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Units: Actions:
- absorption
- distillation
- extraction
- adsorption
- drying
Section Lectures Tutorial
1. Introduction, revision, 1.1 Introduction to Unit Operations;
binary distillation with non- Equilibrium stage operations (L1)
constant molar overflow
1.2 Thermodynamics of distillation (L2)
1.3 Binary distillations review (L3)
2. Separation of 2.1 Multicomponent Distillation: Flash
multicomponent mixtures distillation (L4)
2.2 Multicomponent Distillation: Short
Cut Methods (L5)
2.3 Multicomponent Distillation: Short
Cut Methods (L6)
http://www.see.ed.ac.uk/~lsarkiso/UnitOps/syllabus.htm
Total 18 lectures and at least 6 tutorials
Tutorials We will have a number of tutorials
focusing on specific examples of unit
operations.
Assessment Unit operations 1.5h exam. 2
questions
Text books 1) Warren L. McCabe, Julian C. Smith and
Peter Harriot, Unit Operations
of Chemical Engineering,
(Seventh Edition). McGrawHill, 2005.
2) Robert E. Treybal, Mass Transfer
Operations (McGraw-Hill Classic
Textbook Reissue Series) (Paperback)
3) J.D. Seader and Ernest J. Henley,
Separation Process Principles, John Wiley
& Sons, 1998.
Chemical separation processes:
required background
- How do we know that at pressure P
V and temperature T, vapour and liquid
D phase are present in the system?
B
Chemical engineering thermodynamics
Va,ya
- How do we know the amount of mass
La,xa exchanged by two phases?
Vb,yb Lb,xb
Mass transfer methods
Chemical separation processes
Distillation
Gas Absorption
Crystallization
Use
Adsortion
Membranes
Chromatography
Technology maturity
Chemical separation processes
Objective:
take a mixture of components and
produce one or more products with
desired composition/purity
n1
- A and B an be somehow different:
A B
- boiling points
A+B - size
- polarity
nF - etc.
B A SF n1 ( A) / nF ( A) split factor
n2
SR n1 ( A) / n2 ( A) split ratio
T V
Tb(B)
L V L
T, P
Tb(A)
x* y*
xA
Thermodynamic considerations and phase
equilibria: Binary fluids
T V
V
Tb(B)
L
T, P
Tb(A)
L
x* y*
xA P=const
Thermodynamic considerations and phase
equilibria
T
V
Tb(B)
Tb(A)
L
x* y* xA
P=const
Thermodynamic considerations and phase
equilibria
Distribution of a component
T
V among the two phases can
be characterized with a K-value
Tb(B)
KA = yA/xA
KB = yB/xB
Tb(A)
=(1-yA)/(1-xA)
L
Relative volatility
x* y* xA
K A y A / xA
AB
K B y B / xB
Thermodynamic considerations and phase
equilibria: Binary fluids
Lets consider a binary mixture AB, where B is a heavy component (high boiling point) and
a is a light component (low boiling point). A T-x phase diagram of AB mixture, where x is a
mole fraction of component a might look like this at some constant pressure P. This phase diagram
can be also transformed in y-x diagram where composition of vapour phase in terms of mole
fraction of component A is plotted as function of the liquid phase composition.
T
Tb(B) yA T4
V
T1 T3
T2
T3 T2
T4
L Tb(A)
T1
x1 x2 x3 y1 x4 y2 y3 y4
xA xA
Thermodynamic considerations and phase
equilibria: Binary fluids
P4 P1<P2<P3<P4
T
P3
Tb(B)
P2
P1
Tb(A)
xA
Thermodynamic data for mixtures
- graphs (T-y-x, P-y-x, y-x), tables (usually limited to binary mixtures)
Promax
- Simplified models
Ideal gas/Ideal solution
Thermodynamic considerations and phase
equilibria: multicomponent mixtures
For multicomponent mixtures simple graphical representations of
vapour-liquid equilibria data do not exist
Ki = yi/xi
correlated empirically or theoretically in terms of temperature pressure
and composition
The ratio of two K-values, or relative volatility, indicates the relative ease
or difficulty of separating components i and j
Ki yi / xi
ij
K j yj / xj
Light hydrocarbon mixtures: DePriester charts
(1953)
Light hydrocarbon mixtures: DePriester charts
(1953)
Thermodynamic data for mixtures:
Simplified models
Raoult’s law (Ideal solution/ideal gas): V
pi yi P
K-value for ideal gas/ideal solution system:
K i Pi s / P
Relative volatility for ideal gas/ideal solution system:
Ki / K j Pi s / Pjs
Antoine equation: Bi
ln Pi s (T ) Ai
T Ci
Thermodynamic calculations using K-values
Bubble point P
Dew point T
V
Two phase systems Tb(B)
x* y*
xA
Easy for 2 component system, if T-x-y diagram is available
(remember the lever rule?)
