1

Separation System
- Synthesis of Separation System

- Distillation Systems for Separating Azeotropes
(a). Not Adding third component
- Pressure-swing distillation (THF-H
2
O)
- Binary heterogeneous azeotropic distillation (n-butanol-H
2
O)
- Hybrid distillation with pervaporation (membrane)
- Hybrid distillation with adsorbent (molecular sieve)
(b). Adding third component
- Review of residue curve maps
- Extractive distillation (IPA-H
2
O+DMSO)
- Heterogeneous azeotropic distillation (IPA and HAc dehydration)
- Salt distillation (Saline extractive distillation)
2 2
Design of Separation System
1. General Structure
3 3
Design of Separation System
Liquid Exit Stream
4 4
Design of Separation System
Reactor Exit is Vapor and Liquid
5 5
Design of Separation System
Vapor Exit Stream
6 6
Vapor Recovery System Location
7 7
Types of Vapor Recovery System
Condensation high pressure or low temperature, or both
e.g. recovering of acetone from an air stream

Absorption
e.g. using water as a solvent to recover acetone from a air stream

Adsorption
e.g. design procedure is available.

Membrane separation process
Design procedure and cost correlation from vendors.

Reaction systems
e. g. to remove CO
2
from gas stream, or H
2
S is recovered with amines.
8 8
Design Vapor Recovery System First
(usually generates a liquid stream or a new recycle loop)
9 9
Liquid Separation System
Alternatives for Light-Ends Removal
1. Drop P or increase T, and remove it in a phase splitter.

or by the following options:
10 10
Group the components with relative volatility < 1.1
11 11
Column Sequencing Simple Columns
For sharp splits of a ternary mixture
(much more alternatives for more components)
12 12
General Heuristics for Column Sequencing
1. Remove corrosive components as soon as possible.
- material of construction much more expensive than carbon steel.

2. Remove reactive components or monomers as soon as
possible.
- reactive components change the separation problem, monomers foul
reboiler so needs to run at vacuum to decrease column temperature.

