Aaaaah!
xxxxday xx December 2011
xx.xx xm xx.xx xm
CHEMICAL ENGINEERING UNIT OPERATIONS 3
This paper consists of TWO questions.
All candidates should attempt ALL questions
Students should assume reasonable values for any data not given in a question nor available on a datasheet,
and should make any such assumptions clear on their script.
Students in any doubt as to the interpretation of the wording of a question, should make their own decision,
and should state it clearly on their script.
Only a calculator from the list approved by the College of Science and Engineering may
be used in this examination.
The examination paper that you are now sitting is to be marked ANONYMOUSLY.
Please write your name in the space indicated at the top right hand corner on the front cover of the answer book.
Also enter your examination number in the appropriate space on the front cover.
Write ONLY your examination number on any extra sheets,
worksheets or graph paper used and firmly attach these to the answer book(s).
Relevant supporting data and equations are bound with the examination paper.
Exams
 Graphs: submit your graphs with the exam books
 Derivation: if you do not know how move one
 Precise answer is not expected show correct steps of solution
1. Absorption (tray towers)  (Minimum) L/V ratio
 Equilibrium number of stages
+ McCabeThiele
2. Multicomponent distillation Bubble, dew points, enthalpy of multicomponent
mixtures
 Single stage flash separation
 Minimum reflux (Underwood equations)
 Minimum number of stages (Fenske equation)
 FenskeUnderwoodGilliland method to estate
the actual number of stages
 Efficiency analysis and actual number of stages
 Further design detail: flooding analysis and
column diameter, condenser reboiler duties
3. Absorption/distillation in packed beds  Minimum L/V (absorption); minimum reflux (dis)
 Pressure drop, D
 Height of packing (HTU, NTU)
 Further design: condenser/reboiler duties etc
4. Humidification/Cooling towers  Psychrometric chart
 L/G ratio (minimum air flow rate requirement)
 HTU, NTU analysis
 Height of contact zone
5. Drying  Drying medium (air) requirement
6. Adsorption Batch
 Minimum S/G (equilibrium adsorbent required)
 Equilibrium number of stages
Stagewise countercurrent (purasiv)
 Minimum S/G, actual S/G
 Number of equilibrium stages (McCabeThiele)
Continuous contact (hypersorb)
 Minimum S/G, actual S/G
 HTU, NTU, height of contact zone
Fixed bed:
 Minimum bed requirement (S/G)
 Adsorption time (online)
 Minimum purge requirement
 Desorption time
Thermodynamic relations:
Simplified models
Raoults law (Ideal solution/ideal gas):
s
i i i
P x p =
p
i
is the partial pressure of component i
Daltons law (Ideal gas):
P y p
i i
=
Composition and Kvalue for ideal gas/ideal solution system:
P P x y K
s
i i i i
/ / = =
Relative volatility for ideal gas/ideal solution system:
s
j
s
i j i
P P K K / / =
Antoine equation:
i
i
i
s
i
C T
B
A T P
+
= ) ( ln
T, P
V
L
P x P y
i
s
i i
/ =
P is total pressure in the system
Thermodynamic relations:
Simplified models
Henrys law:
i i i
x T H p ) ( =
H(T) is the Henrys constant
Daltons law (Ideal gas):
P y p
i i
=
Composition and Kvalue:
P T H x y K
i i i i
/ ) ( / = =
Relative volatility in the Henrys law regime:
) ( / ) ( / T H T H K K
j i j i
=
T, P
V
L
P x T H y
i i i
/ ) ( =
P is total pressure in the system
1. Absorption: Design considerations
Limiting conditions: Liquid/gas ratio; straight operating line
Condition: L, V constant > L/V constant
This is possible for very dilute (<3% mole fraction) mixtures
so change in total number of moles of each flow is
insignificant
A) Limiting (L/V)
min
value:
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
B) Number of ideal stages: the actual L/V ratio is
calculated as a multiple of the limiting value (f* (L/V)
min
)
this gives a steeper slope of the operating line.
The number of ideal stages can be then constructed using
McCabeThiele method.
a b
a b a a
b b
x x
y y
V
L
V
Lx Vy
x
V
L
y
=

.

\

+ =
*
min
*

1. Absorption: Design considerations
Limiting conditions: Gasliquid ratio; straight operating and equilibrium lines
Condition: L, V constant > L/V constant, y
e
=mx
e
This is possible for very dilute (<3% mole fraction) mixtures
so change in total number of moles of each flow is
insignificant
and
the region of interest is in the Henrys law regime
A) Limiting (L/V)
min
value:
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
B) Number of ideal stages: can be calculated
analytically
a b
a b
a b
a b
a a
b b
x m y
y y
x x
y y
V
L
V
Lx Vy
x
V
L
y
=

.

