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Distillation
Distillation
Distillation is the mass transfer separation technique of preferential separation of the more
volatile component(s) from the less volatile ones by partial vaporization of the feed followed
by condensation of the resulting vapour phase. For a greater degree of separation to be
achieved, a multistage contact arrangement is setup between the liquid and vapour phases
in a suitable equipment known as the Distillation column.
The most important parts of a distillation unit as shown in the diagram below are (a)
A column having trays or a packing and suitable internals (b) A reboiler (which supplies
heat energy to the system), and (c) a condenser (to condense the resultant vapour
phase back to liquid for collection)
N.B: -do- connotes same as above (e.g. petrochemical in the above table)
At a given temperature, the unique atmospheric pressure at which a pure liquid boils is called
its vapor pressure. If the atmospheric pressure is higher than the vapor pressure, the liquid
will not boil.
Multiple-Component Phase Equilibrium: Phase Diagrams
We deal often with equilibrium of mixtures. When a mixture begins to boil, the vapor
does not, in general, have the same composition as the liquid. Instead, the substance with
the lower boiling temperature (or higher vapor pressure) will have a vapor concentration
higher than that with the higher boiling temperature, though both will be present in the
vapor. A similar argument applies when a vapor mixture condenses.
The concentrations of the vapor and liquid when the overall concentration and one of the
temperature or pressure are fixed can easily be read off of a phase diagram. In order to
read and understand a phase diagram, it is necessary to understand the concepts of bubble
point and dew point for a mixture.
Bubble Point and Dew Point
In order to be able to predict the phase behavior of a mixture, scientists and engineers
examine the limits of phase changes, and then utilize the laws of thermodynamics to
determine what happens in between those limits. The limits in the case of gas-liquid phase
changes are called the bubble point and the dew point.
The names imply which one is which:
1. The bubble point is the point (a set of conditions of temperature and pressure) at
which the first drop of a liquid mixture begins to vaporize.
2. The dew point is the point (a set of conditions of temperature and pressure) at which
the first drop of a gaseous mixture begins to condense.
If you are able to plot both the bubble and the dew points on the same graph, you come up
with what is called a Pxy or a Txy diagram, depending on whether it is graphed at constant
temperature or constant pressure. If it is graphed at constant temperature, we get a Pxy
phase diagram and if the Vapor-Liquid Equilibrium (VLE) data is plotted at constant pressure,
we get a Txy phase diagram. The "xy" implies that the curve is able to provide information on
both liquid and vapor compositions.
𝐷1
% 𝑉𝑎𝑝𝑜𝑢𝑟 = … … … … 𝑒𝑞𝑢 2
𝐷1 + 𝐷2
Another form of the lever rule is given as;
𝐿 𝑦𝐴∗ − 𝑧𝐴𝐹
= … … … … … … … … … 𝑒𝑞𝑢 3
𝑉 𝑧𝐴𝐹 − 𝑥𝐴
Where,
𝑧𝐴𝐹 represents the overall composition of the component A in the feed mixture.
The phase whose percent you're calculating is simply the one which you are
going away from for the line segment in the numerator; for example, D2 is going from the
point of interest to the vapor phase, so if D2 is in the numerator then you're calculating
percent of liquid.
Txy diagrams have entirely analogous rules, but just be aware that the graph is "reversed"
somewhat in shape. It's somewhat harder to calculate even in an ideal case, requiring an
iterative solution, but is more useful for isobaric (constant-pressure) systems and is worth
the effort. The extreme ends of the txy diagram are the boiling temperatures of pure
toluene (xb = 0) and benzene (xb = 1) at 760 mmHg.
Bubble Point
Let us first consider how to calculate the bubble point (at a constant temperature) of a
mixture of 2 components A and B, assuming that the mixture follows Raoult's Law under all
conditions. To begin, write Raoult's Law for each component in the mixture. Recall equ. 7
𝑃𝐴∗ 𝑥𝐴 𝑃𝐴𝑣
𝑦𝐴∗ = =
𝑃 𝑃
For component B, we also have
𝑃𝐵∗ 𝑥𝐴 𝑃𝐵𝑣
𝑦𝐵∗ = =
𝑃 𝑃
We can add these two equations together and multiply through by P to get,
∗ ) = 𝑥 𝑃𝑣 + 𝑥 𝑃 𝑣
𝑃(𝑦𝐴∗ + 𝑦𝐵 𝐴 𝐴 𝐵 𝐵
Now since 𝑦𝐴∗ and 𝑦𝐵∗ are mole fractions with A and B being the only components of the
∗ = 1 . In addition, recall that since we are considering the bubble point,
mixture, 𝑦𝐴∗ + 𝑦𝐵
the liquid composition is essentially equal to the overall composition. Therefore 𝑥𝐴 =
𝑧𝐴 𝑎𝑛𝑑 𝑥𝐵 = 𝑧𝐵 . Note that this is only true at the bubble point.
