Azeotropic distillation methods

Dr. Stathis Skouras Gas Treating Technologies, Statoil RDI Centre Trondheim, Norway
Classification: Internal 2014-02-07

Schedule
Tuesday 11.02.2014: 09:45 11:30

Lecture: Natural Gas Processing (Part 1-2)

Thursday 13.02.2014: 11:45 14:30 Lecture: Distillation of azeotropic mixtures Tuesday 18.02.2014: 09:45 11:30 PC-lab o Lecture: Natural Gas Processing (Part 3) o HYSYS exercise: Dew Point Control Unit (DPCU) o Aspen exercise: Extractive Distillation (Acetone/methanol + water)

Outline
Introduction Lecture objectives Importance and industrial relevance of azeotropic distillation Main part Overview of azeotropic distillation methods Azeotropic phase equilibrium diagrams - residue curve maps and distillation curve maps Tools for feasibility analysis and conceptual design of azeotropic distillation Summary

Objectives
Introduce you to the topic of azeotropic distillation (enhanced distillation) Present the theory behind azeotropic phase equilibrium diagrams Show you how such diagrams can be used for analysis of the behaviour of azeotropic mixtures in distillation columns Present methods for feasibility analysis and conceptual design of distillation processes in a systematic and comprehensive manner

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 synthesis and conceptual 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 Thus, 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

Overview: Azeotropic distillation methods

i) Pressure swing distillation No entrainer required

ii) Hybrid methods (membrane + distillation)

iii) Homogeneous azeotropic (homoazeotropic) distillation iv) Heterogeneous azeotropic (heteroazeotropic) distillation

v) Extractive distillation

Entrainer enhanced methods

i) Pressure swing distillation

Principle: Overcome the azeotropic composition by changing the pressure Key factors: Azeotropic composition sensitivity in pressure changes, recycle ratio which increases costs Application: Tetrahydrofuran/water*

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

ii) Hybrid methods (distillation + membrane)

Principle: Membrane used as the mass separating agent by absorbing and diffusing one of the azeotrope-forming components (Pervaporation-distillation hybrid)

Key factors: Membrane efficiency (high mass transfer flux, selectivity, life-time)
Applications: dehydration of alcohols, removal of Volatile Organic Components (VOC) from wastewater*

* Hilmen, Separation of azeotropic mixtures: tools for analysis and studies on batch distillation operation, PhD thesis, NTNU, Norway, 2000

iii) Homogeneous azeotropic (homoazeotropic) distillation

Definition:
o The distillation is carried out in a conventional single-feed column o Entrainer completely miscible with the original components. It may form homoazeotropes with the original azeotropic components

Principle: The addition of the entrainer results in a ternary phase equlibrium diagram promising for separation Applicability: Limited because the entrainers resulting in promising phase diagrams are rare Examples: hydrochloric acid/water + sulphuric acid *, nitric acid/water + sulphuric water **
* Stichlmair and Fair, Distillation: Principles and practice, Wiley-VCH, (1998) ** Perry et al., Perrys chemical engineers handbook, 7th ed., 1997

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iv) Heterogeneous azeotropic (heterozeotropic) distillation

Definition:
o The distillation is carried out in a combined column-decanter column o Entrainer forms heteroazeotrope with at least one of the original azeotropic components

Principle: Liquid-liquid immiscibilities provide a powerful way to overcome azeotropic compositions Applicability: Widely used in the industry Examples: Dehydration of ethanol by using benzene, diethylether or pentane, separate acetic acid/water by using ethyl acetate *
* Seader et al., Separation Process Principles, 3rd ed., 2011

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v) Extractive distillation
Definition:
o The distillation is carried out in a two-feed column with a heavy entrainer added continously in the top stages o Entrainer has a boiling point substantially higher than the original azeotropic components and interacts selectively with one of them o The entrainer is recovered as a bottom product in the second column

Principle: The entrainer alters the relative volatility of the original components Applicability: The most widely used method in the industry