3. Remove recycle streams as distillate, particularly if they are
recycled to a packed bed reactor.
- avoid contamination with heavy materials, rust, etc., which always
accumulate in a process.
13 13
Select sequence to minimize # of columns in recycle loop
14 14
Column Sequence Example HDA Process
(After light-ends, lightest and plentiful first)
15 15
Complex Column Sequence (Designs 3-7)
- Design guidelines available
16 16
Other choices with relative volatility < 1.1
Extraction
17 17
Other choices with relative volatility < 1.1
Extractive Distillation (will study later)
18 18
Other choices with relative volatility < 1.1
Azeotropic Distillation (will study later)
19 19
Other choices with relative volatility < 1.1
Reactive Distillation (reaction reverse in second column)
20 20
Other choices with relative volatility < 1.1
Crystallization
21
Introduction of Azeotrope
Minimum-boiling Azeotrope (e.g. IPA-H
2
O)
IPA
X
F1
Azeotrope
Azeotrope @ 31 mol%
H
2
O and 80.0 C
Water
X
F2
Azeotrope
x
F1
x
F2
22
Maximum-boiling Azeotrope (e.g. Acetone-Chloroform)
Chloroform
X
F1
Azeotrope
Acetone
X
F2
Azeotrope
Azeotrope @ 34 mol%
Acetone and 64.5 C
x
F1
x
F2
23
Thermodynamic Model
Extremely important for any design study
Check your application and select the proper class of
property method
Use Aspen Plus built-in model parameters or the
parameters from literature to predict VLE (Txy, yx),
LLE, and azeotropic compositions and azeotropic
temperatures
Verify from data in DECHEMA, Azeotropic Data III
(Horsely, 1973), Azeotropic Data (Gmehling, 2004),
and also from literatures
You may need to re-fit model parameters using
parameter estimation capability in Aspen Plus
24
Pressure-Swing Distillation
Can be used in systems where there is significant change
in the azeotropic composition with pressure.
Azeotrope: @1.01 bar 82.3 mol% THF, 64 C
@7.9 bar 63.9 mol% THF, 137 C
Minimum-boiling homogeneous azeotrope varies with
pressure.
63.9 mol% THF
At 7.9 bar
82.3 mol% THF
At 1.01 bar
25
Design Flowsheet
(estimation of recycle rate from above information)
THF-H
2
O
H
2
O
THF
LP
Column
HP
Column
LP Azeotrope
HP Azeotrope
26
Remarks about the Design Flowsheet
Two pressures are design variables to be optimized, as well as
the number of trays in each column and feed-tray locations.
The larger the difference in the two pressures, further apart the
azeotropic compositions, less recycle is required and the
lower of the energy consumption.
However, the lower the pressure in the low-pressure column,
the larger the diameter and the coolant required in the
condenser. The higher the pressure in the high-pressure
column, the higher the pressure of the steam that must be
used in the reboiler and other problems with high temperature
at reboiler.
Possible heat integration of the condenser (HPCOL) and the
reboiler (LPCOL).
27
Total Annualized Cost (TAC) Analysis
The design variables can be determined by minimizing
TAC of the overall system.
TAC includes: stream costs, annualized capital costs,
and utility costs.
If feed stream and product streams are with fixed flow
rates and compositions, the stream costs can be
neglected.
Annualized capital costs for the above system include:
LPCOL column, LPCOL column trays, reboiler for LPCOL,
condenser for LPCOL, and another four terms for
HPCOL column. (payback period is assumed to be 3 yrs)
Utility costs include: steam costs for the two reboilers and
cooling water costs for the two condensers
28
Cost Data for Column
29
Cost Data for Reboiler and Condenser
30
Information on Estimation of U in Calculating A
31
Information on Utility Costs
32
Control Strategy for this System
33
Isobaric Phase Diagrams for
Binary Azeotropic Mixtures
Homogeneous Azeotrope Heterogeneous Azeotrope
34
Separation of a Binary Heterogeneous
Azeotropic Mixture (excerpt from Doherty and Malone, 2001)
35
Design when Feed Composition is in
miscible Region (e.g. 20% water)
36
Examples of Binary Mixture Systems
No need to add entrainer.
Examples include: purifying water-hydrocarbon
mixtures (e.g., water with any one of the
following components: C4-C10, benzene,
toluene, xylene, etc.).
Water-alcohol mixtures (e.g. butanol, pentanol,
etc.) as another example.
C5s and methanol separation.

37
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
V
a
p
o
r

y

(
m
o
l
e

f
r
a
c
t
i
o
n

i
C
5
)

Liquid x (mole fraction iC5)
Another Example: iC5/methanol binary system
1 atm
5 atm
2.6 atm
10 atm
38
1
7
1
5
Feed
1126 kmol/hr
320 K
0.4446 iC5
0.0783 nC5
0.03371-Pentene
0.1431 2-Pentene
0.2814 MeOH
0.0037 2M1b
0.0149 2m2B
0.0003 H2O
Light
1301 kmol/hr
Heavy
418 kmol/hr
320 K
391 K
10.02 atm
328 K
2.6 atm
375 K
10 atm
7.213 MW
4.30 MW
1.187 MW
C1
ID 0.751 m
C2
ID 2.785 m
2.4 atm
B1
314 kmol/hr
0.999 MeOH
0.001 H2O
Ovhd1
104 kmol/hr
0.4633 iC5
0.0750 nC5
0.0382 1-Pentene
0.1622 2-Pentene
0.2407 MeOH
0.0045 2M1B
0.0160 2m2B
0.0001 H2O
365 K
2.64 atm
0.778 MW
B2
812 kmol/hr
0.6166 iC5
0.1086 nC5
0.0467 1-Pentene
0.1984 2-Pentene
0.0039 MeOH
0.0051 2M1B
0.0207 2m2B
Ovhd2
489 kmol/hr
0.4627 iC5
0.0605 nC5
0.0264 1-Pentene
0.1121 2-Pentene
0.3235 MeOH
0.0037 2M1B
0.0109 2m2B
0.0001 H2O
Decanter
39
1
7
1
5
Feed
Light
Heavy
320 K
2.4 atm
391 K
10.02 atm
328 K
2.6 atm
375 K
10atm
7.21 MW
4.30MW
1.19 MW
ID 0.751 m
VLE
ID 2.78 m
VLLE
B1
0.999 MeOH
365 K
2.64 atm
0.778 MW
B2
0.0039 MeOH
FC
LC
LC
LC
LC PC PC
TC TC
320 K
2.4 atm
TC TC
0.17 MW
320 K
2.4 atm
40
Review of Residue Curve Maps
Y X

