CHEE2030

Process
Engineering
Project
Dr. Hainam Do and Dr. Di Hu
Contents

• Basics Principles - Raoult’s Law

• Binary Systems
• T-x-y Diagram
• X-y Diagram
• Bubble Point and Dew Point

• Distillation
Basic Principles

Our starting point is Raoult’s Law, which states that the partial
pressure of a component in an ideal mixture is equal to the product
of its liquid phase mole fraction and of the vapour pressure of the
pure component*. For any component i,
pi = xi pi * (1.1)
This is combined with Dalton’s Law for the gas phase

pi = yi P (1.2)

to give an equation relating the vapour and liquid equilibrium

compositions at any temperature:
xi pi *
yi = (1.3)
P
 *
xi p
yi = i
P
• This equation forms the basis of vapour-liquid equilibrium, and
hence the theoretical basis of distillation
• It relates the mole fraction of a component in the vapour phase (y) to its
mole fraction in the liquid phase (x)
• Equilibrium is influenced by total vapour/liquid pressure (P), and
temperature via the saturated vapour pressure (pi*)
• But what is the saturated vapour pressure, and how do we calculate it?
Binary Systems (Ideal)

Both components contribute to the total pressure: P = p1 + p2

Substituting the partial pressure expression from Raoult’s Law:

P = x p + x2 p
*
1 1
*
2

P = x p + (1 - x1 ) p
*
1 1
*
2

Rearranging:

x p (1 - x1 ) p
* *
1= +1 1 2 (1.4)
P P
Binary System

x p (1 - x1 ) p
* *
1= +
1 1 2 (1.4)
P P
At a given pressure P and temperature T (which fixes p1* and p2* from
Equation 1.4) we can solve Equation 1.4 for x1, the liquid composition
which would just boil at the given conditions:

P - p2 *
x1 = (1.6)
(1.5)
p1 * - p2 *
Substitution into Equation 1.3 then gives the corresponding
equilibrium vapour composition y1.

x1 p1*
y1 = (1.3)
P
 Example

At 95 °C, the vapour pressure of benzene and toluene are 1180 and 478
mmHg respectively. What mole fraction of benzene will give a liquid phase
boiling at 95 °C under a pressure of 760 mmHg, and what is the
corresponding equilibrium vapour mole fraction?

P - p2 * x1 p1*
x1 = (1.6) y1 =
p1 * - p2 * P
T – x – y Diagram

This calculation can be repeated for a number of different temperatures

between the two boiling points (why not outside this range?) and the
results plotted as graphs of temperature against mole fraction at constant
pressure (a T-x-y diagram).

Pure 120
Toluene
110
y1 = 0.62
T (deg C)

100 95°C
90
x1 = 0.4
80 Pure
Benzene
70
0 0.2 0.4 0.6 0.8 1
x or y
x – y Diagram

x1 = 0.4,
y1 = 0.62
1

0.8
y=x

0.6
y1

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
x1
x – y Diagram
What is the Bubble Point of a Mixture?

Consider a binary mixture of component (1) and (2)

T
VAPOUR
Dew Point

Boiling point Boiling point

of comp (2) L+V
of comp (1)

LIQUID Bubble Point

x1, y1

By definition, a mixture does not have a boiling point. Instead we

can refer to a ‘bubble point’ and a ‘dew point’
What is the Bubble Point of a Mixture?

condenser

F 95°C D XD

heat W Xw
T
VAPOUR
Dew Point

Boiling point Boiling point

of comp (2) L+V
of comp (1)

LIQUID Bubble Point

Xw x1, y1 XD
 Example: Vapour – Liquid Equilibrium

If a 60% mole isobutane and 40% mole propane at 15oC (liquid)

and 1100 kPa is heated, at what temperature does it first begin
to boil ? What is the composition of the first bubble of vapor?
 DePriester Chart

Provides an efficient method to

find the vapor-liquid
equilibrium ratios for different
substances at different
conditions of pressure and
temperature.
 Flash Distillation

♯ They are limited by the Vapour-Liquid Equilibrium, and the

fraction of feed evaporated

condenser

D
F

D/F can be increased by:

W
1. Higher temperature (isothermal flash)
2. Lower pressure (adiabatic flash)
- Lower pressure, lower boiling point,
higher D
Continuous Multistage Distillation

D2

D1

D0
W2

F W1

W0

How would this process work?

Temperature in each stage determines D/F, xD and xW

Product flowrate gets progressively smaller as the number of stages

increases
 Continuous Multistage Distillation

If we have a feed
composition of 30%:
xD2 = 0.872

xD1 = 0.763

y=-
(1- f )
x+
xF
xD0 = 0.584
f f
Y
D xF - xW
f = =
F xD - xW
Temperature
determines D/F in each
stage, hence the
gradient

XF1 = XF2 = XF3 = Top product gets

0.3 0.584 0.763 continually richer in the
X MVC
McCbe – Thiele Method

McCabe and Thiele (1925) proposed a very convenient

graphical method for design of binary columns with the
following assumptions:

• Constant molar latent heat – hence constant molar

overflow
• L0 = L1 = L2 = L3 = Ln+1
• V0 = V1 = V2 = V3 = Vn+1
• No heat losses
• No heat of mixing

• The liquid mixture need not be ideal, provided there is

no heat of mixing, since equilibrium is expressed by
an x-y diagram, and such diagrams can be drawn for any
binary system.
Binary Counter – Current Plate (Trayed) Column

Condenser

Reflux
Top product

Reflux drum Enriching (rectifying) section

Feed

Stripping section

Reboiler

Bottom product
 Total and Partial Condenser

There are two main categories of condenser, differentiated by the extent of condensation:

The "reflux ratio" is an important parameter in column operation. It is normally defined as the ratio of
reflux to distillate (L/D), although other formulations (L/L+D, etc.) are occasionally used.
Summary

• Basics Principles

• Binary Systems

• Distillation