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CHEE3004 Unit Operations

Phase Equilibria & Flash Distillation

Greg Siemon
Contact details
Office: Not UQ Based
Email: g.siemon@uq.edu.au
Semester consultation hours:
By arrangement

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Week 8 Tasks
1. Attend Monday 14:00 lecture
2. Attend Wednesday 12:00 lecture
3. Read for this Lecture
Heat and Mass Transfer Notes from Semester 1 (Phase Equilibria)
4. Watch for this Lecture (University of Colorado LearnChemE videos)
– Binary Phase Diagrams (Txy and xy)
– Lever Rule Derivation
– Flash Calculation: Raoult's Law
– Flash Distillation Derivation
– Flash Distillation Energy Balance
5. Attend Wednesday Tutorial (2:00-4:00 or 4:00-6:00)
MBEB4
6. Complete MBEB4
Compulsory: Estimate 1-1.5 hours independent study required
Due 17:00 Friday in Blackboard
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Lecture Outline / Agenda
• Introduction
• Vapour Liquid Equlibrium (Ideal systems)
– Pxy, Txy and xy diagrams
– Flash Distillation System
– Operating Lines & Associated Calculations
• Non-Ideal Systems

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Introduction
• So far in this course we have looked at
processes to:
– transport and store materials (eg pumps, tanks etc),
– transform materials (eg grinding, spray drying,
agglomeration) and
– separate materials using physical means (eg filters, etc).

• For the next two weeks we are going to be


looking at one of the most widely used
separation processes in the Chemical and Oil
and Gas industries: Distillation

• Distillation may be
– a batch or continuous process.
– binary (ie two components) or multicomponent

• Involves the separation of components from a


liquid mixture at feed conditions to produce two
(or more) new streams that have been enriched
in some of the components.
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Objectives of this session
• Where distillation fits into the course
• Understanding of Pxy and Txy plot and how to construct
an xy plot from a Txy plot.
• Understand a simple flash distillation system and be able
to calculate mass balances using an xy plot.
• Understand difference between ideal and non-ideal
systems with respect to Txy, Pxy and xy plots.

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Definitions
• 𝑥𝑥𝐴𝐴 Molar Concentration of Component A in Liquid
• 𝑦𝑦𝐴𝐴 Molar Concentration of Component A in Vapour
• 𝑧𝑧𝐴𝐴 Molar Concentration of Component A in a Mixture of
Vapour and Liquid
• PASat Saturation Pressure of A in Vapour Phase, also
known as Vapour Pressure
• P Overall System Pressure
• T System Temperature
• MVC Most Volatile Component

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Benzene/Toluene System
• Antoine Equation
𝐵𝐵
𝐿𝐿𝐿𝐿𝐿𝐿10 𝑃𝑃 𝑆𝑆𝑆𝑆𝑆𝑆 = 𝐴𝐴 −
𝑇𝑇 + 𝐶𝐶
A, B & C are constants and T is the temperature of the system

• This is an Ideal Liquid System so Raoult’s Law applies:


𝑃𝑃 = 𝑥𝑥𝐵𝐵 𝑃𝑃𝐵𝐵𝑆𝑆𝑆𝑆𝑆𝑆 + 𝑥𝑥𝑇𝑇 𝑃𝑃𝑇𝑇𝑆𝑆𝑆𝑆𝑆𝑆

• Since only two components we can simplify to:


𝑃𝑃 = 𝑥𝑥𝐵𝐵 𝑃𝑃𝐵𝐵𝑆𝑆𝑆𝑆𝑆𝑆 + (1 − 𝑥𝑥𝐵𝐵 )𝑃𝑃𝑇𝑇𝑆𝑆𝑆𝑆𝑆𝑆
• Or
𝑃𝑃𝐵𝐵𝑆𝑆𝑆𝑆𝑆𝑆 𝑃𝑃𝑇𝑇𝑆𝑆𝑆𝑆𝑆𝑆 Bubble Point Line
1 = 𝑥𝑥𝐵𝐵 + (1 − 𝑥𝑥𝐵𝐵 )
𝑃𝑃 𝑃𝑃
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B/T System continued
• For an ideal gas system the Partial Pressure of Benzene,
PB is given by:
𝑃𝑃𝐵𝐵 = 𝑦𝑦𝐵𝐵 𝑃𝑃

