Vapor-liquid Separation Process

MULTICOMPONENT
DISTILLATION
Outline:
 Introduction to multicomponent distillation
 Phase Equilibria in Multicomponent Distillation (Pg. 737)
 Bubble-point and dew-point calculation
 Flash Distillation of Multicomponent Mixtures (pg. 741)
 Fractionation of Multicomponent Mixtures (pg. 742)
 Key Components
 Minimum number of plates
 Minimum reflux ratio
 Azeotropic and Extractive Distillation (pg. 759)

Prepared by, Dr. Nora JULLOK/ UniMAP

Introduction to Multicomponent
Distillation
Binary Mixtures
• The calculation of equilibrium stages
uses mass and enthalpy balances and VLE.
• Much simpler phase equilibria
 Equilibria change from stage to
stage, but except with azeotropes,
the more volatile component is
more volatile than the other
component throughout the
column.
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Multicomponent Mixtures
• The calculation of equilibrium stages
uses mass and enthalpy balances and VLE.
• Phase equilibria are much more complex
because:
 Several components
 Equilibria depend on T, which
changes from stage to stage.
• 1 component may be more volatile than
the average in 1 part of the column and
less volatile than the average in another
part, which leads to complex
concentration profiles.
Phase equilibria in Multicomponent
Distillation
 The VLE for a mixture are described by distribution coefficients or
K factors, where K for each component is the ratio of mole
fractions in the vapor and liquid phase at equilibrium:
 (22.1)
 If Raoult’s law and Dalton’s law hold, values of Ki can be
calculated from the vapor pressure and the total pressure of the
system:
 (22.2)
 (22.3)

 (22.4)

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 Raoult’s law is a good approximation for mixtures of similar
compounds.
 The K-factor strongly temperature-dependent because of the
change in vapor pressure, but the relative value of K for 2
components change only moderately with temperature.
 The ratio of K factors is the same as the relative volatility of the
components:
/
 (22.5)
/
 When Raoult’s law applies,

 (22.6)

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Bubble-point and Dew-point
Calculation
 Determination of the bubble point (initial boiling point of a liquid mixture)
or a dew-point (initial condensation temperature) is required for a flash
distillation calculation and for each stage of a multicomponent distillation.
 The basic equation, for bubble-point:

∑ =∑ 1.0 (assume ,T) (22.7)

 If the summation of Kixi >1.0, choose lower T and repeat calculation

until Eq. (22.7) is satisfied.
 For ∑ 1.00, the composition of the vapor in equilibrium.
 If ∑ 1.00 , the vapor composition can be determined with little
error from relative contribution of each term to the summation (Eq.
(22.9):

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Bubble-point and Dew-point
Calculation
 For dew-point
= (22.8)
Where Nc is the number of components.

(22.9)
∑

 Similar procedure is used to determine the dew point of

a vapor mixture abd composition of the liquid in
equilibrium with this mixture.
Prepared by, Dr. Nora JULLOK/ UniMAP
Example 22.1
 Find the bubble-point and dew-point temperatures and the
corresponding vapor and liquid compositions for a mixture
of 33 mole % n-hexane, 37 mole% n-heptane, and 30 mole%
n-octaneat 1.2 atm total pressure.

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Flash Distillation of Multicomponent
Mixtures
 Eq. (21.1): xF =fyD + (1-f)xB ,can be written for each component in a flash distillation in
the form
(22.10)

Since the distillate and bottom streams are in equilibrium, this equation may changed to
1 (22.11)

Solving Eq. (22.11) for xBi and summing over Nc components gives
∑ 1 ∑ (22.12)

This equation is solved by iteration in the same manner as the dew-point calculation using
Eq. (22.8), and the final values of T and Ki are used to calculate the composition of the
product streams.
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Example 22.2
 The mixture of Example 22.1 is subected to a falsh
distillation at 1.2 atm pressure, and 60% of the feed is
vaporized.
(a) Find the temperature of the flash and the composition of the
liquid and vapor products.
(b) (b) To what temperature must the feed be heated for 60%
vaporization of flashing?
Solution:
Page 741.

