Equilibrium separation processes

The adsorptive separation is achieved by one of the three mechanisms steric, kinetic, or equilibrium effect. The steric effect derives from the molecular sieving property of zeolites. In this case only small and properly shaped molecules can diffuse into the adsorbent, whereas other molecules are totally excluded. Kinetic separation is achieved by virtue of the differences in diffusion rates of different molecules. A large majority of processes operate through the equilibrium adsorption of mixture and hence are called equilibrium separation processes. 

Jobson, M., D. Hildebrandt, et al. (1996). "Variables indicating the cost of vapour-liquid equilibrium separation processes." Chemical Engineering Science 51,21,4749-4757. 

The transfer of mass within a fluid mixture or across a phase boundary is a process that plays a major role in various engineering and physiological applications. Typical operations where mass transfer is the dominant step are falling film evaporation and reaction, total and partial condensation, distillation and absorption in packed columns, liquid-liquid extraction, multiphase reactors, membrane separation, etc. The various mass transfer processes are classified according to equilibrium separation processes and rate-governed separation processes. Fig. 1 lists some of the prominent mass transfer operations showing the physical or chemical principle upon which the processes are based. 

In Section 3.3, we illustrated the thermodynamic relations that govern the conditions of equilibrium distribution of a species between two or more immiscible phases under thermodynamic equilibrium. In Section 4.1, we focus on the value of the separation factor or other separation indices for two or more species present in a variety of two-phase separation systems under thermodynamic equilibrium in a closed vessel. The closed vessels of Figure 1.1.2 are appropriate for such equilibrium separation calculations. There is no bulk or diffusive flow into or out of the system in the closed vessel. The processes achieving such separations are called equilibrium separation processes. Separations based on such phenomena in an open vessel with bulk flow in and out are studied in Chapters 6, 7 and 8. No chemical reactions are considered here however, partitioning between a bulk fluid phase and an individual molecule/macromolecule or collection of molecules for noncovalent solute binding has been touched upon here. The effects of chemical reactions are treated in Chapter 5. Partitioning of one species between two phases is an important aspect ever present in this section. 

The separation achieved between two species distributed between two phases or two regions is considered in this section. In Section 3.3.7, the equilibrium distribution of one species between two phases was determined in many two-phase systems. Those results will be employed here for individual equilibrium separation processes in a closed vessel which becomes an ideal stage. There will be additional considerations here on the distribution of one species between two immiscible phases at equilibrium. First, however, a few general results are provided for estimating the separation factor i2 between two species 1 and 2 in a two-phase system at equilibrium. We ignore chemical reactions for any separation conditions discussed here. 

In Section 5.2, we considered the change in separation equiUhrium due to chemical reactions. Many such separation processes in practice do not have phases in equUih-rium. This may have come about, for example, due to inadequate contact time between the phases in the device being used. The extent of separation achieved wiU be controlled by the extent of transfer of the species between the phases. Other conditions remaining constant, the higher the rate of transfer, the larger the extent of separation achieved. The species transport rate from one phase to another then controls the actual separation achieved. Chemical reactions can influence this interphase species transport rate. The role of chemical reactions in the separation achieved in rate-controlled equilibrium separation processes is, therefore, the subject of this section. Mass transfer and separation in gas-Uquid systems are covered first, followed by liquid-liquid systems. 

Section 6.4 covers continuous stirred tank separators. Section 6.4.1 studies equilibrium separation processes most of this section is devoted to crystallization, with additional coverage of liquid extraction. Membrane separation processes/devices are sometimes modeled as CSTRs. Section 6.4.2 touches upon a few of these examples, encountered, for example, in ultrafllUation and gas permeation. There are brief treatments of batch systems that are well-stirred in Sections 6.4.1 and 6.4.2 for both equilibrium based and membrane separation processes. 

In Section 6.3.1, we cover external forces, specifically gravitational, electrical and centrifugal forces inertial force is also included here. In Section 6.3.2, chemical potential gradient driven equilibrium separation processes involving vapor-liquid, liquid-liquid, solid-melt and solid-vapor systems are considered the processes are flash vaporization, flash devolatilization, batch distillation, liquid-liquid extraction, zone melting, normal freezing and drying. Section 6.3.3 illustrates a number of membrane separation processes in the so-called dead-end filtration mode achieved when the feed bulk flow is parallel to the... 

We have seen in Section 8.1.1.3 that in a two-phase countercurrent flow system, where an equilibrium separation process is going on, the separation system lacks... 

The most frequent application of phase-equilibrium calculations in chemical process design and analysis is probably in treatment of equilibrium separations. In these operations, often called flash processes, a feed stream (or several feed streams) enters a separation stage where it is split into two streams of different composition that are in equilibrium with each other. 