• So Raoult’s Law becomes:


𝑦𝑦𝐵𝐵 𝑃𝑃 = 𝑥𝑥𝐵𝐵 𝑃𝑃𝐵𝐵𝑆𝑆𝑆𝑆𝑆𝑆
• Since
𝑥𝑥𝐵𝐵 + 𝑥𝑥𝑇𝑇 = 1

• Then
𝑃𝑃 𝑃𝑃
𝑦𝑦𝐵𝐵 + 𝑦𝑦𝑇𝑇 =1 Dew Point Line
𝑃𝑃𝐵𝐵𝑆𝑆𝑆𝑆𝑆𝑆 𝑃𝑃𝑇𝑇𝑆𝑆𝑆𝑆𝑆𝑆
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P-xy plot

T=100C

Liquid

Vapour

• Constant temperature, variable pressure.


• By convention: Most Volatile Component (MVC) is always on the x axis
• Above the bubble point line we have 100% liquid.
• At the bubble point line we have the first vapour formed.
• Then Vapour and liquid in equilibrium
• At the dew point line we have the last droplet of liquid before everything is vapour or if
condensing vapour the point where the first droplet of liquid is formed.
• MVC is enriched (ie concentration increases) going from liquid to vapour phase.
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T-xy plot
P=760mmHg

Vapour

Liquid

• Constant Pressure, Variable Temperature


• Again: Most Volatile Component (MVC) is always on the x axis
• Below the bubble point line we have 100% liquid.
• At the bubble point line we have the first vapour formed.
• Then Vapour and liquid in equilibrium.
• At the dew point line we have the last droplet of liquid before everything is vapour
• MVC is enriched (ie concentration increases) going from liquid to vapour phase.

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Tie Lines
• Liquid Feed @80C with Benzene Composition, zB =0.6 mol fraction is heated
to 100°C. Pressure is kept constant at 760mmHg.
What is the percentage of vapour and liquid at equilibirum?

Vapour

𝑥𝑥𝐵𝐵 𝑦𝑦𝐵𝐵
𝑧𝑧𝐵𝐵
Liquid

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Use the Level Rule
• Liquid Feed @80C with Composition, zB =0.6 mol fraction is heated to 100C.
What is the percentage of vapour and liquid at equilibirum?

𝑏𝑏 𝑦𝑦 −𝑧𝑧 0.8−0.6
% Liquid = = 𝑦𝑦𝐵𝐵−𝑥𝑥𝐵𝐵 = = 57.14%
𝑎𝑎+𝑏𝑏 𝐵𝐵 𝐵𝐵 0.8−0.45
𝑎𝑎 𝑧𝑧 −𝑥𝑥 0.6−0.45
% Vapour = = 𝑦𝑦𝐵𝐵 −𝑥𝑥𝐵𝐵 = = 42.86%
𝑎𝑎+𝑏𝑏 𝐵𝐵 𝐵𝐵 0.8−0.45

Vapour

a b
𝑥𝑥𝐵𝐵 𝑦𝑦𝐵𝐵
𝑧𝑧𝐵𝐵
Liquid

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xy Plot
• Txy plots are the more commonly used as in separation
processes the temperature is usually the main variable
and pressure is kept (relatively) constant.
• Txy plots are useful for doing some basic calculations as
we have just done but for separation calculations an xy
plot is much more useful.
• xy plot is generated by plotting the corresponding 𝑥𝑥𝐴𝐴 and
𝑦𝑦𝐴𝐴 pairs as temperature changes on the Txy plot.

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xy Plot
• Read off xB and yB of Txy as T increases (Constant Pressure).
Plot xB versus yB.
xy Plot for Benzene Toluene at 760mmHg
1

xB yB 0.9
0 0
0.028 0.11 0.8

0.041 0.16
0.7
0.069 0.25
0.1 0.33 0.6
0.15 0.45
0.2 0.53
yB
0.5 x=y line is
0.3 0.67 always shown
0.4
0.4 0.76
0.5 0.83
for reference
0.3
0.6 0.88
0.7 0.92 0.2
0.8 0.95
0.9 0.98 0.1
0.95 0.99
0
1 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xB

