C AP E C

Synthesis and Design of

Distillation based
Separation Schemes
Erik Bek-Pedersen
January 15, 2003
Computer Aided Process Engineering Center (CAPEC)
Department of Chemical Engineering
Technical University of Denmark

Outline
Separation synthesis and design
- Background
- Methods available for design of separation schemes

Definition of driving force

Objectives of this work

The driving force approach to synthesis/design problems
- Highlights of driving force based algorithms illustrated through examples
Framework of design and synthesis methods
Conclusions
Suggestions for future work

Separation synthesis and design

Separations take place in nearly every chemical plant.
A major separation technique is distillation and hybrid distillation schemes.
Separation (distillation) requires a lot of energy.

Separation system synthesis/design problem:

The problem is to determine the separation tasks, the
techniques employed to perform the tasks and the sequence of
the tasks that would achieve the desired separation, and the
design of the individual separation units.

Methods for design of separation schemes

Synthesis of separation schemes
- Heuristics

e.g. Barnicki and Fair 1990, 1992, Douglas 1985, King 1980

- Optimisation techniques

e.g. Aggerwal and Floudas 1990

- Insights based methods

e.g. Jaksland 1996, Hostrup 2001

Design of distillation columns

- Graphical design

- frequently used to get a visual idea of the process behavior

Binary

e.g. McCabe and Thiele 1925, Ponchon and Savarit 1921, 1922

Ternary

e.g. Laroche et al. 1992, Stichlmair et al. 1989

- Empirical design methods

- frequently used to obtain a design fast

Binary

e.g. Underwood 1932-1948, Kirkbride 1944

Complex

e.g. Glinos and Malone 1985, Meiers et al. 1995

- Mathematical formulations e.g. Dnnebier and Pantelides 1999

Definition of driving force (I)

Phase 1

Phase 1
Feed

Feed

Phase
Creation

(b)
(a)

Phase 2

MSA
(Solvent)

Phase 1
Feed

Barrier

(c)

Phase 2

Feed

Phase 2

Phase 1
Phase 1

(d)

Phase 2

Feed

Force field
or gradient

(e)
Phase 2

Different separation mechanisms exist, and the generation of a

two-phase (composition dependent ) separation can be
achieved in different ways.

Definition of driving force (II)

Bulk Phase 1

xi

Transport
Mechanisms

yi

Equilibrium
and
Reaction

FDi = yi x i =

Bulk Phase 2

P HASE T RANSITION

x iij
1 + x i ( ij 1)

xi

Definition of driving force (III)

FDi = yi x i =
Size of the largest
driving force (DY)

Driving Force, FDi

0.3

Largest driving force (D)

0.2

0.1

Location of the largest

driving force (DX)
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Light compound composition, xi

0.9

1.0

x iij
1 + x i (ij 1)

xi

Operation with the

largest driving
force leads to the
easiest separation,
and the optimal
design
(including energy
consumption).

Objectives
Design/Synthesis/Analysis Problems:
Distillation Column Design
Complex Distillation Column Design
Separation Synthesis
Operating Conditions
Retrofit Distillation Design
Controllability Analysis
Etc....

Apply the driving

force principle to
develop algorithms
that solve these
problems.

Propose methods for optimal (or near optimal) solutions for the
synthesis and design of separation processes in general, and
distillation based separation in particular.

Design of simple distillation columns (I)

Given a mixture to be separated into two products in a distillation column with N
trays. What is the optimal (with respect to the costs of operation) feed plate location
and the corresponding reflux ratio for different product purity specifications ?
0.4

Pinch point

Driving Force, FDi

0.3

DY

Slope correponding
to RRmin

Slope correponding
to RR > RRmin

D'

0.2

I
D

0.1

Dx
II

0.0

0.1

0.2

0.3

0.4

0.5

NF

NF = N(1-Dx)

II

DX F ' F
X
X

A
0.0

0.6

0.7

0.8

Light compound composition, xi

0.9

1.0

B
B

Design of simple distillation columns (IIa)

Design of simple distillation columns (IIb)

10

x(MeOH)=0.80
x(MeOH)=0.50
x(MeOH)=0.22

Reboiler duty (GJ/hr)

x(MeOH)=0.15

10

12

14

16

Feed stage, NF

18

20

Design of simple distillation columns (IIb)

Design of simple distillation columns (IIIa)

Design of simple distillation columns (IIIb)

2100

Reboiler duty (MJ/hr)

2050

2000

1950

1900

1850

1800
22

24

26

Feed stage, NF

28

30

Design of simple distillation columns (IIIb)

Design of side-draw distillation columns (I)

D

III

FDi

0.12

Bottom
Product
Top Product

Ds, Position
of the
side-draw

II
0.00
0.00

Relative composition

1.00

0.12

Specify: top and bottom

compositions.
Determine: Dx (NF), Ds (NS)
and RRmin.

