Advanced Heat and

Mass Transfer 422

Multicomponent Distillation
Why Multi Component Distillation (MCD) is more
complex than binary distillation?
While we can graphically solve a binary component distillation
system using the McCabe-Thiele method, it is also possible to do a
complete analytical solution using mass and energy balances with
the equilibrium relationship.

However, for multi-component systems, C > 2, one would find that

the number of equations obtained from mass and energy balances
with the equilibrium relationship will always be one less than the
number of unknowns.

Consequently, one cannot do a complete analytical solution for

multi-component distillation it requires a trial-and-error solution
with the additional unknown assumed to be known, as well as
special considerations as to enhancing convergence of the solution.
 Additional terminology for
MCD
When dealing with multi-component systems, we
introduce some new terminology in addition to the
terms used in binary distillation:

Fractional recoveries
Key components
Non-key components
Distributed and non-distributed components

Note that binary systems can be handled in the same

terms.
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MCD- Fractional Recoveries

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MCD Fractional Recoveries
Fractional recoveries are often specified in MCD.

A fractional recovery, FRi, is the amount or flow rate of component i in the

distillate or bottoms stream with respect to the amount or flow rate of
component i in the feed stream:
(Dx i )dist Dx D, i
(FR i )dist = = (FR i )dist = 1 (FR i )bot
Fz F, i Fz F, i

(Bx i )bot Bx B, i
(FR i )bot = 1 (FR i )dist
(FR i )bot = =
Fz F, i Fz F, i
It is the simple relationships expressed by the right-hand-side equations that
make the use of fractional recoveries useful.

These are also often specified simply as % recovery.

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MCD Key Components

The components that have their distillate and bottoms

composition specified are known as the key components.

The more volatile components that is mostly distributed to

the top is termed the light key (LK).

The less volatile components is mostly distributed to the

bottom is termed the heavy key (HK).

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MCD Non-Key Components

All other components not specified in the distillate or

bottoms are termed non-key components (NKs).

If a non-key component is more volatile than the light

key, then it is termed a light non-key (LNK).

If a non-key component is less volatile than the heavy

key, it is a heavy non-key (HNK).

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Key and Non-key component

TbpA <TbpB < TbpC TbpA <TbpB < TbpC

A Light key A Light non-key
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B Heavy key B Light key
C Heavy non-key C Heavy key
 How do we determine the keys (LK and HK) and the nonkeys
(LNKs, HNKs) in MCD?

The classification of components in MCD can be determined from their

relative volatilities.

Relative volatility is defined as the ratio of the K values for two

components, which is trivial for a binary system.

In order to use relative volatilities in MCD, we choose a reference

component and define all other component volatilities with respect to the
reference component.

The relative volatility for the reference component, of course, will be 1.

We can then define relative volatilities using equilibrium coefficient K

values for each component, e.g., from the DePriester charts for
hydrocarbon systems.
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The choice of the reference component depends upon the problem, but in
general it will be the HK component since it is less volatile than the LK
component.
Key and Non-Key Example
Consider a distillation column with the following feed components:
propane
nbutane
npentane
nhexane

The recoveries for nbutane (say 99%) and npentane (2%) are
specified for the distillation.

What are the key and nonkey designations for this separation?

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Key and Non-Key Example
Component volatilities can be determined from the
K values.

From the DePriester charts, the order of volatility is:

propane > nbutane > npentane > nhexane

Since the recoveries of nbutane and npentane are

specified

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Key and Non-Key Example
We have:
Volatilities
propane > nbutane > npentane > nhexane

Component Designation
Propane Light NonKey
nbutane Light Key
npentane Heavy Key
nhexane Heavy NonKey
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Multicomponent Distillation
Design
Design Requirement

Equilibrium data key equilibrium data: relative volatility

Methods
Assumptions
Material and energy balances
Column Height
Column diameter
Number of trays
Feed location
Operating Conditions 13
Constant Molar Overflow(CMO)
Assumption
Definition:
CMO is the assumption that all liquid (L) and vapour (V) flows (on a
molar basis) in the rectifying section are constant and that all liquid
(L) and vapour (V) flows (on a molar basis) in the stripping section
are constant (but are not the same as the ones in the rectifying
section) refer to lecture 1 for material balance of distillation
column

