Week 3

KKEK 3152 Modelling of Chemical Processes
Week 3: Model Development
Lecturer: Tan Chee Keong

Semester 1, Session 2016/2017
Department of Chemical Engineering
University of Malaya
Refresh of Previous Lecture

Chemical Process Models
Degree of Freedom Analysis
Summary
Previous Lecture
Introduction to process models: what is process modelling,
why process modelling etc
Different types of modelling equations, i.e., algebraic equations, ordinary differential equations and partial differential
equations
Different classification of process models, e.g. linear vs
nonlinear.
Today we are going to learn to develop chemical process
models from the first principle.
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Summary
Conservation Principle
Examples
Constitutive Relationships
Examples
The basis for all theoretical process models is the conversation principle.
[Input] [Output] + [Internal Production] = [Accumulation]
(1)
We can also express the conservation principle in terms of
rates (per unit time):

Rate of
Rate of
Rate of
+
input of S
output of S
production of S

Rate of
=
accumulation of S
where S is a conserved quantity within the boundaries of a
system.
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Summary
Examples
Examples
Mass Balance
Mass balance:

Rate of
Rate of
input of mass
output of mass

Rate of
Rate of
+
=
generation of mass
accumulation of mass
The rate of mass accumulation in a system has the form
where m is the total mass in the system.
dm
in m
out + m
generated
=m
dt
dm
dt
(2)
If Ni is used to represent the moles of component i in a

i
system, then dN
dt represents the molar rate of accumulation
of component i in the system.
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Summary
Examples
Examples
Energy Balance
Energy balance:

Rate of
Rate of
input of energy
output of energy

Rate of
Rate of
+
=
generation of energy
accumulation of energy
Similarly, the rate of energy accumulation has the form
where E is the total energy in ta system.
dE
= E in E out + E generated
dt
dE
dt
(3)
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Summary
Examples
Examples
Liquid Surge Tank
Fi
Consider a liquid surge tank with one inlet stream and one
outlet stream, as shown in Figure 1. Find how the height of
the tank varies as a function of time.
Here we define:
Fi = inlet volumetric flow rate
(vol/time)
Fo = outlet volumetric flow
rate
V = volume of liquid
Fo
Figure 1: A tank system
h = height of liquid
= liquid density (mass/vol)
A = cross-sectional area
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Summary
Examples
Examples
Liquid Surge Tank

By using the conservation of mass:

Rate of
Rate of
input of mass
output of mass

Rate of
=
accumulation of mass
Rate of input of mass: Fi
Rate of output of mass: Fo
Rate of accumulation of mass:
dm
dt
d(V )
dt
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Summary
Examples
Examples
Liquid Surge Tank

Conservation of mass gives:
d(V )
= Fi Fo
dt
Assuming constant density , (4) can be simplified to:
(4)
dh
= Fi Fo
(5)
dt
The outlet flow rate can be assumed to be proportional to
the square root of the height of liquid in the tank:
dh
Fi
k
=
h
(6)
dt
A
A
Given the initial condition, we can predict how the height of
the tank changes with the inlet flow rate Fi (t), by solving
ODE (6).
A
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Summary
Examples
Examples
Blending System
Consider an isothermal blending system as shown in Figure 2. w represents mass flow rate (mass/time) while x, x1
and x2 represent the mass fraction of component A. Obtain
the overall mass balance and mass balance on component
A.
Figure 2: A blending system

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Summary
Examples
Examples
Blending System
Mass balance:
dm
= w1 + w2 w
dt
dV
= w1 + w2 w
dt
(7)
(8)
(assuming constant density)

Component A mass balance:
d(mx)
= w1 x1 + w2 x2 wx
dt
(9)
(assuming perfect mixing)

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Summary
Examples
Examples
Blending System
Substituting m = V into (9)
d(Vx)
= w1 x1 + w2 x2 wx
dt
dV
dx
x
+ V
= w1 x1 + w2 x2 wx
dt
dt
(10)
(11)
Substitute (8) into (11):

x(w1 + w2 w) + V
dx
= w1 x1 + w2 x2 wx
dt
(12)
Simplifying:
dx
w1
w2
=
(x1 x) +
(x2 x)
dt
V
V
(13)
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Summary
Examples
Examples
Some chemical processes require more than simple material balances to define the modelling equations.
These required relationships are known as constitutive equations.
Examples: Ideal gas law, chemical reactions and heat transfer correlations.
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Summary
Examples
Examples
Ideal Gas Law
Process systems containing a gas will normally require a

gas law expression in the model.
The ideal gas law is commonly used to relate molar volume,
pressure and temperature:
= RT
PV
(14)
represents the molar volume.

