Liquid-Vapor Calculations

When there are three equilibrium phases, two sets of relationships must be satisfied for each component in each of the phases. 

Determine a value for each binary kij by fitting available P—x isotherms to the EOS. 

Calculate the ternary phase diagram for the ternary mixture using the best-fit values of k with no more adjustable parameters. 

Compare the calculated phase diagram with the experimentally obtained diagram and adjust the kfj values for each binary pair to obtain a better fit of the experimental data if so desired. 

The fit of the last binary pair, the methane-octane system, is shown in figure 5.3. This fit was obtained with a value of kij equal to 0.01. A few words of caution are warranted in this case. As noted in chapter 3, methane-hydrocarbon mixtures are expected to deviate from type-I behavior if the methane-solute carbon ratio is greater than 5. The P-x data shown in figure 5.3 are far above the temperatures where a three-phase LLV line is expected for this binary system. However, a three-phase LLV line is predicted near the critical point of methane using A ,y equal to 0.01. 

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This problem is similar in some ways to a vapor-liquid flash and here is referred to as a liquid-liquid flash calculation. 

In vapor-liquid equilibria, it is relatively easy to start the iteration because assumption of ideal behavior (Raoult s law) provides a reasonable zeroth approximation. By contrast, there is no obvious corresponding method to start the iteration calculation for liquid-liquid equilibria. Further, when two liquid phases are present, we must calculate for each component activity coefficients in two phases since these are often strongly nonlinear functions of compositions, liquid-liquid equilibrium calculations are highly sensitive to small changes in composition. In vapor-liquid equilibria at modest pressures, this sensitivity is lower because vapor-phase fugacity coefficients are usually close to unity and only weak functions of composition. For liquid-liquid equilibria, it is therefore more difficult to construct a numerical iteration procedure that converges both rapidly and consistently. 

The same fundamental development as presented here for vapor-liquid flash calculations can be applied to liquid-liquid equilibrium separations. In this case, the feed splits into an extract at rate E and a raffinate at rate R, which are in equilibrium with each other. The compositions of these phases are... 

Both vapor-liquid flash calculations are implemented by the FORTRAN IV subroutine FLASH, which is described and listed in Appendix F. This subroutine can accept vapor and liquid feed streams simultaneously. It provides for input of estimates of vaporization, vapor and liquid compositions, and, for the adiabatic calculation, temperature, but makes its own initial estimates as specified above in the absence (0 values) of the external estimates. No cases have been encountered in which convergence is not achieved from internal initial estimates. 

Examples of Vapor-Liquid Separation Calculations Conducted with Subroutine FLASH... 

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. )... 

VALIK calculates vapor-liquid vaporization equilibrium ratios, K(I), for each component in a mixture of N components (N 20) at specified liquid composition, vapor composition, temperature, and pressure. 

SKIP FUGACITV CALCULATIONS IF VALIK CALLED AT SAME CONDITIONS IFIKEY.LT.O) GO TO 120 SKIP VAPOR CALCULATIONS FOR LIQUID IFILEV.LT.2 GO TO 110... 

Examples of main programs calling subroutines FLASH and ELIPS for vapor-liquid and liquid-liquid separation calculations, respectively, are described in this Appendix. These are intended only to illustrate the use of the subroutines and to provide a means of quickly evaluating their performance on systems of interest. It is expected that most users will write their own main prograns utilizing FLASH and ELIPS, and the other subroutines presented in this monograph,to suit the requirements of their separation calculations. 

A vapor-liquid equilibrium calculation shows that a good separation is obtained, but the required product purity of butadiene <0.5 wt% and sulphur... 

Solution The fraction of liquid vaporized on release is calculated from a heat balance. The sensible heat above saturated conditions at atmospheric pressure provides the heat of vaporization. The sensible heat of the superheat is given by... 

