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Chapter 5.

Introduction to
Multicomponent Distillation
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Calculation difficulties
Binary

problems:

straightforward

solution

using stage-by-stage calculation


Use graphical approach with the McCabe &
Thiele diagram or computer calculation
Multicomponent problem: is significantly more
difficult
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Consider distillation column and assume CMO,


constant pressure and adiabatic column

Number of degrees of freedom = C+6


Binary mixture C=2
Degrees of freedom=8
Specify 8 variables: F, z, feed quality q, distillate
composition xD, distillate temperature TD
(saturated liquid), xB, L/D (R), NF (optimal feed
location)
Operating lines are fully defined and one can step
off stages using the McCabe & Thiele graphical
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method

Ternary mixture C=3, Degrees of freedom=9


Number of variables

Variable

Feed rate, F

Feed composition, z1, z2 (z3 = 1 - z1 -z2)

Feed quality, q (or hF or TF)

Distillate, x1,dist (or x3,dist or D or one


fractional recovery)

Bottoms, x2,bot (or x3,bot or one fractional


recovery)

L0/D or V/B or QR

Saturated liquid reflux or Treflux

Optimum feed plate location

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Column pressure and Qcol = 0 are already specified.
Also assume column pressure is fixed and the column is adiabatic

For C=3, the extra degree of freedom is


used to specify the feed composition.
Thus,

neither

bottom

nor

distillate

composition is completely specified.

Multi-Component Distillation (MCD) The Problem

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.

Off-the-Shelf Solutions
Fortunately, numerical design packages, such
as Aspen Plus, Aspen Hysys /UniSim 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.

MCD Some Additional


Terminology
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
Splits distributing and
non-distributing systems

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:

FR i dist
FR i bot

Dx i dist
Fz F, i

Bx i bot
Fz F, i

Dx D, i
Fz F, i

Bx B, i
Fz F, i

FR i dist

1 FR i bot

FR i bot

1 FR i dist

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 most volatile of the key components is
termed the light key (LK).
The least volatile of the key components is
termed the heavy key (HK).
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MCD Non-Key Components

All other components not specified in the distillate or


botoms 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).

If a non-key component is neither a heavy non-key nor a


light non-key, then it is an intermediate non-key (INK) or
simply NK.
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Decreasing volatility

1. LNKs: light non-keys


2. LK: light key
3. HK: heavy key
4. HNKs: heavy non-keys

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MCD Non-Key Component Splits


The split of the nonkey components is
generally defined as to where the nonkey
components are obtained with respect to the
distillate or bottoms stream.
One can have two types of situations
concerning the split of the nonkey
components:
Sharp split Non-distribution of non-keys
Split Distribution of non-keys
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MCD Non-distribution of NKs


Nondistribution of nonkeys means that
essentially all of the nonkeys are obtained in
either the distillate stream or the bottoms
stream. We obtain a sharp split of the NKs.
Nondistribution of nonkeys can be assumed
when:
All of the non-keys are either HNKs or LNKs
The fractional recoveries of the LK in the
distillate and HK in the bottoms are relatively
large.
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MCD Distribution of NKs


Distribution of nonkeys means that the non keys are not sharply split between the distillate
stream or the bottoms stream. We obtain a
split of the NKs.
Distribution of nonkeys occurs when:
Not all of the non-keys are either HNKs or
LNKs we have NKs.
The fractional recoveries of the LK in the
distillate and HK in the bottoms are not
relatively large.
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How do we determine the keys (LK and HK) and


the nonkeys (LNKs, HNKs and NKs) 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.

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.
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Key and Non-Key Example


Consider a distillation column with the following feed
components:

propane
nbutane
npentane
nhexane

The recoveries for nbutane and npentane 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 n


pentane are specified
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Key and Non-Key Example


We have:
Volatilities
propane > nbutane > npentane > nhexane
Component
Propane
nbutane
npentane
nhexane

Designation
Light NonKey
Light Key
Heavy Key
Heavy NonKey
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Key and Non-Key Example


If the recoveries of n-butane and nhexane are specified:
Volatilities
propane > n-butane > n-pentane > n-hexane
Component
Propane Light
n-butane
n-pentane
n-hexane

Designation
Non-Key
Light Key
Non-Key
Heavy Key
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Key and Non-Key Example


If only the recovery of nbutane is
specified:
Volatilities
propane > nbutane > npentane > nhexane
Component
Propane
nbutane
npentane
nhexane

Designation
Light NonKey
Key
NonKey
NonKey
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Missing Keys

In typical MCD problems, one specifies the LK and the HK recoveries.

