Extractive distillation (ED) for

separating azeotropic mixtures or

zeotropic mixtures with very low
relative volatility
Definition:
Extractive distillation is a form of distillation involving the
addition of a solvent which modifies the vapor-liquid equilibria
of the components to be separated such the separation becomes
easier. The added solvent has a volatility lower than the
components to be separated (i.e., the added solvent has a boiling
point higher than those of the components to be separated). Also,
it is usually introduced near the top of a column.
The selection of the most suitable solvent (called
entrainer) plays an important role in the economical
design of ED. Solvents with high selectivity (degree of
separation) and high solubility (no liquid-phase splitting)
are recommended, but usually, the solvents with high
selectivity have a reduced capacity
When a suitable solvent is found, this should be
optimised to improve its separation ability, decrease the
solvent-to-feed ratio. The objectives are: optimal
entrainer choice, optimal column design and optimal
operating point
While a high selectivity is the main criterion for the selection
of a solvent, there are several other constraints that need to be
fulfilled:
There are several classes of entrainers suitable for ED:
 Liquid solvents: This is the most common class of
solvents
 Solid salt
 Liquid solvent and solid salt combined
 Hyperbranched polymers
 Ionic liquids: a class of ionic chemicals with melting
temperature below 100 oC
Examples of Extractive Distillation :
Mixture Solvent
1-Butene(-6.3 C) and 1,3
Butadiene(-4.41C) Acetonitrile(81.6 C)
Nitric Acid(83 C) and Water
(100C) Sulfuric Acid(300 C)
Methl Cyclohexane(100 C) and
Benzene(80.1 C) N-Formylmorpholine(243 C)
Isooctane(99.2 C) and doiuene
(110.6 C) Phenol(181.75 C)
Monomethyiamine(-6.3 C).
Dimethylamine(7.4 C) and
Trmethylamine(2.87 C) Water(100 C)
Methy1 Cyclohexane(100 C) and
Toluene(110.6 C) Phenol(181.75 C)
Acetone(56.2 C) and Methanol
(62.5 C) Water(100 C)
Example 1 Extractive Distillation
Normal Boiling Points, C
MCH 100.9  MCH(M) Toluene(T)
Toluene 110.6  T 9.7  C

distillation
extractive
Phenol  Feed Phenol(P):C6H5OH
181.75 

Recovery
Solvent
(Solvent) (Make-up

(Recycled
solvent)

solvent)
CH3C6H5: Toluene(T)
CH3C6H11: MCH(M)

 

Phenol(P)
 If :
1. T type of two-product separators are allowed.
2. Any mass-separating agent is recovered for recycle in
the separator following the one into which it is introduced.
Then :

SN 
2N  1! T N  1
For example : N !N  1!
N = 4 components
Ordinary distillation only gives
SN = 5
Ordinary distillation plus extractive distillation with phenol
gives

S N 52 
4 1
40
N 10
S N 4862T 1
S N 48622 
10  1

Extractive Distillation with reactive component
Add reactive component (ionic liquid) to modify vapor-liquid equilibrium

B S

B
C

C
C+S
e. g., B, C = xylenes:  = 1.03
S = organometallic: B, CS:  30
B : meta-xylene
C : para-xylene
S : sodium cumene
Avoid Vacuum and Refrigeration

a. All other things being equal, avoid excursions in temperature

and pressure, but aim high rather than low.
b. If vacuum operation of ordinary distillation is required, liquid-
liquid extraction with various solvents might be considered.
c. If refrigeration is required, cheaper alternatives to distillation
such as absorption might be considered.
 Fuel oil
$/K cal Burner

High pressure
steam
Cooling
Low pressure
steam

Heating
 Temperature
Room
temperature
Cooling water

Ammonia refrigerant
Liquid nitrogen

Relative Costs of Cooling and Heating at Different

Temperatures (Berthouex and Rudd, 1977)
 100

Avoid:
Pressure of operation, atm

10
High ”P” and ”T”
or
1.0 Low ”P” and ”T"

0.1

-200 -100 0 100 200 300 400 500 600

Atmospheric boiling point, C

Recommended Ranges of Pressure and Temperature

for Separation Operations (Souders, 1964)

Favor: High ”P” and Low ”T”

Low ”P” and High ”T"
Coefficient of Ease of Separation (CES)
If it is difficult to judge which split is closest to 50/50
and with a reasonable separator factor or relative
volatility, then perform the split with the highest value
of the coefficient of ease of separation (CES)

1
CES  f  
d b
log[( ) LK ( ) HK ]
b d

Where f B / D or D / B Such that f 1

 T or (  1) 100
Fractional recoveries of light-key(LK) and heavy-key(HK)
components in sharp or high-recovery separations :
Overhead Bottoms
LK dLK  0.98 bLK  0.02
HK dHK  0.02 bHK  0.98
As an approximation,
d 0.98 b 0.98
     
 b  LK 0.02  d  HK 0.02

To simplify the calculations of CES in sharp separations, we

may
use CES  f 
 More on CES (Coefficient of Ease of Separation)
moles
Overhead, D hr
e. g., 70, 60, 50, 30, 20
Feed Separator
moles
100 hr
moles
Bottoms, B hr
e. g., 30, 40, 50, 70, 80
 Split ratio 30 40 50 30 20
D/B or B/D , , , , 1
70
 60 50 70
 80
B/D
D/B
 T (Boiling-Point Difference) or   1 LK , HK  1
D B
 or  T
CES   B D
The larger the T or (-1), the easier the separation
D B
 or    1
 B D
Close to one, 50/50 split
Examples of the Synthesis of Sharp or High-Recovery Separation Sequences
Example 1: Multicomponent Distillation Sequencing for
Thermal Cracking of Hvdrocarbons