FDi

Primary Separation

Dx, The relative

position of the
feed stream
0.00
0.00

Secondary
Separation

Composition (x light key)

1.00

Design of side-draw distillation columns (II)

D

III
F

FDi

0.12

Bottom
Product
Top Product
Ds, Position
of the
side-draw

II
0.00
0.00

Relative composition

1.00

0.12

NS = N(1-Ds)
NF = N(1-Dx)

FDi

Primary Separation

Dx, The relative

position of the
feed stream
0.00
0.00

Secondary
Separation

Composition (x light key)

1.00

Design of side-draw distillation columns (III)

Specified:
N = 36
XD (Pentane) = 0.995
XB (Heptane) = 0.88
Determined:
NS = 24
NF = 14
RRmin = 2.1
(Tedder & Rudd, 1978)

1
F=100
kmole/h

III

(0.05,
0.90,
0.05)

II

Pentane
XD = 0.995

P=5 bar
Hexane
S = 90

I
36

Heptane
XB = 0.88

Design of side-draw distillation columns (IV)

Validation of methodology through rigorous simulation
26

Reboiler Duty (GJ/h)

Reboiler Duty (GJ/h)

58

38

18

19

17

20

23

26

11

14

17

20

NS

NF

Predicted NS = 24,
Actual Optimum NS= 22

Predicted NF = 14,
Actual Optimum NF = 14

RR = 151, V/F = 7.8

Retrofit of distillation columns (I)

0.6

0.6

Xi Max
Max FDi

0.5

0.4

0.4

0.3

0.3

0.2

0.2

0.1

0.1

0.0

0.0
0

Alfa (Constant)

10

12

Max FDi

Xi Max

0.5

Retrofit of distillation columns (II)

Retrofit of distillation columns (II)

Retrofit of distillation columns (I)

0.6

0.6

Xi Max
Max FDi

0.5

0.4

0.4

0.3

0.3

0.2

0.2

0.1

0.1

0.0

0.0
0

Alfa (Constant)

10

12

Max FDi

Xi Max

0.5

Retrofit of distillation columns (III)

Design of thermally coupled columns (I)

The Petlyuk Column:

Combines two column shells
in one separation unit with one
reboiler and one condenser, in a
fully thermally coupled system.
The work of separation with
this configuration is the
minimum (Petlyuk et al., 1965).

III

IV

A
B
C

B
II

VI

Design of thermally coupled columns (II)

How
much
?

Which
Plate
?
How
much
?

Which
Plate
?

Which
Plate
?

How
much
?

How
many
Plates
?
How
much
?

How
much
?

Which
Plate
?

How
many
Plates
?

Design of thermally coupled columns (II)

How
much
?

Which
Plate
?
How
much
?

Which
Plate
?

How
much
?

Which
Plate
?

Which
Plate
?

How
much
?

How
many
Plates
?
How
much
?

How
much
?

Which
Plate
?

How
many
Plates
?

Which
Plate
?
How
much
?

Which
Plate
?

How
much
?

How
many
Plates
?
How
much
?

How
much
?

Wh ch
P ate
?

How
many
Plates
?

