Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Introduction to Residue Curve Maps

Distillation Synthesis and Design

Using Aspen Split

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Binary Systems
T-xy for ACETONE/METHANOL Y-x for ACETONE/METHANOL
96

3.0 bar
95

T-x 3.0 bar

T-y 3.0 bar
0.8
94

Vapor Molefrac METHANOL

93
Temperature C

0.6
92

0.4
91 90

0.2
89

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.2 0.4 0.6 0.8 1
Liquid/Vapor Molefrac METHANOL Liquid Molefrac METHANOL

Easy to understand and visualize azeotropic behavior

Limited number of possible topologies

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Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Ternary Systems are More Complex

• How do we graphically represent phase equilibrium?

• How do azeotropes affect phase equilibrium?

• How do we graphically represent composition for a
three-component system?
• How do we apply material balance principles in a ternary
system?

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Simple Distillation

Questions:
• How does vapor and liquid (residue)
composition change with time?
• What products are possible from mixture?

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Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Mathematical Representation of Simple Distillation

Equilibrium problem: Given P, x cal. T, y

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How Would the Residue Composition Change

for a Binary System?
Y-x for ACETONE/METHANOL
94.95 C
1

3.0 bar
0.8
Vapor Molefrac METHANOL
0.4 0.6

88.81 C
0.2

91.78 C0 0.2 0.4 0.6 0.8 1

Liquid Molefrac METHANOL
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Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Simple Distillation Trajectories

Y-x for ACETONE/METHANOL 94.95 C

1

3.0 bar
0.8
Vapor Molefrac METHANOL
0.4 0.6

88.81 C
0.2

91.780C 0.2 0.4 0.6 0.8 1

Liquid Molefrac METHANOL

- Time axis is generally not important, only trajectory in composition space

- Final composition depends on starting point!

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Residue Curve Map

Mathematically it is possible to calculate a complete curve passing

though a selected point, to complete a residue curve map

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Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Ternary Diagram for Ideal System

Ternary Map (Mass Basis)
ETHANOL (108.72 C)

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1

BUTANOL METHANOL
(152.09 C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 (94.95 C)
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Ternary Diagram for Complex System

Ternary Map (Mole Basis)
METHANOL (64.20 C)
0.9
0.8
0.7
0.6
0.5

54.57 C
0.4

52.99 C

53.28 C
0.3
0.2
0.1

MEAC CHLOROFO
(56.68 C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 (60.70 C)
64.30 C

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Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Calculation of Residue Curve Maps (1)

• Solution Methodology
– The Geometric Theory of Multicomponent Distillation

• Based on:
– Differential Geometry
– Topology
– Dynamical Systems theory
– Thermodynamics

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Calculation of Residue Curve Maps (2)

• Academic Research
– Doherty and co-workers – University of Massachusetts
• Geometric theory of residue curve maps
• Use as a tool for distillation synthesis
• Geometric design procedures
– Westerberg and co-workers – Carneige Mellon University
• Product distribution regions
• Systematic separation process synthesis
– Blass, Stichlmain and co-workers – Technical University of Munich
– Platinon, Petlyuk and co-workers – Russia
– Others

• Software
– Aspen Split

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Distillation Synthesis and Design Using Aspen Split Introduction to Residue Curve Maps

Properties of the Residue Curve Map

dx
• State Equation : = x− y
dζ

• Singular Points : x= y
• The singular points of the residue curve map are all the pure
components and azeotropes exhibited by the mixture
– The geometry of the residue curves in the neighborhood of the
singular points is determined by the eigenvalues of the Jacobian
matrix [I – Y] evaluated at the singular point, where I is the identity
matrix, and
 ∂y 
Yij =  i 
 ∂x j  P, x ′

– All the eigenvalues of [I – Y] are real, positive and distinct è all the
singular points of the residue curve map are either stable nodes ,
unstable nodes, or saddles
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Classification of Singular Points in Residue

Curves

• Residue curve maps

cannot exhibit limit cycles

• Temperature always
increases along the
residue curves, i.e.

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