Unit Operations: Introduction

What is chemical engineering? Chemical Engineering is a group of

industrial processes in which row materials are changed or separated
into useful products

Historical development: As the Industrial Revolution steamed along

certain basic chemicals quickly became necessary to sustain growth

- Example: Sulfuric acid was first among these "industrial chemicals".

Chemistry: Chemical Engineering:

- to create a new substance - to design the most optimal technology

- to study its properties
- to investigate all possible
pathways from one substance to
another
for production of a specified substance
from row materials
- to develop and discover new
technological applications for materials
http://www.pafko.com/
Process flowsheet: Example 1
Process flowsheet: Example 2
 Comparison of two processes

Units: Actions:

- Heaters/heat exchangers - Heat exchange

- Pumps - Material transport
- Distillation units - Separation
- Reactors - Mixing
-… -…
Unit Operations:

- Unit Operations is a method of analysis and design of chemical

engineering processes in terms of individual tasks/operations

- It is a way of organizing chemical engineering knowledge into

groups of individual tasks/operations

- A unit operation: basic step in a chemical engineering process

Unit Operations: Classification

Fluid flow processes Thermodynamic processes

- fluid transport - liquifaction

- solids fluidization - refrigeration
- mixing
Mechanical processes
Heat transfer processes
- crushing
- heating/cooling - sieving
- evaporation/condensation - solid transportation

Mass transfer processes

- absorption
- distillation
- extraction
- adsorption
- drying
 Section
1. Introduction, revision,
binary distillation with non-
constant molar overflow
2. Separation of
multicomponent mixtures
3. Separations in packed
columns. Absorption
4. Adsorption processes
5. Humidification processes
6. Drying processes
7. Revision and problems
http://www.see.ed.ac.uk/~lsarkiso/UnitOps/syllabus.htm
Lectures Tutorial
1.1 Introduction to Unit Operations;
Equilibrium stage operations (L1)
1.2 Thermodynamics of distillation (L2)
1.3 Binary distillations review (L3)
2.1 Multicomponent Distillation: Flash
distillation (L4)
2.2 Multicomponent Distillation: Short
Cut Methods (L5)
2.3 Multicomponent Distillation: Short
Cut Methods (L6)
3.1 Mass transport theories review (L7)
3.2 Mass transport theories review (L8)
3.3 Packed bed columns (L9)
3.4 Packed bed columns (L10)
4.1 Principles of adsorption (L11)
4.2 Principles of adsorption (L12)
5.1 Principles of humidification (L13)
5.2 Methods of humidification (L14)
6.1 Principles of drying (L15)
6.2 Methods of drying (L16)
7.1 Revision (L17)
7.2 Revision (L18)
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?

- What is the composition of the phases?

B
Chemical engineering thermodynamics

Va,ya
- How do we know the amount of mass
La,xa exchanged by two phases?

- What is the new composition of the

phases?

Vb,yb Lb,xb
Mass transfer methods
 Chemical separation processes

- play a central role in chemical engineering

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

SP  SR( A) / SR( B) separation power

Distillation process design

- Separation utilizes the difference in volatility of

components

Step 1: Thermodynamics data and methods to predict equilibrium

phase compositions
Thermodynamic considerations and phase
equilibria: Binary fluids

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)

- K-values, relative volatilities

DePriester charts

- Analytical methods (part of most chemical process design software)

ASPEN Tech
See a brief ‘Thermodynamics of multicomponent
phase equilibria file’

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

Most often such data (including binary systems) is represented in terms of

K values defined as:

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  xi Pi s pi is the partial pressure of component i

L
T, P
Dalton’s law (Ideal gas):

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)

-Given P, T, V/(V+L), find

x*, y*
Tb(A)
- Given P, T, x*, y* , find
V/(V+L) L

x* y*
xA
Easy for 2 component system, if T-x-y diagram is available
(remember the lever rule?)

What about the multi-component system?

