Chapter 7

Separation System
If we exclude solid phase processes, our decision is broken
down to three separate parts:

1. General Structure
2. Vapor Recovery System
3. Liquid Recovery System

General Structure of the Separation System

To determine the general structure of the system, we first focus on

the phase of the reactor effluent stream.
Purge

Reactor Separation
Feed streams Products
system system

Focus on reactor exit stream

There are only three possibilities :

1 – If the reactor effluent is in liquid phase, we realize that we

only need a liquid separation system. This system might
include distillation columns, extraction units, etc., but
normally there will not be any gas absorber, gas adsorption
units, etc.

Reactor Liquid Liquid Separation

Feeds Products
system system

Liquid recycle
2 – If the reactor effluent is a two-phase mixture, we can use
the reactor as a phase splitter (or put a flash drum after the
reactor).
Gas recycle Purge

Vapor Vapor
35°C Phase recovery Products
split Liquid
system
Vapor
Liquid
Reactor Liquid Liquid Separation
Feeds Products
system system

Liquid recycle

If the flash liquid we obtain contains mostly
reactants (and no products) then we recycle them
to the reactor (we have the equivalent of a reflux
condenser).

However if flash liquid contains mostly products,

we send this stream to the liquid recovery system.

But, if the reactor effluent streams contains only a

small amount of vapor, we often send the reactor
effluent directly to the liquid recovery system.
3 – If the reactor effluent is all vapor, we cool the stream to
100°F (by cooling water) and we attempt to achieve a phase
split or to completely condense this stream.

Purge

Vapor recovery
Products
system
Vapor
Reactor Vapor 35°C
Feeds Phase split
system
Liquid
Liquid Separation Products
Liquid recycle system
In case that no phase split can be obtained without
refrigeration, we also consider the possibility of sending
The reactor effluent directly to a vapor recovery system.

Approximate Flash Calculations

To determine the phase split, we use a sharp split approximation

procedure to avoid the trail and error solutions associated with
flash calculation. V
The flash equations are: yi
Overall balance: F=V+L
F
Component balance: F zi = V yi + L xi
Equilibrium: yi = Ki xi zi

L
or xi
 When we combine these equations, we have:

zi
yi = if K i >> 1 ⇒ V yi = F zi
V V 1
+ (1 − )( )
F F Ki
zi
xi = if K i << 1 ⇒ L xi = F zi
V
( K i − 1) + 1
F
Thus as a first estimate of the vapor and liquid flow rates, we can
write
V = ∑ fi for all components where Ki > 10
L = ∑ fj for all components where Kj < 0.1

The expressions are equivalent to a perfect split, providing
there are no components with a Ki value between 0.1to 10.

In this case we have ignored the vapor-liquid equilibrium.

Superimpose these equilibrium relationships on our
expressions for the flows.

Thus, the liquid composition in the equilibrium with a vapor
component having a mole fraction
fi fi yi fi
yi = = is xi = =
V ∑ fi Ki Ki ∑ fi
The liquid flow of this component is then
fi ∑ f j
li = L xi =
Ki ∑ fi
Now, we can go back and adjust the vapor flow for this loss:

 fj 
vi = fi − li = fi 1− 
 Ki ∑ fi 
The corresponding expressions for components that are
predominately in the liquid phase are
Kj f j ∑ fi  K j ∑ fi 
vj = l j = f j 1− 
∑ fj
and
 ∑ f 
 j 
HDA flash
Approximate Exact
Component fi Ki vi li vi li
H2 1549 99.07 1547.5 1.5 1548 1
CH4 2323 20.00 2312 11 2313 10

Approximate Exact
Component fi Ki vi li vi li
Benzene 265 0.01040 29.6 235.4 28.2 236.8
Toluene 91 0.00363 3.6 87.4 3.6 87.4
Diphenyl 4 0.00008 0 4 0 4
∑ fi = 1549 + 2323 = 3872
∑ fj = 265 + 91 + 4 = 360

 360 
vH 2 = 1549  1 −  = 1547 .5
 99 .07 (3872 ) 
 360 
vCH 4 = 2323 1 −  = 2312
 20 (3872 ) 

 0.0104 (3872) 
l Benzene = 265 1 −  = 235.4
 360 
Alternative Approximate Procedure for Flash Calculations

F=V+L
F zi = V yi + L xi (A)
yi = Ki xi (B)

F zi = fi (A),(B) ⇒  yi  L
if f i = vi + L  ⇒ f i = vi + vi
V yi = vi  Ki  Ki V
 L  fi L
⇒ fi = vi 1+  ⇒ −1 =
 Ki V  vi Ki V
If we divide these equation by similar expression for
component j , we obtain

fi
−1
vi Kj 1
= = (Z)
fj K i α ij
−1
vj

vi
= fractional recovery of component i in vapor phase.
fi

If we specify fractional recovery of one component we
can use equation (Z) to find the fractional recovery of the
other components, (having relative volatility of the other
components, αij ).