Prepared by, Dr. Nora JULLOK/ UniMAP

Fractionation of Multicomponent
Mixtures
 Ideal plates are assumed in the design of cascades, and the number
of stages is subsequently corrected for plate efficiencies.
 2 limiting conditions of total reflux (minimum number of plates)
and minimum reflux are also determined to help validate the
design.
 In binary distillation, a desired separation of components is
assumed, and the numbers of plates above and below the feed are
calculated for chosen reflux ratio (Method 1).
 In multicomponent distillation, the number of plates above and
below the feed is assumed, and the separation of components is
calculated using assumed flows of reflux from the condenser and
vapor from the reboiler.

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Key Components
 Objective of distillation: to separate the feed into streams of nearly
pure products.
 In binary distillation:
 The purity is usually defined by specifying xD and xB, the mole
fraction of light component in the distillate and bottoms products.
 In multicomponent distillation:
 3 or more components in the products, and specifying the
concentrations of one component in each does not fully characterize
these products.
 If the concentration of 2/3or ¾ components are specified the
distillate and bottoms products, it is generally impossible to meet
these specification exactly.

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Key Components
 An increase in reflux ratio number or number of plates would
increase the sharpness of the separation, and the desired
concentration of 1 component in each product can be achieved.
 Often designer chooses 2 components whose concentrations or
fractional recoveries in the distillate and bottoms products are a
good index of the separation achieved.
 Once the components are identified, they are called KEY
COMPONENTS.
 Keys must differ in volatility
 More volatile = Light Key (L)
 Less volatile = Heavy key (H)

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Key Components
 Components lighter than the light key are nearly completely
recovered in the distillate.
 Components heavier than the heavy key are usually
completely recovered in the bottoms.
 Exceptions to distillation of close boiling materials, such as
mixtures of isomers.
 The choice of 2 keys does not give deteminate mass balance,
because not all other mole fractions are calculable by mass
balance alone, and equilibrium calculations are required to
calculate the concentration of dew-point vapor from the top
plate and bubble-point liquid leaving the reboiler.

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Minimum Number of Plates
 The Fenske equation (21.45) applies to any 2 components I and j
in a conventional pant at infinite reflux ratio. In this case the
equation has the form

/ / /
 (22.13)

 (22.14)

 The subscripts D, F, and B in Eq. (22.14) refer to the temperatures

of the distillate, feed plate, and bottom in the column.
 Refer to Example 22.3.

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Minimum Reflux Ratio
 The minimum reflux ratio in multicomponent distillation has
similar significance as for binary distillation; at this reflux
ratio, the desired separation is just barely possible, but an
infinite number of plates are required.

 It is a guide in choosing a reasonable reflux ratio for an

operating column and in estimating the number of plates
needed for a given separation at certain values of the reflux
ratio.

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 An alternate equation for a saturated liquid feed gives the
minimum ratio of liquid rate to feed rate for a binary mixture of A
and B:
/ /
(22.15)
 The term in parentheses in Eq. (22.15) are the fractional recovery
of A and B in the distillate product.
 For a multicomponent mixture, these terms would be the
specified recovery of light key in the distillate .
 Note that the minimum value of L depends mainly on the relative
volatility.
 Eq. (22.15) gives good approximation for multicomponent
mixtures if the key components make up 90% or more of the
feed.

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Azeotropic and Extractive Distillation
 Separation of components that have nearly the same boiling point
is difficult by simple distillation, because of azeotrope formation.
 Separtion can be improved by adding 3rd component to alter the
relative volatility of the original components.
 The 3rd component can be:
 Higher-boiling liquid
 Solvent
That is miscible with both of the key components but is chemically
more similar to one of them.
The key component that is more like the solvent will have a lower
activity coefficient in the solution than the other component, so the
separation is enhanced.

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 Azeotropic distillation = Separation of the original
mixture may also be enhanced by adding a solvent that forms
an azeotrope with one of the key components.
 Usually the material added forms a low-boiling azeotrope
and is taken overhead, and such materials are called,
entrainers.
 the azeotrope will surely contain some of all components in
the feed, bit it will have much different ratio of the keys than
the feed.

Prepared by, Dr. Nora JULLOK/ UniMAP