Introduction to multicomponent distillation

• Most of the distillation processes deal with multicomponent mixtures

• Multicomponent phase behaviour is much more complex than that

for the binary mixtures

• Rigorous design requires computers

• Short cut methods exist to outline the scope and limitations of a

particular process
Multicomponent distillation in tray towers

• Objective of any distillation process is

to recover pure products

• In case of multicomponent mixtures we

y1,y2,y3,y4…
may be interested in one, two
or more components
D
• Unlike in binary distillation, fixing mole
fraction of one of the components in a
product does not fix the mole fraction of other
components B

• On the other hand fixing compositions of all

the components in the distillate and the bottoms
product, makes almost impossible to meet
specifications exactly
Key components
• In practice we usually choose two components
separation of which serves as an good indication
that a desired degree of separation is achieved

These two components are called key components

- light key
- heavy key

• There are different strategies to select these key

components

• Choosing two components that are next to each other

on the relative volatility scale often leads to all the components
lighter then the light key components accumulating in the distillate
and all the components heavier then the heavy key component
accumulating in the bottoms product: sharp separation
 Distributed and undistributed components
• Components that are present in both the distillate and
the bottoms product are called distributed components

- The key components are always distributed components

• Components with negligible concentration (<10-6) in one

of the products are called undistributed

A B C D E G

light non-distributed components key heavy non-distributed components

(will end up in the overhead product) components (will end up in bottoms product)
Fenske equation for multicomponent
distillations
Assumption: relative volatilities of components remain constant
throughout the column

LK – light component
 xD , LK xB , HK  HK – heavy component
ln  
 xB , LK xD , HK  K LK (T )
N min = −1 α LK , HK (T ) =
ln α LK , HK K HK (T )
Fenske equation for multicomponent
distillations
Choices for relative volatility: T
D
K LK (T )
α LK , HK (T ) =
K HK (T )
B
1) Relative volatility at saturated feed condition
α LK , HK = α LKF ,HK (TF )

2) Geometric mean relative volatility

why geometric mean?
α LK , HK = α LKD ,HK (TD )α LKB ,HK (TB )

α LK , HK = 3 α LKF ,HK (TF )α LKD ,HK (TD )α LKB ,HK (TB )

Non key component distribution from
the Fenske equation

x D ,i N min +1
 xD , HK  Ki
=α i , HK   α i , HK =
x B ,i  xB , HK  K HK

 DxD , HK 
N min +1
FxF ,i ⋅ α ⋅
i , HK 
 BxB , HK 
DxD ,i =
N min +1
 DxD , HK  Convince yourself and
1 + α i , HK ⋅   derive for
 BxB , HK  BxB ,i
Minimum reflux ratio analysis

• At the minimum reflux ratio condition y

there are invariant zones that occur y1
above and below the feed plate, where
the number of plates is infinite and the
liquid and vapour compositions do not
change from plate to plate zf

• Unlike in binary distillations, in yB

multicomponent mixtures these zones
are not necessarily adjacent to the feed xB xN zf xD
plate location x
Minimum reflux ratio analysis
Underwood method

* Relative volatility of each component has to be the same for each invariant zone

* Constant molar overflow

* αi=Ki/Kref (Usually Kref=KHK)

The operating line equations for each section of the column become:

L
Vyi ,n +1 = yi ,n + Dxi , D rectifying section
α i K REF
L
V yi ,m +1 = yi ,m − Bxi , B stripping section
α i K REF
Minimum reflux ratio analysis
Underwood method

L
Vyi ,n +1 = yi ,n + Dxi , D rectifying section
α i K REF
L
V yi ,m +1 = yi ,m − Bxi , B stripping section
α i K REF
In the invariant zones: yi ,n +1 = yi ,n = yi ,∞
 L  V α i xi , D α i xi , D
V −  yi ,∞ = Dxi , D yi , ∞ = =
 α i K REF  D α i − ( L VK REF ) α i − A
 L  V α i xi , B α i xi , B
V −  y i ,∞ = Bxi , B − y i ,∞ = =

 α i K REF 
 D ( )
α i − L VK REF α i − A
Minimum reflux ratio analysis
Underwood method

V V α i xi , D
∑ D yi , ∞ = D = ∑ α − A We are looking for a condition where
i this is correct. In general there are
multiple solutions
V V α i xi , B
− ∑ y i ,∞ = − = ∑
D B αi − A

But consider the following

α i xi , D α i xi , B
V − V = D∑ + B∑ = F (1 − q )
αi − A αi − A
Minimum reflux ratio analysis
Underwood method

α i xi , D α i xi , B
V − V = D∑ + B∑ = F (1 − q)
αi − A αi − A
In other words:

α1 x1, D α 1 x1, B α 2 x2 , D α 2 x2 , B
F (1 − q ) = D +B +D +B 
α1 − A α1 − A α2 − A α2 − A
Under Underwood conditions: A=Ā, αi = α i
α1 x1, F α 2 x2, F α i xi , F
(1 − q ) = + = ∑
α1 − A α 2 − A αi − A
 Minimum reflux ratio analysis:
Underwood equations

α i , HK xF ,i
(1 − q ) = ∑ For a given q, and the feed composition
i α i , HK − A
we are looking for A satisfies this equation
(usually A is between αLK and αHK.

