Chemical Engineering Technology

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 study its properties
- to investigate all possible
pathways from one substance to
another

- to design the most optimal technology

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
- Pumps
- Distillation units
- Reactors
-

- Heat exchange
- Material transport
- Separation
- Mixing
-

What is 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
- fluid transport
- solids fluidization
- mixing

Thermodynamic processes
- liquifaction
- refrigeration
Mechanical processes

Heat transfer processes

- heating/cooling
- evaporation/condensation
Mass transfer processes
- absorption
- distillation
- extraction
- adsorption
- drying

- crushing
- sieving
- solid transportation

Chemical separation processes:

required background
V

- How do we know that at pressure P

and temperature T, vapour and liquid
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

exchanged by two phases?

La,xa

- 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

Use

Gas Absorption
Crystallization
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+B
nF

n2

- A and B an be somehow different:

- boiling points
- size
- polarity
- etc.

SF n1 ( A) / nF ( A) split factor
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

Tb(B)

L
T, P
Tb(A)
L

x*

y*

xA

Thermodynamic considerations and phase

equilibria
T

Tb(B)

Tb(A)
L

x*

y*

xA

Thermodynamic considerations and phase

equilibria
T

Distribution of a component
among the two phases can
be characterized with a K-value

Tb(B)

KA = yA/xA
KB = yB/xB
=(1-yA)/(1-xA)

Tb(A)
L

Relative volatility
x*

y* xA

AB

K A y A / xA

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
T3

T1
T2
T3

T2

T4
Tb(A)

x1

x2

T1

x3 y1

x4 y2

y3 y4

xA

xA

Binary fluids: Examples

Benzene-toluene binary mixture

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

- 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
Raoults law (Ideal solution/ideal gas):

pi xi Pi s

pi is the partial pressure of component i

pi yi P
K-value for ideal gas/ideal solution system:

K i Pi s / P
Relative volatility for ideal gas/ideal solution system:

K i / K j Pi s / Pjs
ln Pi s Ai

L
T, P

Daltons law (Ideal gas):

Antoine equation:

Bi
T Ci

Thermodynamic calculations using K-values

Bubble point
- Model system: binary mixture A, B

x A xB 1
- Consider the process in the figure: we start with
a mixture of composition 1 and temperature T1
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:

y A yB 1

- On the other hand:

K A (T ) x A 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

d) if

K x

i i

1T is too high

e) Adjusting T
g) Final composition can be corrected using

K i xi
yi
K i xi
i

Thermodynamic calculations using K-values

Dew point
1

- Model system: binary mixture A, B

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
- 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:

x A xB 1

- On the other hand:

y A / K A (T ) y B / 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
i K
i
yi
1
d) if
i Ki
c)

T is too low

e) Adjusting T
g) Final composition can be corrected using

yi / K i
xi
yi / K i
i

Distillation processes

Distillation is a process where a

feed mixture of two or more
components is separated into
products, of compositions different
from the feed. This process takes
advantage of the differences in
distribution of components between
the vapour and liquid phase.

Va, ya
condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

The feed is material is introduced

at one or more points along the
column.
Liquid runs down the column from
tray to tray, where as vapour is
ascending along the column.
At each tray vapour and liquid
contact and mix with each other

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

Liquid at the bottom of the column

is partially vaporized in a heated
reboiler.
The boil-up is send back to the
column.
The rest is withdrawn as bottoms,
or bottoms product

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

Vapour at the top of the column is

cooled and condensed in the
overhead condenser.
Part of this liquid is returned back
to the column and the rest is
withdrawn as distillate or overhead
product

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

At each stage of the column two

phases come in contact with each
other, mix, approach thermal and
composition equilibrium to the
extent which depends on the
efficiency of the contact stage

Va, ya
condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Lin,xin

Lout,xout

Vout,yout

Vin,yin

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Definition of a stage in a process