X
=
=
=
=
d
d
) y x (
H
V
dt
dx
Vy
dt
) Hx ( d
V
dt
dH
i i
i
i
i
41
Simple Distillation Residue Curves
42
RCM for Ternary Mixture without Azeotrope
43
RCM for Ternary Mixture with one Binary
Minimum-Boiling Azeotrope
44
True Systems for Above Cases
45
Selected RCMs for Ternary Mixtures
with Multiple Azeotropes
46
RCM vs. Distillation Lines
column staged as same the 1 h Assume
h
r at column packed for tion representa Euler
x : column staged For
x ) 0 h (
dh
d
: column packed For r When
x x
1 r
1
1 r
r
: Column Staged
x ) 0 h (
r
x
r
1 r
dh
d
: Column Packed
n 1 n
1 n 1 n
n 1 n
D 0 n 1 n
D
D 0 D n 1 n
D
D
X Y A
Y X
A
X X
X X Y
X Y X
X
X X Y
X Y X
X
= =
=

= =
= = =
=
|
.
|

\
|
+
+
|
.
|

\
|
+
=
= = +
|
.
|

\
|
+
=
+
+ +
+
+
+

47
Example of RCM vs. Distillation Lines
48
Total Reflux vs. Finite Reflux Ratio
(Notice also the mass balance line)
49
Summary of RCM
Easily sketched with the help of Aspen Plus.
The residue curve through any given liquid
composition point is tangent to the vapor-liquid tie-line
through the same point.
The structure of the RCM is the underlying
thermodynamic principle that governs the shape of
composition profiles and consequently the products
that can be obtained from a distillation.
The composition of the desired products from each
column should lie in the same distillation region (not
necessary including F). If the distillation boundaries
are linear, the products from the entire sequence must
lie in the same distillation region.
50
Exception for Curved Distillation Boundary
51
Extractive Distillation
Separating minimum-boiling binary azeotrope by using
heavy entrainer.
Two-column sequence with first extractive distillation
column separating out one product and second entrainer
recovery column separating out entrainer and another
product.
Most widely used form of homogeneous azeotropic
distillation in industries
Examples include: n-butane-butadiene using furfural;
dehydration of ethanol using ethylene glycol; acetone-
methanol using water; pyridine-water using bisphenol.
52
Conceptual Design Flowsheet
Qr
1
Extractive
distillation column
Entrainer
recovery column
Qc
1
F2
D1
IPA-water feed (FF)
Entrainer feed (FE)
Entrainer recycle
Entrainer makeup
D2
Qc
2
Qr
2
B2
N
FE
N
FF
N
F2
N
1
=.?
N
FE
=.?
N
FF
=.?
N
2
=.?
N
F2
=.?
53
Which will be the D1 product?
Isovolatility curve
Adding entrainer
causing
1
Acetone
Methanol
o >
54
Using Different Entrainer
Isovolatility curve
Adding entrainer
causing
1
Acetone
Methanol
o <
55
Case Study of an Extractive Distillation
Column System
Isopropyl Alcohol (IPA) is widely used in semi-conductor
industry as a cleaning agent, thus the recovery of IPA
from waste solvent stream is an important issue worthy
of study.
Dehydration of IPA using Dimethyl Sulfoxide (DMSO) as
entrainer.
Minimum-boiling azeotrope with heavy entrainer, thus an
extractive distillation system.
Two-column system with an extractive distillation column
and an entrainer recovery column.
Optimum design and control of the overall system.
56
Compare of Candidate Entrainers
(adding DMSO keeps IPA toward the top of the column)
WATER
(100.02
o
C)
DMSO
(190.74
o
C)
IPA (82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
80.00
o
C
1
1.5
2
3
4
5
6
7
8
X
E
= 0.15
Isovolatility curve
