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)
P p1
Both components contribute to the total pressure: p2
Substituting the partial pressure expression from Raoult’s
Law:
* *
P x p x p
1 1 2 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 =
T (deg C)
100 0.62 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 15 oC (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
Summary
• Basics Principles
• Binary Systems
• Distillation
