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. Dünnebier and Pantelides 1999
Definition of driving force (I)

Phase 1 Phase 1 Phase 1

Feed Phase Feed Feed Barrier

Creation
(b)
(a) MSA (c)
Phase 2 (Solvent) Phase 2 Phase 2
Feed Phase 1

Phase 1
Feed Force field
or gradient

(d) Phase 2 (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)

P HASE T RANSITION

Bulk Phase 2
xi Transport
Mechanisms

Bulk Phase 1

Equilibrium yi
and
Reaction

x iβij
FDi = yi − x i = − xi
1 + x i (β ij − 1)
Definition of driving force (III)

x iβij
FDi = yi − x i = − xi
Size of the largest 1 + x i (βij − 1)
0.3 driving force (DY)
Largest driving force (D)

Operation with the

largest driving
Driving Force, FDi

0.2

force leads to the

0.1
easiest separation,
Location of the largest
driving force (DX) and the optimal
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6

Light compound composition, xi

0.7 0.8 0.9 1.0
design
(including energy
consumption).
 Objectives
Design/Synthesis/Analysis Problems:
• Distillation Column Design
• Complex Distillation Column Design
• Separation Synthesis Apply the driving
• Operating Conditions force principle to
• Retrofit Distillation Design develop algorithms
• Controllability Analysis
that solve these
• Etc....
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

A
Pinch point A
0.3 Slope correponding
DY D to RRmin
Driving Force, FDi

Slope correponding
0.2 D' to RR > RRmin
I I

D D’ NF
0.1 Dx NF = N(1-Dx)
II II
A DX F ' F B
X X
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
B
Light compound composition, xi
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
8 x(MeOH)=0.15
Reboiler duty (GJ/hr)

10 12 14 16 18 20

Feed stage, NF
Design of simple distillation columns (IIb)
Design of simple distillation columns (IIIa)
Design of simple distillation columns (IIIb)
2100

2050
Reboiler duty (MJ/hr)

2000

1950

1900

1850

1800
22 24 26 28 30

Feed stage, NF
Design of simple distillation columns (IIIb)
Design of side-draw distillation columns (I)
0.12

Bottom
III D Product

FDi
Top Product
F
Ds, Position
of the
II side-draw
0.00
0.00 1.00
Relative composition
S
I 0.12

Primary Separation

B
FDi
Dx, The relative
Specify: top and bottom position of the
feed stream
Secondary
Separation
compositions. 0.00

Determine: Dx (NF), Ds (NS)

0.00 Composition (x light key) 1.00

and RRmin.
Design of side-draw distillation columns (II)
0.12

III D Bottom
Product

FDi
Top Product
F
Ds, Position

II
of the
side-draw
0.00
0.00 1.00
Relative composition
S
I 0.12

Primary Separation

B
FDi
Dx, The relative
position of the Secondary

NS = N(1-Ds)
feed stream Separation

0.00
0.00 Composition (x light key) 1.00

NF = N(1-Dx)
Design of side-draw distillation columns (III)
Specified:
N = 36 1
Pentane
XD = 0.995
XD (Pentane) = 0.995 F=100 III
kmole/h
XB (Heptane) = 0.88 P=5 bar
(0.05, II
0.90, Hexane
Determined: 0.05)
I
S = 90

NS = 24
Heptane
NF = 14 36
XB = 0.88
RRmin = 2.1
(Tedder & Rudd, 1978)
Design of side-draw distillation columns (IV)
Validation of methodology through rigorous simulation
26

58

Reboiler Duty (GJ/h)

Reboiler Duty (GJ/h)

38

18 19
17 20 23 26 8 11 14 17 20
NS NF

Predicted NS = 24, Predicted NF = 14,

Actual Optimum NS= 22 Actual Optimum NF = 14
RR = 151, V/F = 7.8
Retrofit of distillation columns (I)

0.6 0.6
Xi Max
0.5 Max FDi 0.5

0.4 0.4
Xi Max

Max FDi
0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0 2 4 6 8 10 12
Alfa (Constant)
Retrofit of distillation columns (II)
Retrofit of distillation columns (II)
Retrofit of distillation columns (I)

0.6 0.6
Xi Max
0.5 Max FDi 0.5

0.4 0.4
Xi Max

Max FDi
0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0 2 4 6 8 10 12
Alfa (Constant)
Retrofit of distillation columns (III)
Design of thermally coupled columns (I)

A
The Petlyuk Column: III

• Combines two column shells

in one separation unit with one I
IV

reboiler and one condenser, in a A

B B
fully thermally coupled system. C
II V

• The work of separation with

this configuration is the
minimum (Petlyuk et al., 1965). VI

C
Design of thermally coupled columns (II)

How Which How

much Plate much
? ? ?

How Which
Which much Plate
Plate ? ?
?