Equalvolatility curve
with =2.0
57
Compare to EG as Entrainer
(enhancement of is less)
WATER
(100.02
o
C)
EG
(197.08
o
C)
IPA (82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
80.00
o
C
1
1.5
2
3
4
5
6
7 8
x
E
= 0.20
58
Counterexample by only Observing
Isovolatility Curve
DMC
(90.22 C)
EG
(197.08 C)
MeOH (64.53 C)
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95
0
.
0
5
0
.
1
0
.
1
5
0
.
2
0
.
2
5
0
.
3
0
.
3
5
0
.
4
0
.
4
5
0
.
5
0
.
5
5
0
.
6
0
.
6
5
0
.
7
0
.
7
5
0
.
8
0
.
8
5
0
.
9
0
.
9
5
63.60 C
1.5
2
3
4
5
Appeared better?
More effective in
changing
Entrainer #1
Entrainer #2
(183.88 C)
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95
0
.
0
5
0
.
1
0
.
1
5
0
.
2
0
.
2
5
0
.
3
0
.
3
5
0
.
4
0
.
4
5
0
.
5
0
.
5
5
0
.
6
0
.
6
5
0
.
7
0
.
7
5
0
.
8
0
.
8
5
0
.
9
0
.
9
5
MeOH (64.53 C)
DMC
(90.22 C)
Aniline
63.60 C
59
Check VLE of IPA-DMSO
60
Check VLE of H
2
O-DMSO
61
Optimum Design of the Flowsheet
The design variables include: total stages for extractive
column and recovery column; feed location for extractive
column, recycled entrainer location, and feed location for
recovery column; ratio of recycled entrainer and fresh
feed; and recycled entrainer feed temperature.
Equal molar fresh feed composition of IPA and water.
IPA product spec. at 99.9999 mol% for semi-conductor
industry usage, bottom spec. of extractive column set at
x
IPA
/(x
IPA
+x
H2O
)=0.001, and Water spec. at 99.9 mol%.
Do optimization for the extractive distillation column first
and then for the overall flowsheet.
62
Material Balance Lines for the System
WATER
(100.02
o
C)
DMSO
(190.74
o
C)
IPA (82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
80.00
o
C
D1
FF
D2
B2
DMSO makeup
F2
FF + B2 + DMSO makeup
B2 + DMSO makeup
63
Liquid Composition Profiles for the two Columns
Pure IPA
Water diminished
Pure DMSO
Pure water
DMSO maintained in
extractive section
64
Overall Control Strategy
C-2
C-1
IPA product Water product
IPA-Water
Reflux
drum
LC
PC
LC
PC
LC
38 TC1
TC2
12
Reflux
drum
FC
DMSO
makeup
FC
FC
TC
LC LC
RC
RC
FC FC
RC
65
Conclusions for Extractive Distillation Study
Isovolatility curve can be used to determine D1 product.
Iso- and equalvolatility curves to find more effective
entrainer.
Check VLE of the other two pairs to confirm easy
separation in rectifying section of the extractive column
and also in entrainer recovery column.
Extractive agent (DMSO) was added to alter the relative
volatility between IPA and H
2
O.
IPA goes toward top of the extractive column and water
goes toward bottom of this column.
Two-column design to obtain pure IPA and H
2
O.
A pre-concentrator column is needed for diluted fresh
feed.
Simple control strategy is developed with only one tray
temperature control loop in each column to handle feed
variations.
66
Same Separation Using Heterogeneous
Azeotropic Distillation
Minimum Temp
Distillation Boundary
67
Three-Column Design with a
Pre-concentrator Column
NF2
Decanter
C-3 C-2
IPA Water
IPA-Water
Cyclohexane makeup
Organic reflux
Aqueous outlet flow
Water
C-1
NF1
D1 D3
NF3
WATER
(100.02
o
C)
CyH
(80.78
o
C)
IPA (82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
69.44
o
C
63.77
o
C
80.00
o
C
69.34
o
C
D1
FF
D3
Organic reflux
Aqueous outlet flow
B1 and B3
D1 + D3
B2
Total liquid in decanter