There is, of course, a mass of rather direct evidence on orientation at the liquid-vapor interface, much of which is at least implicit in this chapter and in Chapter IV. The methods of statistical mechanics are applicable to the calculation of surface orientation of assymmetric molecules, usually by introducing an angular dependence to the inter-molecular potential function (see Refs. 67, 68, 77 as examples). Widom has applied a mean-held approximation to a lattice model to predict the tendency of AB molecules to adsorb and orient perpendicular to the interface between phases of AA and BB [78]. In the case of water, a molecular dynamics calculation concluded that the surface dipole density corresponded to a tendency for surface-OH groups to point toward the vapor phase [79]. 

The study of the infrared spectrum of thiazole under various physical states (solid, liquid, vapor, in solution) by Sbrana et al. (202) and a similar study, extended to isotopically labeled molecules, by Davidovics et al. (203, 204), gave the symmetry properties of the main vibrations of the thiazole molecule. More recently, the calculation of the normal modes of vibration of the molecule defined a force field for it and confirmed quantitatively the preceeding assignments (205, 206). 

These are general equations that do not depend on the particular mixing rules adopted for the composition dependence of a and b. The mixing rules given by Eqs. (4-221) and (4-222) can certainly be employed with these equations. However, for purposes of vapor/liquid equilibrium calculations, a special pair of mixing rules is far more appropriate, and will be introduced when these calculations are treated. Solution of Eq. (4-232) for fugacity coefficient at given T and P reqmres prior solution of Eq. (4-231) for V, from which is found Z = PV/RT. 

Figure 2. Determine the vapor pressure/critical pressure ratio by dividing the liquid vapor pressure at the valve inlet by the critical pressure of the liquid. Enter on the abscissa at the ratio just calculated and proceed vertically to intersect the curve. Move horizontally to the left and read r< on the ordinate (Reference 1).

The application of information in Figure 6.19 requires some explanation. The decision as to which calculation method to choose should be based upon the phase of the vessel s contents, its boiling point at ambient pressure T its critical temperature Tf, and its actual temperature T. For the purpose of selecting a calculation method, three different phases can be distinguished liquid, vapor or nonideal gas, and ideal gas. Should more than be performed separately for each phase, and the... 

Haman, S. E. M. et al, Generalized Temperature-Dependent Parameters of the Redlich-Kwong of State for Vapor-Liquid Equilibrium Calculations, Ind. Eng. Chem. Process Des. Dev. 16, 1, (1977) p. 51. 

Several authors, notably Leland and co-workers (L2), have discussed vapor-liquid equilibrium calculations based on corresponding-states correlations. As mentioned in Section II, such calculations rest not only on the general assumptions of corresponding-states theory, but also on the additional assumption that the characterizing parameters for a mixture do not depend on temperature or density but are functions of composition only. Further, it is necessary clearly to specify these functions (commonly known as mixing rules), and experience has shown that if good results are to be obtained, these... 

Equation 4.26 defines the relationship between the vapor and liquid mole fractions and provides the basis for vapor-liquid equilibrium calculations on the basis of equations of state. Thermodynamic models are required for (/) and [ from an equation of state. Alternatively, Equations 4.21, 4.22 and 4.25 can be combined to give... 

These expressions form the basis for two alternative approaches to vapor-liquid equilibrium calculations ... 

The vapor-liquid x-y diagram in Figures 4.6c and d can be calculated by setting a liquid composition and calculating the corresponding vapor composition in a bubble point calculation. Alternatively, vapor composition can be set and the liquid composition determined by a dew point calculation. If the mixture forms two-liquid phases, the vapor-liquid equilibrium calculation predicts a maximum in the x-y diagram, as shown in Figures 4.6c and d. Note that such a maximum cannot appear with the Wilson equation. 

For preliminary design, liquid entrainment is usually used as a reference. To prevent entrainment, the vapor velocity for tray columns is usually in the range 1.5 to 3.5 ms-1. However, the entrainment of liquid droplets can be predicted using Equation 8.3 to calculate the settling velocity. To apply Equation 8.3 requires the parameter KT to be specified. For distillation using tray columns, KT is correlated in terms of a liquid-vapor flow parameter FLV, defined by ... 

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