Petrochemical Engineering

UGPA2043
Unit Operation I

Continuous Distillation with

Reflux

Multicomponent
Distillation

Multicomponent Distillation:
Introduction
The objective of distillation is to separate the feed
into streams of nearly pure products.
Multicomponent distillation involved several
components and is more complex than binary
distillation due to the increase of variables.
The Fenske-Underwood-Gilliland method is a
method widely used for making preliminary
designs.
In practice, multicomponent distillation is solved by
using computers due to the numerous variables
and the many iterations required to obtain
convergence of the solutions to the equations.

Multicomponent Distillation:
Introduction

In multicomponent distillation, specifying the

concentrations of one component in each of the top
and bottom products does not fully characterise
them.

If more than one concentration are specified for

each of the top and bottom products, it is
generally impossible to meet these specifications
exactly.

Multicomponent Distillation:
Introduction

The desired separation usually refers to the

amount of light key and heavy recovered in the
distillate and bottom products respectively.

The actual mole fractions of the key components in

the products are not usually specified, since they
depend on the amount of non-keys in the feed.

Small changes of non-keys in the feed would

significantly change the product compositions
without significantly affecting the basic separation
of light and heavy keys.

Multicomponent Distillation:
Key Components
Generally two components, known as the key
components, are chosen whose concentrations or
fractional recoveries in the top and bottom products
are a good index of the separation achieved.
The more volatile component is the light key (LK)
The less volatile component is the heavy key (HK)
The rest of the components are non-keys.
If the non-key is more volatile than LK, it is called
light non-key (LNK). If less volatile than HK,
then is called heavy non-key (HNK).

Multicomponent Distillation:
Key Components

The distillate may be pure LK if the keys are the two most
volatile components, since components heavier than the HK
will tend to concentrate in the liquid phase.
Often, there are components lighter than the LK, and they
are nearly completely recovered in the distillate. xB,LNK = 0

Any components heavier than the HK are usually completely

recovered in the bottoms. xD,HNK = 0

Although any two components can be nominated as keys,

usually they are adjacent in the rank order of volatility. Such
a choice is called a sharp separation.
In sharp separations, the keys are the only components that
appear in both top and bottom products in appreciable
concentrations.

Multicomponent Distillation:
Fenske Equation - Nmin
The minimum number of equilibrium stages
(including partial reboiler) corresponds to total
reflux:

L/V = 1, hence top and bottom operating line

reduced to yn = xn+1 (numbered from bottom up).

Other assumptions:

Constant molal overflow is valid.

Relative volatility is taken as constant.

Multicomponent
Distillation:
For component
i at Stage-1:- N
Fenske
Equation
min
y1,i K1,i x1,i

...... (1.39)

From operating line, yn = xn+1 :

yi ,1 x2,i

x2,i K1,i x1,i ...... (1.40)

Similarly for Stage-2:

y 2 ,i K 2 ,i x2 , i

...... (1.41)

Multicomponent Distillation:
Fenske Equation - Nmin
Combining Eq.(1.40) and (1.41):

y2,i K 2,i K1,i x1,i

...... (1.42)

Eq.(1.42) is readily extended into:

yn ,i K n ,i K n 1,i K n 2,i K 2,i K1,i x1,i ...... (1.43)

Similarly for component j :

yn , j K n , j K n 1, j K n 2, j K 2, j K1, j x1, j

...... (1.44)

Multicomponent Distillation:
Fenske Equation - Nmin
Combining Eq.(1.43) and (1.44):

y n ,i
yn , j
xn 1,i
xn 1, j
xn 1,i x1, j

x x
1,i n 1, j

K n ,i K n 1,i K n 2,i K 2,i K1,i x1,i

K n , j K n 1, j K n 2, j K 2, j K1, j x1, j
n n 1 n 2 21

x
1, j

k ,ij

x1,i

N min

k 1

where k ,ij

K k ,i... (1.45)

Kk, j

Multicomponent Distillation:
Fenske Equation - Nmin
With the assumption that ij is constant:

xn 1,i x1, j

x x
1,i n 1, j

N min

ijn

x D ,i

ln

x
B ,i

xB , j

x
D , j
ln ij

Fenske Equation

Top: xn+1 = xD
Bot: x1 = xB

...... (1.46)

Multicomponent Distillation:
Fenske Equation - Nmin

A more convenient form of Eq.(1.46) is obtained

by using distillate and bottom flowrates (di , bi), and
replaced by a geometric mean of the top and
bottom stage values.

N min

where d i DxD ,i

d bj

log i
d b
j i

log m

and

m [( ij ) n ( ij )1 ]

bi BxB ,i

...... (1.47)

Multicomponent Distillation:
Fenske Equation - Nmin
The minimum number of equilibrium
stages depends on the degree of
separation of the two key components
and their relative volatility.
It is independent of feed-phase condition.
Fenske equation is quite reliable except
when the relative volatility varies
appreciably over the column, and/or when
the mixture forms nonideal liquid
solutions.

Distributed &Undistributed
Components

Distributed component is found in both

distillate and bottom products. LK and HK
are always distributed, as are any
components having volatilities between
those two keys.

Undistributed component is only found in

one product. LNK are almost completely
recovered in the distillate and HNK are found
almost completely in bottom products.

Location of Invariant Zones

at Minimum Reflux, Rmin

At invariant (pinch-point) zone, there is no

change in either liquid or vapour
concentrations from plate to plate, so xn-1 =
xn and yn+1 = yn .

For binary distillation at Rmin, pinch-point

occurs at the feed plate (refer McCabe-Thiele
diagram at Rmin).
For multicomponent distillation, there are
pinch-point zones at or above and/or below
the feed plate.