Hence we have the following equation valid at the bubble point for an ideal equilibrium:
𝑣
𝑃 = 𝑧𝐴 𝑃𝐴𝑣 + 𝑧𝐵 𝑃𝐵 … … … 𝑒𝑞𝑢 9
Therefore, if the temperature and overall composition are known, the bubble pressure can
be determined directly. P represents the bubble point pressure, 𝑃𝐴𝑣 and 𝑃𝐵𝑣 can be
calculated from the Antoine’s equation using the given temperature.
If the pressure is held constant and the bubble point temperature is required, it is necessary
to calculate the temperature by an iterative method. The temperature dependence is
contained in the Antoine equation for vapor pressure of each component. One method to
solve for the temperature is to:
1. Guess a temperature
2. Use the guess and the Antoine equation to calculate the vapor pressure of each
component in the mixture.
3. Calculate an equilibrium pressure using the bubble point pressure equation.
4. If the calculated pressure does not equal the known pressure, it is necessary to
change the temperature and try again.
If there are more than two-components (multi-component mixtures), The Raoult’s law
equation for calculating the bubble point pressure becomes;
𝑃 = Σ(𝑧𝑖 × 𝑃𝑖𝑣 ) … … … 𝑒𝑞𝑢 10
Summed over all components i.
Dew Point
The derivation of the dew point pressure equation for a two-component system under
Raoult’s law is similar to that for bubble point only that since we are dealing with dew point,
we eliminate the liquid phase compositions just as we did the vapor phase compositions when
dealing with the bubble point pressure.
The dew point pressure equation for a two-component system under Raoult’s law is given by
1 𝑧𝐴 𝑧𝐵
= 𝑣 + 𝑣 … … … … … 𝑒𝑞𝑢 11
𝑃 𝑃𝐴 𝑃𝐵
For a multi component system having i components, we have that;
1 𝑧𝑖
= Σ ( 𝑣 ) … … … … … 𝑒𝑞𝑢 12
𝑃 𝑃𝑖
The procedure for determining the dew point temperature at a fixed pressure is similar to
that described for bubble point temperature and requires an iterative method with the major
difference in step 3 of the process in the sense that instead of using the bubble point pressure
equation (equ 9), we would use the dew point pressure equation (equ 11) to evaluate the
pressure which we would then compare with the fixed value to ascertain if our initial guess
of the temperature is correct.
Example 1
Cyclo-pentane (A) and benzene (B) form nearly ideal solutions.
The Antoine’s equation constant for Cyclo-pentane are A’, B’ and C’ = 15.8602, 2589.2 and
231.36 respectively while those for Benzene are A’, B’ and C’ = 15.9037, 2789.01 and 220.79
respectively.
a) Using the vapour pressure data given and assuming ideal behaviour, prepare the
bubble point curve, the dew point curve and the vapour-liquid equilibrium curves for
this binary at 1 atm total pressure.
b) If one kilomole of a two-phase mixture having 42 mole% A at 68oC and 1 atm total
pressure is allowed to separate into a liquid and vapour phase at 1 atm total pressure,
calculate the amounts and compositions of the two phases.
c) If an equimolar mixture of the compounds has a bubble point of 100 oC, calculate the
total pressure exerted at that temperature at equilibrium.
Solution
a) The bubble point and dew point values of a Cyclo-pentane – Benzene mixture remains
within 49.2oC (boiling point of pure Cyclo-pentane at 1 atm) and 80oC (boiling point of
pure Benzene at 1 atm). The total pressure remains constant at 1 atm (760mm Hg)
In order to compute the T-x-y data with which we would obtain the T-x-y diagram, we
employ the procedure already outlined previously.
