Heterogeneous Azeotropic

Distillation Column Design

Paritta Prayoonyong

Supervisor:
Dr. Megan Jobson

L07 - 1 XXIV PIRC Annual Research Meeting 2007

 Outline
1. Introduction and objective
2. Column design methods: review
3. Column design method:
New boundary value method
a. Simple column
b. Double-feed column
c. Column with an intermediate decanter
4. Case study
5. Conclusions and future work

L07 - 2 Heterogeneous Azeotropic Distillation Column Design

 1. Introduction and Objective

L07 - 3 Heterogeneous Azeotropic Distillation Column Design

 Azeotropes
Pentane / dichloromethane mixture

T
P liquid and vapour
Vapour
compositions are the same
Liquid xi = yi
Azeotrope x, y

P cannot be separated by
conventional distillation

xpentane
L07 - 4 Heterogeneous Azeotropic Distillation Column Design
 Breaking azeotropes
P Adding an entrainer that does not induce two liquid phases
0 Homogeneous azeotropic distillation
Chloroform
(61.15oC)
1

0.9

0.8

Azeotrope
0.7
(63.81oC)
0.6 (0.38, 0.62, 0)
0.5

0.4

0.3
(0.4, 0.2, 0.4)
0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Toluene Acetone
(110.6oC) (56.05oC)
(Entrainer)
L07 - 5 Heterogeneous Azeotropic Distillation Column Design
 Breaking azeotropes
P Adding an entrainer that does not induce two liquid phases
0 Homogeneous azeotropic distillation
Chloroform
o
(61.15
1
C)

0.9
Vapour
0.8 y(t)
0.7
Azeotrope
(63.81oC)
0.6

0.5 Residue Liquid

0.4
curve x(t)
0.3

x(t) x(t=0)
0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Toluene Acetone
(110.6oC) (56.05oC)
(Entrainer)
L07 - 6 Heterogeneous Azeotropic Distillation Column Design
 Breaking azeotropes
P Adding an entrainer that does not induce two liquid phases
0 Homogeneous azeotropic distillation
Chloroform
(61.15oC)
1

0.9 Residue curve map

0.8

0.7 Azeotrope
(63.81oC)
0.6
Distilation
0.5 boundary
0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Toluene Acetone
(110.6oC) (56.05oC)
(Entrainer)
L07 - 7 Heterogeneous Azeotropic Distillation Column Design
 Breaking azeotropes
0 Homogeneous azeotropic distillation
Chloroform
D3
Chloroform
D2 Acetone D3
D1
B3
D2

F
B1 F

B1 B2 B3

D1
B2
Toluene Acetone
(Entrainer)
Thong, D.Y.C. and Jobson, M., (2001), Chem. Eng. Sci., 56, 4423.
L07 - 8 Heterogeneous Azeotropic Distillation Column Design
 Breaking azeotropes
P Adding an entrainer that induces two liquid phases
0 Heterogeneousazeotropicdistillation
Ethanol

Liquid-liquid tie line Aqueous

rich
phase
A

A A
F
B

F B
B
Entrainer
rich
phase

Water Benzene
Immiscible (Entrainer)
region
L07 - 9 Heterogeneous Azeotropic Distillation Column Design
 Heterogeneous azeotropic distillation
V, y2
Ethanol

B I
II
Decanter tie line D, xD
F, xF L, xR

D B, xB

y2

I
xR P Distillation boundary to be
crossed by using a decanter
P Decanter is a cheap unit
Water Benzene operation

L07 - 10 Heterogeneous Azeotropic Distillation Column Design

 Challengesforcolumndesign

Representingvapour-liquid-liquidequilibrium:
highlynon-idealthermodynamicsystem

Lack of design methods for columns with

heterogeneousstages
 Phasesplittingofrefluxisadegreeoffreedom
 Multiplesolutionstypicallyfound

Lack of methods to exploit in flowsheet design

L07 - 11 Heterogeneous Azeotropic Distillation Column Design

 Objective of this work

Developa design method for

heterogeneous azeotropic columns
 To be applicable to various types of columns
and decanters
 To evaluate column designs
 To apply to distillation sequence synthesis

L07 - 12 Heterogeneous Azeotropic Distillation Column Design

 2. Column Design Methods:
Review

L07 - 13 Heterogeneous Azeotropic Distillation Column Design

 Columndesignmethods
forheterogeneousazeotropicdistillation
P No shortcut design method available

