Advances in Distillation System

Design

Part I: Separation of Azeotropic mixtures

Amgad Salah Moussa

•B. Eng Hons, Cairo University, Egypt, 2000
•DEA, Rovira i Virgili University, Spain & University of Manchester, UK, 2003
•Dr. Sc., ETH Zürich, Switzerland, 2008
•Bayer Technology Services, Germany, as of Jan 2009

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Objective of the talk
To present the tools and the methodology needed to
systematically design distillation flowsheets for separating
azeotropic mixture.
RECOVER 1- Sasol Technology and
OCTENE from
C6-C10 Linde AG
K2CO3
mixtures of acids,
hydrocarbons, 1-Octene
oxygenates C8
Acid Extraction with
Fractionation
wash polar solvent
Organic salts to Oxygenates
incineration for + solvent
K2CO3 recovery

1st train 1999

25 pieces of equipment and an incinerator
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Objective of the talk
To present the tools and the methodology needed to
systematically design distillation flowsheets for separating
azeotropic mixture.
Sasol Technology and
Linde AG
2nd train 2004
12 pieces of
equipment no
incinerator
Diamond Chem Eng Proc 2004

It was known in 1998 that Azeotropic distillation is

probably a cheaper alternative !!!!
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Contents of part I

Stages of process design

Basic concepts
• Residue curve maps (RCM), and types of singular points
• Classification of residue curve maps
Serafimovclasses
The temperature profile as a way to identify the mixture’s RCM

• Types of Distillation regions in RCMs

Feasibility constraints on composition specifications
• The concept of operation leaves and their intersection

Conceptual design of distillation flowsheets
• Homogeneous azeotropic distillation and extractive distillation
• Heterogonous azeotropic distillation
Examples

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Stages in Process design
 Conceptualization
• Establishing the chemical routes and
physical principles to be employed
 Synthesis
• Generation of alternatives Systematic and generic
process synthesis methods
• Screening for feasibility
are required
• Selection of the most promising
alternatives
 Evaluation and Analysis
• Simulation, cost optimization,
controllability assessment, etc.

Westerberg Comp. Chem. Eng. 1989

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Why are azeotropic mixtures
different?
An azeotrope is a point in the composition space where boiling occurs
while the vapour composition and the overall liquid composition are equal
Points at which the liquid and the vapour composition are the same are
fixed points of the mass balance equations describing distillation columns

 r + 1
 (x − y )
dx dx
=  x=y→ =0
dh  r  dh
x (h = 0) = x d
Azeotropic mixtures have more fixed points, compared to ordinary
mixtures, therefore the composition space have complicated features, e.g.
it can be divided into more than one region
A useful representation of the composition space is the Residue Curve
Map (RCM).
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Representation of phase equilibrium
by Residue Curve Map
• The Residue Curve Map is the phase plane of a simple
distillation still
a residue curve,
XL
i.e., a trajectory,

T1
T2

dx
= x − y (0, 0), XI=1 XH
dτ

• Its importance stems from the fact that it represents the

composition profile of a packed column at infinite reflux
 r + 1
 (x − y ) r→∞
dx
=  dx
dh  r  = x − y
dh
x (h = 0) = x d
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Types of fixed points

Stable node (SN) Unstable node (UN) Saddle (S)

Examples of Residue Curve Maps

Distillation boundaries, Distillation regions

i.e., stable manifold of
the saddle point
Calculations
carried out by
Distill®

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Classification of Residue curve maps
26 mathematically feasible classes
of RCMs for ternary mixtures,
according to the classification by
Serafimov (1970). If we differentiate
based on the type of the azeotrope,
the number of classes becomes
113. the probability of encountering
a certain class vary considerably.
The 8 classes highlighted were
found to represent 90% of the
mixtures in a large data base of
industrial relevance

() stable (unstable) node,

(O) unstable (stable) node,
(
) saddle.

Kiva, et al, Chem. Eng. Sci. 2003

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Identification of the RCM of a mixture
• Temperature profile

Intermediate boiler
3
Chloroform

4 7

Methanol Acetone
5 1
6
Higher boiler Light boiler
For the mixture shown
Peterson and Partin, Ind. Eng Chem. 1997.
the temperature profile is
4617352
• In the case of indeterminacy few detailed calculations of
residue curves are sufficient

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Types of distillation regions in RCMs

Residue
curves

Hilmen, et al, AICHE J. 2002 A compartment

Two consecutive
saddles can lead to
multiplicity of
steady states. In
cells of types III, IV

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 What is a feasible composition
specification?
• A composition specification for
which a range of reflux ratios exists
XA=0.99, XB=0.005
such that column profiles (stripping
and rectifying sections) intersect
• A section operation leaf is an area
of the composition space the
Calculations carried out by Column®
envelopes all the possible section
Stripping section operation leaf for
profiles that would lead to the a point spec in acetic acid- water-
desired product specifications n-butyl acetate