1. Feed
Normal Boiling
Species Moles/Hr Point, T C T CES
A: Hydrogen 18 -253
B: Methane 5 -161 92 23.0
C: Ethylene 24 -104 57 19.6
D: Ethane 15 -88 16 14.6
E: Propylene 14 -48 40
F: Propane 6 72 -42 18.1
1.1
G: Heavies 8 -1 6
41 4.0
2. Products : C, D, E, F and G.
Example:
AB, D B 18
3. Key Questions : CESA/BCDEFG =
 or  T  92 23.0
 B D 72
a. Products: Any multi-component products ?
b. Species: Any corrosive and hazardous components ?
c. T: Any difficult separations ?
d. Moles/hr: Any plentiful components ?
e. CES: Any easy and balanced (50/50) splits ?
1. Favor ordinary distillation and Avoid vacuum and refrigeration:
Use ordinary distillation with refrigeration at high pressure.

2. Favor smallest product set:

Avoid splitting AB (a single product).

3. Remove corrosive and hazardous components first:

Not applicable.

4. Perform difficult separations last:

Split C/D and E/F last,
TC / D 6 C

T 16
5. Remove most plentiful componentsE /first:
F C
Not applicable.

6. Favor 50/50 split:

Split AB/CDEFG with the largest CES = 19.6
and AB as a single product.
 A
CES B
A
Initial
Separation
B
Sequence
19.6 C
D C
18.1 E D
F E
G F
G
For separating CDEFG, splits C/D and E/F are performed last
so that the remaining splits to be chosen are CD/EFG and
CDEF/G. Split CD/EFG is done first since it has a larger CES
of 28.7:
CD/EFG CDEF/G
f 28/39 8/59
T 40 41
CES 28.7 5.6
 A
B
A 24 C
B 16C
15 D
C Difficult Split 14 E ? CD/EFG
C 6C
D C C
6F
8G ? CDEF/G
E D D D
F E
G F
E E E Difficult Split
G F
F F
G
G

This sequence performs splits C/D and E/F last, which is exactly
the same as the one being practiced in the industry.
The second sequence can be obtained by making the split
ABCD/EFG first, which has the second largest CES of 18.1.
A Single product
A B ?
B C
16C(last)
C D
D
E
F E
G F 6C(last)
G
Another Initial Separation Sequence :
A
A B
A B
CES B C C C
=19.6
C D 16C
(large) D D
D
CES Last Separations
=18.1 E
(2nd largest) F E E E
G F 6C
F F
G G

[See King, C. J., Separation Processes,

2nd Edition, McGraw Hill (1980), P.718]
Example 2: Multi-component Distillation Sequencing for n-Butylene
Purification by Ordinary and Extractive Distillation.

1. Feed:
Relative Volatility*
Species Mole % ()
I ()
II (CES)
I (CES)
II
A: Propane 1.47
B: 1-Butene 14.75 2.45 2.163
C: n-Butane 1.18 1.17 3.485 3.29
D: trans-Butene-2 50.30
15.62 1.03 1.70 1.510
35.25
E: cis-Butene-2 11.96
F: n-Pentane 5.90 2.50 9.404
*()I = adjacent relative volatility at 150 F for separation method I, ordinary
distillation
()
II = adjacent relative volatility at 150 F for separation method II, ordinary
extractive distillation with furfural (C4H3OCHO)

2. Products: A, B, C, and F.
(Example) (CES)I,A/BCDEF =
DE
D 1.47
(CES)
II,ABCDE/F = B   12 100  98.53 2.45  1100 2.163
D B 5.90
 or  d  12 100  2.50  1100 9.404
 B D 94.50
3. Key Question :
a. Products: Any multi-component products ?
b. Species: Any corrosive and hazardous components ?
c. Mole%: Any plentiful components ?
d. Relative Volatilities: Any difficult separations ?
e. (CES): Any easy and balanced (50/50) splits ?
 1. Favor ordinary distillation:
Use extractive distillation for C/D and ordinary distillation for all other splits.
2. Avoid vacuum and refrigeration:
Use refrigeration at high pressure.
3. Favor smallest product set:
Avoid splitting DE (a single product)
4. Remove corrosive and hazardous components first:
Not applicable.
5. Perform difficult separations last:
Split C/DE last (difficult extractive distillation), so that the added solvent
(furfural) can be recovered at the end without having to worry about its
presence as a contaminant in earlier splits.
6. Remove most plentiful components first:
C(50.30 mole %) dominates the feed, but it is not separated first due to heuristic 5.

Note: Heuristics are ranked in their relative importance according to their given order, e. g.,
Heuristic 5 overrides Heuristic 6
Separation Sequencing for Example 2

7. Favor 50/50 split:

(a) Split ABCDE/F first with the largest (b)Favor AB/CDE over A/BCDE
(CES)I = 9.404 (Split C/DE last)
(Split C/DE last, avoid splitting DE) A/BCDE AB/CDE
A 1.47 f 1.47/92.63 16.22/77.88
A B 14.75
B C 50.30 (-1)100 145 18
C D 15.62 CES 2.301 3.749
D E 11.95
E
F F
A
A
A B B
Initial A B
Separation B C C
Sequence C D C 
 
D E  D
E D
E
F   II E
F
 The industrial separation sequence for n-butylene purification
1-BUTENE COLUMN DEPROPANIZER
A
B
C AB C3 C
FEED A D
D
E E II
F
1-BUTENE B

C+S
CDE
DE DE
+ Solvent

Recovery
Solvenet
nDistillatio
Extractive
2-BUTENES

RECIRCULATED
SOLVENT
n-BUTANE
C3 C
F

EXTRACTIVE
DEOILER DISTILLATION SOLVENT STRIPPER
COLUMN