BITS, PILANI K. K.

BIRLA GOA CAMPUS

Process Control- CHE C441
Chapter #2
Theoretical Models of Chemical Processes

Dr. Saroj Sundar Baral

Department of Chemical Engineering
9/27/2013 1 BITS, PILANI K. K. BIRLA GOA
CAMPUS
The purpose of the chapter
BITS, PILANI K. K. BIRLA GOA CAMPUS 2
3. To determine the scope and difficulties of
the mathematical modeling for process
control
1. To understand why we need to develop a
mathematical model of a chemical process as
an prerequisite to the design of its controller

2. To describe a methodology for the
modeling a chemical process.
9/27/2013
3 BITS, PILANI K. K. BIRLA GOA CAMPUS
To find the effect of disturbance on the
chemical process
1. Experimental approach
This approach is time and effort
consuming
Cost involve is high
2. Theoretical approach
Why mathematical models
are required?
9/27/2013 3 BITS, PILANI K. K. BIRLA GOA
CAMPUS
4 BITS, PILANI K. K. BIRLA GOA CAMPUS
Use of mathematical models
1.Improve understanding of the
process
2.Train plant operational personnel
3.Develop control strategy for a
new process
4.Optimize process operating
conditions
9/27/2013 4 BITS, PILANI K. K. BIRLA GOA
CAMPUS
5 BITS, PILANI K. K. BIRLA GOA CAMPUS
Different mathematical models
1. Theoretical (Provide physical insight,
applicable to wide ranges of conditions, Time
consuming, non availability of model parameter)
2. Empirical (Easier to develop, applicable to
small ranges of conditions, Few operating
conditions are included)
3. Semi-empirical (Incorporate theoretical back
ground, applicable to wide ranges of conditions,
required less effort)
9/27/2013 5 BITS, PILANI K. K. BIRLA GOA
CAMPUS
6 BITS, PILANI K. K. BIRLA GOA CAMPUS
General modeling principles
9/27/2013 6 BITS, PILANI K. K. BIRLA GOA
CAMPUS
7 BITS, PILANI K. K. BIRLA GOA CAMPUS
Conservation of mass
Conservation of mass
Conservation of Component i
Conservation of energy
9/27/2013 7 BITS, PILANI K. K. BIRLA GOA
CAMPUS
8 BITS, PILANI K. K. BIRLA GOA CAMPUS
For thermodynamic system the
Total energy is given by
Assumptions:
1.Change in potential and kinetic energy
is zero
2.The net rate of work can be neglected
because it is small compared to the rate
of heat transfer and convection
9/27/2013 8 BITS, PILANI K. K. BIRLA GOA
CAMPUS
9 BITS, PILANI K. K. BIRLA GOA CAMPUS
Degrees of freedom analysis
N
F
=N
V
-N
E

N
F
- Number of degrees of freedom
N
V
- The number of process variables
N
E
- Number of independent equations
N
F
=0: Exactly specified
N
F
>0: Under specified
N
E
<0: Over specified
9/27/2013 9 BITS, PILANI K. K. BIRLA GOA
CAMPUS
10 BITS, PILANI K. K. BIRLA GOA CAMPUS
Degrees of freedom analysis
1.List all parameter that can be specified
2.Determine the number of equation and
number of process variable
3.Calculate the number of degrees of freedom
4.Identify the output variable that can be obtain
5.Identify the input variable that must be
specified
9/27/2013 10 BITS, PILANI K. K. BIRLA GOA
CAMPUS
11 BITS, PILANI K. K. BIRLA GOA CAMPUS
Blending process
Assumption:
1. Blending tank is
perfectly mixing (No
concentration gradient
in the tank contents
and the composition in
the exit stream equal to
the tank composition)
2. Density is constant
9/27/2013 11 BITS, PILANI K. K. BIRLA GOA
CAMPUS
12 BITS, PILANI K. K. BIRLA GOA CAMPUS
Unsteady state mass balance
Unsteady state component balance
Corresponding steady state equations are
9/27/2013
13 BITS, PILANI K. K. BIRLA GOA CAMPUS
Simplified Overall mass balance equation
Simplified component balance equation
9/27/2013 13 BITS, PILANI K. K. BIRLA GOA
CAMPUS
14 BITS, PILANI K. K. BIRLA GOA CAMPUS
Modified Blending process
Assumption:
1. Blending tank is
perfectly mixing
2. Density is constant
2 1
w w w + =
9/27/2013 14 BITS, PILANI K. K. BIRLA GOA
CAMPUS
15 BITS, PILANI K. K. BIRLA GOA CAMPUS
Example:
9/27/2013 15 BITS, PILANI K. K. BIRLA GOA
CAMPUS
16 BITS, PILANI K. K. BIRLA GOA CAMPUS
Example
Analyze the degrees of freedom for the blending
system as shown in figure.
Assume that the blending tank is perfectly
mixing and density is constant
9/27/2013 16 BITS, PILANI K. K. BIRLA GOA
CAMPUS
17 BITS, PILANI K. K. BIRLA GOA CAMPUS
Example: Analyze the degrees of freedom for the
blending system as shown in figure.
Assume that the blending tank is perfectly mixing
and density is constant
9/27/2013 17 BITS, PILANI K. K. BIRLA GOA
CAMPUS
18 BITS, PILANI K. K. BIRLA GOA CAMPUS
Mathematical model for
mercury thermometer
T- Temperature of the mercury manometer
T
a
-Ambient temperature
H- is the convective heat transfer coefficient
of the fluid
L- is the length of the bulb
D- is the diameter of the bulb
Surface area of the film=dl
Mass of mercury=d
2
l/4