P Two graphical methods available

< Boundary value design method

Pham et al., 1989

< Continuous distillation region based method

Urdaneta et al., 2002
Computationally intensive
Does not explicitly give details of column design
e.g. number of stages, feed location

Pham, H.N., Ryan, P.J., and Doherty, M.F., (1989), AIChE J., 35, 1585.
Urdaneta, R.Y., Bausa, J., Bruggemann, S., and Marquardt, W., (2002), Ind. Eng.. Chem. Res., 41, 3849.
L07 - 14 Heterogeneous Azeotropic Distillation Column Design
 Boundaryvaluedesignmethod(BVM)
P First
developed
for
homogeneous V2, y2

azeotropic
distillation*
PCalculation
ofcompositionprofiles L 1, x 1
2
D, xD, hD

Hexane n P Composition profiles at a

1
Stripping Vn+1
yn+1
Ln given reflux ratio starting
xn
profile V
hn+1 from
hnL
0.8
< distillate
composition
(XD)
< bottoms composition
(XB)
0.6 Rectifying Vm Lm+1
profile ym xm+1
L
B
V
hm hm+1 P Calculate column
0.4
m profiles from
F
0.2
< materialandenergy
2 V1, y1, hV
1
balances
< phase
equilibrium
0 D
0 0.2 0.4 0.6 0.8 1

Nonane Pentane
L2, x2, h2L B, xB, hB

Levy, S.G., Van Dongen, D.B., and Doherty, M.F., (1985), Ind. Eng. Chem. Fundam. 24, 1463.
L07 - 15 Heterogeneous Azeotropic Distillation Column Design
 Boundaryvaluedesignmethod(BVM)

Hexane
1
Stripping P The intersection of the profiles is
profile necessary for the design to be
0.8

feasible
0.6 Rectifying
profile
B
0.4
P The intersection point of the profiles
is the location of the feed
F
0.2

P Number of stages can be counted

0 D
0 0.2 0.4 0.6 0.8 1

Nonane Pentane

L07 - 16 Heterogeneous Azeotropic Distillation Column Design

 Boundaryvaluedesignmethod:
state-of- the-art

Assess the feasibility of a proposed column

Give column design details, e.g.
< number of stages, feed location, heat duty of
condenser and reboiler
Able to determine minimum reflux ratio
Able to evaluate separation sequences

Gaps: Consider columns with homogeneous stages

only
Double-feed column
< developed for homogeneous mixtures only
Column with an intermediate decanter
< not yet developed

L07 - 17 Heterogeneous Azeotropic Distillation Column Design

 Objectives to extend the boundary value
method for heterogeneous azeotropic
distillation
! BVM is to be developed to be applicable to
" Multiple heterogeneous-stage columns
" Double-feed columns
" Columns with intermediate decanters

! New BVM should be able to be exploited to screen

different designs
" Feasibility of a column specification is identified by the
intersection of composition profiles
" Feasible designs are screened for economic designs by
capital and operating costs

! BVM will be applied to flowsheet synthesis

" Evaluate separation flowsheets
takingintoaccountvarioustypesofcolumns
L07 - 18 Heterogeneous Azeotropic Distillation Column Design
 3. Column Design Method:
New Boundary Value
Design Method

a. Simple Column

L07 - 19 Heterogeneous Azeotropic Distillation Column Design

 SpecificationsofBVM
g Homogeneous distillation g Heterogeneous distillation
by new BVM

1
B
Stripping
profile
0.8 Decanter tie line
F
0.6 Rectifying D
profile
B
0.4

F x1
0.2

0 D
0 0.2 0.4 0.6 0.8 1

" Distillate composition " Distillate composition

" Bottom composition " Bottom composition
" Phase split ratio of reflux

L07 - 20 Heterogeneous Azeotropic Distillation Column Design

 Definition: Phase split ratio of a heterogeneous stage
V2 , y
2
I I Phase split Ratio of heavy liquid
L1, x1
1 I ratio of = rate to total liquid rate at
D, xD
2
II stage n stage n
L1, x1
II II
L1, x1
n L IIn
I II
V
Ln Ln n =
L In + L IIn
y n+1 xnI xnII
0 < Nn < 1
n , Ln , xn

Degree of freedom : Phase split ratio of reflux (N1)