How
How
much
many
?
Plates
? How
many
How Plates
Which
much ?
Plate
? ?
Design of thermally coupled columns (II)

How Which How How Which How

much Plate much much Plate much
? ? ? ? ? ?

How Which How Which

Which much Which much
Plate Plate
Plate ? Plate ?
? ?
? ?

How How
How How
much much
many many
? ?
Plates Plates
? How ? How
many many
How Plates How Plates
Which Wh ch
much ? much ?
Plate P ate
? ? ? ?
 Design of thermally coupled columns (III)
(Kim, 2001)

Nmain = 72 0.10
Npre-frac = 20 A sButanol-iButanol
6
III iButanol-nButanol
Combined pre-
0.08
2

NF2
fractionator
4

IV
I 0.06
A
1
FDi

B NF1 NS B
7
C
II V 0.04
5

NF3
3

0.02
VI

0.00
8 0.0 0.2 0.4 0.6 0.8 1.0
C
Light key compound composition
 Design of thermally coupled columns (III)

Nmain = 72
Npre-frac = 20 A 0.10
6
III sButanol-iButanol
iButanol-nButanol
2
Combined pre-
NF2 0.08
fractionator
4

IV
I
A 0.06
1
B NF1 NS B
FDi
7
C
II V
0.04
5

NF3
3

0.02
VI

0.00
8
0.0 0.2 0.4 0.6 0.8 1.0
C
Light key compound composition
 Design of thermally coupled columns (III)

Nmain = 72 0.10
sButanol-iButanol
Npre-frac = 20

2
III
6
A

? 0.08
iButanol-nButanol
Combined pre-
fractionator
NF2
4

IV 0.06
I
A

FDi
1
B NF1 NS B
7
C
0.04
II V
5

NF3
3
0.02

VI

0.00
0.0 0.2 0.4 0.6 0.8 1.0
8
C
Light key compound composition
Design of thermally coupled columns (IIIb)
 Design of thermally coupled columns (IV)
0.10
Combined pre- Which A
frationator
iButanol-nButanol Plate III
6

0.08
sButanol-iButanol ? Which
2

NF2 Plate
0.06
4
?
IV
I
FDi

A
1
B NF1 NS B
0.04 C
7

II V
5
0.02
3
NF3 Which
Plate
0.00 Which VI ?
0.0 0.2 0.4 0.6 0.8 1.0
Plate
Light key compound composition
? 8
C
Design of thermally coupled columns (IV)
Nmain = 72
0.10
Combined pre-
frationator
iButanol-nButanol
(Kim, 2001) Npre-frac = 20
III
6
A

0.08
sButanol-iButanol
2

NF2
0.06
4
FDi

0.04
IV
I
A
1
0.02 B NF1 NS B
7
C
0.00 II V
0.0 0.2 0.4 0.6 0.8 1.0

Light key compound composition 5

NF3
3

VI

8
C

Validation:
Sequencing of distillation column trains (I)
Example reported by 0.18

A/B (T1)

Shah and Kokossis, 1997

0.16
C/D (T2)
B/C (T3)
0.14
F/G (T4)
D/E (T5)

Driving Force, FDi

0.12
G/H (T6)
0.10 E/F (T7)

0.08

0.06

0.04

0.02

0.00
0.0 0.2 0.4 0.6 0.8 1.0

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.
Sequencing of distillation column trains (II)
Algorithm S1 Shah & Kokossis, 1997
A B A B

≠
T1 T3 T2 T3

C C
T1
T2 D E D E

T5
T5 T7 T7

F F
T4 T4
G
G

T6 T6

H C

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)

By simple
0.30 Distillation, 1 atm. comparison of
Distillation, 5 atm.
Pervaporation
Extractive distillation
driving forces for
0.25
various separation
techniques, an
Driving Force, FDi

0.20

0.15 optimal hybrid

separation scheme
0.10
is visually
0.05
generated .
0.00
0.0 0.2 0.4 0.6 0.8 1.0 (Mixture of MTBE
Liquid composition, xi and MeOH)
Hybrid separation schemes (II)
0.30 Distillation, 1 atm.
Distillation, 5 atm.
Pervaporation
0.25 Extractive distillation
Driving Force, FDi

0.20

Distillation
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: Products:
Methanol 50 Kmol/hr Methanol 0.950
Water 50.5 Kmol/hr Water 0.947
Temperature 300 K
Pressure 1 atm.
Controllability analysis (II)
By varying the reboiler and
0.4
condenser specifications in
0.3
DYNSIM, simulations have
been made that meet the
FDi

0.2
required purities for
0.1 different designs.
0.0
0.0 0.2 0.4 0.6 0.8 1.0
RGA analysis has been
Methanol liq. composition
performed on base case
(feed stage 7), and for
comparison with feed on
NF = 10(1-.25) stage 3.
NF = 7.5 ~ 7
 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