There is no shortcut procedure for flash calculation of
non-ideal mixtures. However, all CAD packages, i.e.,
FLOWTRAN, PROCESS, DESIGN 2000, ASPEN, etc.,
will handle these problems.
Vapor Recovery System
For synthesizing a vapor recovery system we need to make
two decisions:

What is the best location?

What type of vapor recovery system is cheapest?
Location of Vapor Recover System
There are four choices for the location of the vapor recovery
system:

1. The purge stream

2. The gas-recycle stream
3. The flash vapor stream
4. None
Gas Purge
recycle

Prevent recycle of Prevent loss of

certain components valuable or
undesirable material
Vapor from
phase split
(Heuristics) Rules we use to make the decision of location
of vapor recovery system:

1. Place the vapor recovery system on purge stream if

significant amounts of valuable materials are being lost in
the purge. The reason for this heuristic is that the purge
stream normally has the smallest flow rate.
2. Place the vapor recovery system on the gas-recycle
stream if materials that are deleterious to the reactor
operation (catalyst poisoning, etc.) are present in this
stream or if recycling of some components degrades the
products distribution. The gas-recycle stream normally
has the second smallest flow rate.
3. Place the vapor recovery system on the flash vapor
stream if both items in 1 and 2 are valid, i.e., the
flowrate is higher, but we accomplish two objectives.
4. Do not use a vapor recovery system if neither item 1nor
item 2 are important.

Adjust the Material Balance

Note that our simple material balance equations will not be

valid for these cases and the material balance should be
adjusted. However, in many cases the errors introduced are
small and our previous approximation still provide good
estimates.
Use your engineering judgment to decide
whether the adjustment is needed.
Example – HDA process
Do we need a vapor recovery system for HDA process?

Solution:
for a conversion of x = 0.75 and purge composition of
yPH = 0.4 , the vapor flows from phase splitter are given in Table
7.1-1 (page 169).
Purge = 496 mol/hr
Recycle stream = 3371 mol/hr

PG 496
fraction purged = = = 0.128
PG + RG 496 + 3371
From the Table we have

benzene in purge stream = 0.128 (29.6) = 3.79 mol/hr

toluene in purge stream = 0.128 (3.6) = 0.461 mol/hr

On an annual basis and by neglecting the fuel value of these

components this loss is

benzene loss = ($ 9.04/mol) (3.79 mol/hr) (8150 hr/yr) = 279200 $/yr

toluene loss = ($ 6.4/mol) (0.461 mol/hr) (8150 hr/yr) = 24000 $/yr
total loss of valuable materials = 279200 + 24000 = 0.3032 ×106 $/yr
This value is small compared with our economic potential. Thus, we
decide not to include a vapor recovery system at this point of design.

There is a significant amount of benzene in the flash vapor
stream (12% of benzene flow), see the HDA flash Table.

Most of the benzene will be recycled to the reactor.

(29.6 mol/hr – 3.79 mol/hr lost in purge)

This amount of benzene may change the selectivity and

ultimately change the product distribution. Thus, we may
consider a vapor recovery system on recycle stream or flash
vapor stream.

We use knockout drums at each stage of compressor and cool

the gas to recover the condensable materials and send them to
the liquid recovery system, benzene is assumed to be recovered.
Type of Vapor Recovery System

The most common choices are:

1. Condensation – high pressure or low temperature or both
2. Absorption
3. Adsorption
4. Membrane separation process
5. Reaction systems

Shortcut design for gas absorbers were discussed in Chap. 3.

The economic trade-offs for the design of a condensation
process are considered in Exercise 3.5-2.

A design procedure for adsorption processes has been
presented by Fair
(J. R. Fair, “ Mixed Solvent Recovery and Purification,” p. 1,
Washington University Design Case Study No. 7, edited by
B.D. Smith, Washington University, St. Louis, Mo., 1969)

Neither a design procedure nor a cost correlation for
membrane recovery processes seem to be available in the
open literature. Only a simple model that can be used to
estimate the area of a membrane process has been published
by J. E. Hogsett and W.H. Mazur, Hydrocarbon Process
August 1983, p. 52.