9/27/2013 18 BITS, PILANI K. K. BIRLA GOA
CAMPUS
19 BITS, PILANI K. K. BIRLA GOA CAMPUS
Assumptions:
1.There is no resistance offered by the bulb
2.Density of mercury is constant
( ) T T dl h T lC d

dt
d
a p
=
|
.
|

\
|
t
2
4
a
p p
T
C d
h
T
C d
h
dt
dT

4 4
= +
Parameter: h, , C
p
, d, t
Variables: T, T
a
(output T and Disturbance T
a
)
N
v
=2, N
E
=1
N
F
= N
v
-N
E
=2-1=1
For given T
a
the above equation can be used to find
out how T changing with time

9/27/2013 19 BITS, PILANI K. K. BIRLA GOA
CAMPUS
20 BITS, PILANI K. K. BIRLA GOA CAMPUS
Stirred tank heating process
(constant holdup)
Assumptions:
1.Perfect mixing
2.Liquid holdup is constant
(w
i
=w)
3. and C
p
are constant
4.Heat losses are negligible
9/27/2013 20 BITS, PILANI K. K. BIRLA GOA
CAMPUS
21 BITS, PILANI K. K. BIRLA GOA CAMPUS
Energy balance equation
Parameter: V, , C
p

Variables: T, T
i
, w, Q (output: T, Disturbance: T
i
, w and
Manipulated: Q)
N
v
=4, N
E
=1
N
F
= N
v
-N
E
=4-1=3
For given T
i
, w and Q the above equation can be used to
find out how T changing with time
9/27/2013 21 BITS, PILANI K. K. BIRLA GOA
CAMPUS
22 BITS, PILANI K. K. BIRLA GOA CAMPUS
Stirred tank heating
process (variable holdup)
9/27/2013 22 BITS, PILANI K. K. BIRLA GOA
CAMPUS
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
23
Ex. 2.1
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
24
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
25
Liquid storage tank
9/27/2013 26 BITS, PILANI K. K. BIRLA GOA
CAMPUS
If Valve is there in outlet line
9/27/2013 27 BITS, PILANI K. K. BIRLA GOA
CAMPUS

9/27/2013 28 BITS, PILANI K. K. BIRLA GOA
CAMPUS
9/27/2013 29 BITS, PILANI K. K. BIRLA GOA
CAMPUS
9/27/2013 30 BITS, PILANI K. K. BIRLA GOA
CAMPUS
9/27/2013 31 BITS, PILANI K. K. BIRLA GOA
CAMPUS
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
32
Example
Electrically heated stirred tank heater
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
33
Energy balance for the liquid in the tank
Energy balance for the heating element
Steam heated stirred tank
Assumption: The thermal capacitance of liquid
condensate is negligible compare to the thermal
capacitance of tank liquid and the wall of the coil.
Energy balance in the liquid


Energy balance in the coil
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
34
Non Isothermal CSTR
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
35
Assumption:
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
36
1.Perfect mixing
2.Mass density of product and feed are constant
3.Constant holdup
4.The thermal capacitance of coolant and coil
wall is negligible
5.All the coolant is at a uniform temperature T
C
6.The rate of heat transfer from the reactor
content to the coolant is
7.Heat of mixing is negligible to the heat of
reaction
8.Shaft work and heat loss is negligible
Mass balance

9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
37
and V are
constant
Component balance of A
Energy balance