V α i , HK xD ,i
Rm + 1 = = ∑ Once A is found, we can calculate the
D i α i , HK − A minimum reflux ratio
Gilliland correlation: Number of ideal
plates at the operating reflux

N − N min  R − RDm 
= f  D 
N +1  RD + 1 
Kirkbride equation: Feed stage location

0.206
N R  xF , HK  B
2
 xB , LK
=    
N S  xF , LK  x  D
  D , HK  
Complete short cut design:
Fenske-Underwood-Gilliland method
Given a multicomponent distillation problem:

a) Identify light and heavy key components

b) Guess splits of the non-key components and compositions

of the distillate and bottoms products

c) Calculate α LK , HK
d) Use Fenske equation to find Nmin

e) Calculate distribution of non key components

f) Use Underwood method to find RDm

g) Use Gilliland correlation to find actual number of ideal stages

given operating reflux

h) Use Kirkbride equation to locate the feed stage

 Complete short cut design: example
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.

a) Find minimum number of stages and minimum reflux ratio

b) Given operating reflux of 1.5 of the minimum find the operating
number of ideal stages

xF F xF Moles in D xD Moles in B xB Ki
Pentane 0.04 4 3.62

Hexane 0.4 40 1.39

Heptane 0.5 50 0.56

Octane 0.06 6 0.23

100
 Stage efficiency analysis

Step 1: Thermodynamics data and methods to predict equilibrium

phase compositions

Step 2: Design of equilibrium stage separation

Step 3: Develop an actual design by applying the stage efficiency analysis

to equilibrium stage design
Stage efficiency analysis

In general the overall efficiency will depend:

1) Geometry and design of contact stages

2) Flow rates and patterns on the tray

3) Composition and properties of vapour and

liquid streams
Stage efficiency analysis

Lin,xin Vout,yout
What are the sources of inefficiencies?

Lout,xout Vin,yin For this we need to look at what actually happens

on the tray

Local efficiency

y′n − yn +1 Actual separation

Emv = *
yn − yn +1 Separation that
would have been
achieved on an
ideal tray

Point efficiency
 Stage efficiency analysis

stagnation points Depending on the location on the tray

the point efficiency will vary

The overall plate efficiency can

be characterized by the Murphree
plate efficiency:

yn − yn +1
high concentration low concentration EmV = *
gradients gradients
yn − yn +1

When both the vapour and liquid

phases are perfectly mixed the plate EmV = Emv
efficiency is equal to the point
efficiency
Stage efficiency analysis

In general a number of
empirical correlations exist
that relate point and plate
efficiencies

Peclet number

Z L2 length of liquid
N Pe = flow path

Detc
eddy diffusivity residence time of liquid
on the tray
Stage efficiency analysis: O’Connell (1946)
Stage efficiency analysis: Van Winkle (1972)
Stage efficiency analysis

- AICHE method

- Fair-Chan
Chan, H., J.R. Fair,” Prediction of Point Efficiencies for Sieve Trays, 1. Binary Systems”,
Ind Eng. Chem. .Process Des. Dev., 23, 814-819 (1984)

Chan, H., J.R. Fair, ,” Prediction of Point Efficiencies for Sieve Trays, 1. Multi-component Systems”,
Ind Eng. Chem. .Process Des. Dev., 23, 820-827 (1984)
Stage efficiency analysis

In addition we need to take in account effects of

entrainment

Entrained liquid droplets

Dry Murphree efficiency can be corrected for the

entrainment effects by Colburn equation:

EmV
Ea = entrainment fraction =
 ϕ 
1 + EmV   entrained liquid/gross liquid flow

1−ϕ 
Stage efficiency analysis

EmV
Ea =
 ϕ 
1 + EmV  
1−ϕ 
Stage efficiency analysis

Finally the overall efficiency of the process defined as

N actual
EO =
N theoretical
Types of trays

1. Sieve plates

2. Bubble-cap plates

3. Valve plates
Types of trays