II
L1
N1 = I II
L 1 + L1

! The existence of heterogeneous stages in the column

depends on the specification of the phase split ratio of
the reflux ( N1)
L07 - 21 Heterogeneous Azeotropic Distillation Column Design
 Separation of an acetic acid/water/
n-butyl acetate mixture

Aceticacid
(118oC)
1 B DI
Stage ?
0.8 F DII
(Water)
Ntotal = ?
0.6

0.4 F B
(Acetic acid)

0.2
Specify:
distillate
- andbottomcompositions
DI DII -feedcondition=saturatedliquid
0
0 0.2 0.4 0.6
D 0.8 1 -refluxratio=1.45
n-Butylacetate Azeotrope
o
Water -phasesplitratioofreflux=0.58
(126.1oC) (91 C) (100oC)
(Entrainer)

L07 - 22 Heterogeneous Azeotropic Distillation Column Design

 Example: multiple column designs
P N1 = 0.58 causes many heterogeneous stages in the
rectifying section of the column
P At the final heterogeneous stage (stage 10), multiple
rectifying profiles can be generated corresponding to
Acetic acid
various phase split ratios of this stage
B
1
N10 < 0.38 Infeasible designs
Stripping profile
0.38 < N10 < 1 Feasible designs
0.8 Rectifying profile

N 10 NR NS N Total
0.6
1 13.4 18 31.4
F 0.9 12.8 18 30.8
0.8 12.2 18.1 30.3
0.4 Attractive
designs 0.7 11.6 18.6 30.2
0.6 11 19.2 30.2
0.2 0.5 10.6 20.3 30.9
0.4 10.2 22 32.2
D 0.38 10.1 25 35.1
0
0 0.2 0.4 0.6 0.8 1
n-butyl acetate Water
L07 - 23 Heterogeneous Azeotropic Distillation Column Design
 Validation of the method by rigorous simulation
Acetic acid Acetic acid
N10 = 0.6
B N10 = 0.38
B 1
1
NTotal = 30 NTotal = 35

0.8 0.8
HYSYS
BVM
0.6 0.6

F F
0.4 0.4

0.2 0.2

D D
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1
n-butyl Water n-butyl Water
acetate acetate
P Heterogeneous stages in the column give multiple column designs
at an operating reflux ratio
P Results from BVM are in good agreement with rigorous simulation
L07 - 24 Heterogeneous Azeotropic Distillation Column Design
 Homogeneous-stage column vs. Heterogeneous-stage column
g Phase splitting only Heterogeneousstages
g
occursinthedecanter in the column
Acetic acid Acetic acid
1 B 1 B

0.8 0.8

0.6
Identical 0.6

reflux and
F reboil ratios F
0.4 0.4

0.2 0.2

D D
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
n-butyl Water n-butyl
acetate acetate
87 stages 30 stages Water

0 Column with multiple heterogeneous stages gives more attractive design

L07 - 25 Heterogeneous Azeotropic Distillation Column Design
 ColumndesignbynewBVM

Initialisation steps : Identify feasible designs

< Liquid-liquid
equilibrium
calculation from the intersection of the
< SpecificationsFeed
- and products compositions profiles
- Phase split ratio of reflux < Design
parameters
are
obtained
< Specify - reflux ratio and reboil ratio or feed condition Number of stages in each section
Feed location
Feed condition or reboil ratio
Condenser and reboiler duty
Composition profile calculation of
stripping and rectifying sections from
Material and energy balances
Phase equilibrium Evaluate designs by
< Capital
cost
< Calculate multiple rectifying profiles for a range of
Nfinal when there are many heterogeneous stages in
< Operating
cost
the rectifying section

L07 - 26 Heterogeneous Azeotropic Distillation Column Design

 3. Column Design Method:
New Boundary Value
Design Method

b. Double-feed Column

L07 - 27 Heterogeneous Azeotropic Distillation Column Design

 Double-feed
column
V, y2

I
UpperFeed II
x FU D, xD
L, xR

LowerFeed
xFL

B, xB

P Double-feed
columnmaybemoreeconomic P BVMhasbeendevelopedfordouble-
thanasingle-feedcolumn feed
columns separating
homogeneous
< Requirefewerstages mixtures***
P Somemixturescannotbeseparatedbya P For
heterogeneous
mixtures,
columns
single-feedcolumn, with
multiple
heterogeneous
stages
have
1-propanol/1-butanol/water**
< e.g.
not
beenaddressed