9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
38
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
39
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
40
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
41
Three stage absorber
Assumptions:
1.Each stage is an ideal one
2.Constant liquid holdup
3.Perfect mixing
4.Gas holdup is negligible
5.Molar liquid and gas flow
rate are constant
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
42
Component material balance
Equilibrium relation:
Stage liquid residence time
The stripping factor
Gas to liquid ratio
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
43
The models for all the
three stages are
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
44
Double pipe heat exchanger
(Distributed parameter system)
Assumptions:
1. Assume plug flow
2. Steam condensation is a
lumped process
3. The wall temperature is
different than T
L
and T
S
4. The resistance to heat
transfer is within the metal
wall and thermal heat
capacitance in the steam
condensate
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
45
The energy balance for a
differential shell length z
Energy balance for the wall
Characteristic time
Biological Reactions
Biological reactions that involve micro-organisms
and enzyme catalysts are pervasive and play a
crucial role in the natural world.
Without such bioreactions, plant and animal life, as
we know it, simply could not exist.
Bioreactions also provide the basis for production of
a wide variety of pharmaceuticals and healthcare
and food products.
Important industrial processes that involve
bioreactions include fermentation and wastewater
treatment.
Chemical engineers are heavily involved with
biochemical and biomedical processes.
C
h
a
p
t
e
r

2

Bioreactions

Are typically performed in a batch or fed-batch reactor.
Fed-batch is a synonym for semi-batch.
Fed-batch reactors are widely used in the pharmaceutical
and other process industries.
Bioreactions:


Yield Coefficients:







substrate more cells + products (2-90)
cells

/
(2-92)
P S
mass of product formed
Y
mass of substrate consumed to form product
=
/
(2-91)
X S
mass of newcells formed
Y
mass of substrate consumed to form newcells
=
Fed-Batch Bioreactor

Figure 2.11. Fed-batch reactor
for a bioreaction.
Monod Equation


Specific Growth Rate



(2-93)
g
r X =
max
(2-94)
s
S
K S
=
+
C
h
a
p
t
e
r

2

Modeling Assumptions

1. The exponential cell growth stage is of interest.
2. The fed-batch reactor is perfectly mixed.
3. Heat effects are small so that isothermal reactor
operation can be assumed.
4. The liquid density is constant.
5. The broth in the bioreactor consists of liquid plus
solid material, the mass of cells. This heterogenous
mixture can be approximated as a homogenous liquid.
6. The rate of cell growth r
g
is given by the Monod
equation in (2-93) and (2-94).
General Form of Each Balance

/
(2-96)
P X
mass of product formed
Y
mass of newcells formed
=
Modeling Assumptions (continued)

7. The rate of product formation per unit volume r
p
can
be expressed as
/
(2-95)
p P X g
r Y r =
where the product yield coefficient Y
P/X
is defined as:
8. The feed stream is sterile and thus contains no cells.
{ } { } { }
(2-97) Rate of accumulation rate in rate of formation = +
C
h
a
p
t
e
r

2

Individual Component Balances

Cells:

Product:

Substrate:


Overall Mass Balance
( )
(2-98)
g
d XV
V r
dt
=
1 1
(2-100)
f g P
X / S P / S
d( SV )
F S V r V r
dt Y Y
=
( )
(2-101)
d V
F
dt
=
( )
(2-99)
p
d PV
Vr
dt
=
C
h
a
p
t
e
r

2

9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
52
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
53
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
54
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
55
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
56
Solution
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
57
Ideal binary distillation column
Assumptions:
1. Vapor holdup in each tray is negligible
2. Molar heat of vaporization of both component A and B
are approximately constant
3. Heat loss to the surrounding is negligible
4. The relative volatility is constant throughout the column
5. Each tray is assume to be ideal
The 1
st
three assumption imply that V
1
=V
2
==V
N
and no energy
balance for each tray is required.
The last two assumptions imply that V-L relationship can be used
to find y
i
and x
i
6. Neglect the dynamic of the condenser and reboiler
7. Neglect the momentum balance for each tray. Also assumed
that the liquid flow rate in each tray depends on the liquid
holdup L
i
=f(M
i
)

9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
58
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
59
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
60
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
61
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
62
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
63
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
64
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
65
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
66
Modeling difficulties
Difficulties in modeling of CSTR
Determining the process parameter, k
0
, E & U
C
p
, and H
r
is function of Temperature
and concentration
U
0
changes with time because of fouling
Reaction rate
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
67
The three type of difficulties
in process modeling
Poorly understand process
Imprecise known parameters
Size and complexity of the
model
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
68
Poorly understand process
Exa. Fluidized catalytic cracking
The reaction rate of the cracking process
The rate with which carbon and heavy materials
deposited on catalyst surface
The dependence of the above two rate on the
temperature and quality of feed
The rate of regeneration and its temperature
dependancy
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
69
Imprecise known parameters
Accuracy of the process parameter (,
Hr, U0, Cp, Activity of catalyst, dead
time
Even if catalyst activity is known it is
time dependant
Experimental values are required
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
70
Size and complexity of the model
Example: Distillation with 20 trays (two
component system)
2N+4=2*20+4=44 differential equation
2N+1=2*20+1=41 algebraic equation
Most distillation column deals with multi-
component system with large number of trays
9/27/2013 BITS, PILANI K. K. BIRLA GOA
CAMPUS
71