Liquid-liquid equilibrium separation calculations are superficially similar to isothermal vapor-liquid flash calculations. They also use the objective function. Equation (7-13), in a step-limited Newton-Raphson iteration for a, which is here E/F. However, because of the very strong dependence of equilibrium ratios on phase compositions, a computation as described for isothermal flash processes can converge very slowly, especially near the plait point. (Sometimes 50 or more iterations are required. )... 

Data on the gas-liquid or vapor-liquid equilibrium for the system at hand. If absorption, stripping, and distillation operations are considered equilibrium-limited processes, which is the usual approach, these data are critical for determining the maximum possible separation. In some cases, the operations are are considerea rate-based (see Sec. 13) but require knowledge of eqmlibrium at the phase interface. Other data required include physical properties such as viscosity and density and thermodynamic properties such as enthalpy. Section 2 deals with sources of such data. 

Precipitation involves the alteration of the ionic equilibrium to produce insoluble precipitates. To remove the sediment, chemical precipitation is allied with solids separation processes such as filtration. Undesirable metal ions and anions are commonly removed from waste streams by converting them to an insoluble form. The process is sometimes preceded by chemical reduction of the metal ions to a form that can be precipitated more easily. Chemical equilibrium can be affected by a variety of means to change the solubility of certain compounds. For e.xample, precipitation can be induced by alkaline agents, sulfides, sulfates, and carbonates. Precipitation with chemicals is a common waste stream treatment process and is effective and reliable. The treatment of sludges is covered next. 

This chapter provides (i) a brief review of the chemistry involved in chiral host-chiral guest recognition involving primary amines (ii) a description of a nonchromatographic (equilibrium or bind-release based) separation process devel-... 

In processing, it is frequently necessary to separate a mixture into its components and, in a physical process, differences in a particular property are exploited as the basis for the separation process. Thus, fractional distillation depends on differences in volatility. gas absorption on differences in solubility of the gases in a selective absorbent and, similarly, liquid-liquid extraction is based on on the selectivity of an immiscible liquid solvent for one of the constituents. The rate at which the process takes place is dependent both on the driving force (concentration difference) and on the mass transfer resistance. In most of these applications, mass transfer takes place across a phase boundary where the concentrations on either side of the interface are related by the phase equilibrium relationship. Where a chemical reaction takes place during the course of the mass transfer process, the overall transfer rate depends on both the chemical kinetics of the reaction and on the mass transfer resistance, and it is important to understand the relative significance of these two factors in any practical application. 

Separation processes are based on some difference in the properties of the substances to be separated and may operate kinetically, as in settling and centrifugation, or by establishing an equilibrium, as in absorption and extraction. Typical separation processes are shown in Table 6.1. Better separations follow from higher selectivity or higher rates of transport or transformation. The economics of separation hinges on the required purity of the separated substance or on the extent to which an unwanted impurity must be removed (Figure 6.13). 

In principle, the calculation of concentrations of species of a complexation equilibrium is no different from any other calculation involving equilibrium constant expressions. In practice, we have to consider multiple equilibria whenever a complex is present. This is because each ligand associates with the complex in a separate process with its own equilibrium expression. For instance, the silver-ammonia equilibrium is composed of two steps ... 

Phase equilibrium data are needed for the design of all separation processes that depend on differences in concentration between phases. 

The UNIQUAC equation developed by Abrams and Prausnitz is usually preferred to the NRTL equation in the computer aided design of separation processes. It is suitable for miscible and immiscible systems, and so can be used for vapour-liquid and liquid-liquid systems. As with the Wilson and NRTL equations, the equilibrium compositions for a multicomponent mixture can be predicted from experimental data for the binary pairs that comprise the mixture. Also, in the absence of experimental data for the binary pairs, the coefficients for use in the UNIQUAC equation can be predicted by a group contribution method UNIFAC, described below. 

These four equations are the so-called MESH equations for the stage Material balance, Equilibrium, Summation and Heat (energy) balance, equations. MESH equations can be written for each stage, and for the reboiler and condenser. The solution of this set of equations forms the basis of the rigorous methods that have been developed for the analysis for staged separation processes. 

In an equilibrium flash process a feed stream is separated into liquid and vapour streams at equilibrium. The composition of the streams will depend on the quantity of the feed vaporised (flashed). The equations used for equilibrium flash calculations are developed below and a typical calculation is shown in Example 11.1. 

The groups incorporating the liquid and vapour flow-rates and the equilibrium constants have a general significance in separation process calculations. 

Figure 224. Separation process for enhancement of energy media transformation, (a) Schematic of the process, (A) an original equilibrium, (B) separation of hydrogen, (C) secondary equilibrium, (b) Relationship between separation process and reaction equilibrium line...

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