*Wasylkiewicz, S.K., Kobylka, L.C. and Castillo, F.J.L., (2000), Chem. Eng. J., 79, 219.
**Moussa, A.S. and Jimnez, L., (2006), Ind. Eng. Chem. Res., 45, 4304.
***Levy, S.G., Van Dongen, D.B., and Doherty, M.F., (1985), Ind. Eng. Chem. Fundam. 24, 1463.
L07 - 28 Heterogeneous Azeotropic Distillation Column Design
 Double-feed column design by new BVM

Identify feasible designs from

Initialisation steps: the intersection of rectifying
< Liquid-liquid equilibrium calculation and middle profiles
< Specifications - compositions of upper and lower feeds < The location of lower feed is chosen
- compositions of products such that the smallest number of
- phase split ratio of reflux stages is required
< Specify - reflux ratio and reboil ratio or feed quality < The intersection point is the upper
feed location
< Design parameters are obtained
Composition profile calculation of stripping, Number of stages in each section
rectifying and middle sections from Upper feed location
Material and energy balances Feed condition or reboil ratio
Phase equilibrium Condenser and reboiler duty
< Calculate multiple profiles of rectifying section for a
range of Nfinal if the column stages are heterogeneous
Evaluate multiple designs by
< Middle profiles are calculated starting from stages of < Capital cost
stripping section
< Operating cost

L07 - 29 Heterogeneous Azeotropic Distillation Column Design

 Separation of 1-propanol/water/1-butanol mixture
1-propanol Water/Butanol
(97.15oC) D-1 mixture
1 D2
D1I
FU
0.8 C-1 D1II Relatively
FL pure water

0.6
B1
FL C-2
D2
AZ 0.4
(88.43oC) C-2
B1 1-Propanol
C-1
0.2

FU
B2
0
D-1 D1 D1I
0 D1II 0.2 0.4 0.6 0.8 1
B2
AZ 1-Butanol
Water (93.95oC) 1-Butanol
(100oC) (117.7oC)
Entrainer
L07 - 30 Heterogeneous Azeotropic Distillation Column Design
 Double-feed column design by BVM
1-propanol
1

0.8
FU Stage ?
D Lower feed location
xD (degree of freedom)
xFU
0.6

Ntotal = ? FL Stripping
FL Stage ? profile
xFL 0.4
5
4
6 B Middle
profiles
B 0.2

xB
Reflux ratio = 3 FU
0
N1=0.57 0 0.2
D 0.4 0.6 0.8 1
Water
Rectifying 1-butanol
Lower feed location profile
NR NM Ntotal Upper
(from a stripping stage) feed
4 3 28 33 location
5 3 26 32
6 3 26 33

L07 - 31 Heterogeneous Azeotropic Distillation Column Design

 Validation of the method by rigorous simulation
BVM
FU FL D B
Composition :
1-Propanol 0 0.5 0.0001 0.2733
3 Water 0 0.5 0.6999 0.0167
FU
D 1-Butanol 1 0.0 0.3000 0.7100
FL 28 Flow rate (kmol/h) 60.00 40.00 26.83 73.17
31 Condenser duty (kJ/h) 4.54E+06
Reboiler duty (kJ/h) 4.69E+06
B
HYSYS
Reflux ratio = 3
FU FL D B
N1=0.57
Composition :
1-Propanol 0 0.5 0.0001 0.2733
Water 0 0.5 0.6999 0.0167
1-Butanol 1 0.0 0.3000 0.7100
Flow rate (kmol/h) 60.00 40.00 26.83 73.17
Condenser duty (kJ/h) 4.51E+06
Reboiler duty (kJ/h) 4.45E+06

P Results from HYSYS are in good agreement with the specified

compositions for the design method
L07 - 32 Heterogeneous Azeotropic Distillation Column Design
 3. Column Design Method:
New Boundary Value
Design Method

c. Column with an Intermediate Decanter

L07 - 33 Heterogeneous Azeotropic Distillation Column Design

 Column with an intermediate decanter

D
P Two-phase liquid on a stage is
withdrawn and split into a decanter
F
P One phase is recovered as a product