Location of Invariant Zones

at Minimum Reflux, Rmin

For class 1 (one pinch-point) separation,

all components in the feed distribute to
both the distillate and bottom products.
The single pinch point bridges the feed
stage.
Feed

Feed
invariant
zone

Class 1
(one pinch point)

Class 2
(two pinch point)

Location of Invariant Zones

at Minimum Reflux, Rmin

For class 2 (two pinch-point) separation, one

or more of the components appear in only one
of the products. (feed with undistributed
components)

Stages between the feed stage and the

rectifying section invariant zone remove heavy
components that do not appear in the
distillate.
Stages between the feed stage and the
stripping section invariant zone remove light
components that do not appear in the bottom.

Multicomponent Distillation:
Underwood Equation - Rmin
From top operating line,
yn 1,i

DxD ,i
Ln

x n ,i
Vn 1
Vn 1

yn 1,i

Ln yn ,i

Vn 1 K n ,i

DxD ,i

Vn 1

and

x n ,i

y n ,i
K n ,i

At invariant zone, yn+1,i = yn,i and n = ,

V yi

L yi
DxD ,i
K i

Multicomponent Distillation:
Underwood Equation - Rmin
Rearrange,
y i

x D ,i

1 L V K i

D
1 .0
V

x D ,i

1 L V K i

......(1.48)

Similarly for stripping section,

B
1.0
V

x B ,i
L V K i 1

......(1.49)

Multicomponent Distillation:
Underwood Equation - Rmin
To solve Eq.(1.48) and (1.49), an approximate but
fairly accurate method to determine Rmin was
developed by Underwood, by introducing a term .
Assumptions:
constant molal overflow
for each component is the same in the upper and
lower invariant zones,

HK usually taken as ref.

Multicomponent Distillation:
Underwood Equation - Rmin
Rectifying section:

D
1.0
V

x D ,i

1 L V K i

i x D ,i

V D
i

......(1.50)

Similarly for stripping section,

i x B ,i

V B
i

......(1.51)

Multicomponent Distillation:
Underwood Equation - Rmin
Combine Eq.(1.50), (1.51), feed line:
V V 1 q F
i x B ,i
i x D ,i
D
1 q F
B
i
i

1 q

DxD ,i BxB ,i

F
F

i x F ,i
f i
1 q
i

Underwood Equation

......(1.52)

Multicomponent Distillation:
Underwood Equation - Rmin
When only the two key components
distribute, Eq.(1.52) is solved iteratively
for a root of that satisfies:
HK < < LK
The value of is then used to get Rmin by Eq.
i x D ,i
Vmin
(1.50),

Rmin 1
D

......(1.53)

Multicomponent Distillation:
Underwood Equation - Rmin
If any non-key components are suspected of
distributing, Underwood equation Eq.(1.52)
is solved for m roots of , where m = C - 1
and C = number of distributing components.
Each root of lies between an adjacent pair
of relative volatilities of distributing
components.

LNK > 1 > LK > 2 > HK > 3 > HNK

Multicomponent Distillation:
Underwood Equation - Rmin
With these m roots of , Eq.(1.53) is written
m times and solved simultaneously to yield
Rmin and the unknown value of xD,i .
And the solution must satisfy the condition

D ,i

1.0

Underwood Equation - Rmin:

Example
A mixture of 4 mol% n-pentane, 40% nhexane, 50% n-heptane and the rest noctane is to be distilled at 1 atm with 98%
of the hexane and 1% of the heptane
recovered in the distillate.
Find the minimum reflux ratio for a liquid
feed at the boiling point.

Example Solution

Only for saturated

liquid. Terms in ()
are the fractional
recovery of A & B
in distillate.

DxDA

FxFA AB DxDB FxFB

AB 1

Example Solution
(1.52)

Multicomponent
Distillation:
A simple empirical method by Gilliland is much
Gilliland
Correlation
R, precise
N
used for preliminary
estimates, although

calculation is best accomplished by computer.

Gilliland correlation relates the actual number of
stage, N, with minimum reflux ratio, Rmin and
minimum number of stages, Nmin .
The correlation is based mainly on calculations
for systems with nearly constant relative
volatility and may be considered in error for
nonideal systems.

Multicomponent Distillation:
Gilliland Correlation R, N
The data for Gilliland correlation cover the
following ranges of conditions:

Number
q
=
P
=

=
Rmin =

of component = 2 to 11
0.28 to 1.42
vacuum to 600 psig
1.11 to 4.05
0.53 to 9.09

Nmin = 3.4 to 60.3

Use this correlation only for rough estimates.
The error for N can be 30% but usually is
7%.

Multicomponent Distillation:
Gilliland Correlation R, N

R Rmin
R 1

Multicomponent Distillation:
Gilliland Correlation R, N
The line in the graph can be represent by the
following equation developed by Molokanov et. al.:

N N min
Y
1 exp
N 1

where

1 54.4 X X 1

0.5
11 117 .2 X X

R Rmin
X
R 1

Nmin from Fenske equation

Rmin from Underwood equation

......(1.54)

Multicomponent Distillation:
Feed-Stage Location
The optimum feed stage can be located by assuming
that the ratio of stages above the feed to stages
below the feed is the same as the ratio determined
by simply applying the Fenske equation to the
separate section at total reflux conditions to give:
N R N R min log xD , LK xF , LK xF , HK xD , HK log B F

N S min log xF , LK xB , LK xB , HK xF , HK log D F

NS

Unfortunately, this equation is not reliable except for

fairly symmetrical feeds and separations.

Multicomponent Distillation:
Feed-Stage Location
A reasonably good approximation of
optimum feed-stage location can be made
by employing the empirical equation of
Kirkbride:
N R xF , HK

N S xF , LK

xB , LK

x
D , HK

0.206

......(1.55)