\

+ =
/

*
min
*
1. Kremser equation: the number of ideal
stages
 
A
y y y y
N
a a b b
ln
) /( ) ( ln
* *
=
n n e e
mx y mx y = =
Straight equilibrium line
const mV L A = = /
Adsorption factor, straight operating line
The Kremser equation (1930)
y
x
(mole fraction of A in L)
x
a
x
b
equilibrium line
y*
b
y
b
y*
b
y
b
2. Thermodynamic calculations using Kvalues
Bubble point
T
V
L
 Model system: binary mixture A, B
 Consider the process in the figure: we start with
a mixture of composition 1 and temperature T
1
and start increasing the temperature
 As we increase the temperature we are going to
reach a point where the first bubble forms
 The vapour in this bubble obeys:
 On the other hand:
 Thus as we increase the temperature we put new
Kvalues in the above equation until this condition is met
1 = +
B A
x x
1 = +
B A
y y
1 ) ( ) ( = +
B B A A
x T K x T K
1
2. Thermodynamic calculations using Kvalues
Bubble point
Procedure:
a) Select T
b) K
i
(T)
c)
d) if T is too high
e) Adjusting T
g) Final composition can be corrected using
i
i i
x K
1 >
i
i i
x K
=
i
i i
i i
i
x K
x K
y
2. Thermodynamic calculations using Kvalues
Dew point
 Model system: binary mixture A, B
 Consider the process in the figure: we start with
a mixture of composition 1 and temperature T
1
and start decreasing the temperature
 As we decrease the temperature we are going to
reach a point where the first drop of liquid forms
 The liquid in the droplet obeys:
 On the other hand:
 Thus as we decrease the temperature we put new
Kvalues the above equation until this condition is met
1 = +
B A
y y
1 = +
B A
x x
1 ) ( / ) ( / = + T K y T K y
B B A A
T
V
L
1
2. Thermodynamic calculations using Kvalues
Procedure:
a) Select T
b) K
i
(T)
c)
d) if T is too low
e) Adjusting T
g) Final composition can be corrected using
i
i
i
K
y
=
i
i i
i i
i
K y
K y
x
/
/
1 >
i
i
i
K
y
Dew point
2. Isothermal multicomponent flash separation
D
D
i
h y D , ,
F F F
F
i
T P h z F , , , ,
1 1
,T P
Objective: find D, B, and
their compositions
B
B
i
h x B , ,
) 1 ( 1 +
=
i
F
i
i
K
z
x

) 1 ( 1 +
=
i
F
i i
i
K
z K
y

=
+
=
i
i
i
F
i
i
i
i
i
K
K z
y x 0
) 1 ( 1
) 1 (

2. Multicomponent flash separation (Adiabatic)
B i
h x B , ,
D i
h y D , ,
F F F
F
i
T P h z F , , , ,
1 1
,T P
 Liquid feed is heated under pressure and then adiabatically flashed through
the pressure reducing valve
F
F
T T
P P
=
=
1
1
F
i i i
Fz Dy Bx = +
F D B = +
F D B
Fh Dh Bh = + 0 ) 1 ( = +
F D B
h h h  
2. Binary distillation
D n n
x
R
x
R
R
y
1
1
1
1
+
+
+
=
+
B m n
x
V
B
x
V
L
y =
+1
q
z
x
q
q
y
F
=
1 1
y
x
z
f
z
f
x
B
x
D
y
1
y
B
x
N
D
x
R 1
1
+
2. Fenske Equation: binary case
1
ln
)] 1 ( / ) 1 ( ln[
min
=
AB
D B B D
x x x x
N
o
Fenske equation
2. Limiting cases: minimum reflux
D n n
x
R
x
R
R
y
1
1
1
1
+
+
+
=
+
y
x
z
f
z
f
x
B
x
D
y
1
y
B
x
N
At this point: x
n
=x* and y
n+1
=y*
x*
y*
* *
*
1
1
*
1
*
min
min min
min
x y
y x
R
x
R
x
R
R
y
D
D
=
+
+
+
=
2. Fenske equation for multicomponent
distillations
Assumption: relative volatilities of components remain constant
throughout the column
1
ln
ln
,
,
,
,
,
min
(
=
HK LK
HK D
HK B
LK B
LK D
x
x
x
x
N
o
LK light component
HK heavy component
) (
) (
) (
,
T K
T K
T
HK
LK
HK LK
= o
2. Fenske equation for multicomponent
distillations: any stages/any components
Assumption: relative volatilities of components remain constant
throughout the column
j i
j n
j N n
i N n
i n
x
x
x
x
N
,
,
,
,
,
min
ln
ln
min
min
o
(
(
=
+
+
i light component
j heavy component
) (
) (
) (
,
T K
T K
T
j
i
j i
= o
2. Fenske equation for multicomponent
distillations
) (
) (
) (
,
T K
T K
T
HK
LK
HK LK
= o
Choices for relative volatility:
D
B
T
1) Relative volatility at saturated feed condition
) (
,
, F
F
HK LK
T
HK LK
o o =
2) Geometric mean relative volatility
) ( ) (
, ,
, B
B
D
D
HK LK
T T
HK LK HK LK
o o o =
3
,
) ( ) ( ) (
, , ,
B
B
D
D
F
F
HK LK
T T T
HK LK HK LK HK LK
o o o o =
why geometric mean?
2. Minimum reflux ratio analysis:
Underwood equations
=
i
HK i
i F HK i
x
q
 o
o
,
, ,
) 1 (
= = +
i
HK i
i D HK i
m
x
D
V
R
 o
o
,
, ,
1
For a given q, and the feed composition
we are looking for A satisfies this equation
(usually A is between
LK
and
HK.
Once A is found, we can calculate the
minimum reflux ratio
2. Gilliland correlation: Number of ideal
plates at the operating reflux