Design of thermally coupled columns (III)

(Kim, 2001)

Nmain = 72
Npre-frac = 20

0.10

sButanol-iButanol
iButanol-nButanol
Combined prefractionator

A
6

III

0.08

NF2
4

IV

I
1

0.06
B

NS

NF1

FDi

A
B
C

II

0.04

NF3
3

0.02
VI

0.00
0.0

0.2

0.4

0.6

Light key compound composition

0.8

1.0

Design of thermally coupled columns (III)

Nmain = 72
Npre-frac = 20

0.10

III

sButanol-iButanol
iButanol-nButanol
Combined prefractionator

0.08

NF2
4

IV

0.06
1

NS

NF1

FDi

A
B
C

II

0.04

NF3
3

0.02
VI

0.00
0.0

0.2

0.4

0.6

Light key compound composition

0.8

1.0

Design of thermally coupled columns (III)

0.10

Nmain = 72
Npre-frac = 20

A
6

III

sButanol-iButanol
iButanol-nButanol
Combined prefractionator

0.08

NF2
4

IV

A
B
C

0.06
B

NS

NF1

FDi

II

0.04

V
5

NF3
3

0.02
VI

0.00
0.0

0.2

0.4

0.6

Light key compound composition

0.8

1.0

Design of thermally coupled columns (IIIb)

Design of thermally coupled columns (IV)

0.10

Combined prefrationator
iButanol-nButanol
sButanol-iButanol

0.08

Which
Plate
?

A
6

III

Which
Plate
?

NF2
4

0.06

IV

FDi

I
A
B
C

0.04

NS

NF1

II

V
5

0.02

Which
Plate
?

NF3
3

0.00
0.0

0.2

0.4

0.6

Light key compound composition

0.8

1.0

Which
Plate
?

VI

Design of thermally coupled columns (IV)

0.10

Combined prefrationator
iButanol-nButanol
sButanol-iButanol

0.08

(Kim, 2001)

Nmain = 72
Npre-frac = 20

A
6

III
2

NF2

0.06

FDi

0.04

IV

I
A
B
C

0.02

II

0.00
0.0

0.2

0.4

0.6

0.8

NS

NF1

1.0
5

Light key compound composition

NF3
3

VI

Validation:

Sequencing of distillation column trains (I)

Example reported by

0.18

Shah and Kokossis, 1997

A/B (T1)
C/D (T2)
B/C (T3)
F/G (T4)
D/E (T5)
G/H (T6)
E/F (T7)

0.16

Driving Force, FDi

0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
0.0

0.2

0.4

0.6

0.8

Composition of light key compund

* For determination of the near optimum sequence of distillation

columns, the splits are ordered by the size of the driving forces
at uniform pressure. Note, the azeotropic split is placed last in
the sequence.
* Each column is then designed such that the use of the largest
driving force is achieved.

1.0

Sequencing of distillation column trains (II)

Algorithm S1
A

Shah & Kokossis, 1997

T1

T3

C
T2

D
T5

T7

T4
G

T2

T3

T1

D
T5

T7

T4
G

T6

T6

1. The flowsheet obtained from the driving force approach

differ from the one reported in the literature.
2. Rigorous simulations show that the driving force based
sequence consumes 8 % less energy.
3. Note, this flowsheet was obtained visually, without any
rigorous simulations or optimisation.

Hybrid separation schemes (I)

Distillation, 1 atm.
Distillation, 5 atm.
Pervaporation
Extractive distillation

0.30

Driving Force, FDi

0.25

0.20

0.15

0.10

0.05

0.00
0.0

0.2

0.4

0.6

Liquid composition, xi

0.8

1.0

By simple
comparison of
driving forces for
various separation
techniques, an
optimal hybrid
separation scheme
is visually
generated .
(Mixture of MTBE
and MeOH)

Hybrid separation schemes (II)

Distillation, 1 atm.
Distillation, 5 atm.
Pervaporation
Extractive distillation

0.30

0.20

Distillation

Driving Force, FDi

0.25

0.15

0.10

Pervaporation

0.05

0.00
0.0

0.2

0.4

0.6

0.8

1.0

Liquid composition, xi

The configuration exhibiting the largest driving force, is the

combination of pervaporation and distillation.
Detailed simulations have shown that this configuration is at
least 35 % more energy efficient than any other configuration
considered.

Controllability analysis (I)

Theory: Largest driving force Easier separation Lower energy
consumption Easier to control
Verification: Linear controllability analysis.
Method: Perform simulations of a binary distillation column,
calculate the Relative Gain Array, perform the controllability
analysis.

System:
Methanol
Water
Temperature
Pressure

Products:
50 Kmol/hr
50.5 Kmol/hr
300 K
1 atm.

Methanol
Water

0.950
0.947

Controllability analysis (II)

By varying the reboiler and
condenser specifications in
DYNSIM, simulations have
been made that meet the
required purities for
different designs.

