers, the formation of rocks from melted magma or the crystallization of sodium chloride or sulfate from salty lakes, the gas–oil–water system of petroleum reservoirs, and so on. The phase scenarios created by man in the transformation of raw materials to valuable products, in the development of sustainable processes, or in the solution of environmental problems, are the main goal of phase equilibrium engineering.

The difference in composition between phases in equilibrium has been the driving force for the development of a large number of different separation processes. Distillation, the most popular separation operation of fluid mixtures, is based on the differences in the vapor and liquid composition at equilibrium. The coordinates of pressure, temperature, and composition of the mixture are modified to reach the desired phase condition of VL equilibria. This process can be carried out at very low temperatures (cryogenic conditions) for the separation of air or natural gas processing, at high pressures for the distillation of light hydrocarbons, or under vacuum for the fractionation of high boiling products. As a separation operation, distillation is so highly efficient that if it can be applied for the separation of a given mixture, it will be the natural choice. Heat added or removed from the mixture is the separation agent in distillation.

The process of desorption and absorption, so common in the removal of pollutants from water or air, is also based on GL equilibrium. The main difference of this operation with respect to distillation is that they introduce a solvent (gas or liquid) to generate a liquid–gas phase scenario. Solvents are also used to modify the selectivity of ordinary distillation in the azeotropic and extractive distillation processes. Azeotropic distillation also combines a LL separation stage to achieve the separation goal. LL equilibrium is the basis of multistage liquid extractions in which again a solvent is selected to generate the required solvent power and selectivity.

The use of liquid solvents is also a common practice in chemical synthesis for achieving complete miscibility between the reactants or for the removal of reaction products to increase the reaction yield or to recover a catalyst. GL reactions, in general, are limited by mass transfer if unfavorable heterogeneous phase conditions prevail, like for instance in hydrogenation of oils employing a solid catalyst. The application of a supercritical cosolvent to carry out efficiently GL reactions under single-homogeneous phase conditions has opened the way to the application of SCF technology. The history of reactions in supercritical medium is relatively short. Subramaniam and McHugh [2] give a comprehensive introduction to the subject. Savage et al. [3] present a wide variety of applications of SCFs as reaction media. A special issue of Chemical Reviews, edited by Noyori [4], covers different types of supercritical reactions, including the use of supercritical water [5], heterogeneous [6] and homogeneous catalysis [7], biocatalysis [8], inorganic and organometallic systems [9], and polymerization reactions [10]. The polymerization of ethylene to produce low-density polyethylene in high pressure reactors operating above 2000 bar is an early example of using the solvent power of SCFs to operate in the homogeneous regime a chemical reactor.

The chemical industry will need green solvents for its sustainable development besides using renewable raw materials. The residue of solvents in final products, the hazards on workers’ health by volatile organic chemicals, and their release to the atmosphere are a matter of high social concern and are carefully controlled by governments and international organizations. Two solvents are expected to play a major role in this regard: water and CO2. Both solvents under near critical conditions exhibit attractive solvent properties, and they are nonflammable, nontoxic, and of low cost. Smith and Fang [11] discuss the use of supercritical water and carbon dioxide in the synthesis of new materials, in the conversion of biomass in renewable energy, and in the removal of pollutants. Carbon dioxide has been the solvent of choice in most supercritical processes, that is, natural products extraction and fractionation, cleaning, materials processing, chemical reaction medium, and supercritical chromatography. The design of the required phase condition for supercritical process is of great interest considering that not only density but also most of the key solvent properties are very sensitive to changes in pressure, temperature, and composition.

Supercritical applications in the area of particle design or micronization has been a very active area of research and application in recent years. The supercritical micronization processes are based on creating a high degree of solution supersaturation that leads to a great number of nucleation sites and very small crystals. Many applications of these processes have been presented in the past decade [12]. The main application of the process has been in the micronization of pharmaceutical and food solid compounds and formation of polymeric particles. Usually several components may participate in the process: the solute to be crystallized, the solvent, an SCF, a cosolvent, and in some cases also the encapsulating material. In the micronization processes, the phase equilibrium between these components plays a key role in the selection of the proper technology [13]. The phase scenario that leads to high supersaturations depends mainly on the high or low solubility of the solute to be micronized in the SCFs. Different processes have been developed to create the required phase scenario. The two main approaches are rapid expansion of supercritical solutions or gas antisolvent process.

The same motivation in the search for greener solvents has pushed forward the use of preparative and analytical supercritical gas chromatography [14]. The tuneable solvent properties of SCFs combined with the separation power of gas chromatography open the way to highly efficient purification