Distillation
Introduction Distillation is the thermal process used to separate or purify liquid mixtures. There are two big categories of distillation: simple distillation based on one-stage equilibrium and the fractional distillation (fractionation) based on multiple-stage equilibrium. In our laboratory exercise, we will be doing a multiple-stage equilibrium distillation of biofuel-water mixture. The objective here is to distill ethanol from the mixture to produce concentrated ethanol, which can be further processed to be used as biofuel or biochemical. A schematic diagram of a multiple-stage fractional distillation is shown in Figure 1. Here the feed F
(mol/h) at a known initial concentration of ethanol (mole fraction) (xF) enters the distillation column at some intermediate tray (stage). The boiled vapor and the liquid are in equilibrium on each tray in the column, the vapor moving up the column and the liquid down the column through the sieve trays ensuring good contact between the two reaching equilibrium. The distilled vapor is condensed (using cold water in heat exchanger) in a condenser in the top, part of it is recycled back to the column (L (mol/h)) and the distillate product D (mol/hr) at a higher concentration of ethanol (xD) is removed from the top. The majority liquid that is flowing down the column is heated in a reboiler and the vapor returned back to the column while removing some portion as bottom product W (mol/h) at an ethanol concentration (xw).
Figure 1. Multiple-stage fractional distillation (single) column with reflux
Figure 2 is another schematic of the fractional multiple-stage distillation showing the trays inside and the vapor and liquid flows. Here, the section above the feeding position is call enriching section while the section below the feeding position is call stripping section. There are several sieve trays installed inside. The vapor and the liquid from each stage/tray flow countercurrent to each other. The liquid in a stage flows to the stage below and the vapor from a stage flows through the pores of sieve upward to the stage above. Hence, in each stage a vapor stream and a liquid stream are mixed, and a vapor and a liquid stream leave in equilibrium.
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Figure 2. Fractional distillation with sieve trays or stages Some of the key assumptions in distillation are that there is equilibrium between the vapor and liquid leaving the tray; for ideal mixtures this can be described by Raoult’s law. The latent heats of vaporization of the components being distilled are approximately the same. So, the energy needed for vaporizing 1 mol of component A is the same as energy released from condensing 1 mol of component B. This results in a constant equimolar counter flow assumption in distillation. Figure 3 shows the vapor liquid equilibrium diagram for ethanol-vapor mixture.
Figure 3. Vapor Liquid Equilibrium (VLE) diagram for ethanol-water system. x is the mole fraction of ethanol in the liquid phase and y is the mole fraction of ethanol in the vapor phase – they both are in equilibrium. Blue is the equilibrium line and Red is the 45◦ line.
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As you can see in Figure 3 above about 0.8 mole fraction of ethanol in the liquid mixture (x) there is an azeotrope formed; beyond which the mole fractions of ethanol in the liquid and vapor phases are the same. Hence, they cannot be further purified or concentrated. For an ideal system, using Raoult’s law the relationship between mole fractions and partial pressures for a binary system can be given as,
yA = xA PA*/P
yB = xB PB*/P
Where xA, xB are the mole fractions of components A and B in the liquid phase in a binary mixture Where yA, yB are the mole fractions of components A and B in the vapor phase in a binary mixture PA* and PB* are the saturation vapor pressures of pure component A and B at a given temperature P is the total pressure in the vapor phase. General format of above equations:
* yi =Pi /P= xiPi /P
where yi is the mole fraction of component i (A or B) in the vapor phase.
For a binary mixture of A and B, the relative volatility of component A with respect to B is defined as: