THE FRACTIONATING COLUMN

In analysing the operation on each tray it is important to note that the vapour rising to it, and the reflux flowing down to it, are not in equilibrium, and adequate rates of mass and heat transfer are essential for the proper functioning of the tray. 

The tray as described is known as a sieve tray and it has perforations of up to about 12 mm diameter, although there are several alternative arrangements for promoting mass transfer on the tray, such as valve units, bubble caps and other devices described in Section 11.10.1. In all cases the aim is to promote good mixing of vapour and liquid with a low drop in pressure across the tray. 

On each tray the system tends to reach equilibrium because  

The number of molecules passing in each direction from vapour to liquid and in reverse is approximately the same since the heat given out by one mole of the vapour on condensing is approximately equal to the heat required to vaporise one mole of the liquid. The problem is thus one of equimolecular counterdiffusion, described in Volume 1, Chapter 10. If the molar heats of vaporisation are approximately constant, the flows of liquid and vapour in each part of the column will not vary from tray to tray. This is the concept of constant molar overflow which is discussed under the heat balance heading in Section 11.4.2. Conditions of varying molar overflow, arising from unequal molar latent heats of the components, are discussed in Section 11.5. 

In the arrangement discussed, the feed is introduced continuously to the column and two product streams are obtained, one at the top much richer than the feed in the MVC and the second from the base of the column weaker in the MVC. For the separation of small quantities of mixtures, a batch still may be used. Here the column rises directly from a large drum which acts as the still and reboiler and holds the charge of feed. The trays in the column form a rectifying column and distillation is continued until it is no longer possible to obtain the desired product quality from the column. The concentration of the MVC steadily falls in the liquid remaining in the still so that enrichment to the desired level of the MVC is not possible. This problem is discussed in more detail in Section 11.6. 

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When a more delicate fractional vacuum-distillation is required, the flask and column shown in Fig. ii(b), p. 26, may be used, the side-arm of the column being fitted directly into receiver C (Fig. 14). A rubber stopper must then be used to fit the flask on to the fractionating column, and it should also carry a capillary tube leading to the bottom of the flask, to provide the usual fine stream of bubbles to prevent bumping. 

Fractional Distillation. Fractional distillation on a semi-micro scale can be carried out satisfactorily with the fractionating column shown in Fig. 39. The column is 10 cm. long and is filled with pieces... 

Reflux ratio. This is defined as the ratio between the number of moles of vapour returned as refluxed liquid to the fractionating column and the number of moles of final product (collected as distillate), both per unit time. The reflux ratio should be varied according to the difficulty of fractionation, rather than be maintained constant a high efficiency of separation requires a liigh reflux ratio. ... 

If a bolt-head fiask is used and a rubber stopper is permissible, there is ample room for the insertion of a capillary tube and the fractionating column in the wide neck. 

A two-necked flask (compare Fig.//, 56, 13), with the wide neck for the fractionating column and the small neck for the capillary tube, is widely employed. 

Any of the fractionating columns previously described may be used. Precision fractionating columns, which And application under diminished pressure, are shown in Figs. II, 17, 2-4. 

To obtain pure acetaldehyde, the product must be redistilled. Clean and dry the 200-250 ml. flask first used, immerse it in cold or ice water pour in the crude acetaldehyde rapidly, attach the fractionating column, etc. Immerse the receiver in crushed ice. Heat the flask gently in a water bath and adjust the temperature so that the aldehyde distils slowly and at a uniform temperature. The temperature recorded at the top of the column may depend partly upon the temperature of the laboratory, if this is above 21°. Pure acetaldehyde boils at 21°. 

Fractional distillation at atmospheric pressure.—The flask may have the fractionating column attached (compare Figs. II, 24, 4-5) the latter may be —... 

Alternatively, an independent column (Fig. XII, 2, 8, c) may be inserted into a flask the column may be of the Vigreux, Widmer or Hempel form. The fractionating column should be lagged with asbestos cloth or string for distillation temperatures above 100° for the best results the column should be heated electrically (compare Section 11,15) to a temperature 5-10° below the b.p. of the fraction being collected. The side arm of the flask or fractionating column may be attached to a cold spot condenser and receiver as in Fig. XII, 2, 4 or to a Liebig s condenser and receiver as in Fig. XII, 2, 1. 

A semimicro assembly, suitable for precision fractiona tion, used in the author s laboratory is illustrated in Fig. XII, 3, 4 the mode of heating the fractionating column is not shown for reasons of clarity (compare Fig. II, 17, 2). 

Several descriptions have been pubUshed of the continuous tar stills used in the CIS (9—11). These appear to be of the single-pass, atmospheric-pressure type, but are noteworthy in three respects the stills do not employ heat exchange and they incorporate a column having a bubble-cap fractionating section and a baffled enrichment section instead of the simple baffled-pitch flash chamber used in other designs. Both this column and the fractionation column, from which light oil and water overhead distillates, carboHc and naphthalene oil side streams, and a wash oil-base product are taken, are equipped with reboilers. 

The fix for the erratic reflux drum pressure problem was to provide for separate pressure control of the fractionator column and the reflux drum. A new pressure control valve was installed upstream of the condenser and the old condenser outlet control valve was removed. A hot gas bypass, designed for 20% vapor flow, was installed around the pressure control valve and condenser. A control valve was installed in the hot gas bypass line. The column pressure was then maintained by throttling the new control valve upstream of the condenser. The reflux drum pressure w as controlled by the hot gas bypass control valve and the psv saver working in split range. The new system is shown in the figure below. 

The term still is applied only to the vessel in which liquids are boiled during distillation, but the term is sometimes applied to the entire apparatus, including the fractionating column, the condenser, and the receiver in which the distillate is collected. If a water and alcohol distillate is returned from the condenser and made to drip down through a long column onto a series of plates, and if the vapor, as it rises to the condenser, is made to bubble through this liquid at each plate, the vapor and liquid will interact so that some of the water in the vapor condenses and some of the alcohol in the liquid vaporizes. The interaction at each plate is equivalent to a redistillation. This process is referred to by several names in the industry namely rectification, fractionation, or fractional distillation. 

The theoretical treatment which has been developed in Sections 10.2-10.4 relates to mass transfer within a single phase in which no discontinuities exist. In many important applications of mass transfer, however, material is transferred across a phase boundary. Thus, in distillation a vapour and liquid are brought into contact in the fractionating column and the more volatile material is transferred from the liquid to the vapour while the less volatile constituent is transferred in the opposite direction this is an example of equimolecular counterdiffusion. In gas absorption, the soluble gas diffuses to the surface, dissolves in the liquid, and then passes into the bulk of the liquid, and the carrier gas is not transferred. In both of these examples, one phase is a liquid and the other a gas. In liquid -liquid extraction however, a solute is transferred from one liquid solvent to another across a phase boundary, and in the dissolution of a crystal the solute is transferred from a solid to a liquid. 

FIGURE 8.39 A schematic illustration of the process of fractional distillation. The temperature in the fractionating column decreases with height. The condensations and reboilings illustrated in Fig. 8.38 occur at increasing heights in the column. The less volatile component returns to the flask beneath the fractionating column, and the more volatile component escapes from the top, to be condensed and collected. 

Volatile liquids can be separated by fractional distillation. Liquid and vapor are in equilibrium at each point in the fractionating column, but their compositions vary with height. As a result, the lowest-boiling-point component can be removed from the top of the column before the next-higher-boiling-point component distills. 

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