Under CMO assumptions, the following conditions are assumed:

The column is adiabatic (except or condenser and reboiler)

The specific heat changes are negligible compare to latent heat
changes
The heat of vaporization per mole is constant
The saturated liquid and vapour lines on the enthalpy composition
diagram are parallel 14
Class Problem: Fractional
Recoveries and Key components
It is required to separate a saturated quaternary mixture
containing propane (component 1, Z1=0.060), n-
butane(component 2, Z2 =0.33), n-pentane (component 3, Z3
=0.45) and n-hexane (component 4). The feed rate is 1000
kmol/hr and the total pressure is 1atm. The reflux ratio is R
=3.0 . It is desired to recover 99% of the butane in the
distillate and 99.5% of pentane in the bottoms.

Calculate the flow rates and compositions of the distillate and

the bottom product

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 There are 4
components,
i=1,2,3,4
FR of component 2
and 3 are given
light and heavy
key respectively
Unknowns
variables D,W,
x1D, x2D ,x3D, x4D,
x1W, x2W, x3W, x4W
Assumption: 16
x4D=0, x1W = 0
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 Multicomponent methods
Shortcut Method Rigorous Method

Fenske min plate number Thiele-Geddes Rating Method

Underwood min reflux Lewis-Matheson Design

Method
Gilliland (Erbar-Maddox)

FUG Approach
Smith Brinkley

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Lewis Matheson vs McCabe-
Thiele diagram
Both methods based on CMO assumptions
Graphical method is faster
Graphical method presents very clear picture, easier to
understand than analytical method
Graphical method is a useful tool to help determine the effect
of changing variables
McCabe-Thiele method is tedious when designing column
with large number of stages

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Rigorous method VS Short cut
Method
Rigorous method is Shortcut method is
done using software used to outline the
such as ASPEN or scope and limitations
HYSYS of a particular
process
Short Cut
Calculation:
Fenske-Underwood-
Gilliland (+Kirkbride)
method 21
Off-the-Shelf Solutions
Fortunately, numerical design packages, such as
Aspen Plus and HYSYS, have been developed to
perform the rigorous solution of multi-
component distillation systems

However, as a design engineer, one always needs

to know the underlying theory and methods of
calculation to enable one to make decisions
about the validity of these offthe shelf
packages and to verify the results. 22
HYSYS Example Short Cut
Column

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Hysys example Rigorous
Column input requirement

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Hysys rigorous column input
requirement

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Why Multi Component Distillation (MCD) is more
complex than binary distillation?

In binary mixture the concentration of the other component is

always fixed with respect to the 1st component

In MCD, the relationship between the concentration of the

liquid phase of a particular component and its vapour phase
varies depending on the % of other components in the system

For this reason, the composition of liquid and vapour must be

determined for each multicomponent system by using
equilibrium data (K=y/x) for each component

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Why do we need to determine composition of
liquid and vapour in MCD?
We need to calculate bubble point and dew point to
estimate the stage and the condenser and reboiler
temperatures
For Vapour-Liquid equilibrium, the dew point and
bubble point can be calculated from:
Bubble point =

Dew point =
For multicomponent system the temperature that
satisfies these equations at a given system pressure,
can be found using trial and error
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Bubble and Dew point
Calculation
Bubble point calculation: In an n-component mixture, let us
selsect r-th component as a reference component. The relative
volatility of the i-th component with respect to the r-th
component is given as
1

= = =

Therefore:
= = =
= =1 = =1

For dew point calculation:

1
=1 = =1 = = =1

Bubble point and Dew Point
calculation
The K values can be obtain from DePriester charts or
from the Priester equation or Antoine eqn:
DePriester eqn:
ln(K) = aT1(1/T2) + aT2(1/T) + aT6 + aP1(ln P) + aP2(1/P2) +
aP3(1/P)
Note that T in R and P is in psia. (The constant for the first 14
hydrocarbons can be found in p.33, Wankat, 2011,3rd ed.)

