Azeotropic Distillation Methods

Dr. Stathis Skouras, Gas Processing and LNG

RDI Centre Trondheim, Statoil, Norway

Schedule
Tuesday 09.12.2014: 09:45 12:30

Lecture: Natural Gas Processing

Thursday 11.12.2014: 11:45 14:30

Lecture: Distillation of azeotropic mixtures
Tuesday 16.12.2014: 09:45 11:30
PC-lab / HYSYS exercises
o Dew Point Control Unit (DPCU)
o Extractive Distillation (Acetone-methanol with water as entrainer)

Outline
Introduction
Phase diagrams of azeotropic mixtures (Prof. E. Voutsas)

Importance and industrial relevance of azeotropic distillation

Main part

Theory: residue curve maps and distillation curve maps

Feasibility analysis of azeotropic distillation
Examples of azeotropic distillation methods
Summary

Importance and industrial relevance of

azeotropic distillation
Need for efficient recovery and recycle of organic solvents in chemical industry
Most liquid mixtures of organic solvents form azeotropes that complicate the
design of recovery processes
Distillation is the most common unit operation in recovery processes because of
its ability to produce high purity products
Azeotropes make separation impossible by normal distillation but can be also
utilised to separate mixtures not ordinarily separable by normal distillation
Azeotropic mixtures may often be effectively separated by distillation by adding a
third component, called entrainer
Knowledge of the limitations and possibilities in azeotropic
distillation is a topic of great practical and industrial interest

Terminology
The methods and tools presented in this lecture also appply for:
Azeotropic mixtures, close boiling systems, low relative volatility systems
Original components A and B: The components that form the azeotrope and need
to be separated
Entrainer: A third component (E or C) added to enhance separation
Binary azeotrope: Azeotrope formed by two components
Ternary azeotrope: Azeotrope formed by three components
Homogeneous azeotrope: Azeotrope where the forming components are miscible
Heterogeneous azeotrope: Azeotrope where the forming components are
immiscible
Minimum boiling azeotrope: Azeotrope with lower boiling point than its constituent
components
Minimum boiling azeotrope: Azeotrope with lower boiling point than its constituent
components
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Overview: Azeotropic distillation methods

1) Pressure swing distillation

No entrainer required

2) Homogeneous azeotropic (homoazeotropic) distillation

3) Heterogeneous azeotropic (heteroazeotropic) distillation
4) Extractive distillation

Entrainer
enhanced
methods

Theory: Residue curve maps (RCM) and

distillation curve maps (DCM)
For ordinary multicomponent distillation
determination of feasible schemes and column
design is straightforward
McCabe-Thiele method and Fenske-UnderwoodGilliland equations are powerful tools
Azeotropic phase equilibrium diagrams such as
residue curve maps (RCM) or distillation curve
maps (DCM) are sometimes nicknamed the
McCabe-Thiele of azeotropic distillation and
provide insight and understanding
RCM or DCM sketched together with material
balance lines and operating lines are used to
identify feasible distillation schemes and products

Residue curves
Consider the process of differential (open)
distillation (Rayleigh distillation)
The component mass balance is written:
dxi
dW
( yi xi )
dt
Wdt

and by considering the dimensionless time variable

(d=dV/W)

A (TA)

dxi
xi yi
d

TA< TB < TC

Integrating the above equation from any initial

composition (xw0) will generate a residue curve

The residue curve describes the change of

the still pot composition with time (trajectory)

xW0

Still pot
composition
trajectory

C (TC)

B (TB)

Distillation curves

Total reflux
(V = L = R)

Condenser

Consider the process of continuous distillation at

total reflux (45 line at McCabe-Thiele diagram)

V, yD

Starting with a liquid composition at stage n (xi,n)

and by doing repeated phase equilibrium
calculations (E-mapping) upwards we get:

Yi,n-1

L, xD

Stage n-1
n

E
xi , n
yi , n

yi , n xi , n 1

yi,n

xi,n-1

n1

E
xi , n 1
yi , n 1

yi , n 1 xi , n 2
...