Lin,xin

Vout,yout

Lout,xout

Vin,yin

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
with new compositions

- Mass balance
Overall
Components

Lin Vin Lout Vout

Lin xin Vin y in Lout xout Vout yout

- Energy balance
Lin,hin

Vout,hout

Lout,hout

Vin,hin

Lin hin Vin h in Q Lout hout Vout hout

Equilibrium stage processes

Lin,xin

Vout,yout

Lout,xout

Vin,yin

Streams leaving the stage are in thermodynamic

equilibrium with each other

Streams coming to the stage: not in equilibrium

Va, ya
condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, zf

R=La/D

Overhead product D, xd

The idea is then to consider a

hypothetical column, composed
of equilibrium stages

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

This idealistic design can be

converted to the actual design via
analysis of tray efficiency

Distillation processes

Va, ya

The lighter component tends to

accumulate in the vapour phase

condenser
La, xa=xd=y1=ya

The heavier component tends to

accumulate in the liquid phase

Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

In general, the overall separation

process depends on:

condenser
La, xa=xd=y1=ya

- relative volatilities

Ln-1 xn-1
Vn yn
Ln xn

- number of contacting
stages
- ratio of liquid and
vapour flowrates

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

If the feed is introduced at one point, it

divides the column into a rectifying
and stripping sections
But usually there are multiple feed
location and various side streams

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, z f

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym
Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

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
Ln-1 xn-1

Ln xn

condenser
Overhead product

Vn yn

D, xd

Vn+1 yn+1

F, z f
Lm-1 xm-1
Vm ym

Bottom product

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

B, xb

Operating lines
Rectifying section

Va, ya
La, xa=xd=y1=ya
Ln-1 xn-1

Ln xn

R=La/D

Vn yn

condenser
Overhead product

D, xd

Vn+1 yn+1

F, z f
Lm-1 xm-1
Vm ym

Bottom product

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

B, xb

Operating lines
Vn 1 yn 1 Ln xn DxD yn 1

Ln
D

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

y n 1

Va, ya

L
D

xn
xD
V
V

La, xa
R=L/D

Ln xn

L
;
D

yn 1

Overhead product

Vn+1 yn+1

L
L
L/D
R

V L D L / D D / D R 1

R
1

xn
xD
R 1
R 1

condenser

Reflux ratio

D, xd

Operating lines

yn 1

R
1

xn
xD
R 1
R 1
y

slope=R/(R+1)

1
xD
R 1
xD
x

Operating lines
Va, ya
La, xa
Ln-1 xn-1

Ln xn

R=La/D

Vn yn

condenser
Overhead product

D, xd

Vn+1 yn+1

Stripping section

F, z f
Lm-1 xm-1
Vm ym

Bottom product

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

B, xb

Operating lines

L xm V ym 1 BxB

L
B
yn 1 xm xB
V
V

Lm xm
Vm+1 ym+1

Bottom product
boiler

B, xb

slope= V

yB

xB

Operating line equation: Stage-by-stage

La, xa
y

L1, x1

ya

Va, ya
Plate 1

Plate 2

Plate 3

x1

xa

Operating line equation: Stage-by-stage

La, xa
y

L1, x1

ya

Va, ya
Plate 1

Plate 2

Plate 3

x1

xa

Operating line equation: Stage-by-stage

y
ya

La, xa

Va, ya

L1, x1

V2, y2

Plate 1

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.

x1

xa

This process can be continued to

calculated the number of theoretical
stages. This method of graphical
construction of theoretical stages is called
McCabe Thiele method