.

\

+
=
+
1 1
min
D
Dm D
R
R R
f
N
N N
2. Complete short cut design:
FenskeUnderwoodGilliland method
Given a multicomponent distillation problem:
a) Identify light and heavy key components
b) Guess splits of the nonkey components and compositions
of the distillate and bottoms products
c) Calculate
d) Use Fenske equation to find Nmin
e) Calculate distribution of non key components
f) Use Underwood method to find R
Dm
g) Use Gilliland correlation to find actual number of ideal stages
given operating reflux
h) Use Kirkbride equation to locate the feed stage
HK LK ,
o
2. Distillation: energy balance
F
D
B
B F C B D
Q Fh Q Bh Dh + = + +
) 1 ( + = R D Q
C
Condenser duty:
=
i
i i
x
vap
H A
or
2. Distillation: energy balance
F
D
B
) 1 ( + = R D Q
C
Condenser duty:
=
i
i i
x
vap
H A
or
Tutorial 2: (R+1) is missing!
B F C B D
Q Fh Q Bh Dh + = + +
L
a
,x
a
V
a
,y
a
V
b
,y
b
L
b
,x
b
Z
S
}
=
b
a
y
y
y
y y
dy
a K
S V
Z
*
/
}
b
a
y
y
y y
dy
*
change in the concentration divided
by driving force. This property is
called the number of transfer units
(NTU)
a K
S V
y
/
This property has units of length, is
constant for constant L/V and is called
the height of transfer units
(HTU)
3. Absorption in packed towers
L
a
,x
a
V
a
,y
a
V
b
,y
b
L
b
,x
b
Z
S
Oy Oy
b
a
y
N H
y y
dy
a K
S V
Z =
=
}
*
/
3. Absorption in packed towers
Oy Oy
b
a y
N H
y y
dy
a K
S V
Z =
=
}
*
/
y
y y
N
a b
Oy
A
=
*
*
* *
ln
] [ ] [
a a
b b
a a b b
y y
y y
y y y y
y
= A
Simplification using
average driving force
notion
Average driving force
calculated as logarithmic
mean of driving forces at
the top and bottom of the
column
3. Absorption in packed towers
Properties of air water systems are summarized in
psychrometric charts:
4. Air/water systems
4. Design of cooling towers
E
air
T
H2O
T
H2O,b
T
H2O,a
equilibrium line
Minimum air flow
condition
E
air,a
E
air,b
'
, ,
,
*
,
2 2
2 2
air
O H O H
b O H a O H
b air a air
G
c L
T T
E E
=
=
) ( ) (
2
a s const O H
Y Y kA N =
t time
a mass of dry material
Xo the initial moisture of material
Xc final moisture of material
k mass transfer coefficient
A surface area
6. Adsorption: Conventions for the isotherm
(equilibrium line)
Y [kg of adsorbate/kg carrier gas]
q [kg of adsorbate]/
[kg of pure adsorbent]
bY
HY
q
+
=
1
H
H
Y
q
(More like in
absorption studies)
(flip)
(Langmuir equation)
6. Adsorption: Conventions for the isotherm
(equilibrium line)
Y [kg of adsorbate/kg carrier gas]
q [kg of adsorbate]/
[kg of pure adsorbent]
bY
HY
q
+
=
1
H
Y>0, q>HY, where
H is Henrys constant
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S, q
0
S, q
1
G, Y
1
1
Weight, or mole ratios:
Y = y/(1y) [kg adsorbate]/ [kg carrier gas]
q=x/(1x) [kg adsorbate]/[kg adsorbent]
kg/s
kg/s
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S, q
0
S, q
1
G, Y
1
1
Weight, or mole ratios:
Y = y/(1y) [kg adsorbate]/ [kg carrier gas]
q=x/(1x) [kg adsorbate]/[kg adsorbent]
kg/s
kg/s
Design objectives:
Adsorption:
 the amount S of adsorbent required