Stage n

xi,n

By doing this from any initial composition (x0) the

distillation curve can be constructed
The distillation curve describes the change of the
component composition along the column (trajectory)

Reboiler
xB

Singular points in RCM and DCM

Pure component vertices and azeotropes are singular points in the RCM and DCM
dxi
xi yi 0
d

The behaviour at the vicinity of singular points depends on the two eigenvalues
a) Stable node ( ): Point with the highest boiling point Bottom product in
distillation. All residue curves end at this point - Both eigenvalues negative

b) Unstable node ( ): Point with the lowest boiling point Top product in distillation.
All residue curves start at this point - Both eigenvalues positive
c) Saddles ( ): Point with an intermediate boiling point Residue curves move
towards and then away from these points One positive and one negative
eigenvalue

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Relationship between residue curves and

distillation curves
Both are pure representations of the VLE and no
other information needed to construct them
Have the same topological structure and singular
points
Distillation boundaries exist and split the
composition space into distillation regions
DO NOT completely coincide to each other
BUT provide the same information and can be
equally used for feasibility analysis

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Residue curve
------- Distillation curve

Feasibility analysis based on RCM and DCM

For a feasible separation the material
balances should be fulfilled:

xB

F=D+B
F zF = D xD + B xB
Feasibility rules

a) The top (xD) and bottom (xB) compositions

must lie in a straight line through feed (zF)

xD

b) The top (xD) and bottom (xB) compositions

must lie on the same residue (distillation) curve

Products xD and xB must lie on the same distillation region

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Feasibility analysis based on RCM and DCM

Zeotropic mixture
No distillation boundaries
Only one distillation region exists
No limitations regarding possible
products independently of feed location

Direct split: The most volatile is taken

at the first column

Indirect split: The less volatile is taken

at the first column

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Feasibility analysis based on RCM and DCM

Azeotropic mixtures
Case 1

Case 1
o One boundary exists
o Two distillation regions (I and II)
o Different porducts for feeds F1 and F2

Case 2 - Possible products?

o Feed F1

Case 2
AzAB

- Distillate: AzAB
- Bottom: B

o Feed F2
- Distillate: AzAB
- Bottom: C

B
AzBC

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1) Pressure swing distillation

Principle: Overcome the azeotropic composition by changing the
system pressure

Key factors: Azeotrope sensitive to pressure changes, recycle ratio

which increases costs
Application: Tetrahydrofuran/water*

* Stichlmair and Fair, Distillation: Principles and practice, Wiley-VCH, (1998)

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2) Homogeneous azeotropic distillation

Definition:
o Entrainer completely miscible with the original
components
o Entrainer may (or not) form additional azeotropes
with the original components
o The distillation is carried out in a sequence of
columns
Principle:
o The addition of the entrainer results in a residue
curve map promising for separation

o Both original components must belong to the

same distillation region

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Feasibility for homogeneous azeotropic distillation

Example Use of intermediate entrainer

Original components A and B form a min. AzAB

Components A and B belong to the same distillation region

Original feed (F) is close to the azeotrope AzAB

D1
F
A

Total feed (F) is a mix of fresh feed (F) and entrainer (E)

Component A is taken as bottom product in Column 1

Component B is taken as top product in Column 2

Entrainer (E) is recovered as bottom product in Column 2

Entrainer (E) is recycled to Column 1

AzAB=F

D1
F

A
Applicability of homoazeotropic distillation is limited
Quite restrictive feasibility rules
Other distillation methods are preferably applied

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3) Heterogeneous azeotropic distillation

Definition:
o Entrainer is immiscible and forms azeotrope with at
least one of the original azeotropic components

o The distillation is carried out in a combined columndecanter column

o Entrainer is recovered and recycled to the first column

Principle:
o Liquid-liquid immiscibilities are used to overcome
azeotropic compositions
o Distillation boundaries can be crossed by immiscibility

Applicability:
o Widely used in the industry
o One of the oldest methods of azeotropic distillation

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Feasibility for heterogeneous azeotropic distillation

Classic example ternary heterogeneous azeotrope
Entrainer forms a ternary heterogeneous azeotrope with orginal components
(unstable node Az12E)
Ternary heteroazeotrope will be the top product and will split in two liquid phases
Liquid-liquid tie-lines are located in different distillation regions
A12E