P The other phase is refluxed back into

S
the column at one stage lower than the
B draw stage

P A column with an intermediate decanter may be more

economic than a simple column*
< fewer columns required
P BVM has not been developed for columns with
intermediate decanters
* Pucci, A., Mikitenko, P., and Asselineau, L., (1986), Chem. Eng. Sci. 41, 485.
Stichlmair, J.G. and Fair, J.R. (1998), Distillation: principles and practice, Wiley-VCH, 222.
L07 - 34 Heterogeneous Azeotropic Distillation Column Design
 Column with an intermediate decanter design
by BVM
Identify feasible designs from
Initialisation steps: the intersection of rectifying
< Liquid-liquid
equilibrium
calculation and middle profiles
< Specifications
- compositions of feed < The location of side stream is chosen
- compositions of three products such that the smallest number of
- phase split ratio of reflux stages is required
< Specify- reflux ratio and reboil ratio or feed quality < The intersection point is the upper
feed location
< Design parameters are obtained
Composition profile calculation of stripping, Number of stages in each section
rectifying and middle sections from Locations of feed and side stream
Material and energy balances Feed condition or reboil ratio
Phase equilibrium Condenser and reboiler duty
< Middle profiles are calculated starting from a stage in
stripping section where liquid phase splitting occurs
side stream location is a degree of freedom
Evaluate designs by
< Capital cost
< Operating cost

L07 - 35 Heterogeneous Azeotropic Distillation Column Design

 Summary
P BVM has been extended to
< Columns with many heterogeneous stages
< Double-feed columns
< Columns with intermediate decanters

P Method can be used for assessing the feasibility

of a proposed specification and setting up
designs
< Number of stages
< Feed locations
< Reboiler/Condenser duties

P BVM provides reliable designs that agree well

with rigorous simulation

L07 - 36 Heterogeneous Azeotropic Distillation Column Design

 4. Case Study

L07 - 37 Heterogeneous Azeotropic Distillation Column Design

 Separation of an acetone/water/1-butanol mixture
Acetone
(56.13oC)
1

Distilation Residue curve map:

0.8
boundary

0.6
P One heterogeneous
azeotrope (saddle)
0.4 II I
P Two distillation regions

0.2
F

0
0 0.2 0.4 0.6 0.8 1

1-Butanol Azeotrope Water

(117.92oC) (93.26oC) (100oC)

L07 - 38 Heterogeneous Azeotropic Distillation Column Design

 A typical solution

Acetone
D

C-1
F

C-2
D-1
1-Butanol
B Water
S

Lets look at how we might develop a simpler

design in three stages

L07 - 39 Heterogeneous Azeotropic Distillation Column Design

 Acetone/water/1-butanol Separation

Simple-column sequence
Option 1

L07 - 40 Heterogeneous Azeotropic Distillation Column Design

 Flowsheet synthesis: Column 1
Feed: homogeneous in Region I
Acetone Alternative 1: D - acetone
(56.13oC) M - water/1-butanol mixture,
1 D
heterogeneous
Alternative 1
0.8 Decanting
relatively pure water
0.6

Alternative 2: M - water
0.4
II I Alternative 2 D - ternary homogeneous
mixture, near distillation
0.2 D F boundary
M
0 P not a useful product
0 0.2 0.4 0.6 M 0.8 1
1-Butanol Azeotrope
o
Water P mix with other streams
(117.92oC) (93.26 C) (100oC) or recycle

Choose Alternative 1
L07 - 41 Heterogeneous Azeotropic Distillation Column Design
 Flowsheet synthesis: Liquid-phase splitting

Acetone water/1-butanol mixture,

1.0
D D heterogeneous
C-1
F
0.8 water/1-butanol
mixture in Region II
M
0.6
M1
D-1
Feed to
M2
0.4
II
Column 2
I
C-1 relatively
0.2
F pure water
M1 M2
0.0
0.0 0.2 0.4 0.6 D-1 0.8 M 1.0

1-Butanol Water

L07 - 42 Heterogeneous Azeotropic Distillation Column Design

 Flowsheet synthesis: Column 2
Column 2: Simple column with integrated decanter
The distillation boundary can be crossed
< High recovery of 1-butanol
Acetone
1.0
D

D
0.8
C-1
F

0.6
S1
M
M1 C-2 S2
0.4
II
D-1
I
M2
0.2 C-1 B
F
B C-2 M1 M2
0.0
S2
0.0 0.2 0.4 0.6
S1 D-1 0.8 M 1.0

1-Butanol Water
L07 - 43 Heterogeneous Azeotropic Distillation Column Design
 Column design by boundary value method
P Feasibility test
P Column design } by Boundary Value Method