Examples: Acetone/methanol by using water*

* Seader et al., Separation Process Principles, 3rd ed., 2011

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Azeotropic phase equilibrium diagrams general issues

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, operating lines and composition trajectories are used to identify feasible distillation schemes and screen infeasible specifications

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Residue curve maps (RCM)

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)

dxi xi yi d

A (TA)
TA< TB < TC xW0

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
C (TC)

Still pot composition trajectory

B (TB)

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Residue curve maps (RCM)

Properties
A residue curve map is a representation of the VLE Residue curves move along the direction of increasing temperature Residue curves cannot intersect each other Residue curve split the composition space into distillation regions and boundaries exist Residue curves do not say anything about the ease of separation Residue curves represent the liquid composition profile in a packed distillation column at infinite reflux

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Distillation curve maps (DCM)

Distillation curves (or distillation lines)
Consider the process of continuous distillation at total reflux (45 line at McCabe-Thiele diagram) Starting with a liquid composition at stage n (xi,n) and by doing repeated phase equilibrium calculations (E-mapping) upwards we get:
E xi , n yi , n n

Total reflux (V = L = R)

Condenser V, yD Yi,n-1 Stage n-1 xi,n-1 yi,n Stage n L, xD

yi , n xi , n 1 xi , n 1 yi , n 1 yi , n 1 xi , n 2
...
E n1

xi,n

By doing this from any initial composition (x0) the distillation curve map (DCM) can be constructed

Reboiler xB

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Distillation curve maps (DCM)

Properties
DCM is also a representation of the VLE

Distillation curves move along the direction of decreasing temperature (xy), opposite that of residue curves
BUT this is a matter of definition. The curve will be the same on the opposite direction (yx) Distillation curves are discrete vectors (tie-lines) but smoothed curves are usually constructed

Distillation curves cannot intersect each other

Distillation curves split the composition space into distillation regions and boundaries exist Distillation curves (discrete) say something about the ease of separation (long line easy separation)

Distillation curves represent the liquid composition profile in a staged distillation column at total reflux

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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 of the residue curves at the vicinity of singular points depends on the two eigenvalues, of the above equation
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 Cannot be recovered as pure product in distillation. Residue curves move towards and then away from these points One positive and one negative eigenvalue

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Relationship between RCM and DCM

Both are pure representations of the VLE Provide the same information and can be equally used for synthesis of azeotropic distillation Have the same topological structure and singular points Sometimes are sketched in different directions (opposite singular points) but this is a matter of definition and does not change the synthesis work They DO NOT coincide to each other

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Feasible phase diagrams for azeotropic mixtures

Rule of azeotropy ternary systems
The singular points (SN, S, UN) should always satisfy the rule: 2N3 + N2 + N1 = 2S3 + S2 + 2
where: o N3 (S3) is the number of ternary nodes (saddles) o N2 (S2) is the number of binary nodes (saddles) o N1 (S1) is the number of pure component nodes (saddles)

This rule dictates feasible phase diagrams for azeotropic mixtures (Serafimovs topological classes) Experimental VLE data indicates the natural occurence of 16 out of 26 classes

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Distillation regions and boundaries

a) Zeotropic mixture (Class 0.0-1) No distillation boundary/one distillation region Same distillation products at any feed (F)
F

b) Azeotropic mixture (Class 1.0-2) One distillation boundary/two distillation regions Different distillation products at feeds (F1 and F2) c) Azeotropic mixture (Class 3.1-2) Three distillation boundaries/three distillation regions Different distillation products at feeds (F1, F2 and F3)
F2 F1 F3

F1

F2

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Feasibility analysis based on RCM and DCM

Simple zeotropic mixture (Class 0.0-1) Only one distillation region exists No matter where the feed (F) is located the products will be the same 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

Simple zeotropic mixture (Class 0.0-1)
For a feasible separation the material balances should be fulfilled 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) b) The top (xD) and bottom (xB) compositions must lie on the same residue curve (distillation curve)

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Feasibility analysis based on RCM and DCM

Azeotropic mixture (Class 2.0-2b) One boundary exists Two distillation regions Different porducts for feeds F1 and F2 at different regions
A

Question: What will the products be? a) At region I Feed F1?