Reactions are sometimes used to remove CO2 from gas
streams, and H2S is recovered with amines.
Strategy

We design the vapor recovery system before liquid recovery

system because each of the vapor recovery processes usually
generates a liquid stream that must be further purified.

For the case of a gas absorber where we need to supply a

solvent to the absorber, we also introduce a new recycle loop
between separation streams.

Normally we need to estimate the size and costs of each unit to

determine which is cheapest.
Liquid Separation System

To synthesize the liquid separation system the following

decisions should be made:

1. How should the light ends be removed if they might

contaminate the product?
2. What should be the destination of the light ends?
3. Do we recycle components that form azeotropes with the
reactants, or do we split the azeotropes?
4. What separations can be made by distillation?
5. What sequence of columns do we use?
6. How should we accomplish separations if distillation is not
feasible?
Q.1 – Light Ends

Some light ends will be dissolved in the liquid leaving the phase
splitters (shown in the case of vapor reactor effluent or mixture
of vapor and liquid reactor effluent), and normally some will be
dissolved in liquid streams leaving the vapor recovery systems.

If these light ends might contaminate the product, they must be removed.

Alternatives for Light Ends Removal

increasing cost

1. Drop the pressure or increase the temperature of a

stream, and remove the light ends in a phase splitter.
2. Use a partial condenser on the product column.
3. Use a pasteurization section on the product column.
4. Use a stabilizer column before the product column.
 light ends light ends light ends

Partial condenser Pasteurization section Stabilizer column

Note : recycle vapor stream to vapor recovery

system if possible.
Pasteurization Columns:

For the special case of side-stream columns where the desired

product is the intermediate boiler and there is a waste or fuel
byproduct that is ether much lighter than product (so we recover
the product as a side stream above the feed) or else is much heavier
than the product (so we recover the product as a side stream below
the feed).
K. Glinos and M. F. Malone have published a shortcut design
procedure for pasteurization columns. (see Appendix A.5).
Stabilizer Columns:
This is a normal distillation column that recovers light ends.
Q.2- Destination of Light Ends

1. Vent , if the light ends have very little value. Also if this
venting causes air pollution problems, we try to vent them
through a flare system.
2. Fuel , if most of the light ends are flammable, we try to
recover the fuel value.
3. Recover and recycle to the vapor recovery system , if the
light ends are valuable, we want to retain them in the
process.
Summery for Light Ends

If light ends will not contaminate the product we
merely recycle them to the reactor with a reactant
recycle stream or remove them from the process
with a byproduct stream that is sent to the fuel
supply. If light ends will contaminate the product,
they must be removed from the process.

The method of removal and the destination of the
light ends, depend on the amount of the light ends.
Hence, we must determine the amount of the light
ends as a function of the design variables before
we can make a decision.
 Q.3– Azeotropes with reactants

If a component forms an azeotrope with a reactant, we

have two choices:

1. Recycling the azeotrope (over sizing all the

equipments in the recycle loop to handle the
incremental flow of the extra components).
2. Splitting the azeotrope and just recycling the
reactant (requires two columns and therefore is
expensive).

There is no general heuristic available for

making this decision and so we usually need to
evaluate both alternatives.
Q.4 – What separations can be made by distillation?

In general, distillation is the least expensive means of

separating mixtures of liquids.

However, if the relative volatilities of two components with

neighboring boiling points is less than 1.1 or so, distillation
becomes very expensive; i.e., a large reflux ratio, large vapor
rate, large column diameter, large condensers and reboilers,
large steam and cooling water costs.
 Component K value
increasing boiling point

A B, C
Separate B
A 3.2
lump design task C
B 1.7
C 1.6
D 1.0 D

E 0.4

D, E
B, C, D, E
E
Q.5– Column Sequencing - Simple Columns

For sharp splits of a three component mixture (with no

azeotropes) we can use:

a) Direct sequence
b) Indirect sequence
A, B
A B A

A A
B B
C C

C C B
B, C

Direct sequence Indirect sequence

When the number of components increases, the number of
alternatives increases very rapidly

Number of components 2 3 4 5 6
Number of sequences 1 2 5 14 42

Therefore it seems to be a major task to decide the best

sequence of distillation columns and we might need to look
for heuristics for column sequencing.
General Heuristics for Column Sequencing

1 – Remove corrosive components as soon as possible.

2 – Remove reactive components such as monomers as soon as possible.
3 – Remove products as distillates.
4 – Remove recycle streams as distillates, particularly if they are
recycled to a packed bed reactor.

Number 3 and 4 is because we want to avoid the contamination

of the product or recycle stream with heavy materials, rust, etc.,
which always accumulate in a process (usually in the reboiler).