Specifications: P Feed, top and bottom product compositions relate to

each other by overall material balance
P Reflux ratio is specified by trial and error

Column 1 97.4 mol% acetone in distillate

0.13 mol% acetone in bottom product
Reflux ratio = 20

Column 2 99 mol% 1-butanol in bottom product

0.34 mol% acetone in distillate
Phase split ratio of reflux = 0.086
Reflux ratio = 0.8
L07 - 44 Heterogeneous Azeotropic Distillation Column Design
 Column 1 designed by using BVM

Fixed: P Feed, top and bottom product

Acetone
compositions
1 D
P Feed condition = saturated liquid
P Reflux ratio = 20
0.8

0.6 Results:
D

0.4
F
8

0.2 11
F M

C-1
0
0 0.2 0.4 0.6 0.8 M 1
1-butanol Water Condenser duty (kJ/h) 6.27E+06
Reboiler duty (kJ/h) 6.36E+06

L07 - 45 Heterogeneous Azeotropic Distillation Column Design

 Two-liquid phase splitting

Acetone
1.0
D

0.8
D

8 C-1
0.6 F

11
0.4 M

M1
C-1
0.2
F D-1
M2
M1 M2
0.0
0.0 0.2 0.4 0.6 D-1 0.8 M 1.0
1-butanol Water

L07 - 46 Heterogeneous Azeotropic Distillation Column Design

 Column 2 designed by using BVM
Fixed: P Feed, top and bottom product
compositions
P Feed condition = saturated liquid
Acetone
1 D P Reflux ratio = 0.8
P Phase split ratio of reflux = 0.086
0.8 Results:
D
0.6
8 C-1
F

0.4 11 2 S1
M
M1 C-2 S2
0.2 D-1
F 5
M2
B M S2 B
0
0 0.2 0.4 0.6 M1 S0
0.8 1
1-butanol S1 Water Condenser duty (kJ/h) 1.68E+06
Reboiler duty (kJ/h) 1.72E+06
L07 - 47 Heterogeneous Azeotropic Distillation Column Design
 Validation of the method by rigorous simulation
BVM
F D S1 S2 M2 B
Composition :
Acetone 0.0995 0.9700 0.0060 0.0017 0.0009 0.0000
Water 0.7859 0.0300 0.6396 0.9854 0.9864 0.0101
1-Butanol 0.1146 0.0000 0.3544 0.0129 0.0127 0.9899
Flow rate (kmol/h) 100 10.10 8.80 13.46 60.17 7.48
Total condenser duty (kJ/h) 7.95E+06
Total reboiler duty (kJ/h) 8.08E+06

HYSYS
F D S1 S2 M2 B
Composition :
Acetone 0.0995 0.9735 0.0057 0.0017 0.0007 0.0000
Water 0.7859 0.0265 0.6396 0.9854 0.9866 0.0101
1-Butanol 0.1146 0.0000 0.3545 0.0129 0.0127 0.9899
Flow rate (kmol/h) 100 10.10 8.74 13.37 60.28 7.50
Total condenser duty (kJ/h) 7.93E+06
Total reboiler duty (kJ/h) 8.06E+06

P Results from HYSYS give good agreement with the specified

compositions for Column 1 and 2
L07 - 48 Heterogeneous Azeotropic Distillation Column Design
 Flowsheet

water/1-butanol
Acetone D mixture
1.0
D
8 C-1
F

0.8
11 2 S1
M

0.6
M1 C-2 S2
D-1
5
M2 B
0.4
II I

0.2 C-1
F

0.0
B C-2 M1 M2 Relatively pure
0.0 0.2 0.4 0.6 D-1 0.8 M 1.0
S2 water
S1
1-Butanol Water

L07 - 49 Heterogeneous Azeotropic Distillation Column Design

 Flowsheet: Introduce a recycle
Acetone
1.0 D Recycling

D
0.8

8 C-1
F
0.6
S1
11 2
M
0.4 M1 C-2
S2
II I D-1
C-1 5
0.2 M2
F B
B C-2 S S
0.0
0.0 0.2 0.4 0.6 D-1 0.8 M 1.0
1-butanol Water
Results from HYSYS:
F D S B Recycle Large recycle
Composition :
Acetone 0.0995 0.9735 0.0015 0.0000 0.0055
Water 0.7859 0.0265 0.9857 0.0101 0.6391
1-Butanol 0.1146 0.0000 0.0129 0.9899 0.3554
condenser and reboiler duty
Flow rate (kmol/h) 100 10.10 79.32 10.58 435.70
Total condenser duty (kJ/h) 4.06E+07 increases by 400%
Total reboiler duty (kJ/h) 4.07E+07

L07 - 50 Heterogeneous Azeotropic Distillation Column Design

 Motivations

P Can we share decanter between two columns?