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Flash Distillation
V
𝑦𝑦𝐵𝐵

Flash
F Drum
𝑧𝑧𝐵𝐵

L
𝑥𝑥𝐵𝐵

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More Definitions
• F Feed flowrate into flash stage
• L Liquid florware leaving flash stage
• V Vapour flowrate leaving flash stage
• 𝑧𝑧𝐴𝐴 Molar Composition of Component A in Feed (mixture
of Vapour & Liquid)
• 𝑥𝑥𝐴𝐴 Molar Composition of Component A in Liquid
• 𝑦𝑦𝐴𝐴 Molar Composition of Component A in Vapour

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Flash Distillation Mass Balance
Overall Mass Balance:
𝐹𝐹 = 𝐿𝐿 + 𝑉𝑉

V Benzene Mass Balance:


𝑦𝑦𝐵𝐵 𝑧𝑧𝐵𝐵 𝐹𝐹 = 𝑥𝑥𝐵𝐵 𝐿𝐿 + 𝑦𝑦𝐵𝐵 𝑉𝑉

𝐿𝐿 = 𝐹𝐹 − 𝑉𝑉
Flash
F
Drum
𝑧𝑧𝐵𝐵 Substitute into the Benzne balance:
𝑧𝑧𝐵𝐵 𝐹𝐹 = 𝑥𝑥𝐵𝐵 𝐹𝐹 − 𝑉𝑉 + 𝑦𝑦𝐵𝐵 𝑉𝑉

−𝑥𝑥𝐵𝐵 𝐹𝐹 − 𝑉𝑉 +𝑧𝑧𝐵𝐵 𝐹𝐹 = 𝑦𝑦𝐵𝐵 𝑉𝑉


L
𝑥𝑥𝐵𝐵 𝑉𝑉 − 𝐹𝐹 𝐹𝐹
𝑥𝑥𝐵𝐵 + 𝑧𝑧 = 𝑦𝑦𝐵𝐵
𝑉𝑉 𝑉𝑉 𝐵𝐵

𝐹𝐹 𝐹𝐹
𝑦𝑦𝐵𝐵 = 1 − 𝑥𝑥𝐵𝐵 + 𝑧𝑧
𝑉𝑉 𝑉𝑉 𝐵𝐵

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Flash Distillation Mass Balance
𝑉𝑉
Multiply each side by :
𝐹𝐹

𝑉𝑉 𝑉𝑉
V 𝑦𝑦𝐵𝐵 = − 1 𝑥𝑥𝐵𝐵 + 𝑧𝑧𝐵𝐵
𝐹𝐹 𝐹𝐹
𝑦𝑦𝐵𝐵
𝑉𝑉
−1 1
𝑦𝑦𝐵𝐵 = 𝐹𝐹 𝑥𝑥𝐵𝐵 + 𝑧𝑧
Flash 𝑉𝑉 𝑉𝑉 𝐵𝐵
F
Drum 𝐹𝐹 𝐹𝐹
𝑧𝑧𝐵𝐵
Equation is of the form 𝑦𝑦 = 𝑚𝑚𝑚𝑚 + 𝑏𝑏!
𝑉𝑉
𝐹𝐹
−1
Slope: 𝑉𝑉
L 𝐹𝐹
1
𝑥𝑥𝐵𝐵 Intercept: 𝑉𝑉 𝑧𝑧𝐵𝐵
𝐹𝐹

This equation is known as the


Flash Distillation Operating Line.
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Example
• Feed composition
xy Plot for Benzene Toluene at 760mmHg
𝑧𝑧𝐵𝐵 = 50% 1

• Feed is flashed 0.9

adiabatically and 0.8

45% of the Feed 0.7

vapourises 0.6

0.5
• What is the
yB 0.4
composition of the
0.3
Vapour and the
0.2
Liquid?
0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xB

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Example
𝑉𝑉
−1 1
𝐹𝐹
• 𝑦𝑦𝐵𝐵 = 𝑉𝑉 𝑥𝑥𝐵𝐵 + 𝑉𝑉 𝑧𝑧𝐵𝐵 xy Plot for Benzene Toluene at 760mmHg
𝐹𝐹 𝐹𝐹 1