To start with, take T = 70oC. (Note that TA < T < TB as 49.2oC < 70oC < 80oC)
(b) The state of the feed (68oC; 1 atm; ZAF = 0.42) is represented by the point F that lies in
the two-phase region in the figure above. In order to find the compositions of the liquid and
vapour phases at equilibrium, we draw a horizontal line through F to meet the bubble point
curve at L and the dew point curve at V. The point where the line meets the bubble point
curve (T-x) gives the equilibrium composition of the liquid as 𝑥𝐴 = 0.294 and the point
where the line meets the dew point curve (T-y) gives the equilibrium composition of the
vapour as 𝑦𝐴∗ = 0.521
We have that the total amount of mixture 𝐹 = 1 𝑘𝑖𝑙𝑜𝑚𝑜𝑙𝑒
𝐹 =𝐿+𝑉 =1
Recalling equation 3, we have
𝐿 𝑦𝐴∗ − 𝑧𝐴𝐹
=
𝑉 𝑧𝐴𝐹 − 𝑥𝐴
By substituting the values of 𝑥𝐴 , 𝑦𝐴∗ and 𝑧𝐴𝐹 and solving the equations above
simultaneously, we find moles of liquid 𝐿 = 0.555 𝑘𝑚𝑜𝑙 and moles of vapor 𝑉 =
0.445 𝑘𝑚𝑜𝑙.
(c) The equimolar composition at bubble point means 𝑥𝐴 = 0.5 𝑎𝑛𝑑 𝑥𝐵 = 0.5
At a temperature of 100oC, the vapour pressures are calculated using the Antoine’s
equation to give 𝑃𝐴𝑣 = 3120.2 𝑚𝑚 𝐻𝑔 𝑎𝑛𝑑 𝑃𝐵𝑣 = 1350.5 𝑚𝑚 𝐻𝑔
The equilibrium total pressure exerted above an equimolar mixture at 100oC is given by
𝑃 = 𝑃𝐴𝑣 𝑥𝐴 + 𝑃𝐵𝑣 (1 − 𝑥𝐵 ) = (0.5)(3120.2) + (1350.5)(1 − 0.5) = 2235.3 𝑚𝑚 𝐻𝑔
Relative Volatility
The relative volatility of a component A in a mixture indicates the ease of its separation from
another component B. It is defined as the concentration ratio of the more volatile component
A in the vapour phase divided by the same ratio in the liquid phase.
It is usually denoted by α. For a binary mixture,
𝑦𝐴∗ /(1 − 𝑦𝐴∗ )
α𝐴𝐵 = … … … … 𝑒𝑞𝑢 13
𝑥𝐴 /(1 − 𝑥𝐴 )
𝑥𝐴 α𝐴𝐵
𝑦𝐴∗ = … … … … 𝑒𝑞𝑢 14
1 + (α𝐴𝐵 − 1)𝑥𝐴
Equation 14 shows us that an algebraic equation can be established between 𝑦𝐴∗ and 𝑥𝐴 if the
relative volatility between A and B is known.
In order to separate a binary mixture using distillation process, there must be a substantial
difference in the volatilities of the components. Being that A is the more volatile component,
α𝐴𝐵 should be much greater than 1 if separation by distillation is to be effective. The higher
α𝐴𝐵 is than 1, the better the separation process by distillation.
The relative volatility α𝐴𝐵 in an ideal binary solution can be expressed in terms of the vapour
pressures of the components as shown below;
𝑦𝐴∗ /(1 − 𝑦𝐴∗ ) (𝑃𝐴∗ ⁄𝑃) (𝑃𝐵∗ ⁄𝑃) 𝑃𝐴𝑣
α𝐴𝐵 = = = 𝑣 … … … 𝑒𝑞𝑢 15
𝑥𝐴 /(1 − 𝑥𝐴 ) (𝑃𝐴∗ ⁄𝑃𝐴𝑣 ) (𝑃𝐵∗ ⁄𝑃𝐵𝑣 ) 𝑃𝐵
Batch Distillation
In batch distillation, the feed is charged to the still pot to which heat is supplied continuously
through a steam jacket or a steam coil. As the mixture boils, it generates a vapour richer in
the more volatiles. As the boiling continues, concentrations of more volatiles in the liquid
decrease. The vapour is led to a condenser and the condensate or top product is collected in
a receiver. At the beginning, the condensate will be pretty rich in the more volatiles, but the
concentrations of the more volatiles in it will decrease as the condensate keeps on
accumulating in the receiver.
In batch distillation, the condensate is usually withdrawn intermittently having products or
cuts of different concentrations.
Batch distillation is used when the feed rate is not large enough to justify installation of a
continuous distillation unit. It may also be used when the constituents greatly differ in
volatility.
When small amounts of products of varying compositions are required, a batch distillation
provides several advantages over the continuous distillation.
Batch distillation is versatile and commonly employed for producing biochemical, biomedical,
and/or pharmaceutical products, in which the production amounts are small but a very high
purity and/or an ultra-clean product is needed
Theoretical analysis of batch distillation is based on a ‘differential mass balance’ because the
liquid and the vapour phase concentrations of the components change continuously as
distillation proceeds. Let, at any moment, the number of moles of liquid in the still be L having
a mole fraction x of the more volatile component (i.e. A) and let the moles of accumulated
condensate be D. Concentration of the equilibrium vapour is 𝑦𝐴∗ . Over a small time, the
change in the amount of liquid in the still is 𝑑𝐿 and the amount of vapor withdrawn is 𝑑𝐷.