0.4

FDi

0.3

0.2

0.1

0.0
0.0

0.2

0.4

0.6

Methanol liq. composition

NF = 10(1-.25)
NF = 7.5 ~ 7

0.8

1.0

RGA analysis has been

performed on base case
(feed stage 7), and for
comparison with feed on
stage 3.

Controllability analysis (III)

Specifications: QB and L

Specifications: QB and D

Feed tray 7, QB = 3500, L = 37

Feed Tray 7, QB = 3500 D = 49.7677

Feed tray 3, QB = 5032, L = 80

Feed tray 3, QB = 5032 D= 49.8296

Level 2

Level 1

Framework of Methodologies
Synthesis of
Distillation Based
Separation Schemes

Design of Distillation
Columns

Retrofit of
Distillation Columns

Sequencing of
Distillation
Columns

Hybrid
Separation
Schemes

Simple
Distillation
Column Design

Complex
Distillation
Column Design

Reactive
Distillation
Column Design

Operating
Conditions

Thermally
coupled column
design

Retrofit Design
of Distillation
Columns

algorithm S1

algorithm S1

algorithm D1

algorithm D2

algorithm D3

algorithm D4

algorithm D5

algorithm R1

Given:
Compounds in
splits, Inlet
Pressure

Given:
P, NP, x Dist, xBot,
xside

Given:

Find:
Operating
Pressure in
Distillation Seq.

Find:

Find:

Given:
Composition
and Key
Compounds

Given:
xDist, xBot,
Experimental
Phase Eq. Data

Given:

Given:

Given:

P, NP, xDist, xBot

P, NP, x Dist, xBot

P, NP, x Dist, xBot

(element basis)

Find:
Order of splits in
the distillation
scheme

Find:
Combination of
Units to achieve
separation

Find:

Find:

Find:

RRmin, NF

RRmin, NF, NS

NF, RR min
(element basis)

RRmin, NFs, NS

NP, RR min

NF, x Dist, xBot

Conclusions (I)
Achievements:
Synthesis: New methods have been developed for
sequencing of distillation trains and generation of
hybrid separation schemes.
Design: For a large number of (distillation) design
problems, driving force based methods have been
developed.
Analysis: Performing driving force analysis can provide
valuable insights, as to whether processes are feasible.
Retrofit: Design/analysis of distillation column retrofits
predicts feasible separations (mixtures).

Conclusions (II)

A new driving force based approach has been developed for

synthesis and design of distillation based separation systems.

The methods are graphical, easy to apply and accurate. They

produce near-optimum solutions, without performing any rigorous
simulation.

The design is based on identification (visual or numeric) of the

largest driving force - leading to near minimum energy
consumption (and easiest separation) - i.e. near optimum design.

Applies to a large range of separation synthesis/design problems.

Forms an excellent basis of an associated structural mathematical

optimisation problem.

Suggestions for future work

Extension of the driving force approach:
Taking heating and cooling duties into consideration, to
make heat-integrated distillation column sequences.
Extend the method to also consider design of batch
distillation.
Extend the concept of scaling factors to include, for
example, a scaling of the cost of alternative separation
methods/techniques.
Extend the controllability analysis for various distillation
column configurations.

The End

Reactive Distillation
The Driving force based approach to Reactive
Distillation Column design is based on the Elements
concept (Prez-Cisneros et al., 1997)
Vapour Composition, WA (I-Butene)

1.00

0.00
0.00

MTBE
i-Butene

MeOH
Liquid Composition, WA (I-Butene)

1.00

The reaction in terms of components and elements can be written as:

I-Butene (C4H8=A) + MeOH (CH3OH=B) ! MTBE (C5H12O=AB)
A + B ! AB

Reactive Distillation Algorithm I

Take the data from the binary
Elements vapour-liquid
diagram, and transfer it into a
Elements based Driving force
diagram

Vapour Composition, WA (I-Butene)

1.00

MTBE
i-Butene

MeOH

0.00
0.00

Liquid Composition, WA (I-Butene)

1.00

0.3

FDi

0.3

MTBE
MeOH

FDi

i-Butene
0.0

MTBE

Dx

i-Butene

0.0

0.0
0.0

Liquid Composition, WA (I-Butene)

1.0

Liquid Composition, WA (I-Butene)