A1E
A12E

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A2E

Example: Ethanol/water + benzene (E)

3) Entrainer recovery column

1) Preconcentrator

Aqueous feed dilute in EtOH (F1)

EtOH-Water azeotrope at top (D1)
Pure water at bottom (B1)

Aqueous phase from decanter is column feed

Pure water is taken at the bottom (B3)
Top product (D3) is close to the EtOH-water
azeotrope + some benzene left

2) Azeotropic column

Ternary heterogeneous azeotrope (A12E) at top

Splits in two liquid phases in a decanter
Benzene-rich phase is recycled at the top
Pure EtOH is taken at bottom (B2)
Benzene

A12E

H2O

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EtOH

4) Extractive distillation
Definition:
o Heavy entrainer is used with high boiling point
o Distillation is carried out in a two-feed column with
a heavy entrainer added continously at the top
o Entrainer is recovered in a second column

Principle:
o The entrainer alters the relative volatility of the
original components

o The entrainer has a substantial higher affinity to

one of the original components and extracts it
downwards the azeotropic column

Applicability:
o Most widely used method in the industry

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Feasibility and synthesis for extractive distillation

Pure component 1 (D1) is taken as top product from extractive column
Entrainer extracts component 2 at the bottom (B1)
Entrainer recovery column separates entrainer from component 2
Pure entrainer (E) is recovered at bottom (B2) and used as reflux in extractive column
Rectifying
section
Rectifying
section
Binary feed
(1 & 2)
F
Bottom
section
Bottom section
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Examples from Oil & Gas: Ryan-Holmes process

Invented by Jim Ryan and Art Holmes*

Cryogenic distillation process for the removal of CO2 from natural gas
Uses extractive distillation to break the CO2/ C2 azeotrope
Uses Natural Gas Liquid (NGL) as entrainer, which is extracted from the
feed stream itself
Various configurations with 2, 3 and 4 columns

* A. S. Holmes, J. M. Ryan, Cryogenic distillation separation of acid gases from methane, US patent, 1982

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Added
entrainer

De-C1
column

Azeo
CO2/C2

Extractive
column

CO2/C2+

Entrainer
recovery column

C2+
C4+
Entrainer (C4+) recycle

24

MTBE Production and Separation Unit

Azeo
C4-MeOH
+ water (E)

Feed
C3 C5+
MTBE
methanol
MeOHwater

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Process description
Feed to 1st separation column
C3
C4 (with excess isobutylene)
C5+
Water
Methanol

First Column (Distillation Column)

Bottom: MTBE
Top: C4 methanol azeotrope

Second Column (Extraction Column)

Addition of water countercurrent to flow
Methanol has more affinity for water pass to aqueous phase
Top: Raffinate (C3,C4,C5+)
Bottom: Methanol/Water

Third Column (Distillation Column)

Top: methanol
Bottom: Water

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Summary
Separation of azeotropic mixtures is a topic of great practical and
industrial interest
Azeotropic mixtures are impossible to separate by ordinary distillation,
but may be effectively be separated by adding a third component, called
entrainer
Residue curve maps (RCM) and distillation curve maps (DCM) are
representations of the thermodynamic behavior (VLE and VLLE) of
azeotropic mixtures
RCM and DCM are used to identify feasible distillation schemes

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Summary
Homogeneous azeotropic distillation
o Only few RCM and DCM lead to feasible schemes
o Limiting use in the industry
Heteroazeotropic distillation
o Ordinary distillation combined with a decanter is used
o Liquid-liquid immiscibilities are used to overcome azeotropic compositions
o Method widely used in the industry
Extractive distillation
o Heavy entrainer used that extracts one of the original components and
enhances separation
o Broad range of feasible entrainers (no liquid-liquid immiscibility required)
o The most widely used method in the industry

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Presentation title: Azeotropic distillation methods

Presenters name: Stathis Skouras
Presenters title: Principal researcher
E-mail address efss@statoil.com
Tel: +47-97695962
www.statoil.com

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