68
Two-Column Design
(with larger top vapor rate)
N
F
Decanter
C-2 C-1
IPA Water
IPA-Water
Cyclohexane make up
Organic reflux
Aqueous outlet flow
D2
N
F
WATER
(100.02
o
C)
CyH
(80.78
o
C)
IPA (82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
69.44
o
C
63.77
o
C
80.00
o
C
69.34
o
C
D2
FF+D2
B1
B2
FF
Aqueous outlet flow
Organic reflux

Total liquid in decanter
69
Proposed Two-Column Design: One column served
as pre-concentrator and also recovery column
WATER
(100.02
o
C)
CyH
(80.78
o
C)
IPA (82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
69.44
o
C
63.77
o
C
80.00
o
C
69.34
o
C
D2
B2
FF + Aqueous outlet flow
FF
Organic reflux
Aqueous outlet flow
B1

Total liquid in decanter
Decanter
C-2
C-1
B1 B2
IPA-Water mixture
Cyclohexane makeup
Organic reflux
Aqueous outlet
D2
Heterogeneous Azeotropic Column
Pre-concentrator/Recovery Column
FF
V1
70
Overall Control Strategy for the Proposed Design
Decanter
C-2 C-1
IPA product Water product
IPA-Water
Cyclohexane makeup
Organic reflux
Aqueous outlet flow
Reflux
drum
TC
FC
FC
LC
PC
LC
TC
LC
LC
PC
FC
LC
7
TC1
TC2
9
RC
RC

71
Deficiency of Using this RCM type
WATER
(100.02
o
C)
CyH
(80.78
o
C)
IPA
(82.35
o
C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
69.44
o
C
63.77
o
C
80.00
o
C
69.34
o
C
V1
FF
Aqueous outlet
Organic reflux
B2
B1
FF + Aqueous outlet
D2
b
a
V1 flowrate = B1 flowrate
|
.
|

\
|
a
b
72
Using Benzene as Entrainer
BENZENE
(80.13 C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
(100.02
o
C)
Aqueous outlet
FF + Aqueous outlet
FF
80.00
o
C
D2
WATER
IPA
(82.35
o
C)
B1
V1
65.38
o
C
Organic reflux
69.35
o
C
71.74
o
C
b
a
V1 flowrate = B1 flowrate
|
.
|

\
|
a
b
B2
73
Even Better Entrainer
Entrainer
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
Minimun-boiling
azotrope
80.00
o
C
D1
FF
B1
Organic reflux
IPA
(82.35
o
C)
WATER
(100.02
o
C)
b
a
V2
Aqueous outlet
B2
V1 flowrate = B1 flowrate
|
.
|

\
|
a
b
74
Other System using Heterogeneous Azeotropic
Distillation (PM-water Separation)
75
Other System using Heterogeneous Azeotropic
Distillation (Pyridine-water Separation)
76
Better Design for the Pyridine-water Separation
77
Conclusions for Heterogeneous Azeotropic
Distillation Study (I)
Heterogeneous Azeotropic Distillation able to cross
distillation boundary and obtain products at different
distillation regions.
Combined pre-concentrator/recovery column design
reduce TAC and operating cost for the IPA dehydration
system, save equipments and instrumentations, and also
dampen disturbances from fresh feed.
Illustration of using heterogeneous azeotropic distillation
for various RCM type.
The most competitive design is to find an entrainer with
only one additional binary heterogeneous azeotrope
which is also minimum-boiling.
78
Case study (II): Acetic Acid Dehydration
No azeotrope exists for the acetic acid
dehydration system.
VLE exhibits tangent pinch near pure water end.
Needing many trays if using simple distillation.
Adding entrainer via heterogeneous azeotropic
distillation to help the separation.
Study the entrainer selection, design, and
control of this system.
79
Thermodynamic model
Nonideal vapor phase with vapor association of
HAc is described via Hayden-OConnells
second virial coefficient method
Liquid phase using NRTL activity coefficient
model
Consider three acetates (ethyl acetate, iso-butyl
acetate, n-butyl acetate) as candidates of
entrainer
Using DECHEMA VLE, LLE data and azeotropic
data to obtain NRTL model parameters