Thermodynamic calculations using K-values
Bubble point
- Model system: binary mixture A, B
T
xA  xB  1
V

- Consider the process in the figure: we start with

a mixture of composition 1 and temperature T1
L and start increasing the temperature
1
- As we increase the temperature we are going to
reach a point where the first bubble forms

- The vapour in this bubble obeys:

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

- The liquid in the droplet obeys:

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

- How do you know that you a 2-phase system?

- How much vapour do you have per mole of the system?

- What is the composition of the vapour and liquid phases?

 Isothermal flash separation
D, yi , hD
T
V
Tb(B) P1 ,T1 F , ziF , hF
P1 ,T1
Tb(A)
L

x* y*
B, xi , hB
xA
- The liquid mixture is partially vaporized
in a boiler (or vapour condensed in a cooler)

- How do you know that you a 2-phase system at a given T and P?

- How much vapour did you form per mole of feed?

- What is the composition of vapour and liquid phases?

Isothermal flash separation
D, yiD , hD

Objective: find D, B, and F , ziF , hF

their compositions P1 ,T1

  D/F

B, xiB , hB
Isothermal multicomponent flash separation
D, yiD , hD

Objective: find D, B, and F , ziF , hF , PF , TF

their compositions P1 ,T1

B, xiB , hB
ziF (1  K i )
i 1   ( K  1)  0
i

Rachford-Rice equation

- drums, condensers, reboilers etc

Isothermal multicomponent flash separation
Objective: find D, B, and
their compositions

Procedure:

1) Check the feasibility of the process: do you have two phases in coexistence
at given T, P?

a) all Ki > 1 – superheated vapour

b) all Ki < 1 – subcooled liquid
c) some Ki>1 and some Ki<1, then try

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 BD  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 BD  F
BhB  DhD  FhF (1   )hB  hD  hF  0
Multicomponent flash separation (Adiabatic)
Objective: find D, B, and
their compositions

Procedure: 1) Guess T1

2) Isothermal flash procedure

ziF (1  K i )
f ( )   0 
i 1   ( K i  1)

3) Validate

(1   )hB  hD  hF  0 not

Multicomponent flash separation (Adiabatic)
Objective: find D, B, and
their compositions

Procedure: 1) Guess   D/F

2) Isothermal flash procedure

find temperature of the flash drum

so that:
ziF (1  K i )
f ( Ki )   0 T1
i 1   ( K i  1)

3) Validate
not hF  hB
(1   )hB  hD  hF  0 
hD  hB
 Distillation processes

Distillation is a process where a Va, ya

feed mixture of two or more
La, xa=xd=y1=ya
condenser
components is separated into
products, of compositions different Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
from the feed. This process takes Ln xn
Vn+1
advantage of the differences in F, z f yn+1

distribution of components between

the vapour and liquid phase. Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

The feed is material is introduced Va, ya

at one or more points along the
La, xa=xd=y1=ya
condenser
column.
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
Liquid runs down the column from Ln xn
Vn+1
tray to tray, where as vapour is F, z f yn+1

ascending along the column.

Lm-1 xm-1
Vm ym
At each tray vapour and liquid Lm xm Bottom product B, xb
contact and mix with each other Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

Liquid at the bottom of the column Va, ya

is partially vaporized in a heated
La, xa=xd=y1=ya
condenser
reboiler.
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
The boil-up is send back to the Ln xn
Vn+1
column. F, z f yn+1

The rest is withdrawn as bottoms, Lm-1 xm-1

Vm ym
or bottoms product Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

Vapour at the top of the column is Va, ya

cooled and condensed in the
La, xa=xd=y1=ya
condenser
overhead condenser.
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
Part of this liquid is returned back Ln xn
Vn+1
to the column and the rest is F, z f yn+1

withdrawn as distillate or overhead

product Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

At each stage of the column two Va, ya

phases come in contact with each
La, xa=xd=y1=ya
condenser
other, mix, approach thermal and
composition equilibrium to the Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
extent which depends on the Ln xn
Vn+1
efficiency of the contact stage F, z f yn+1