If it is necessary to remove a product or recycle stream as a
bottom stream it is often taken as a vapor from reboiler and then
condensed again. At the same time a small liquid purge stream may be
taken from the reboiler to prevent the build up of
contaminants.
Column Sequencing Heuristics for Simple Columns
Simple Columns: columns with one top an d one bottom stream.
1 – Most plentiful first.
2 – Lightest first.
3 – High recovery separation last.
4 – Difficult separation last.
5 – Favor equimolar split.
6 – Next separation should be cheapest.

1,5 depend on feed composition and 2, 4 depend on relative
volatilities, therefore there may be conflict between these
heuristics (e.g. the most plentiful be also the heaviest). Thus, some
people have tried to order the importance of the heuristics

(J. D. Seader and A.W. Westerberg, AIChE, 23: 951 (1977)).
Nishida, Stephanopoulos and Westerberg have published a review
of the literature on the subject (N. Nishida,G. Stephanopoulos and
A.W. Westerberg, AIChE, 29: 326 (1981) ).
An Alternative approach to Selecting Column Sequences
Although as the number of components increase the number of
Alternatives increase very rapidly but, there are a large number of
processes which only use four or less distillation columns. To evaluate
this system maximum of 14 alternatives should be considered.

Using shortcut techniques, Glinos demonstrated that the evaluation of
the 14 sequences was almost instantaneous on a VAX 11-780.
(K. Glinos, “A Global Approach to the Preliminary Design and Synthesis
of Distillation Trains,” Ph.D. thesis, University of Massachusetts,
1984).

Kirkwood has shown that the 14 sequences can be evaluated in only a
few seconds on IBM – PC XT.
(R. L. Kirkwood, “PIP – Process Invention Procedure, ” Ph.D. thesis,
University of Massachusetts, Amherst, 1987)

Thus, for a modest-size sequencing problems, it is
better to develop computer codes that evaluate the
costs of all sequence alternatives than it is to use
heuristics.
Complex Columns
Rather than consider only sequences of simple columns, we
consider the use of sidestream columns, sidestream strippers and
reboilers, prefractionators, etc. one set of heuristics for complex
columns has been published by Tedder and Rudd,
(D. W. Tedder and D. F. Rudd, AIChE J., 24: 303 (1987).
Another set has been published by Glinos and Malone,
(K. Glinos and M. F. Malone, “Complex Column Alternatives in
Distillation Systems,” Chem. Eng. Res. Des., 1985).

See Table 7.3-5 and 7.3-6 (pages 181 and 182).

Complex Columns in Sequence

Our goal is to complete a base-case design as rapidly as

possible in order to make a preliminary evaluation of
whether the process is profitable.

Thus, normally we include only sequences of simple columns
in our first designs.

However, a complex column is often cheaper than two simple
columns, and therefore we need to consider these possibilities at
some point of design. Since we can replace any two neighboring
columns in a sequence by a complex column, we can generate a
large number of alternatives. To avoid such difficulties we defer
a consideration of complex columns until we
consider other process alternatives.
 A B A
Design 1 Design 2
Direct sequence indirect sequence

C C B

Design 3 Design 4 Design 5

Sidestream Sidestream prefractionator A
rectifier A B stripper A A,B

C C B B,C
C
A A
Design 6 Design 7
side-draw
side-draw
B

C C
Q.6– Other types of liquid separations

If distillation is too expensive to use to separate liquid mixtures,

that is , α <1.1, the other choices that are normally the next least
expensive can be used are as follow:

1. Extraction
2. Extractive distillation
3. Azeotropic distillation
4. Reactive distillation
5. Crystallization
6. Adsorption
7. Reaction
Extraction
To separate mixture of B and C having a feed composition corresponding to the point 1,
we counter-currently contact the feed with a solvent S corresponding to point 2 in an
extraction column. Normally, we attempt to recover 99% or more of C, from the original
feed, which corresponds to point 3 . We remove the solvent from this stream by using a
distillation column to obtain the product stream for component B as point 5. the other
stream leaving the extraction unit corresponds to point 4 and when we use distillation to
remove the solvent from this mixture, we obtain the conditions at point 6. This point
corresponds to a binary mixture of B and C, which was the original separation except that
is more concentrated than the original feed, point 1. Also, when we separate B and C by
normal distillation we can set the bottom specification to give us almost pure C, point 7,
and the overhead composition as the original feed mixture, point 1.Thus, with extraction,
we must carry out the same B- C distillation as we would with just distillation,
although the degree of separation required is reduced. Of course, this reduction in
degree of separation must decrease the cost sufficiently to pay for the extraction
column and the other two distillation columns. In some cases this is possible.
 5
Extraction B
7C

