More volatile component

In principle, extractive distillation is more useful than azeotropic distillation because the process does not depend on the accident of azeotrope formation, and thus a greater choice of mass-separating agent is, in principle, possible. In general, the solvent should have a chemical structure similar to that of the less volatile of the two components. It will then tend to form a near-ideal mixture with the less volatile component and a nonideal mixture with the more volatile component. This has the effect of increasing the volatility of the more volatile component. 

Consider the sequence of simple columns shown in Fig. 5.12. In the direct sequence shown in Fig. 5.12, the composition of component B in the first column increases below the feed as the more volatile component A decreases. However, moving further down the column, the composition of component B decreases again as the composition of the less volatile component C increases. Thus the composition of component B reaches a peak only to be remixed. ... 

For both volatile oil and blaok oil the initial reservoir temperature is below the critical point, and the fluid is therefore a liquid in the reservoir. As the pressure drops the bubble point is eventually reached, and the first bubble of gas is released from the liquid. The composition of this gas will be made up of the more volatile components of the mixture. Both volatile oils and black oils will liberate gas in the separators, whose conditions of pressure and temperature are well inside the two-phase envelope. 

If a waste contains a mixture of volatile components that have similar vapor pressures, it is more difficult to separate these components and continuous fractional distillation is required. In this type of distillation unit (Fig. 4), a packed tower or tray column is used. Steam is introduced at the bottom of the column while the waste stream is introduced above and flows downward, countercurrent to the steam. As the steam vaporizes the volatile components and rises, it passes through a rectification section above the waste feed. In this section, vapors that have been condensed from the process are refluxed to the column, contacting the rising vapors and enriching them with the more volatile components. The vapors are then collected and condensed. Organics in the condensate may be separated from the aqueous stream after which the aqueous stream can be recycled to the stripper. 

Basic distillation involves appHcation of heat to a Hquid mixture, vapori2ation of part of the mixture, and removal of the heat from the vapori2ed portion. The resultant condensed Hquid, the distillate, is richer in the more volatile components and the residual unvapori2ed bottoms are richer in the less volatile components. Most commercial distillations involve some form of multiple staging in order to obtain a greater enrichment than is possible by a single vapori2ation and condensation. 

Separation by distillation is dependent on the fact that when a Hquid is partially vaporized the vapor and Hquid compositions differ. The vapor phase becomes enriched ia the more volatile components and depleted ia the less volatile components with respect to its equiUbrium Hquid phase. By segregating the phases and repeating the partial vaporization, it is often possible to achieve the desired degree of separation. One measure of the degree of enrichment or the ease of separation is the relative volatiHty defined as ... 

To force the naturally more volatile component i overhead, the solvent should either behave essentially ideally with component j and cause positive deviations from Raoult s Law for component i (7 1 and 7 > 1), or behave essentially ideally with component i and cause negative deviations from... 

Pressures can be specified at any level below the safe working pressure of the column. The condenser pressure will be set at 275.8 kPa (40 psia), and all pressure drops within the column will be neglected. The eqnihbrinm curve in Fig. 13-35 represents data at that pressure. AU heat leaks will be assumed to be zero. The feed composition is 40 mole percent of the more volatile component 1, and the feed rate is 0.126 (kg-mol)/s [1000 (lb-mol)/h] of saturated liquid (q = 1). The feed-stage location is fixed at stage 4 and the total number of stages at eight. 

In distillation operations, separation results from differences in vapor-and liquid-phase compositions arising from the partial vaporization of a hquid mixture or the partial condensation of a vapor mixture. The vapor phase becomes enriched in the more volatile components while the hquid phase is depleted of those same components. In many situations, however, the change in composition between the vapor and liquid phases in equihbrium becomes small (so-called pinched condition ), and a large number of successive partial vaporizations and partial condensations is required to achieve the desired separation. Alternatively, the vapor and liquid phases may have identical compositions, because of the formation of an azeotrope, and no separation by simple distillation is possible. 

If we represent the moles of vapor by moles of liquid in the pot by M, the mole fraction of the more volatile component in this hquid by X, and the mole fraction of the same component in the vapor by y, 2l material balance yields... 

In operation, a batch of liquid is charged to the pot and the system is first brought to steady state under total reflux. A portion of the overhead condensate is then continuously withdrawn in accordance with the established reflux pohcy. Cuts are made by switching to alternate receivers, at which time operating conditions may be altered. The entire column operates as an enriching section. As time proceeds, composition of the material being distilled becomes less rich in the more volatile components, and distillation of a cut is stopped when accumulated distillate attains the desired average composition. 

This equation can be employed for estimating the fractional absorption of the more volatile components whenever the value of A for the component is smaller than the value of A for the key component by a factor of 3 or more. 

Evaporative emissions from vehicle fuel systems have been found to be a complex mixture of aliphatic, olefinic, and aromatic hydrocarbons [20,24,33]. However, the fuel vapor has been shown to consist primarily of five light paraffins with normal boiling points below 50 °C propane, isobutane, n-butane, isopentane, and n-pentane [33]. These five hydrocarbons represent the more volatile components of gasoline, and they constitute from 70 to 80 per cent mass of the total fuel vapor [24,33]. 

The composition of the vapour in equilibrium with a miscible liquid mixture at any temperature, e.g. on heating during distillation, will be enriched by the more volatile components. The composition of the liquid phase produced on partial condensation will be enriched by the less volatile components. Such fractionation can have implications for safety in tliat tlie flammability and relative toxicity of the mixtures can change significantly. 

Shizuya, M., Itoh, M., and Hijikata, K., Condensation of Nonazeotropic Binaty Refrigerant Mixtures Including R22 as a More Volatile Component Inside a Horizontal Tube, J. Heat trans fer, Vol. 117, 1995. 

During a batch distillation at constant pressure, the temperature rises to accomplish the separation as the more volatile component s concentration is reduced in the bottoms (kettle) or residue. 

Initial mol fraction of more volatile component in mixture... 

Xy, = composition of liquid in still, mol fraction Xj = mol fraction of component in liquid phase X = mol fraction of more volatile component in liquid xjj = instantaneous mol fiaction of the component in the distillate that is leaving the condenser at time 0. X]3i = initial distillate composition, mol fiaction xj = mol fraction component in liquid phase y, = mol fiaction of component in the vapor phase D = mols of distillate per imit time, or mols of distillate at time 0, or distillate drawoff. 

S = mols in mixture in still (kettle) at time 0 xjj = mol fraction of a more volatile component in the distillate entering the receiver at time 0 Xjo = mol fraction of a more volatile component in the initial kettle charge... 

Xj = mol fraction of a more volatile component in the kettle at time 0... 

The area under the curve between Xgo and is the value of the integrtil. Plot the equilibrium curve for the more volatile component on x - y diagram as shown in Figure 8-33. Then, select values of xd from the operating line hav ing the constant slope, L/V, from equation... 

This mode of batch rectification requires the continuous adjustment of the reflux to the colunrn in order to achieve a steady overhead distillate composition. Starting with a kettle obviously rich in the more volatile component, a relatively low reflux ratio will be required to achieve the specified overhead distillate composition. With time, the reflux ratio must be continuously increased to maintain a fixed overhead composition. Ultimately, a practical maximum reflux is reached and the operation normally would be stopped to avoid distillate contamination. 

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