• Intersection of operation leaves is necessary and

sufficient condition
Castillo et al Ind Eng Chem 1997,
for feasibility
R. Smith Chemical Process Design and Integration, 2005
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Determination of feasible composition
specifications
• Product specifications are
usually defined in terms of
XA > 0.99
regions e.g. mole fraction of
component A > 99%.
• For node product regions, the
operation leaf is the whole
XA > 0.99
distillation region
• For saddle type product the
operation leaf is determined by
the residue curve tangent to Calculations carried out by Column®
product region Rectifying (hatched) and stripping (solid) sections
operation leaves for a saddle product region, in acetic
acid- water- n-butyl acetate, 99.5% Acetic acid
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Feasibility constraints on different
types of splits
•Types of splits
–Node-Node, ( Unstable node-Stable node).
•Point specs should be in the same compartment
–Node-Saddle
•Saddle product operation leaf defines the
feasibility constraints
–Saddle-Saddle
•A two feed column have to be used and an upper
bound on reflux ratio exists
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Conceptual Design of Azeotropic
Distillation Columns

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Homogenous azeotropic distillation
and extractive distillation
• What are the RCMs of mixtures separable by homogenous azeotropic
distillation?
– The entrainer must be selected such that A, B are in the same distillation
region and AB azeotrope does not belong to a distillation boundary.
Therefore only mixtures having the following RCM classes can be split

Manan and Alcantara, Ind. Eng. Chem 2001

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Homogenous azeotropic distillation
with boundary crossing
Extremely curved
distillation boundaries
Temperature profile 1325 can be crossed in some
Class 1.0-2 cases
Note the high entrainer
demand in the given
example

Mass balance line of

mixing
Mass balance line of
the azeotropic column

Or Dimethyl sulfoxide

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 State Task network for
heterogeneous azeotropic distillation
A/B
• Two products (A, B) → a minimum of
two distillation tasks
• Essential components of the network
are shown in red
• Non essential components

Group 1 dashed line, EB
if the B rich phase is off specs Azeotrope

Group 2 dotted line,
if the azeotrope is homogenous
• The Main distillation task DT1 splits a
mixture in the distillation region of DT= Distillation task
D=Decanter
component A into pure A and a mixture M= Mixing
in, or close to the immiscibility region Sp=Splitter
• The transition from tasks to equipment Fb two components feed
A non azeotropic component
should consider multi-feed columns B Azeotropic component
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Feasibility constraints on composition
specification for various types of splits
Node-Node Node-Saddle

Stable Node
approximate
compartment boundary

Limits on
Immiscibility entrainer to
gap feed ratio

Saddle Unstable Node Saddle

The unstable node is the top The Node can be the top
product and the stable node is product if it is unstable or the
the bottom product bottom product if it is stable

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Heterogeneous Extractive Distillation
for Saddle-Saddle Splits
C1, Heterogeneous Extractive Column
DT1 is performed in C1 and C2 Make up
A Saddle

C2

B
C3 Binary feed C1

Recycle
A
Di
st
illa
ti o
n

C3
bo

C1
un
da

E
ry

B
C2 Saddle E
Temperature profile of mixtures whose Heterogeneous extractive
RCMs have this topology distillation task
26135, 21435, 24135, 61435, 64135 Moussa and Jimenez Ind. Eng. Chem. 2006
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 A
catalogue
of
probable
RCMs and
the
possible
locations
of the main
task in
each of
them
Moussa and Jimenez
Ind. Eng. Chem. 2006

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Systematic and generic design
procedure
1. Select an entrainer either through CAMD, databank or from a
list of benign materials (non-toxic, non-hazardous, etc.)
2. Calculate the temperature profile to identify the RCM of the
mixture.
3. Identify the main task to separate component A using the
catalogue.
4. Establish feasibility constraints, based on the type of fixed
points to be split in this task (node-node, node-saddle or
saddle-saddle)
5. Start the design and optimization, taking into account the
insights from the following examples.
Moussa and Jimenez Ind. Eng. Chem. 2006
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Examples
• Acetone+water+i-butanol.
Temperature profile 1435, DRD 020, Cell Type I, Node-Saddle
• i-propanol+water+ethyl acetate
Temperature profile 621435, DRD 221, Cell Type II, Node-Node
• n-propanol+water+n-butanol
Temperature profile 61435, DRD 021, Cell Type II, Saddle-Saddle
• Acetonitrile+water+acrylonitrile
Temperature profile 64135, DRD 021, Cell Type II, Node-Node
• Ethanol+water+benzene,
Temperature profile 7246135, DRD 222-m, Cell Type II, Node-Node
• Ethanol+water+ethyl acetate,
Temperature profile 7624135, DRD 222-m, Cell Type II, Node-Node
• Acetic acid+water+ethyl acetate.
Temperature profile 2135, DRD 100, Cell Type II, Node-Node
• Acetic acid+water+n-butyl acetate.
Temperature profile 6135, DRD 001, Cell Type III, Saddle-Node
• Acetic acid+toluene+water (water as entrainer)
Temperature profile 21435, DRD 120, Cell Type II, Node-Node
• Benzene+acetonitrile+n-heptane.
Temperature profile 762135, DRD 202-m, Cell Type IV, Saddle-Node
• Ethyl propanoate+n-heptane+ethanol
Temperature profile 21356, DRD 130, Cell Type IV Saddle-Node
For the sake of brevity only the main distillation task is shown in the following
Moussa and Jimenez Ind. Eng. Chem. 2006
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Example 1: heterogeneous extractive distillation
Binary mixture: n-propanol+water
Entrainer: n-butanol
Temperature profile: 61435 → RCM 2.02b
Main Task: 1-C3ol / water-1-C4ol azeotrope Saddle/Saddle
Separation is feasible only in two columns, a double feed
column followed by an entrainer recovery column
Rratio = 5.0; Nstages = 34;
entrainer to feed ratio = 2.