80
yx and Txy plots of HAc-water system
Tangent Pinch
81
Conceptual design for the separation of acetic acid and water
IBA Makeup
Organic
Reflux
Feed
(HAC+H
2
O mixture)
Steam
Bottom Product
(HAC)
Reboiler
Decanter
Aqueous Product
(H2O)
Inner Material
Balance Envelope
Outer Material
Balance Envelope
Additional Aqueous Reflux
82
Important factors for the selection of entrainer
Azeotropic composition containing more water

organic phase composition containing more
entrainer
Azeotropic temperature the lower the better

Aqueous phase composition containing as
little entrainer as possible

Entrainer pricing the lower the better
83
Using ethyl acetate as entrainer
WATER
(100.02 C)
EtAc
(77.20 C)
HAC (118.01 C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
69.99 C
Highest temp in
ternary system
Outer Material
Balance Line
Outer Material
Balance Line
Inner Material
Balance Lines
84
Using iso-butyl acetate as entrainer
iBuAc
(116.40 C)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
87.72 C
HAC (118.01 C)
WATER
(100.02 C)
Highest temp in
ternary system
Possible Steady-
State Cases with
Aqueous Reflux
85
Using n-butyl acetate as entrainer
nBuAc
(126.01 C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
.
1
0
.
2
0
.
3
0
.
4
0
.
5
0
.
6
0
.
7
0
.
8
0
.
9
90.51 C
HAC (118.01 C)
WATER
(100.02 C)
Highest temp in
ternary system
Possible Steady-
State Cases with
Aqueous Reflux
86
Important factors for the selection of entrainer
Azeotropic composition (NBA-best, EA-worst)

organic phase composition (IBA-best, EA-worst)

Azeotropic temperature (EA-best, NBA-worst)

Aqueous phase composition (IBA-best, EA-worst)

Entrainer pricing (EA-best, IBA-worst)
87
Optimum design for the individual system
Feed flow rate of 500 kg/h with equal molar of HAc and
H
2
O
Minimizing total annual cost (TAC)
TAC including annualized capital costs, utility costs, and
make-up entrainer cost
Column bottom HAc composition is fixed at 99.9 mol%
by varying reboiler duty
Column top aqueous outlet composition is fixed at 0.1
mol% HAc loss by varying entrainer make-up flow rate
Aqueous reflux (if any) is varied to obtain lowest reboiler
duty
Varying total column stages and feed location to
minimize TAC
88
Comparison of TAC for the alternative systems
Entrainer Optimum
Total
Stages
Optimum
Feed
Stage
Capital
Cost ($)
Utility
Cost ($)
Entrainer
Cost ($)
TAC
($)

EA

16

2

6.8410
4


4.2010
4

5.4010
4

1.6410
5

IBA

30

9

6.8110
4

1.8010
4

1.7010
4

1.0310
5

NBA

31

11

8.4410
4

2.7810
4

6.0810
4

1.7310
5
No
entrainer

50

37

1.4210
5

4.3710
4

0


1.8610
5
89
Optimum Operating Condition
Entrainer Entrainer
Make-up
Organic
Reflux
Aqueous
Reflux
Ethyl
Acetate
2.24
mol/min
574
mol/min
0.0
mol/min
i-Butyl
Acetate
0.16
mol/min
92.7
mol/min
33.4
mol/min
n-Butyl
Acetate
0.70
mol/min
102.3
mol/min
98.8
mol/min
90
Vapor and liquid profiles for the optimum system HAc-iBuAc-H2O
Difficult Region
for the Separation
is Avoided
91
Minimum aqueous reflux fraction under various feed compositions
Feed Water Composition
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A
q
u
e
o
u
s

R
e
f
l
u
x

F
r
a
c
t
i
o
n
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
92
Proposed overall control strategy

