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Schedule
Tuesday 1/12/2015:
09.45 12.30: Lecture - Natural Gas Processing
14.00 17.00: Available for questions/discussion at TTPL
Wednesday 2/2/2015
14.00 17.00: Available for questions/discussion at TTPL
Thursday 3/12/2015
11.45 14.30: Lecture - Azeotropic distillation methods
15.00 17.00: Available for questions/discussion at TTPL
Friday 4/12/2015
13:30 15.00: Available for questions/discussion at TTPL
Outline
Introduction
Importance and industrial relevance of azeotropic distillation
Main part
Theory: residue curve maps and distillation curve maps
How to make residue curve maps at Aspen Plus
Feasibility analysis of azeotropic distillation
Azeotropic distillation methods
Examples from the Oil & Gas Industry
Summary
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
Residue curves
Consider the process of differential (open)
distillation (Rayleigh distillation)
The component mass balance is written:
dxi
dW
( yi xi )
dt
Wdt
A (TA)
dxi
xi yi
d
TA< TB < TC
xW0
Still pot
composition
trajectory
C (TC)
B (TB)
Distillation curves
Total reflux
(V = L = R)
Condenser
V, yD
Yi,n-1
L, xD
Stage n-1
En
xi , n yi , n
yi , n xi , n 1
n1
E
xi , n 1
yi , n 1
yi , n 1 xi , n 2
yi,n
xi,n-1
Stage n
xi,n
...
By doing this from any
initial composition (x0) the
distillation curve can be constructed
Reboiler
xB
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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Residue curve
------- Distillation curve
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Find azeotropes
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Residue curves
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F, zF
F zF = D xD + B xB
Feasibility rules
B, xB
xB
xD
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No distillation boundaries
Only one distillation region exists
No limitations regarding possible
products independently of feed location
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F1
AzAC
AzAB
Feed F1 in Area I
F2
Feed F2 in Area II
AzAC as top product
Component B as bottom product
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No entrainer required
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Entrainer
enhanced
methods
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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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F+E
D1
F
A
Total feed (F) is a mix of fresh feed (F) and entrainer (E)
AzAB=F
D1
F
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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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1) Preconcentrator
2) Azeotropic column
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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Rectifying
section
Rectifying
section
Binary feed
(1 & 2)
F
Bottom
section
Bottom section
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C1
C2
C3
* Anette Kornberg, Equation of State for the System CO2 and Ethane, Project report, NTNU, Dec. 2007
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CRAIER column
Az C2/CO2
~ 50 mol% CO2
C2 + CO2 (+ C1)
~ 20 mol% CO2
C2 product (pure)
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* 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
Extractive
column
CO2/C2+
Entrainer
recovery column
C2+
C4+
Entrainer (C4+) recycle
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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
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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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