The following differential mass balance equations may be written:
Equation 20 is the basic equation of batch data distillation and is called the ‘Rayleigh
equation’. If the vapour – liquid equilibrium data (𝑥-𝑦𝐴∗ ) are available in a tabular form, the
right side of equation 20 can be evaluated graphically. If an algebraic relation between
𝑥 and 𝑦𝐴∗ is available, analytical integration may be possible. For example, if the relative
volatility of A in the binary mixture α𝐴𝐵 is constant as in ideal solutions, the relation
between 𝑥 and 𝑦𝐴∗ may be obtained from equation 14 and substituting for 𝑦𝐴∗ in equation 20
and integrating gives,
𝑥𝑊
𝐹 𝑑𝑥 1 𝑥𝐹 (1 − 𝑥𝑊 ) 1 − 𝑥𝑊
ln = ∫ 𝑥𝐴 α𝐴𝐵 = ln + 𝑙𝑛 … … 𝑒𝑞𝑢 21
𝑊 −𝑥 (α𝐴𝐵 − 1) 𝑥𝑊 (1 − 𝑥𝐹 ) 1 − 𝑥𝐹
𝑥𝐹 1 + (α𝐴𝐵 − 1)𝑥𝐴
The above integral can be expressed in a more convenient form by multiplying through by
(α𝐴𝐵 − 1) and simplifying to get
𝐹𝑥𝐹 𝐹 (1 − 𝑥𝐹 )
ln = 𝛼 𝑙𝑛 … … … … … … . 𝑒𝑞𝑢 22
𝑊𝑥𝑊 𝑊(1 − 𝑥𝑊 )
The average composition (𝑦𝐷,𝑎𝑣 ) of the accumulated distillate (D) can be obtained by the
simple material balance.
𝐹𝑥𝐹 = 𝐷𝑦𝐷,𝑎𝑣 + 𝑊𝑥𝑊 𝑎𝑛𝑑 𝐹 = 𝐷 + 𝑊 … … … … … 𝑒𝑞𝑢 23
Example 2
A charge of 50kmol of a mixture of Benzene and Chloro-benzene having 55mol% of the less
volatile is to be batch-distilled. (a) If 25 moles of the solution is vaporized and condensed as
the distillate, calculate the concentration of the accumulated distillate. (b) If the
concentration of the accumulated product is found to be 72mol% benzene, calculate its
amount. The relative volatility of benzene in the mixture is 4.15
Solution
Moles of feed, F = 50kmol;
Feed concentration of the more volatile component, 𝑥𝐹 = 1 − 0.55 = 0.45
(a) Distillate, D = 25 kmol, and W = 25 kmol 𝑎𝑛𝑑 𝑦𝐷,𝑎𝑣 = ?; we will use equ. 22 to obtain 𝑥𝑊
which will in turn be used in equ 23 to finally 𝑔𝑒𝑡 𝑦𝐷,𝑎𝑣 .
50 ∗ 0.45 50 ∗ (1 − 0.45)
ln = 4.15 𝑙𝑛
25 ∗ 𝑥𝑊 25(1 − 𝑥𝑊 )
Solving the above, we get 𝑥𝑊 = 0.218
Material balance: 𝐹𝑥𝐹 = 𝐷𝑦𝐷,𝑎𝑣 + 𝑊𝑥𝑊 ⟹ 50 ∗ 0.45 = 25 ∗ 0.218 + 25 ∗ 𝑦𝐷,𝑎𝑣
𝑦𝐷,𝑎𝑣 = 0.682
1
1) From the tabulated equilibrium data, evaluate the value of y∗A −x
from the values of yA∗ and
1
x for each corresponding value of x. Plot y∗ −x on the vertical axis against x. The area under
A
the plotted graph between xW and xF is the solution of the integral on the right hand side of
equation 20. However, as mentioned above, if the value of xW is not known and the value of
xD is specified then the integral cannot be integrated straight away and we would need to
apply a trial and error procedure
2) Make a first (1st) guess for the value of xW and calculate the value of the integration of Equ
20 according to the guessed value of xW
4) Use the value of final W obtained from step 3 and the guessed value of xW made in 2,
combined with the given values of F and xF , to compute the values of Dcalc and
xD,calc (yD,av calc) using the combined pair of equation 23
5) Compare the value of xD,calc obtained from 4 with the given value of xD : if xD,calc = xD ,
the trial & error procedure is finished; however, if xD,calc ≠ xD , the new trial & error has to
be repeated, until we obtain the guessed value of xW that makes xD,calc = xD
The following Example illustrates the employment of the trial & error technique to solve the
batch distillation problem
Example Use the given equilibrium data of methanol (MeOH) and water for solving the simple
batch distillation problem with the following description:
A single-equilibrium-stage (or a simple) batch still pot is used to separate MeOH from water