3 B+S 6

2 1
B+C 4
S

5
C (+ B) 3 2
6 B S
1
4 7
B+C C
C+S
(+ B)
Extractive Distillation
If we attempt to separate HNO3 and H2O by extractive distillation, we add a heavy
component , H2SO4 , near the top of the tower. The presence of the heavy
component changes the vapor-liquid equilibrium which is in some cases will
simplify the separation. We obtain a pure component, HNO3, overhead in the first
column. Then we recover the other component overhead in a second column, and we
recycle the extractive entrainer, H2SO4 , back to the first column. We see that two
distillation columns are required.
B

C
B = HNO3
C = H2O B

S = H2SO4 C

S+C
S
Azeotropic Distillation
In azeotropic distillation we add a relatively light component that again changes the
vapor-liquid equilibrium of the original liquid mixture, often by forming a new
azeotrope with one of the feed components. For example to split the Ethanol – H2O
azeotrope, we can add benzene, which forms a ternary azeotrope. With this
modification, we can remove pure ethanol from the bottom of the first column and
recover the ternary azeotrope overhead.
BCS ternary heterogeneous azeotrope
B = Ethanol
C = Water
S = Benzene
B+C B + C azeotrope
azeotrope

B
B C

C
Since the ternary azeotrope is a heterogeneous mixture when it is condensed, we use the
benzene-rich layer as a reflux to the first column, and we use the other layer as the feed
to a second column. In the second column, we again take ternary azeotrope overhead and
we recover an Ethanol – H2O mixture as the bottom stream. Now, in a third column, we
recover pure water, our second product, as the bottom stream, along with the original
binary azeotrope overhead. This binary azeotrope is recycled to the first column, and we
obtain pure products from the system of three columns.

Reactive Distillation
In some cases it is possible to add an entrainer that reacts with one component in a
mixture that is difficult to separate. For example, the relative volatility between meta-
and para-xylene is only 1.03 . However, if sodium cumene is added to a mixture of the
xylene isomers, it reacts with the para isomer, and then the relative volatility between the
meta-xylene and the organometallic complex that is produced becomes 30.
The reaction can be reversed in a second column and the entrainer is recycled .
B , C = xylene: α = 1.03 B
S
S = sodium cumene
CS = organometallic: B, CS : α ≈ 30
B
C

C
C+S

Thus, the original separation is greatly simplified, but at the expence of handling sodium
cumene. If entrainers that are simpler to handle can be found, the reactive distillation
become a ,ore important separation alternative.
Crystallization
The separation of xylene isomers is difficult by distillation, so often it is cheaper to use
the difference in freezing points to separate the mixture. Thus, by freezing, separation
of the liquid-solid mixture, and often using some recycle, the desired separation can be
achieved.

Vapor C ( + B)

B, C
Crystallizer Centrifuge Drier

B crystals
Liquid C
HDA Process
Flash liquid stream that is fed to the distillation train is given
In Table 7.1-1 (100 °F and 465 Psia).

Component flow (mol/hr) If we let the light ends leave

H2 2
with the product and
CH4 11
recover all the product, the
composition of the product
Benzene 235.4
stream will be:
Toluene 87.4
Diphenyl 4
235 .4
xD = = 0 .947
2 + 11 + 235 .4

This is less than the required product purity of 0.997

. Hence, we must remove the light ends
We could recover the light ends in a partial condenser at the
top of the product column, but since the required product
purity is so high, expect that we will need to use a stabilizer
column to remove the light ends. We remove the hydrogen and
methane and send them to fuel supply.

Benzene = 235.4 mol/hr

The remaining liquid mixture is: Toluene = 87.4 mol/hr
Diphenyl = 4 mol/hr

The heuristic of lightest first, most plentiful first, and favor

equimolar splits all suggest direct sequence.
 H2 , CH4 Purge
H2 , CH4

Reactor Flash

Benzene H2 , CH4
Toluene H2, CH4, B, T, D

Benzene Col.
Toluene Col.

Stabilizer
Diphenyl
T, D B, T, D
When we add the purge losses and the cost of the distillation
columns to our economic potential calculations for level 3,
we obtain the revised economic potential for level 4.
2,000,000
1,500,000
1,000,000
500,000
yPH
0
E P 4 ($/yr)

-500,000 0.2
-1,000,000 0.4
-1,500,000 0.6
-2,000,000
0.8
-2,500,000
-3,000,000
-3,500,000
0.1 0.2 0.3 0.4 0.5 0.6 0.7

Conversion x