1.0

Reactive Distillation Algorithm II

1.Check if the reactive separation can be exploited on basis of two Elements (possibly
with inert compound(s)). If yes, go to 2, otherwise stop.
2.Generate or retrieve vapour-liquid Element data at the desired operating pressure.
3.Calculate the corresponding driving force diagram
4.Identify the area of operation on the driving force diagram.
5.For visualization purposes, rescale the x-axis accordingly, such that the area of
operation covers the [0;1] composition space.
6.Identify the points Dy and Dx
7.Determine NF from NF = (1 - Dx) NP.
8.Give the product specifications (points A and B). Determine RRmin.
9.Identify whether non-reactive stages are needed (or used) below and /or on top of the
reactive section in the column, i.e., identify whether A and B correspond to the final
desired products on compound basis.
10.If no non-reactive stages are needed, the design is now complete.
11.If A and/or B doest not correspond to the desired compound product, non-reactive
stages can be added in the top and/or bottom.

Example of Algorithm - MTBE

I-Butene (C4H8=A) + MeOH (CH3OH=B) ! MTBE (C5H12O=AB)
A + B ! AB
Number of Stages = 5
(all reactive)

FDi

0.3

MTBE

Dx

Dx'

i-Butene

0.0
0.0

Liquid Composition, WA (I-Butene)

RRmin = 0.5
(Elements)

1.0

Isobutene

70 kmol/hr

Methanol

30 kmol/hr

Temperature

300 K

Pressure

1 Atm.

Degree of Vaporization

0.83

NF = 5(1-0.38)
NF = 3.1 ~ 3

Validation of Algorithm - MTBE

Spec 1: Recovery of MTBE
(and MeOH) = 0.997

Reboiler Duty (Gcal/kr)

0.45

Spec 2: Reflux Ratio = 2.5 (molar)

0.40

0.35
1

3
Feed Stage

NF = 5(1-0.38)
NF = 3.1 ~ 3

Clearly, it is verified that, from an energy point of view,

and with consistent specifications on the column, the actual
optimum feed stage matches with the prediction.

Reverse Extractive Distillation

1

4
5
6
7
8
9

S2

10
11
12
13
14
15

S17

16
17
18
19
20
21
22
S1

2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39

2
3

S5

Hunek et al. (1989) proposed the

flowsheet for separation of EtOH
and IPA from water

2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29

2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
42
44
46
48
50
52
54
56
58
59

S16

S10

S14

S7
C1
M2

23

40

C2

30

C3

C4

60
S15

E1
S3

S9

S6
S8

- The driving force based analysis

verifies the feasibility of the
proposed flowsheet

2
3
4

S11

5
6
7
8
S13
9
10
11

E2

M1

SC1

12
S4

13
C5

14
S12

Driving force based separation efficiency diagram on solvent (MeOH) free

basis for Column T1, P = 1 atm.

Driving force based separation efficiency on solvent (MeOH) free basis

for Column T2, P = 1 atm.

0.40

Water Ethanol

0.40

Water Isopropanol

Water Ethanol

Water 1-Propanol

Water Isopropanol

0.30

0.30

ABS(yi-xi)

ABS(yi-xi)

Water 2-Butanol

0.20

Water 2-Methyl-1-Butanol
Water 1-Butanol

0.20

Water 2-Methyl-1-Propanol
Water 2-Pentanol
0.10

0.10

0.00
0.00

0.00
0.20

0.40

0.60

xi

0.80

1.00

0.00

0.20

0.40

0.60

xi

0.80

1.00

Methodology: Distillation Pressure Allocation

0.3
Top Pressure in
Column K

Bubble Point Pressure

ABS(yi-xi)

Dy

Top Pressure
in Column
k+1

Dx

0.0
0.0

x(Light key component)

1.0

1.0

An important factor in operation of distillation columns is the pressure.

A methodology for determination of operating pressures in single
distillation columns as well as distillation trains has been developed.
The methodology is based on a driving force approach that generates
energy efficient design.

Application - IV: Pressure Allocation

C2

C3
C4's
T-3
Depropanizer

T-2
Deethanizer

T-4
Debutanizer

C5+
V-3

2930
2500
13.68%

V-4

Pressure (KPa)
1758
1550
Energy saved
6.94%

792
1000
-