From the problem: 0.9


𝑉𝑉
𝑧𝑧𝐵𝐵 = 0.5 & = 0.45 0.8
𝐹𝐹
0.7
So
0.45 − 1 1 0.6
𝑦𝑦𝐵𝐵 = 𝑥𝑥𝐵𝐵 + 0.5
0.45 0.45 0.5

yB 0.4

𝑦𝑦𝐵𝐵 = −1.222𝑥𝑥𝐵𝐵 + 1.111 0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xB

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Example
• Plot the Flash xy Plot for Benzene Toluene at 760mmHg
Distillation Operating 1

Line on the xy plot 0.9

0.8 Flash Distillation


• Composition of vapour Operating Line
0.7
and liquid is determined
0.6
by where FDOL
0.5

yB
intersects xy line. 𝑧𝑧𝐵𝐵
0.4

• Therefore: 0.3

𝑦𝑦𝐵𝐵 = 0.70 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 0.2

𝑥𝑥𝐵𝐵 = 0.33 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 0.1

• What temperature was 0


0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

the flash drum at? xB

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Example
• Back to the Txy diagram to find temperature where 𝑥𝑥𝐵𝐵 and
are at equilibrium.

107

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More on Operating Lines
𝑉𝑉
𝐹𝐹
−1 1
• 𝑦𝑦𝐵𝐵 = 𝑉𝑉 𝑥𝑥𝐵𝐵 + 𝑉𝑉 𝑧𝑧𝐵𝐵 xy Plot for Benzene Toluene at 760mmHg
𝐹𝐹 𝐹𝐹 1

0.9

• What would the line like for feed 0.8 Mass Balance
Operating Line Bubble
at its dew point? Point Feed
0.7

𝑉𝑉
For feed at its dew point 𝐹𝐹 = 1 0.6
Dew Point
Feed
0.5

yB
so slope of line is zero (ie 𝑧𝑧𝐵𝐵
horizontal). 0.4

0.3

• What about feed at its bubble 0.2


point?
0.1
𝑉𝑉
For feed at its dew point = 0
𝐹𝐹 0
so slope of line is infinite (ie 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xB
vertical).

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Non Ideal VLE
• Raoult’s Law applies only for ideal liquid and ideal vapour systems.
𝑦𝑦𝐴𝐴 𝑃𝑃 = 𝑥𝑥𝐴𝐴 𝑃𝑃𝐴𝐴𝑆𝑆𝑆𝑆𝑆𝑆

• For systems that are non-ideal possible to use Modified Raoult’s Law
𝜙𝜙𝐴𝐴 𝑦𝑦𝐴𝐴 𝑃𝑃 = 𝛾𝛾𝐴𝐴 𝑥𝑥𝐴𝐴 𝑃𝑃𝐴𝐴𝑆𝑆𝑆𝑆𝑆𝑆

• Where 𝛾𝛾𝐴𝐴 is the activity coefficient of A in the liquid and 𝜙𝜙𝐴𝐴 is the
fugacity coefficient of A in the vapour. Values indicate how far
component is from ideal behaviour (Ideal=1).
𝑅𝑅 𝐸𝐸
𝐺𝐺𝐴𝐴 𝐺𝐺𝐴𝐴
ln 𝜙𝜙𝐴𝐴 = and ln 𝛾𝛾𝐴𝐴 =
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅

• Residual Gibbs Energy 𝐺𝐺 𝑅𝑅 = 𝐺𝐺𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 − 𝐺𝐺𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑔𝑔𝑔𝑔𝑔𝑔


• Excess Gibbs Energy 𝐺𝐺 𝐸𝐸 = 𝐺𝐺𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 − 𝐺𝐺𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠

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Non-ideal Example
• Benzene and Ethanol is an example of a non-ideal liquid system
• Notice there is a point where 𝑥𝑥𝐵𝐵 =𝑦𝑦𝐵𝐵 .
• This is known as an azeotrope. Once an azeotrope is formed it is not possible to
separate the components further via distillation without either changing the system
conditions (eg different pressure) or introducing a third component to break the
azeotrope.
• Alternatively, a non-distillation method may be used eg Molecular Sieves to allow
separation.

Pxy (72°C) Txy (760 mmHg)

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Summary
• Where distillation fits into the course
• Understanding of Pxy and Txy plot and how to construct
an xy plot from a Txy plot.
• Understand a simple flash distillation system and be able
to calculate mass balances using an xy plot.
• Understand difference between ideal and non-ideal
systems with respect to Txy, Pxy and xy plots.

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