If only the LK or the HK recovery is specified, one typically chooses one


of the non-key components to be the HK or LK, respectively, usually
the non-key component with the greatest feed composition.

The fractional recovery of the missing key needs to be determined, but


it must be estimated since not enough information is typically given in
the problem to determine it directly.

One way to estimate the fractional recovery of the missing key


component is to do an external mass balance based upon a binary
system comprised of the LK and HK.

This fractional recovery is then used in the MCD solution. A trailand


error solution may be required to determine the actual fractional
recovery.
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Key and Non-Key Example


Consider a distillation column with the
following feed components:

Methane
Ethane
Ethylene
Propylene
Propane

It is specified that a distillate concentration,


xD, for ethylene is required.
What are the key and non-key designations
for this separation?
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Key and Non-Key Example


One source for determining the order of the
component volatilities can be determined
from the K values, which can be found from
the DePriester charts, for example.
The order of volatility is:
methane > ethylene > ethane >
propylene > propane
Since xD for ethylene is specified it is a key
component.
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Key and Non-Key Example


Component Designation
Methane Light Non-Key
Ethylene Light Key
Ethane Non-Key
Propylene
Non-Key
Propane Non-Key
There is no heavy key specified for this problem.
What if an xD for ethylene and an xB for
propylene are specified?
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Key and Non-Key Example


Component

Designation

Methane
Ethylene
Ethane
Propylene
Propane

Light Non-Key
Light Key
Non-Key
Heavy Key
Heavy Non-Key

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Note that in multicomponent distillation


neither the distillate nor the bottoms
composition is completely specified
because there are not enough variables
to allow complete specification

The external balance equations for the column


shown in Figure 5-1 are easily developed.

Figure 5-1. Distillation column


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The external balance equations for the column


shown in Figure 5-1
Eq. (5-1)

Eqs. (5-2)
For a ternary system, Eqs. (5-2) can be written three times, but these
equations must add to give Eq. (5-1). Thus, only two of Eqs. (5-2) plus
Eq. (5-1) are independent

Summation rules

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Solve mass balances to get D and B

For any components, we only have xi,bot or xi,dist , but


not both.
Thus, we cannot compute D and B
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Ternary mixture
6 unknowns: B, D, x2,dist, x3,dist, x1,bot and x3,bot
5 equations only: 3 mass balances and 2 summation
rules
Energy balance and equilibrium relationships will add
extra variables (vapor mole fractions, condenser and
reboiler duties)
Thus, one cannot start out by solving external mass and
energy balance equations.
For stage-by-stage calculation, need to know all
compositions at one end of the column.

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If sharp separation (split of the NK components)


then one can solve external mass balances
LNK appear only in the distillate
HNK appear only in the bottoms

Need only fractional recoveries to completely


specify Bottom and distillate compositions

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Profiles for Multicomponent


Distillation
Flow rates and temperature profiles are similar to
binary distillation case
Composition profiles look different from binary
distillation

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Profiles for Multicomponent


Distillation
If CMO valid
Vapor and liquid flow rates will be constant in each
section
They change at
withdrawals stage

each

feed

stage

or

side-stream

Non CMO case


Vapor and liquid flow rates will vary from plate to plate
The ratio L/V varies less significantly
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Simulation for distillation of benzene-toluene-cumene


Feed condition
Benzene= 0.233 mole frac,
Toluene= 0.333 mole frac,
Desire 99% recovery of benzene Cumene= 0.434 mole frac
similar to the behavior of binary systems

Saturated liquid. F =
1.0 kmol/h. Feed stage
is number 10 above
the partial reboiler, and
there are 19
equilibrium stages plus
a partial reboiler. A
total condenser is
used. p = 101.3 kPa.
Relative volatilities: ben
= 2.25, tol = 1.0, cum = 0.21.
L/D = 1.0.

Figure 5-2. Total liquid and vapor flow rates


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Temperature profile
Temperature profile decreases
monotonically from reboiler to
condenser
Behavior similar to binary
distillation case
If temperature plateaus then
there is a pinch point in the
column

Figure 5-3. Temperature profile for


benzene-toluene-cumene distillation;
same problem as in Figures 5-2 and 5-4.

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Stage 10 is the feed stage.

