CHEMICAL PROCESS DESIGN

CHAPTER 5. LIQUID SEPARATION

SYSTEMS. DETERMINE

DISTILLATIONS SEQUENCE
 REMOVING LIGHT-END & HEAVY-END

Removing light- and heavy-end impurities is compulsory

before other separations

Methods for removing heavy ends

Common methods for light-end removal
Definitions:

(1) For sharp product streams, we normally use all-

sharp or high-recovery separation sequences to
separate the feed into products. In such sequences,
each component being separated appears almost
completely in one and only one product.

(2) Key component in an all-sharp separation are

commonly defined by:

The light key (LK) is the lightest component in the

bottoms and the heavy key (HK) is the heaviest
component in the overhead.
 (A, B) (C, D) (C)
2
H2 . C1 C .C2
"
2 C22

D
E D C2
M E
E E
T S
Feed . T P
H H
A L
A N I
N I T
I Z T
Z E E
E R R
R (D)
C2"
2 " 
C .C .C
3 3 4 (E, F)
C22 .C2" .C32 .C3" .C4 (E, F, G) C32 .C3" (E)
(C, D, E, F, G) C32

D
E C3
P
R
O S
P P
A L
N I
I T
Z T
E E
R R
(F)
(G)
C3"
C4
 (sequence a) (sequence b)
A
A A B
B B
A (overhead) A C C C
(LK)B C B D D
(HK)C C D
D D
E B C C E E E
F C F E F
G D D F F
D G
E G G
F E E
E
G F F
(bottoms) F
G
G

d LK d B 0.98
(component B’s recovery
fraction in the overhead)
bHK bC 0.98
(component C’s recovery
fraction in the bottoms)
Separation methods for liquid mixtures
A separation is diluted when the distillate or the bottom
product is less than 5% weight with respect to the feed. The
distillation might be not the most economical; hence,
other methods such as extraction, stripping, crystallisation,
adsorption or membrane permeation should be tried.
In bulk separations, the desired product is more than 5% in
the initial mixture. Distillation is the
most economical separation method and should be tried in the
first place.
When employing distillation for zeotropic mixtures, the
optimal sequencing of splits is the central issue. The
optimality criterion should be the total cost of separations, in
terms of investment and operation.
In opposition, when dealing with azeotropic mixtures, the
feasibility of separation is not guaranteed.
Entrainer selection is the central problem.
Methods for liquid separations (+ means applicable, -
n/a)
For N components mixture to be separated by M potential
methods, the number of separation sequences S can be
determined by:

With N = 6, M = 5 : S = 13.125

When only one method (simple distillation) is used:

 Possible Sequences
for a 4-Component Feed
A B C A B

A B C A B B
B C D B C C
C D C D
D D
D D C
(Direct sequence)

Sequence (a) and (b)

 Possible Sequences
for a 4-Component Feed

A C

A A C
B B D
C
D
B D

Sequence (c)
 Possible Sequences
for a 4-Component Feed
A B A

A A B A A A
B B C B B B
C C C C
D D
D C D C B
(Indirect sequence)

Sequence (d) and (e)

 General heuristics for separation sequencing of liquid
mixtures

1. Remove first corrosive, hazardous, fouling, reactive and any

troublesome components. Consider also in the first place the
removal of light ends
2. Deliver high-purity products as top distillate. The same is
valid for reactants sent to reactors sensitive to impurities
3. When separation by distillation is feasible, prefer it in the
first attempt
4. Isolate zeotropic and azeotropic mixtures
 General heuristics for separation sequencing of liquid
mixtures

5. Perform difficult zeotropic separations later but before

azeotropic separations. Examine other options, such as
extractive distillation, L–L extraction, crystallisation,
adsorption or molecular sieves
6. Examine the separation of azeotropic mixtures last
7. Remove the components in order of decreasing percentage of
the feed. This operation will reduce the cost of the
next separation
8. Favour 50/50 splits
EXAMPLE: Liquid-phase oxidation of n-butane to acetic acid
gives formic acid as by-product and some impurities. Propose a
separation sequence to recover the acetic and formic acids as
pure products.
Heuristics for separation sequencing of liquid mixtures by
distillation method

1. Perform difficult separations last but before separations of

azeotropes
2. Remove first the lightest components one by one as
overhead products. In other words, favor the direct sequence
3. Remove components in order of decreasing percentage of
the feed. This operation will reduce the cost of the next
separation
4. Favour near 50/50 splits
 Difficult separations ?

1. Low relative volativity (the difference in boiling points of

components is small)
2. High-purity separation
EXAMPLE: Examine suitable separation sequences for the
mixture of C3-C5 alkanes:
All the four heuristics give contradictory results.
We take the decision to accept the heuristic recommending the split
A/BCDE. Then, the heuristics for the second column are as follows:
 Solution developed from heuristics

A
B A
C B
D
E

B
C C
D
E BC

DE

E
Although in the above example the heuristics do not give a
clear indication of good candidate sequences, in some
problems they might.
A more general method than the heuristics is needed.
 n-Butylene Purification by Ordinary Distillation and Extractive Distillation
Feed: Relative Volatility*
Species Mole % ()I ()II
A: Propane 1.47
2.45
B: 1-Butene 14.75 1.18 1.17(nC4/1-C4)
C: n-Butane 50.29
1.03 1.17(nC4/T-2-C4)
D: trans-Butene-2 15.62
E: cis-Butene-2 11.96
2.50
F: n-Pentane 5.90

*()I = adjacent relative volatility at 150 F for separation

method I, ordinary distillation
()II = adjacent relative volatility at 150 F for separation
method II, extractive distillation with furfural.
(C4H3OCHO)
Products: A, B, C, DE and F.
 How do you get to following industrial separation sequence?
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
 A

A A B
B B
C C
D C C
E
F
D
E
F
()
D
E
II
D
E

F
Paraffin separation problem
Solution developed from heuristics
Aromatics separation problem
 Solution developed from heuristics

A
B A
C C
D
E

B
C D
D
E B
CD

CDE

E
Industrial Sequence for Separating Chlorination and
Alkylation Products in the Manufacture of Detergent

I. Reactions :

(Chlorination)
C12 H 24  Cl2  C12 H 25Cl  HCl
(kerosene) (chlorine) (keryl (hydrogen
chloride) chloride)

(Alkylation)

C12H5Cl + C12H25 - + HCl

(keryl (benzene) (keryl benzene) (hydrogen
chloride) chloride)
Industrial Sequence for Separating Chlorination and
Alkylation Products in the Manufacture of Detergent

II. Reaction Products to be Separated into Pure Components

( Relative
Flow Rate ) Normal Boiling
Species Mole/hr Point, TC T

A: HCl 1 -85
B: Benzene 5 80 165
C: Kerosene 1 214 134
D: Keryl Benzene 1 250 36
E: Heavy Ends
III. Key Questions :
a. Species: Any corrosive and hazardous components?
Split A/BCD (essential first separation)

b. T : Any difficult separations?

Split C/D (essential last separation)

c. C1: Any plentiful components?

Split B/CD (desirable early separation)
IV. Initial Separation Sequence

A(HCl)
A
B B(Benzene)
C B
D C
D C C(Kerosene)
D
D(Keryl Benzene)
 C D
B
COMPLEX COLUMNS - COLUMNS WITH MORE
THAN TWO PRODUCTS
Distillation with Vapor
Side-stream Rectifier
Distillation with Liquid
Side-stream Stripper
 A
A,B

B,C
C

Prefractionator arrangement
Column with side stream – when there is less than 5%
heaviest component (stream C)
Column with side stream – when there is less than
5% lightest component (stream A)