AZEOTROPIC DISTILLATION AND RESIDUE CURVE MAPS

Exploiting L-L Boundaries in Azeotropic Separations e.g. Separation of water / n-butanol mixtures
Feed LL Boundary Pure Water Azeotrope Composition n-butanol n-butanol rich phase LL Equilibrium LL Boundary Pure butanol

Feed Water / n-butanol

Decanter

Water rich phase

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Step I: Use the Decanter to Get Around the Azeotrope

Feed

Decanter LL Boundary Pure Water Feed A LL Boundary Feed B Composition n-butanol Azeotrope Sequence 1
3

Pure butanol

Step II: Distill the Two Phases (Each Phase in a Column)

Feed A LL Boundary Column 1 Pure Water

Feed B LL Boundary

Column 2

Azeotrope
Sequence 1

Composition n-butanol

Pure butanol

Step III: Mix the Two Azeotropic Streams with the Original Feed and Recycle to Decanter
Feed

Decanter LL Boundary Pure Water LL Boundary Composition Azeotrope n-butanol

Sequence 1
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Pure butanol

SEQUENCE I Azeotrope Azeotrope Feed B Feed Column 2

Decanter n-butanol Column 1 Water

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Azeotrope Feed A

AN ALTERNATIVE SEQUENCE: START WITH DISTILLATION

Feed

Column 1 Pure Water LL Boundary LL Boundary Pure Composition butanol Azeotrope n-butanol
Sequence 2
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Step II: Feed Azeotrope to Decanter

Decanter Pure Water LL Boundary Feed A LL Boundary Pure butanol

Feed B Composition Azeotrope n-butanol

Sequence 2

Step III: Take First Liquid Phase to Column I and Second Liquid Phase to Column II

Feed A

Feed B

LL Boundary LL Boundary Column 1 Column 2 Pure Composition Pure Azeotrope Water n-butanol butanol
Sequence 2
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SEQUENCE II
Azeotrope Feed B Azeotrope Feed
Decanter

Column 2

n-butanol

Column 1

Water
Feed A

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SIMPLE GRAPHICAL TOOLS TO DEVELOP AZEOTROPIC SEQUENCES FOR TERNARY SYSTEMS

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Distillation Curves
TAKE A COLUMN WITH TOTAL REFLUX

From Material Balance:

Lk = V k+1 x i,k = y i,k+1

From Equilibrium
k-1

y i,k in eqm with x i,k Take a value for x i,k get corresponding y i,k from Bubble Point Calculations

k Lk x i,k

Vk y i,k V k+1 y i,k+1

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How to construct Distillation Curves ?

Bubble Point Calculation Gives us vapor composition in equilibrium with known liquid composition Can march up the column by doing a series of bubble point calculations

Dew Point Calculation Gives us liquid composition in equilibrium with known vapor composition Can march down the column by doing a series of dew point calculations

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Distillation Curve
Species B

Region 1

Region 2

Species A

Azeotrope

Species C

Curves move in the direction of increasing temperature i.e., towards the least volatile species present in the mixture
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Make sure your Setup, Components, and Properties specifications are complete. From the Tools menu, point to Analysis, then Property, then Residue. On the Residue Curves dialog box, Aspen Plus fills in defaults for all the required information. You can accept the defaults, or make changes to any of the following information: Components: Three are required. Use the Component 1, Component 2, and Component 3 lists to choose the three components you wish to study. Only conventional components that are not solids or ions are allowed. Defaults are the first three conventional components listed on the Components Specifications Selection sheet. Pressure: The default is 1 atm Valid Phases: You can specify rigorous two phase (Vapor-Liquid) or three phase (Vapor-Liquid-Liquid) calculations. The default is Vapor-Liquid. When finished, click Go to generate the residue curves, or first click the Save As Form button to save your interactive Property Analysis to forms within the Data Browser.
Saving an interactive Property Analysis as forms enables you to preserve the input and results of this Property Analysis to view or modify 15 at a later time. Aspen Plus displays the results in tabular form, in a form window and as a triangular plot.

How to Generate Distillation/Residue Curves on ASPEN

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Rules: 1. Cannot (typically) cross distillation boundary 2. Within the same column, feed, top and bottom lie on a straight line Species B (lever arm principle)

Region 1

Region 2

Distillation Boundary Separatrix

Species A

Azeotrope

Species C
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Lever-Arm Principle
D, y F, z
Column 1 Species B

B, x

Arm for D
B, x

F=B+D Fz = Bx + Dy = (F-D)x + Dy ==> D/F = (z -x)/(y-x)

F, z

Arm for B
D, y
Species A Species C

D/F = Arm for D/Total Arm

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Lever Arm
Species B

Say, D / F = 0.0 => D = 0 and B = F

B, x F, z

Species A

Species C

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Distillation Sequencing
Species B

Say, D / F = 0.10 => Distance from F to B is 10% that from D to B

B, x

F, z

Species A

D, y

Species C

Lever Arm helps us determine bottoms and distillate locations on composition diagram
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Distillation Sequencing
Species B

So, ideally, as D/F increases we expect to finally reach a state where distillate is pure A and bottoms is a mixture of pure B and C.But, this is not what really happens !!!!
F, z

B, x

Species A

D, y

Species C

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Remember Rule #I: Cant Cross the Distillation Boundary Species B

We have a distillation boundary which divides composition space into regions 1 and 2. If our feed is in Region 1, it is not possible to cross the boundary ( except in some very special cases) Distillation Boundary

B, x F, z

Region 1 Species A

Region 2 Species C

D, y

So, LOCATION OF FEED plays a very crucial role in design

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EXAMPLE: ACETONE, CHLOROFORM, BENZENE Benzene SYSTEM 80.1 o C

Consider the given feed
Distillation Boundary

F, z

Region 1

Region 2

Acetone D, y 56.5 o C

Azeotrope
34 mol% acetone 64.4 oC

Chloroform 61.2 o C
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Case I: Need pure Acetone and Pure Benzene Benzene

80.1 o C
Distillation Boundary

Column I
F, z

Acetone 56.5 o C

Column II

Azeotrope
34 mol% acetone 64.4 oC

Chloroform 61.2 o C
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Case I: Need pure Acetone and Pure Benzene Benzene

80.1 o C

Column I
F, z

Distillation Boundary

Acetone 56.5 o C

Chloroform Azeotrope Column II 34 mol% acetone o

64.4 oC

61.2 C

Acetone + Chloroform

Acetone

II
Azeotrope
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I
Benzene

USE NON-VLE METHOD TO SEPARATE THE AZEOTROPE (e.g., decanter for LL Boundaries, membrane, etc.)

Acetone + Chloroform

Acetone

II
Azeotrope
Decanter To another column or to recycle

I
Benzene

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Case II: Need pure Benzene and Pure Chloroform Benzene

80.1 o C
Distillation Boundary

Column I
F, z

Acetone 56.5 o C

Column II

Azeotrope
34 mol% acetone 64.4 oC

Chloroform 61.2 o C
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Case II: Need pure Benzene and Pure Chloroform Benzene

80.1 o C
Distillation Boundary

Column I
F, z
Decanter

Acetone 56.5 o C

Column II

Azeotrope
34 mol% acetone 64.4 oC

Chloroform 61.2 o C
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Case II: Need pure Benzene and Pure Chloroform Benzene

80.1 o C
Distillation Boundary

Column I
F, z
Decanter

Column III

Acetone 56.5 o C

Column II

Azeotrope
34 mol% acetone 64.4 oC

Chloroform 61.2 o C
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