< Reduce capital cost

P Is there a benefit in eliminating the external recycle?

L07 - 51 Heterogeneous Azeotropic Distillation Column Design

 Acetone/water/1-butanol Separation

Simple-column sequence
Option 2

L07 - 52 Heterogeneous Azeotropic Distillation Column Design

 Sequence 1:
Two columns with two decanters

Acetone
1.0
D D

C-1
F
0.8
D-2
S1
M
0.6
M1 C-2 S2
D-1
0.4
II I M2
B
0.2
C-1
F
P Tie lines of D-1 and D-2 are very
B C-2 M1 M2
0.0 close to each other
S2
0.0 0.2 0.4 0.6 D-1 0.8 M 1.0

1-Butanol
S1
Water P D-1 and D-2 perform similar
function

L07 - 53 Heterogeneous Azeotropic Distillation Column Design

 Sequence 2:
Two columns with one decanter
P Bottom product of column C-1 (M) is added to the
Acetone
decanter of next column
1 D

D
0.8

C-1
F
0.6

M
0.4
C-2
C-1
0.2 S
F
B C-2 S
0
0 0.2 0.4 0.6 0.8 1 B
M
1-butanol Water

L07 - 54 Heterogeneous Azeotropic Distillation Column Design

 Converting to two-column sequence
with one decanter
P Applicable to other mixtures with residue curve maps similar
to that of acetone/water/1-butanol mixture
Acetone
(56.13oC)
1 D P Azeotrope is a saddle and heterogeneous
< Liquid-phase splitting occurs in the bottom of
0.8
Column 1 and in the top of Column 2

0.6
D
C-1
0.4
D-2
II I M S1
C-1 M1 C-2
0.2 S2
F D-1
C-2 M2 M2
B M1 B
0
0 0.2 0.4 0.6 S1 0.8 M 1S2

1-Butanol Water
(117.92oC) (100oC)

L07 - 55 Heterogeneous Azeotropic Distillation Column Design

 Converting to two-column sequence
with one decanter
P Bottom product of Column 1 is chosen to be on a tie line
P Decanter tie line of Column 2 can be chosen to be close to
the tie line of the bottom product of Column 1

D-1 tie line

D-2 tie line

P Decanter 1 and Decanter 2

have the same function

D
D
C-1
F
C-1 F

D-2 M
M S1
M1 C-2 S2
C-2
D-1
S
M2
B
B
L07 - 56 Heterogeneous Azeotropic Distillation Column Design
 Column 2 designed by BVM
Fixed: P Feed,topandbottomproduct
compositions
P Feedcondition=saturatedliquid
P Refluxratio=0.8
Acetone
1 D
P Phasesplitratioofreflux=0.004

Results for C-2:

0.8
Condenser duty (kJ/h) 2.23E+06
D
Reboiler duty (kJ/h) 2.28E+06
0.6 8 C-1
F

11
M
0.4
2 C-2

0.2 S
F 5
B M S B
0
0 0.2 0.4 0.6 0.8 1

1-butanol Water

L07 - 57 Heterogeneous Azeotropic Distillation Column Design

 Validation of the method by rigorous simulation
BVM
F D S B
Composition :
Acetone 0.0995 0.9700 0.0015 0.0000
Water 0.7859 0.0300 0.9856 0.0101
1-Butanol 0.1146 0.0000 0.0129 0.9899
Flow rate (kmol/h) 100 10.10 79.35 10.55
Total condenser duty (kJ/h) 8.50E+06
Total reboiler duty (kJ/h) 8.64E+06

HYSYS
F D S B
Composition :
Acetone 0.0995 0.9735 0.0015 0.0000
Water 0.7859 0.0265 0.9856 0.0101
1-Butanol 0.1146 0.0000 0.0129 0.9899
Flow rate (kmol/h) 100 10.10 79.35 10.55
Total condenser duty (kJ/h) 8.49E+06
Total reboiler duty (kJ/h) 8.63E+06

