n chemistry, azeotropic distillation[1] is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the example below with the addition of benzene to water and ethanol
n chemistry, azeotropic distillation[1] is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the example below with the addition of benzene to water and ethanol
n chemistry, azeotropic distillation[1] is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the example below with the addition of benzene to water and ethanol
n chemistry, azeotropic distillation[1] is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the example below with the addition of benzene to water and ethanol
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 5
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 22
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
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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