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S, q
0
S, q
1
G, Y
1
1
Y = y/(1y) [kg adsorbate]/ [kg carrier gas]
q=x/(1x) [kg adsorbate]/[kg adsorbent]
) ( ) ( '
0 1 1 0
q q S Y Y G =
Operating line
q
Y
q
1
, Y
1
q
0
, Y
0
S/G
Equilibrium line
(Langmuir)
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S, q
0
S, q
1
G, Y
1
1
Y = y/(1y) [kg adsorbate]/ [kg carrier gas]
q=x/(1x) [kg adsorbate]/[kg adsorbent]
) ( ) ( '
0 1 1 0
q q S Y Y G =
Operating line
q
Y
q
1
, Y
1
q
0
, Y
0
S/G
Equilibrium line
(Langmuir)
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S, q
0
S, q
1
G, Y
1
1
Y = y/(1y) [kg adsorbate]/ [kg carrier gas]
q=x/(1x) [kg adsorbate]/[kg adsorbent]
) ( ) ( '
0 1 1 0
q q S Y Y G =
Operating line
q
Y
q
1
, Y
1
q
0
, Y
0
S/G
Equilibrium line
(Langmuir)
Y
1
: the amount of S required
S : Y1 you can achieve
If adsorption equation is available
an analytical solution is possible
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S
1
, q
0
S
1
, q
1
G, Y
1
1
) ( ) ( '
0 1 1 1 0
q q S Y Y G =
Operating line
q
Y
q
1
, Y
1
q
0
, Y
0
S
1
/G
Adsorbent
S
2
, q
0
S
2
, q
2
G, Y
2
2
q
0
, Y
1
q
2
, Y
2
) ( ) ( '
0 2 2 2 1
q q S Y Y G =
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
Adsorbent
S
1
, q
0
S
1
, q
1
G, Y
1
1
) ( ) ( '
0 1 1 1 0
q q S Y Y G =
Operating line
q
Y
q
1
, Y
1
q
0
, Y
0
S
1
/G
Adsorbent
S
2
, q
0
S
2
, q
2
G, Y
2
2
q
0
, Y
1
q
2
, Y
2
S
2
/G
) ( ) ( '
0 2 2 2 1
q q S Y Y G =
Objective: to minimize
S
1
+ S
2
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
S, q
1
G, Y
1
1
G, Y
2
2
G, Y
N
S, q
N+1
S, q
2
Design objectives:
Adsorption:
 the amount S of adsorbent required
 number of stages
6. Adsorption: Stage operations
Gas or liquid feed
G, Y
0
S, q
1
G, Y
1
1
) ( ) ( '
1 1 0 +
=
N N
q q S Y Y G
Operating line
q
Y
q
1
, Y
0
G,
Y
2
2
q
N+1
, Y
N
S/G
G, Y
N
S, q
N+1
S, q
2
6. Adsorption: Stage operations
) ( ) ( '
1 1 0 +
=
N N
q q S Y Y G
Operating line
q
Y
q
1
, Y
0
q
N+1
, Y
N
Smin/G
Minimum adsorbent requirement:
Design: analogy with stagewise
absorption
Gas or liquid feed
G, Y
0
S, q
1
G, Y
1
1
G, Y
2
2
G, Y
N
S, q
N+1
S, q
2
6. Fixed bed considerations: Design (Adsorption)
Y
q
Y
q
A
A
q*
Y
q
q
Y
A
A
q*
q
Y
q
1
, Y
0
q
N+1
, Y
N
Smin/G
Gas or liquid feed
G, Y
0
S, q
1
G, Y
N
S, q
N+1
6. Fixed bed considerations: Design (Adsorption)
Y
q
Y
q
A
A
q*
Y
q
q
Y
A
A
q*
Gas or liquid feed
G, Y
S, q*
G, Y=0
S, q=0
 minimum bed requirement:
(per kg of gas carrier)
' G
S
q
Y
=
A
A
6. Fixed bed considerations: Design (Adsorption)
Y
q
G
t z V
b
A
A
= =
'
/
Y
q
t
z
AG
A
b
A
A
=
1
'
Bed weight
Weight of gas treated
Y
q
Y
q
A
A
 breakthrough time:
V
L
L
G
Y
q
t
bed
bed
b
b
=
A
A
=
'
'
/
z
Y
q
dY
dq
 desorption time:
bed
b
des
L
G
H
t
'
=
 minimum amount
of purge
H G =
min
'
kg purge/
kg bed
4. Fixed bed considerations: Design (Desorption)
dY
dq
G
t z V
b
= =
/
z
Y
q
dY
dq
 desorption time:
bed
b
des
L
G
H
t
=
 minimum amount
of purge
H G =
min
kg purge/
kg bed
H