y A yB 1
- On the other hand:
K A (T ) xA K B (T ) xB 1
- Thus as we increase the temperature we put new
K-values in the above equation until this condition is met
Thermodynamic calculations using K-values
Bubble point
Procedure:
a) Select T
b) Ki(T)
c) K x
i
i i
d) if K x
i
i i 1 T is too high
e) Adjusting T
K i xi
yi
K i xi
g) Final composition can be corrected using
i
Thermodynamic calculations using K-values
Dew point
- Model system: binary mixture A, B
T 1
V y A yB 1
- Consider the process in the figure: we start with
a mixture of composition 1 and temperature T1
and start decreasing the temperature
L
- As we decrease the temperature we are going to
reach a point where the first drop of liquid forms
xA xB 1
- On the other hand:
y A / K A (T ) yB / K B (T ) 1
- Thus as we decrease the temperature we put new
K-values the above equation until this condition is met
Thermodynamic calculations using K-values
Dew point
Procedure:
a) Select T
b) Ki(T)
yi
c)
i K
i
y
d) if i 1 T is too low
i Ki
e) Adjusting T
yi / K i
xi
yi / Ki
g) Final composition can be corrected using
i
Two phase system
T
V ziF
Tb(B) P1 ,T1
P1 ,T1
Tb(A)
L
x* y* xA
Given the overall composition, P1 ,T1
x* y*
B, xi , hB
xA
- The liquid mixture is partially vaporized
in a boiler (or vapour condensed in a cooler)
D/F
B, xiB , hB
Isothermal multicomponent flash separation
D, yiD , hD
B, xiB , hB
ziF (1 K i )
i 1 ( K 1) 0
i
Rachford-Rice equation
Procedure:
1) Check the feasibility of the process: do you have two phases in coexistence
at given T, P?
ziF (1 K i )
0 ziF (1 K i ) 0 subcooled liquid
i 1 ( K i 1) i
ziF (1 K i ) 1
1 ziF ( 1) 0 overheated vapour
i 1 ( K i 1) i Ki
Isothermal multicomponent flash separation
Objective: find D, B, and
their compositions
Procedure:
ziF (1 K i )
2) solve for D/F f ( ) 0
i 1 ( K i 1)
f ( )
a) Guessing
Isothermal multicomponent flash separation
Objective: find D, B, and
their compositions
Procedure:
ziF (1 K i )
2) solve for D/F f ( ) 0
i 1 ( K i 1)
b) Newton-Raphson
f ( ) (k )
f ' ( )
ziF (1 K i ) 2
( k 1)
(k )
2
f ' ( ( k ) ) i 1 ( K i 1)
Multicomponent flash separation (Adiabatic)
D, yi , hD
F , ziF , hF , PF , TF
P1 ,T1
B, xi , hB
- Liquid feed is heated under pressure and then adiabatically flashed through
the pressure reducing valve
P1 PF Bx i Dy i FziF
T1 TF BD F
BhB DhD FhF (1 )hB hD hF 0
Multicomponent flash separation (Adiabatic)
D, yi , hD
F , ziF , hF , PF , TF
P1 ,T1
B, xi , hB
- Liquid feed is heated under pressure and then adiabatically flashed through
the pressure reducing valve
P1 PF Bx i Dy i FziF
T1 TF BD F
BhB DhD FhF (1 )hB hD hF 0
Multicomponent flash separation (Adiabatic)
Objective: find D, B, and
their compositions
Procedure: 1) Guess T1
ziF (1 K i )
f ( ) 0
i 1 ( K i 1)
3) Validate
3) Validate
not hF hB
(1 )hB hD hF 0
hD hB
Distillation processes
Lb, xN
Distillation processes
Lb, xN
Distillation processes
Lb, xN
Distillation processes
Lb, xN
Distillation processes
Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Lin,xin Vout,yout Vm+1 ym+1
boiler
Vb, yb
Lb, xN
Lout,xout Vin,yin
Definition of a stage in a process
- Mass balance
• Overall Lin Vin Lout Vout
• Components Lin xin Vin y in Lout xout Vout yout
- Energy balance
Lin,hin Vout,hout Q
Linhin Vinhin Q Lout hout Vout hout
Lout,hout Vin,hin
Equilibrium stage processes
Lin,xin Vout,yout
Va, ya
La, xa=xd=y1=ya
condenser The idea is then to consider a