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

Lin,xin Vout,yout A single stage is a device or a subunit of the process,

where two (or more) phases of a different composition
come in contact with each other, exchange and leave
Lout,xout Vin,yin with new compositions

- 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

Streams leaving the stage are in thermodynamic

equilibrium with each other
Lout,xout Vin,yin

Streams coming to the stage: not in equilibrium

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

This idealistic design can be

Lm-1 xm-1
Vm ym converted to the actual design via
Lm xm
Vm+1 ym+1
Bottom product B, xb analysis of tray efficiency
boiler
Vb, yb

Lb, xN
 Distillation processes

The lighter component tends to Va, ya

accumulate in the vapour phase
La, xa=xd=y1=ya
condenser

The heavier component tends to Ln-1 xn-1

Vn yn
R=La/D Overhead product D, xd
accumulate in the liquid phase Ln xn
Vn+1
F, z f yn+1

Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

In general, the overall separation Va, ya

process depends on:
La, xa=xd=y1=ya
condenser

- relative volatilities Ln-1 xn-1

Vn yn
R=La/D Overhead product D, xd
Ln xn
Vn+1
- number of contacting F, z f yn+1

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

If the feed is introduced at one point, it Va, ya

divides the column into a rectifying
La, xa=xd=y1=ya
condenser
and stripping sections
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
But usually there are multiple feed Ln xn
Vn+1
location and various side streams F, z f yn+1

Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
Distillation process design

Step 1: Thermodynamics data and methods to predict equilibrium

phase compositions

Step 2: Design of equilibrium stage separation

• Design problem type 1: To determine the number

of equilibrium stages required to accomplish the
desired separations

• Design problem type 2: Given a particular column

design, determine separation that can be accomplished

Step 3: Develop an actual design by applying the stage efficiency analysis

to equilibrium stage design
Design of equilibrium stage distillation: Binary
Mixtures Review
Va, ya

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:

- Two components have similar and constant molar

enthalpies of vaporization (latent heats)

- Component sensible enthalpies changes and heats of mixing

are negligible (compared to latent heats)

- The column is well insulated (adiabatic)

- Pressure is uniform throughout the column

Operating lines

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
ym1  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

Using the operating line equation we can

calculate y2 from x1. This step is depicted
by think green line in the graphs.

This process can be continued to

calculated the number of theoretical
x1 xa stages. This method of graphical
x construction of theoretical stages is called
McCabe Thiele method
 Feed stage considerations
L V L V L V

F F F

bubble point dew point

liquid feed vapour feed

L V L V L V

F F F

subcooled superheated partially vaporized

liquid feed vapour feed feed
Feed stage considerations
L V
L L V V
q  1 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

subcooled superheated partially vaporized

liquid feed
q>1 vapour feed
q<0 feed 0<q<1
Feed stage considerations
F
L V

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
yn1  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
yn1  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

Total reflux=Minimum number of stages

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

Total reflux=Minimum number of stages

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

b) Short cut methods: Fenske Equation

Fenske Equation

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

If we decrease the reflux ratio, then

y
q zF
y x y1
q 1 1  q

R 1
yn 1  xn  xD
R 1 R 1 zf

L B
yn1  xm  xB
V V yB

xB xN zf xD
x
Limiting cases: minimum reflux

If we decrease the reflux ratio, then we

are arriving at a condition where both
the rectifying, stripping and feed line y
intersect at the equilibrium line.
y1

In order for this process to take place we

need an infinite number of plates

zf

The minimum reflux

ratio condition
yB

xB xN zf xD
x
 Limiting cases: minimum reflux

R 1
yn 1  xn  xD
R 1 R 1 y
y1

At this point: xn=x* and yn+1=y*

y*

Rmin 1
y*  x* xD zf
Rmin  1 Rmin  1
x  y*
Rmin  D yB
y * x *

xB xN zf xD
x* x