Composition profiles
benzene recovery in the
distillate was specified as
99%
Benzene is the LK, and
toluene is the HK.
Thus, cumene is the HNK,
and there is no LNK

Figure 5-4. Liquid-phase composition


profiles for distillation for benzenetoluene-cumene; same conditions as
Figures 5-2 and 5-3 for nonconstant
molal overflow

benzene mole fraction is very


low in the reboiler and
increases monotonically to a
high value in the total
condenser. This is essentially
the same behavior as that of
the more volatile component
in binary distillation. In this
problem benzene is always
most volatile, so its behavior
is simple

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Composition profiles

benzene (LNK), toluene (LK),


and cumene (HK)

99% recovery of toluene


in the distillate is
specified

Note that with no HNKs, the


HK concentration does not
have any maxima

Figure 5-5. Liquid phase composition profiles for distillation of


benzene (LNK), toluene (LK), and cumene (HK); same problem
as in Figure 5-2 to 5-4 except that a 99% recovery of toluene in
the distillate is specified
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Composition profiles
Recovery of toluene in distillate 99%.
primary maxima

secondary maxima
Since there is an LNK, we would expect
the LK curve to show maxima; and
since there is an HNK, we would expect
maxima in the HK concentration profile

Figure 5-6. Liquid composition profiles for distillation of benzene (LNK), toluene (LK),
xylene (HK), and cumene (HNK). Feed is 0.125 benzene, 0.225 toluene, 0.375 xylene,
and 0.275 cumene. Relative volatilities: ben = 2.25, tol = 1.0, xy = 0.33, cum = 0.21

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Sandwich component:
Tend to accumulate in the middle section of the
distillation column
Can cause column flooding and/or
development of a second liquid phase

the

Happens when one separates ethanol/water


mixture: trace components such as butanol are
partially miscible with water
Solution: use sidestream withdrawal to remove
intermediate boiling components
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Differences between binary and


multicomponent distillation
1.key component concentration can have maxima
2.NK usually do not distribute
HNKs present only in the bottoms
LNKs present only in the distillate
3.NK often go through plateau region
4.all component must be present at feed stage but at
that stage a discontinuity in the composition profile is
present
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Example 5-1. External mass balances using


fractional recoveries
We wish to distill 2000 kmol/h of a saturated liquid
feed. The feed is 0.056 mole fraction propane, 0.321
n-butane, 0.482 n-pentane, and the remainder nhexane. The column operates at 101.3 kPa. The
column has a total condenser and a partial reboiler.
Reflux ratio is L0/D = 3.5, and reflux is a saturated
liquid. The optimum feed stage is to be used. A
fractional recovery of 99.4% n-butane is desired in
the distillate and 99.7% of the n-pentane in the
bottoms. Estimate distillate and bottoms
compositions and flow rates.
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The order of volatilities is: propane > n-butane > n-pentane > n-hexane
quite high

Thus, n-butane is the LK, and npentane is the HK.


This automatically makes
propane the LNK and n-hexane
the HNK.
quite high

Find xi,dist, xi,bot, D, and B


Assumption: Since the recoveries of the keys are quite high,
it is reasonable to assume that all of the LNK collects in the
distillate and all of the HNK collects in the bottoms. We will
estimate distillate and bottoms based on these assumptions

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assumptions of the NK splits can be written either as


Eq. 5-8a,b

Eq. 5-9a,b

or
The fractional recovery of n-butane in the distillate can be used to
write
Eq. 5-10

Note that this also implies


For n-pentane the equations are

Eq. 5-11

Eq. 5-12
Eq. 5-13

Eqs. (5-8) to (5-13) represent eight equations with ten


unknowns (four compositions in both distillate and bottoms
plus D and B). Equations (5-4) give two additional equations,
which we will write as
Eq. 5-14a

Eq. 5-14b
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These ten equations can easily be solved, since distillate and


bottoms calculations can be done separately
Do it. Start with the distillate
DxC3,dist
DxC6,dist
DxC4,dist
DxC5,dist

=
=
=
=

FzC3 = (2000)(0.056) = 112


0
(0.9940)(2000)(0.321) = 638.5
(0.003)(2000)(0.482) = 2.89

Then
Now the individual distillate mole
fractions are

Equation 5-15

Check:
Bottoms can be found from Eqs. (5-8b), (5-9a), (5-11), (5-12), and (5-14b). The results are
xC3,bot = 0, xC4,bot = 0.0031, xC5,bot = 0.7708, xC6,bot = 0.2260, and B = 1246.6. Remember that
these are estimates based on our assumptions for the splits of the NK
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Chapter:3, Problem D3.


We have a feed mixture of 22 mol% methanol, 47
mol% ethanol, 18 mol% n-propanol, and 13 mol%
n-butanol. Feed is a saturated liquid, and F =
10,000 kmol/day. We desire a 99.8% recovery of
methanol in the distillate and a methanol mole
fraction in the distillate of 0.99.
Find D and B.
Find compositions of distillate and bottoms.

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