Feed stage considerations

L

V
F

dew point
vapour feed

bubble point
liquid feed

subcooled
liquid feed

superheated
vapour feed

partially vaporized
feed

Feed stage considerations

L

L L
V V
q
1
F
F

Feed stage considerations

L

bubble point
liquid feed

subcooled
liquid feed

q>1

dew point
vapour feed

q=1

q=0

L L
F

superheated
vapour feed

q<0

partially vaporized
feed

0<q<1

Feed stage considerations

F

L L qF L L F
V V (1 q) F V V (1 q ) F

Vy Lx DxD

rectifying section

V y L x BxB

stripping section

y (V V ) ( L L ) x DxD BxB
q
zF
y
x
q 1
1 q

FzF
Feed line

D
F
B

q
zF
y
x
q 1
1 q
x=zf

q
zF
y
zF
zF
q 1
1 q

q>1
q=1

y=
x

Feed line behavior

0<q<1
q=0
x=zf

q<0

y=zf
x

Complete picture
yn 1

R
1

xn
xD
R 1
R 1

q
zF
y
x
q 1
1 q

L
B
yn 1 xm xB
V
V

y
y1

zf

yB
1
xD
R 1
xB xN

zf

xD
x

Complete picture
yn 1

R
1

xn
xD
R 1
R 1

L
B
yn 1 xm xB
V
V
q
zF
y
x
q 1
1 q

y
y1

zf

yB
xB xN

zf

xD
x

Limiting cases
y
R=L/D
slope=R/(R+1)

xD
x

Limiting cases
y
R=L/D

slope=R/(R+1)

Total reflux
Total reflux=Minimum number of stages
D=0
R=L/D=
L/V=1

F=0

y
y1

Ln D Vn 1
Ln Vn 1
B=0
Total reflux

yn 1

R
1
xn
xD
R 1
R 1

zf

yB

If R=L/D= then R/(R+1)=1; also L=V

yn 1 xn

xB

xN

zf

xD
x

Total reflux
Total reflux=Minimum number of stages
D=0
R=L/D=
L/V=1

F=0

y
y1

Ln D Vn 1
Ln Vn 1
B=0
Total reflux

yn 1

R
1
xn
xD
R 1
R 1

zf

yB

If R=L/D= then R/(R+1)=1; also L=V

yn 1 xn

xB

xN

zf

xD
x

Minimum number of stages

a) Graphical methods

D, xD
F, z

R=L/D

B, xB
xB

b) Short cut methods: Fenske Equation

xD

Fenske Equation
Under the total reflux condition: operating line equations become:

y n 1 xn
ym 1 xm
Consider a relative volatility coefficient for a binary mixture of A and B:

AB

y A / xA
y
y
AB B A
y B / xB
xB x A

For a binary mixture, yA+yB=1, and xA+xB=1, so skipping the A, B subscripts and rewriting everything
for the light component A:

1 y y
AB

1 x x

Fenske Equation
1 y y
AB

1 x x
For a particular stage n+1:

1 yn 1 yn 1
yn 1
xn 1
n 1, AB

n 1, AB
1 xn 1 xn 1
1 yn 1
1 xn 1
At the same time:

So

yn 1 xn

xn
xn 1
n 1, AB
1 xn
1 xn 1

Fenske Equation
xn
xn 1
n 1, AB
1 xn
1 xn 1
xD
x1
1, AB
1 xD
1 x1
x1
x2
2, AB
1 x1
1 x2
xn 1
xD
1, AB 2, AB n 1, AB
1 xD
1 xn 1

Fenske Equation
xD
xB
1, AB 2, AB N 1, AB
1 xD
1 xB
xD
xB
N min 1
( )
1 xD
1 xB

N min

ln[ xD (1 xB ) / xB (1 xD )

1
ln AB
Fenske equation

Limiting cases: minimum reflux

y
R=L/D
slope=R/(R+1)

xD
x

Limiting cases: minimum reflux

If we decrease the reflux ratio, then

y
R=L/D
slope=R/(R+1)

Limiting cases: minimum reflux

If we decrease the reflux ratio, then

q
zF
y
x
q 1
1 q
yn 1

R
1

xn
xD
R 1
R 1

L
B
yn 1 xm xB
V
V

y
y1

zf

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
intersect at the equilibrium line.

y
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

yn 1

R
1

xn
xD
R 1
R 1

y
y1

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

y*

Rmin
1
y*
x*
xD
Rmin 1
Rmin 1
Rmin

xD y *

y*X *

zf

yB
xB xN

zf
x*

xD
x