P Results from HYSYS are in good agreement with the specified

compositions for the design method
L07 - 58 Heterogeneous Azeotropic Distillation Column Design
 Acetone/water/1-butanol Separation

Column with an intermediate decanter

Option 3

L07 - 59 Heterogeneous Azeotropic Distillation Column Design

 Column with an intermediate decanter

D
D
C-1
F
V
M F

C-2
S
S

B B

The two columns can be combined,

P when the bottom product of C-1 has approximately the same

vapour composition as the top vapour of C-2

Stichlmair, J.G. and Fair, J.R. (1998), Distillation: principles and practice, Wiley-VCH, 222.
L07 - 60 Heterogeneous Azeotropic Distillation Column Design
 Column with an intermediate decanter
designed using BVM
Fixed: P Feed,topandbottomproduct
Acetone compositions
1
D P Feedcondition=saturatedliquid
Rectifying
profile P Refluxratio=20
0.8 P sidestreamlocation=6(frombottom)

Results:
0.6
D

Middle 8
0.4
profile F
11
Stripping 12
0.2 profile
F 14 S

B S
0
B
0 0.2 0.4 0.6 0.8 1

1-butanol Water Condenser duty (kJ/h) 6.27E+06

Draw Reboiler duty (kJ/h) 6.41E+06
stage

L07 - 61 Heterogeneous Azeotropic Distillation Column Design

 Validation of the method by rigorous simulation

BVM HYSYS
Composition: Distillate Bottoms Side Distillate Bottoms Side
Acetone 0.9724 0 0.0016 0.9724 0 0.0016
Water 0.0276 0.0024 0.9855 0.0276 0.0024 0.9855
1-Butanol 0 0.9976 0.0129 0 0.9976 0.0129
Flow rate (kmol/h) 10.1 10.46 79.44 10.1 10.46 79.44
Condenser duty
6.26E+06 6.26E+06
(kJ/h)
Reboiler duty
6.41E+06 6.41E+06
(kJ/h)

P Results from HYSYS are in good agreement with the

specified compositions for the design method

L07 - 62 Heterogeneous Azeotropic Distillation Column Design

 Comparison with simple-column sequences
Option 1 Option 2 Option 3

D D D
F 8 C-1 8 C-1
S1 F
1 F 8
M 2 1 M 11
M1 C-2 12
D-1 S2 2 C-2
5
M2 S 14 S
B
5
S B
B
xB

Option 1 Option 2 Option 3

Stages 18 18 15
Total condenser duty (kJ/h) 40.54E+06 8.49E+06 6.26E+06
Total reboiler duty (kJ/h) 40.75E+06 8.63E+06 6.41E+06

P Column with intermediate decanter requires fewer

stages and less energy

L07 - 63 Heterogeneous Azeotropic Distillation Column Design

 4. Conclusions and Future work

L07 - 64 Heterogeneous Azeotropic Distillation Column Design

 Conclusions

Boundary value method has been extended to

allow its application to columns with multiple
heterogeneous stages
Phase split ratio of reflux is a degree of freedom
For a multiple stage heterogeneous column, a number of
possible designs corresponding to phase split ratio of the
last heterogeneous stage can be obtained

Boundary value method has been developed for

design of
double-feed columns with heterogeneous stages
columns with intermediate decanters

L07 - 65 Heterogeneous Azeotropic Distillation Column Design

 Conclusions

Boundary value method can be used as a tool for

screening options and assessing the feasibility of
proposed columns prior to rigorous simulation

Boundary value method can be used for the

evaluation of columns and will be used to
evaluate separation flowsheets
Number of stages at a given reflux ratio is obtained
< Capital and operating costs can be estimated

L07 - 66 Heterogeneous Azeotropic Distillation Column Design

 Futurework
Methodology of distillation sequence synthesis for
separating heterogeneous azeotropic mixtures will
be developed

 Various options for synthesis will be taken into

account
< Types of columns: < Types of decanters:
single-feed integrated decanter
double-feed stand alone decanter
intermediate decanter

< Subcooled decanter

< Operating pressures
< Flowsheet structure

L07 - 67 Heterogeneous Azeotropic Distillation Column Design