Distillate: AzAB Bottom: B AzAB

b) At region II Feed F2
Distillate: AzAB
Bottom: C C AzBC
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Special case: Crossing distillation boundaries

In special cases of quite curved boundaries, boundary crossing tecnhiques can be employed

Case 1: Feed F1 can be separated into products D1 and B1, which lie on distillation curve (a)
The feed and the distillation products lie on the same distillation region (Region 1) Case 2: Feed F1 can also be separated into D2 and B2 (or B3), which lie on a distillation curve (b) The feed and the distillation products lie on different distillation regions Boundary crossing is theoritically possible but difficult in practice Require an advanced column control system to maintain product purities and feed compositions at the right place at various disturbances

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Feasibility and synthesis for homogeneous azeotropic distillation

Definition: o Entrainer completely miscible with the original components. It may form homoazeotropes with the original azeotropic components o The distillation is carried out in a conventional single-feed column Here we consider ordinary distillation of ternary mixtures o At least one binary homoazeotrope formed by the original components o The entrainer may or may not form new azeotropes in the system o The only criteria is that the resulting ternary system should form a VLE diagram that is promising for separation Two possibilities exists: o Original components lie within a single distillation region (no boundary crossing) o Original components lie in different regions but some type of boundary crossing technique can be empoyed The applicability of the process is limited

o Difficult to find entrainers that do not introduce additional boundaries

o Practically difficult to implement boundary crossing techniques

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Feasibility and synthesis for homogeneous azeotropic distillation

Case 1: Entrainer does not form azeotropes with the original components
Heavy and light entrainers are infeasible
o Class 1.0-1a: Original components are saddles o Class 1.0-2: Boundary exists (unless boundary crossing is possible)

Intermediate entrainers are feasible

o Class 1.0-1b: Component 1 is a stable (unstable) node and can be taken as bottom (top) product, Component 2 is a saddle and can be taken as a side-product under certain operating conditions o In practice intermediate entrainers are difficult Rare to find entrainer with such a boiling point (class 1-0-1b is rare) Separation sensitive to operating conditions

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Feasibility and synthesis for homogeneous azeotropic distillation

Case 2: Entrainer forms azeotropes with the original components
Class 2.0-1: Original components are saddles Class 2.0-2c: Infeasible due to boundary (unless boundary crossing is possible) Class 2.0-2b: Infeasible due to boundary (unless boundary crossing is possible) Class 3.0-2: Infeasible due to boundaries (unless boundary crossing is possible) Class 2.0-2a: Feasible (same as class 1.01b in previous slide)

Class 3.0-1a: Feasible (same as class 2.02a above)

Homoazeotropic distillation offers in general limiting possibilities and therefore other azeotropic distillation methods are preferably applied

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Feasibility and synthesis for heterogeneous azeotropic distillation

Definition:
o Entrainer forms heteroazeotrope with at least one of the original azeotropic components
o The distillation is carried out in a combined column-decanter system

Principle: Liquid-liquid immiscibilities provide a powerful way to overcome azeotropic compositions and cross distillation boundaries

* Example: Acetone- water 1-butanol (Class 1.0.2)

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Feasibility and synthesis for heterogeneous azeotropic distillation

Most classic example - Class 3.1-2 (26%)
Original components form a homogeneous azeotrope (saddle A12) Entrainer forms two binary homogeneous azeotropes with each one of the orginal components (saddles A2E and A1E) Entrainer forms a ternary heterogeneous azeotrope with the orginal components (unstable node A12E) The ternary heteroazeotrope will be distilled on the top as an unstable node The original azeotropic components 1 and 2 are stable nodes of two distillation regions. The feed composition is located in one region and one end of the liquid-liquid tie-line is located in the other