IBA Makeup
Organic
Reflux
Feed
(HAC+H
2
O mixture)
Steam
Distillate
(H
2
O Rich)
FC
FC
Bottom Product
(HAC)
Reboiler
FC
LC LC
LC
FC
Decanter
TC
6
RC
FC
FC
RC
93
Summary of control strategy
Simple control strategy with only one tray temperature
control loop in the system manipulating the aqueous
reflux flow
The temperature control point is selected from open-loop
sensitivity test
Organic level organic reflux flow
Aqueous level aqueous outlet flow
Bottom level bottom flow
Reboiler duty and entrainer makeup both are ratioed to
the feed flow
Both bottom and top products are maintained at high
purity despite 10% changes in the feed H
2
O
composition or in the feed flow rate
94
Conclusions
Using acetate as entrainer can help in the separation of
HAc and H
2
O via heterogeneous azeotropic distillation
Optimum design of three candidate entrainers are
compared using TAC as objective function
TAC with i-butyl acetate as entrainer is only about 55%
of the TAC for no entrainer system
Simple control strategy is developed with only one tray
temperature control loop
This control strategy is able to hold both bottom HAc
product and top aqueous product at high-purity despite
feed composition or feed flow rate disturbances
95
Process flowsheet of an industrial unit
Aqueous
Reflux
Condenser
F1
F2
F3
F4
F5
Sidedraw
Aqueous
Outlet
IBA Makeup
Organic
Reflux
Decanter
Steam
Reboiler
Bottom
Product
Design and Operation of
this Side Stream
96
Paper References
1. Chien, I-Lung; Zeng, K. L.; Chao, H. Y. Design and Control of a Complete
Heterogeneous Azeotropic Distillation Column System. Ind. Eng. Chem. Res.
2004, 43 (9), 2160-2174.
2. Arifin, Saiful; Chien, I-Lung Combined Preconcentrator/Recovery Column Design
for Isopropyl Alcohol Dehydration Process. Ind. Eng. Chem. Res. 2007, 46 (8),
2535-2543.
3. Arifin, Saiful; Chien, I-Lung Design and Control of an Isopropyl Alcohol
Dehydration Process via Extractive Distillation Using Dimethyl Sulfoxide as an
Entrainer. Ind. Eng. Chem. Res. 2008, 47 (3), 790-803.
4. Chien, I-Lung; Zeng, K. L.; Chao, H. Y.; Liu, J. H. Design and Control of Acetic
Acid Dehydration System via Heterogeneous Azeotropic Distillation Column.
Chem. Eng. Sci. 2004, 59 (21), 4547-4567.
5. Chien, I-Lung and Kuo, Chien-Lin Investigating the Need of a Pre-Concentrator
Column for Acetic Acid Dehydration System via Heterogeneous Azeotropic
Distillation. Chem. Eng. Sci. 2006, 61 (2), 569-585.
6. Chien, I-Lung; Huang, Hsiao-Ping; Gau, Tang-Kai; Wang, Chun-Hui. Influence of
Feed Impurity on the Design and Operation of an Industrial Acetic Acid
Dehydration Column. Ind. Eng. Chem. Res. 2005, 44 (10), 3510-3521.
7. Huang, Hsiao-Ping; Lee, Hao-Yeh; Gau, Tang-Kai; Chien, I-Lung Design and
Control of Acetic Acid Dehydration Column with p-Xylene or m-Xylene Feed
Impurity. 1. Importance of Feed Tray Location on the Process Design. Ind. Eng.
Chem. Res. 2007, 46 (2), 505-517.
8. Huang, Hsiao-Ping; Lee, Hao-Yeh; Chien, I-Lung Design and Control of Acetic
Acid Dehydration Column with p-Xylene or m-Xylene Feed Impurity. 2. Bifurcation
Analysis and Control. Ind. Eng. Chem. Res. 2008, 47 (9), 3046-3059.

97
Book References
Doherty, M. F. and M. F. Malone, Conceptual Design of
Distillation Systems, McGraw-Hill, 2001.

Douglas, J. M., Conceptual Design of Chemical
Processes, McGraw-Hill, 1988.

Turton, R., R. C. Bailie, W. B. Whiting, and J. A.
Shaeiwitz, Analysis, Synthesis, and Design of Chemical
Processes, Prentice Hall, 1998.

Luyben, W. L., Plantwide Dynamic Simulators in
Chemical Processing and Control, Marcel Dekker, 2002.
98
Upcoming New Book to be Published
End of 2009
Williams L. Luyben and I-Lung Chien, Design and
Control of Distillation Systems for Separating
Azeotropes, John Wiley & Sons, Inc., 2009.

Fourteen chapters of real examples using various
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