Mass balance line of

the main distillation
task
Mass balance line of
the extractive column

Calculations carried out by Distill®

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Example 2: use of multiple feeds
Binary mixture: Acetonitrile+water
Entrainer: Acrylonitrile
Temperature profile: 64135 → RCM 2.02b,
Main Task: Acetonitrile / Acrylonitrile-water Node/Node

(a) Rratio = 100; Nstages = 130; entrainer to (b) Rratio = 1.5; Nstages = 38; entrainer to
feed ratio = 1. feed ratio = 1

Striping and rectifying sections are Middle section can bridge the two
not in the same compartment compartments

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Example 3: choice of the compartment
Binary mixture: Acetic acid+water
Entrainer: ethyl acetate
Temperature profile 2135 → RCM 1.0-1a,
Main Task: Acetic acid / water-ethyl acetate Node/Node

(a) entrainer to feed ratio = 0.25; (b) entrainer to feed ratio = 0.50; Rratio = 2.80;
Rratio = 4.26; Nstages = 28 (Nmin=20). Nstages = 16 (Nmin=11); molar ratio of vapor flow to
that in case (a) = 0.95.

Doubling the entrainer reduces the

number of stage and the internal flows
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Example 3: choice of the compartment

(c) entrainer to feed ratio = 1.27; Rratio = (d) operating pressure 2 bars; entrainer to feed
0.27; Nstages = 16 (Nmin=12); molar ratio of ratio = 0.88. Rratio = 0.38; Nstages = 16 (Nmin=13);
vapor flow to that in case (a) = 0.63 molar ratio of vapor flow to that in case (a) = 0.5

Separation in the compartment Exploitation of the pressure

farther from the tangent pinch is sensitivity of the water-ethyl
easier acetate azeotrope to reduce
entrainer requirements

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Example 4: limits on saddle product
Binary mixture: Acetic acid+water
Entrainer: n-butyl acetate
Temperature profile: 6135 → RCM 1.0-1b,
Main Task: Acetic acid / water-n-butyl acetate
Saddle/UnstableNode

(a) Rratio = 2.0 , Nstages = 33 (b) Rratio = 2.0, Nstages = 24

(Nmin=22); entrainer mole fraction (Nmin=17); entrainer mole fraction
in the top vapor = 0.2750. in the top vapor = 0.2755;
Scan all the range of feasible composition specifications to avoid saddle pinches,
is it practically realizable!
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
 Conclusions
1. The RCM of the mixture dictates the feasible distillation
configuration and composition specifications
2. Limited number of RCM topologies exist, and the RCM of a
mixture can be easily identified

3. The designer should consider placing splits in one

compartment, most preferably in the compartment that does
not contain the edge of the problematic binary mixture.
4. The whole range of feasible compositions as well as non-
atmospheric operating pressures should be considered.
5. The combination of heterogeneous and extractive distillation is
feasible in a double feed column. It is necessary when the
main distillation task is Saddle-Saddle
6. The use of multiple feeds help optimize column profiles
The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008
Take-home message
“Knowing the structure of the residue curve map for a
mixture is thus sufficient to determine if a given separation
objective is feasible. (There is, however, no guarantee that
a feasible separation will be economical).”
Doherty and Knapp “DISTILLATION, AZEOTROPIC, AND EXTRACTIVE” In Kirk-Othmer
Encyclopedia of Chemical Technology 4th ed

Acknowledgment
Funding from the Ministry of Education, Spain, FPU (2001-2019) and
discussions with Dr. Megan Jobson, Department of Process Integration,
University of Manchester, are gratefully acknowledged

The 8th International Conference of Chemical Engineering, Cairo – Egypt, November 25 – 28, 2008