* Example: Ethanol dehydration by benzene or cyclohexane (Class 3.1-2)

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Feasibility and synthesis for extractive distillation

Definition:
o Entrainer has a boiling point substantially higher than the original azeotropic components and interacts selectively with one of them (mainly in the liquid phase) o The distillation is carried out in a two-feed column with a heavy entrainer added continously in the top stages o The entrainer is recovered as a bottom product in the second column

Principle: The entrainer interacts selectively with one of the original components and alters their relative volatility
Extractive distillation is the oldest and most widely used enhanced distillation method
Distillation in the presence of a substance which is relatively nonvolatile compared to the components to be separated and which, therefore, is charged continuously near the top of the distilling column so that an appreciable concentration is maintained on all plates of the column. (Benedict and Rubin, 1945)

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Feasibility and synthesis for extractive distillation

Original components form a homogeneous azeotrope (unstable node A12) Entrainer (E) is heavy boiling and forms no azeotropes with the original components (stable node E) The entrainer can be recovered as a bottom product in the second column The original components (1 and 2) become saddles Based on the RCM the original azeotropic components (saddles) cannot be recovered as top or bottom products in a distillation column

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Feasibility and synthesis for extractive distillation

2 Rectifying section 1+E

1+2+E
2+E

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Feasibility and synthesis for extractive distillation

A main characteristic of extractive distillation is that a saddle is obtained as a distillate product which is against the residue curves In the rectifying section, component 1 is the unstable node of the binary edge between component 1 and the entrainer E. Thus, component 1 is recovered in the distillate Component 2 is removed as bottom product with the entrainer E. Thus, the complete extractive distillation scheme requires a sequence of two columns, one extractive distillation column and one ordinary column (or stripper) to separate component 2 from the entrainer
Rectifying section
Rectifying section

Bottom section Bottom section

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Feasibility and synthesis for extractive distillation

A common restriction on the extractive distillation is that the entrainer should not introduce new azeotropes in the system, that is, no distillation boundaries. However, this restriction seems unnecessary High reflux may be harmful in extractive distillation because it weakens the extractive effect (decreases the entrainer concentration in the extractive column section) Previous studies on continuous extractive distillation have shown that there is a maximum as well as a minimum reflux ratio to make the separation scheme feasible

Re-extractive distillation is the symmetrical process of separating a maximumboiling azeotrope by using a light entrainer added continuously below the original mixture feed point, or together with it

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Example of extractive distillation: 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

CO2/C2+ extractive column

Entrainer recovery column

CO2/C2+

C2+
Entrainer recycle

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Summary
Separation of homogeneous azeotropic mixtures is a topic of great practical and industrial interest Most liquid mixtures of organic components form nonideal systems that often results in the formation of azeotropes. Binary homoazeotropes are impossible to separate by ordinary distillation, but may be effectively separated by membrane-distillation hybrids or distillation methods where a third component (entrainer) is added to the system Analysis of phase equilibrium diagrams is an efficient tool to predict feasible separations for entrainer-addition distillation processes Insights into to the thermodynamic behavior of azeotropic mixtures is fundamental for the development of separation system involving azeotropic mixtures

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Summary
Three different entrainer-addition distillation methods depending on the properties of the entrainer and the column configuration, exist:
Homogeneous azeotropic distillation Only a few VLE diagrams lead to feasible separations by ordinary distillation in sequences of single-feed columns. The separation schemes are complex and may be very energy intensive, or difficult to control and maintain Heteroazeotropic distillation Several VLLE diagram structures that involves one or more heteroazeotropes are possible to separate by ordinary distillation combined with decantation. The separation schemes are fairly simple, but the range of feasible entrainers is rather limited

Extractive distillation The most general distillation method for separating homoazeotropic mixtures. The scheme is not sensitive to the type of original mixture as there is a broad range of feasible entrainers

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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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