The feed with the total amount of 50 moles of an 80 mol% MeOH is charged into the still
pot operated at 1 atm. The desired distillate concentration (xD ) is 89.2 mol% MeOH
Determine:
a) The total amount of the distillate collected (Dtotal )
b) The amount of material (liquid or waste) remained in the pot after the distillation has ended
(final W) and its corresponding concentration (final xw )
It is given that
F = 50 moles
xF = 0.80
xD,avg = 0.892
0 0
2.0 13.4
4.0 23.0
6.0 30.4
8.0 36.5
10.0 41.8
15.0 51.7
20.0 57.9
30.0 66.5
40.0 72.9
50.0 77.9
60.0 82.5
70.0 87.0
80.0 91.5
90.0 95.8
95.0 97.9
100.0 100.0
Since 𝑥𝑤 one of the integral boundaries, is NOT known, a trial & error technique must be
𝑥 𝑑𝑥
employed to compute the integral ∫𝑥 𝑊 𝑦 ∗ −𝑥
𝐹 𝐴
To start the calculations, the 1st guess with 𝑥𝑤 of 0.70 is used
1
From the given equilibrium data, the value of 𝑦−𝑥 for each value of x can be summarised in
the following Table (note that interpolations are needed to obtain the values of y and
1
when the values of x are, e.g., 0.75, 0.65):
𝑦−𝑥
x y Y-x 1
𝑦−𝑥
0.80 0.915 0.115 8.69
0.75 0.895 0.145 6.89
0.70 0.871 0.171 5.85
0.65 0.845 0.195 5.13
0.60 0.825 0.225 4.44
0.50 0.780 0.280 3.57
1
Plotting a graph between x (X-axis) and (Y-axis) using the data in the Table above from,
𝑦−𝑥
𝑥𝑤 = 0.70 (the dashed lines) to 𝑥𝐹 = 0.80, yields the following graph
(from “Separation Process Engineering” by Wankat, 2007)
0.70 𝑑𝑥
From the resulting graph, ∫0.80 ∗ −𝑥 is in fact,the area under the curve from x = 0.70 to x
𝑦𝐴
0.80
For this Example, the area under the curve is found to be - 0.7044
The value of final W (i.e. the liquid remained in the still pot) can then be calculated, using Equ
20 to obtain Final W = 24.72 mol
With the new guess of 𝑥𝑤 of 0.60, we obtain the following (by performing similar calculations
as above):
Area under the curve from, 𝑥𝑤 = 0.60 𝑡𝑜 𝑥𝐹 = 0.80 is 1.2084
Final W = 50 exp (-1.2084) = 14.93
𝐷𝑐𝑎𝑙𝑐 = F -W = 50-14.93 = 35.07
𝑥𝐷,𝑐𝑎𝑙𝑐 = 0.885 (Too low!)
Hence, we need to make a new (the 3rd) guess for 𝑥𝑤
Since 𝑥𝐷,𝑐𝑎𝑙𝑐 = 𝑥𝐷,𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑒𝑑 when we use 𝑥𝑤 of 0.65, the 𝑓𝑖𝑛𝑎𝑙 𝑥𝑤 which we seek is = 0.65
The pot is filled with liquid mixture and heated. Vapour flows upwards in the rectifying column
and condenses at the top. Usually, the entire condensate is initially returned to the column
as reflux. This contacting of vapour and liquid considerably improves the separation.
Generally, this step is named start-up. The first condensate is the head, and it contains
undesirable components. The last condensate is the feints and it is also undesirable, although
it adds flavour. In between is the heart and this forms the desired product.
The head and feints may be thrown out, refluxed, or added to the next batch of mash/juice,
according to the practice of the distiller. After some time, a part of the overhead condensate
is withdrawn continuously as distillate and it is accumulated in the receivers, and the other
part is recycled into the column as reflux.
Owing to the differing vapour pressures of the distillate, there will be a change in the
overhead distillation with time, as early on in the batch distillation, the distillate will contain
a high concentration of the component with the higher relative volatility. As the supply of the
material is limited and lighter components are removed, the relative fraction of heavier
components will increase as the distillation progresses.
Batch Distillation with rectification set-up