Antoine Eqn Refer to lecture 1

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Bubble and Dew Point
Calculation
Methods of calculation:
We may assume the values of both bubble point and dew
points
Obtain the vapour pressures or K-values for all components at
these temperatures
Since the total pressure is usually given, we can calculate the
mole fractions (yi for bubble point and xi for dew point)
If the assumed temperatures are correct, the sum of xi= sum
of yi =1

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Bubble and Dew point
calculation: Class problem
Find the bubble point and dew point
temperatures and the corresponding vapour and
liquid compositions of a mixture of 33% mole n-
hexane, 37%mole n-heptane, and 30% mole n-
octane at a total pressure of 1.2 atm

Bubble point first guess: Choose T= 105C, where

the vapour pressure of heptane is 1.2 atm
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Component Pi' at 105C, atm Ki =Pi'/1.2 xi yi=Kixi
Hexane 2.68 2.2333333 0.33 0.737
Heptane 1.21 1.0083333 0.37 0.373083
Octane 0.554 0.4616667 0.3 0.1385
1.248583

Since the sum of yi is too large then try a lower temperature. The
major contribution comes from the first term (Pi hexane), then
pick where Ki is lower by a factor of 1.24. (Ki=2.68/1.24 =2.16
atm, for hexane) which corresponding T = 96 C

Compone Pi' at 96C, Ki yi

nt atm =Pi'/1.2 xi yi=Kixi interpolated
Hexane 2.16 1.8 0.33 0.594 0.604118993
Heptane 0.93 0.775 0.37 0.28675 0.291634884
0.34166
Octane 0.41 67 0.3 0.1025 0.104246123
0.98325 1 32
By interpolation, the bubble point is 97 C. The vapour
equilibrium with the liquid is 60.4% mole hexane, 29.2 % mole
heptane and 10.4% mole octane

Dew point is higher than the bubble point, so use 105 C as the
first guess.
Pi' at 105C,
Component atm Ki =Pi'/1.2 yi xi=yi/Ki
2.233333
Hexane 2.68 3 0.33 0.147761
1.008333
Heptane 1.21 3 0.37 0.366942
0.461666
Octane 0.554 7 0.3 0.649819
1.164523

Since its too high, pick a higher temperature. Pick T =110 C, where Ki
of octane (major contributor) is 16.5% higher 33
 Pi' at 105C, Ki
Component atm =Pi'/1.2 yi xi=yi/Ki yi interpolated
Hexane 3 2.5 0.33 0.132 0.130548088
Heptane 1.38 1.15 0.37 0.321739 0.318200215
Octane 0.645876 0.53823 0.3 0.557383 0.551251697
1.011122 1

By extrapolation, the dew point is 110.5C

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Bubble and dew point
calculation

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MCD Short-Cut Methods
Because of the non-trivial nature of multi-component distillation problems,
short-cut methods and correlations have been developed.

Commonly used in the past until the advent of numerical computer

packages, these were the methods of choice to enable the estimation of
distillation column design for multi-component systems.

Lecture 17
Even so, they are still used in numerical computer packages to provide initial
first estimates for the design of multi-component distillation systems.

The DSTWU distillation package in Aspen Plus/HYSYS uses the

Winn-Underwood-Gilliland short-cut methods and correlation.

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MCD Short-Cut Methods
Limiting Conditions

MCD short-cut methods are based upon the limiting conditions for a
distillation column:
Reflux Ratio L/V L/D N
Total (L/V)max = 1 Nmin
Actual L/V L/D N

Lecture 17
Minimum (L/V)min (L/D)min Nmax =

The actual or operating reflux ratio will lie between the total and
minimum reflux ratios (L/V)min < L/V < 1.

The operating reflux ratio, L/D, is often specified as a multiple of the

minimum reflux ratio, (L/D)min, e.g.,
L/D = 2 (L/D)min.
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MCD Short-Cut Methods
Fenske Equation (Winn) determines the minimum number of
stages, Nmin, and the optimum feed location, NF, min, at total
reflux.

Lecture 17
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Short cuts Methods
Underwood Equations determines the minimum the
reflux ratio, (L/D)min.

Gilliland Correlation determines the actual number of

stages, N, and the optimum feed location, NF, at the
actual L/D.

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Fenske equation Methodology
A mixture of 33% mole n-hexane, 37%mole n-heptane,
and 30% mole n-octane to be distilled to give a distillate
product with 0.01 mole fraction n-heptane and a
bottoms product with 0.01 mole fraction of n-hexane.
The column will operate at a pressure of 1.2 atm with
60% vaporized feed. Calculate the complete product
compositions and min. no. of ideal plates

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