Ln-1 xn-1
hypothetical column, composed
Vn yn
R=La/D Overhead product D, xd of equilibrium stages
Ln x n
Vn+1
F, z f yn+1
Lb, xN
Distillation processes
Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb
Lb, xN
Distillation processes
stages
Lm-1 xm-1
Vm ym
- ratio of liquid and Lm xm Bottom product B, xb
vapour flowrates Vm+1 ym+1
boiler
Vb, yb
Lb, xN
Distillation processes
Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb
Lb, xN
Distillation process design
La, xa=xd
condenser
Ln-1 xn-1
Vn yn Overhead product D, xd
Ln xn
Vn+1 yn+1
F, z f
Lm-1 xm-1
Vm ym
Bottom product B, xb
Lm xm
Vm+1 ym+1
Vb, yb boiler
Lb, xN
Operating lines
Va, ya
Rectifying section
La, xa=xd=y1=ya
condenser
Ln-1 xn-1
Overhead product D, xd
Vn yn
R=La/D
Ln xn
Vn+1 yn+1
F, z f
Lm-1 xm-1
Vm ym
Bottom product B, xb
Lm xm
Vm+1 ym+1
Vb, yb boiler
Lb, xN
Operating lines
Ln D
Vn 1 yn 1 Ln xn Dx D yn 1 xn xD
Vn 1 Vn 1
This equation is a straight line (V=const, L=const, L/V=const) if:
Va, ya
L D
yn 1 xn xD La, xa condenser
V V Overhead product D, xd
R=L/D
Ln xn Vn+1 yn+1
L L L L/D R
R ; Reflux ratio
D V L D L / D D / D R 1
R 1
yn 1 xn xD
R 1 R 1
Operating lines
R 1
yn 1 xn xD
R 1 R 1
y
slope=R/(R+1)
1
xD
R 1
xD
x
Operating lines
Va, ya
La, xa
condenser
Ln-1 xn-1
Overhead product D, xd
Vn yn
R=La/D
Ln xn
Vn+1 yn+1
F, z f
Lm-1 xm-1
Stripping section
Vm ym
Bottom product B, xb
Lm xm
Vm+1 ym+1
Vb, yb boiler
Lb, xN
Operating lines
L xm V ym 1 Bx B Lm xm
Vm+1 ym+1
Bottom product B, xb
boiler
L B
ym1 xm xB y
V V
L
slope= V
yB
xB x
Operating line equation: Stage-by-stage
La, xa Va, ya
y L1, x1
Plate 1
ya Plate 2
Plate 3
x1 xa
x
Operating line equation: Stage-by-stage
La, xa Va, ya
y L1, x1
Plate 1
ya Plate 2
Plate 3
x1 xa
x
Operating line equation: Stage-by-stage
La, xa Va, ya
y L1, x1 V2, y2
Plate 1
ya Plate 2
Plate 3
F F F
L V L V L V
F F F
L
L L
Feed stage considerations q
L V F
L V L V
F F F
dew point
bubble point
q=1 vapour feed q=0
liquid feed
L V L V L V
F F F
q zF
y x
q 1 1 q L V
Feed line
L L
q
F
D
F
B
y q>1
Feed line behavior
q=1
q zF
y x 0<q<1
q 1 1 q
q=0
x=zf
x=zf
q zF
y zF zF q<0
q 1 1 q
y=zf
x
Complete picture
R 1
yn 1 xn xD
R 1 R 1
y
q zF
y x y1
q 1 1 q
L B
yn1 xm xB
V V zf
1 yB
xD
R 1
xB xN zf xD
x
Complete picture
R 1
yn 1 xn xD
R 1 R 1
y
L B
yn1 xm xB y1
V V
q zF
y x
q 1 1 q zf
yB
xB xN zf xD
x
Limiting cases
R=L/D
slope=R/(R+1)
xD
x
Limiting cases
R=L/D
slope=R/(R+1)
x
Total reflux
D=0
y
F=0 R=L/D=∞
y1
L/V=1
Ln D Vn 1
Ln Vn 1
B=0
zf
Total reflux
R 1
yn 1 xn xD
R 1 R 1 yB
If R=L/D= ∞ then R/(R+1)=1; also L=V
xB xN zf xD
yn 1 xn
x
Total reflux
D=0
y
F=0 R=L/D=∞
y1
L/V=1
Ln D Vn 1
Ln Vn 1
B=0
zf
Total reflux
R 1
yn 1 xn xD
R 1 R 1 yB
If R=L/D= ∞ then R/(R+1)=1; also L=V
xB xN zf xD
yn 1 xn
x
Minimum number of stages
a) Graphical methods y
D, xD
F, z R=L/D
B, xB
xB xD
x
xD xB
1, AB 2, AB N 1, AB
1 xD 1 xB
xD xB
( ) N min 1
1 xD 1 xB
ln[ xD (1 xB ) / xB (1 xD )]
N min 1
ln AB
Fenske equation
Limiting cases: minimum reflux
R=L/D
slope=R/(R+1)
xD
x
Limiting cases: minimum reflux
If we decrease the reflux ratio, then
R=L/D
slope=R/(R+1)
x
Limiting cases: minimum reflux
y
q zF
y x y1
q 1 1 q
R 1
yn 1 xn xD
R 1 R 1 zf
L B
yn1 xm xB
V V yB
xB xN zf xD
x
Limiting cases: minimum reflux
zf
xB xN zf xD
x
Limiting cases: minimum reflux
R 1
yn 1 xn xD
R 1 R 1 y
y1
Rmin 1
y* x* xD zf
Rmin 1 Rmin 1
x y*
Rmin D yB
y * x *
xB xN zf xD
x* x