 Framework of Methodologies

Synthesis of
Design of Distillation Retrofit of
Level 1

Distillation Based
Columns Distillation Columns
Separation Schemes

Sequencing of Hybrid Simple Complex Reactive Thermally Retrofit Design

Operating
Distillation Separation Distillation Distillation Distillation coupled column of Distillation
Conditions
Columns Schemes Column Design Column Design Column Design design Columns

algorithm S1 algorithm S1 algorithm D1 algorithm D2 algorithm D3 algorithm D4 algorithm D5 algorithm R1

Level 2

Given: Given: Given: Given: Given: Given: Given: Given:

Composition xDist, xBot, Compounds in P, NP, x Dist, xBot,
and Key Experimental P, NP, xDist, xBot P, NP, x Dist, xBot P, NP, x Dist, xBot splits, Inlet xside NP, RR min
Compounds Phase Eq. Data (element basis) Pressure

Find: Find: Find: Find: Find: Find: Find: Find:

Order of splits in Combination of Operating
the distillation Units to achieve RRmin, NF RRmin, NF, NS NF, RR min Pressure in RRmin, NF’s, NS NF, x Dist, xBot
scheme separation (element basis) Distillation Seq.
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 (Pérez-Cisneros et al., 1997)
1.00

Vapour Composition, WA (I-Butene) MTBE

i-Butene

MeOH
0.00
0.00 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
1.00
Vapour Composition, WA (I-Butene)

MTBE
i-Butene diagram, and transfer it into a
Elements based Driving force
0.00
MeOH diagram
0.00 Liquid Composition, WA (I-Butene) 1.00

0.3

0.3

FDi
MTBE

MeOH
i-Butene
FDi

0.0
MTBE i-Butene 0.0 Liquid Composition, WA (I-Butene) 1.0
Dx

0.0
0.0 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
0.3
(all reactive)
Isobutene 70 kmol/hr
Methanol 30 kmol/hr
FDi

MTBE Dx Dx' i-Butene Temperature 300 K

0.0
0.0 Liquid Composition, WA (I-Butene) 1.0
Pressure 1 Atm.
Degree of Vaporization 0.83

RRmin = 0.5 NF = 5(1-0.38)

(Elements) NF = 3.1 ~ 3
Validation of Algorithm - MTBE
0.45 Spec 1: Recovery of MTBE
(and MeOH) = 0.997
Reboiler Duty (Gcal/kr)

0.40
Spec 2: Reflux Ratio = 2.5 (molar)

0.35
1 2 3 4 5
NF = 5(1-0.38)
Feed Stage
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
Hunek et al. (1989) proposed the
1 1 1 1

2 2 2 S14
2 3 4
4 3
3 5 4 6
6 8
4 7 5
10
5 8 6
9 12
7 14
6 10 8
11 S5 16
7 12 9 18
13 10 20
8 14
15 11 22
9 S2 16 12 24
10 17 13 26
18
11 19 14 28
20 15 30
12 21 16 32

flowsheet for separation of EtOH

22
13 23 17 34
24 18 36
14 25 19 38
15 26 40
S17 27 20 S16
16 28 21 42
29 22 44
17 30 46
31 23
18 32 48
24 S10
33 50
19 34 25
52
20 35 26 54
36 27
21 37 56
38 28 58
22 39 29 59
S1 S7
C1 23 C2 40 C3 30 C4 60

M2 E1 S15

and IPA from water

S3

S9

S6

S8

- The driving force based analysis

2

4
S11
5

8
S13
9

10

verifies the feasibility of the

11
E2 M1
SC1
12
S4
13

C5 14

S12

proposed flowsheet
Driving force based separation efficiency diagram on solvent (MeOH) free Driving force based separation efficiency on solvent (MeOH) free basis
basis for Column T1, P = 1 atm. for Column T2, P = 1 atm.
0.40 Water Ethanol
0.40

Water Ethanol Water Isopropanol

Water 1-Propanol
Water Isopropanol
0.30 0.30
Water 2-Butanol

Water 2-Methyl-1-Butanol
ABS(yi-xi)

ABS(yi-xi)

0.20 0.20 Water 1-Butanol

Water 2-Methyl-1-Propanol

Water 2-Pentanol
0.10 0.10

0.00
0.00
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

xi xi
 Methodology: Distillation Pressure Allocation
0.3
Dy Top Pressure in
Column K

Bubble Point Pressure

ABS(yi-xi)
Top Pressure
in Column
k+1

Dx
0.0 1.0
0.0 x(Light key component) 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-2 T-3
T-4
Deethanizer Depropanizer
Debutanizer

C5+

V-3 V-4

Pressure (KPa)
2930 1758 792
2500 1550 1000
Energy saved
13.68% 6.94% -