where V
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Summary
Examples
Examples
Chemical Reactions
The rate of reaction per unit volume (mol/volume*time) is
usually a function of the concentration of the reacting species.
Consider the following reaction:

k
A + 2B
C + 3D
If the rate of reaction of A is first-order in both A and B, the
rate of reaction can be expressed as:
rA = kCA CB
(15)
where rA is the rate of reaction of A (mol A/volume*time), k

is the reaction rate constant, CA and CB are concentrations
of A and B respectively (mol A or B/volume).
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Summary
Examples
Examples
Chemical Reactions
The minus sign indicates that A is consumed in the reaction.
We can also express the rate of reaction with respect to

other compounds:
rB = 2rA = 2kCA CB
(16)
rC = rA = kCA CB
(17)
rD = 3rA = 3kCA CB
(18)
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Summary
Examples
Examples
Chemical Reactions
Usually the reaction rate coefficient is a function of temperature. The most commonly used representation is the Arrhenius rate law:
k (T ) = AeE/RT
(19)
where k (T ) is the reaction rate constant, A is the preexponential factor, E is the activation energy, R is the ideal
gas constant and T is the absolute temperature.
A and E can be estimated by having the data of the reaction
constant as a function of reaction temperature:

E 1
ln k = ln A
(20)
R T
where A and E can be found from the intercept and slope
of a plot of (ln k ) vs T1 .
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Summary
Examples
Examples
Heat Transfer
The rate of heat transfer through a vessel wall seperating

two fluids (a jacketed reactor, for example) can be described
by:
Q = UAT
(21)
where Q is the rate of heat transferred, U is the overall heat
transfer coefficient, A is the area for heat transfer and T
is the difference between hot and cold fluid temperature.
The heat transfer coefficient is often estimated from experimental data.
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Summary
Examples
Examples
Thermodynamics
The total energy (TE) of a system consists of internal (U),
kinetic (KE) and potential energy (PE).
TE = U + KE + PE
where the kinetic and potential energy terms are:
1
KE = mv 2
2
PE = mgh
(22)
(23)
(24)
For most chemical processes where there are thermal effects, we will neglect the KE and PE terms because their
contribution is significantly less than that of U.
When dealing with flowing systems, we will work with enthalpy. Total enthalpy is defined as:
H = U + pV
(25)
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Summary
Examples
Examples
Stirred Tank Heating System

Consider a perfectly mixed stirred-tank heater, with a single feed stream and a single product stream, as shown in
Figure 3. Assuming that the flow rate and temperature of
the inlet stream and heat added per unit time Q can vary,
develop a model to find the tank temperature as a function
of time. State your assumptions.
Ti
Fi
V
Q
Heater
T
F
Figure 3: Stirred tank heater

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Summary
Examples
Examples

By assuming constant density, mass balance gives:
dV
= Fi F
(26)
dt
Energy balance:

Rate of
Rate of
input of energy
output of energy

Rate of
Rate of
+
=
heat addition
accumulation of energy
dH
+Q
= Fi Hi F H
(27)
dt
is the specific enthalpy:
where H
Z T
H=
Cp dT
(28)
Tref
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Summary
Examples
Examples

Assume constant specific heat capacity:
= Cp (T Tref )
H
Hi = Cp (Ti Tref )
(29)
(30)
where Tref is the reference temperature and Cp is the specific heat capacity.
The total enthalpy of the system is:
H = V H
(31)
Assume perfect mixing such that the outlet temperature is

equal to the temperature T of the bulk liquid. We also assume no heat loss to the surrounding. Combining:
d [VCp (T Tref )]
= Fi Cp (Ti Tref ) FCp (T Tref ) + Q
dt
(32)
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Summary
Examples
Examples

Assume constant physical property Cp , the left-hand-side of
(32) can be expanded into:
d [VCp (T Tref )]
dV
d(T Tref )
= Cp (T Tref )
+ VCp
dt
dt
dt
(33)
Substituting (26) into (33):
d [VCp (T Tref )]
dT
= Cp (T Tref )(Fi F )+VCp
(34)
dt
dt
Substitute (34) into (32):
dT
dt
= Fi Cp (Ti Tref ) FCp (T Tref ) + Q (35)
Cp (T Tref )(Fi F ) + VCp
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Summary
Examples
Examples
Simplifying:
dV
= (Fi F )
dt
dT
Fi
Q
= (Ti T ) +
dt
V
VCp
(36)
(37)
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Summary
Examples
Examples
Batch Reactor
In a batch reactor, a given amount of material (reactant) is

introduced, and no material is fed or collected as the reaction proceeds.
Consider a batch reactor with a reaction where component
A reacts to form the desired component B irreversibly, in a
first-order reaction:
k
1
A
B
Develop a model which describes the concentration of component A as a function of time.
24 / 40

Summary
Examples
Examples
Batch Reactor
Material balance gives:

Rate of flow
Rate of flow
into the system

out of the system

Rate of
Rate of
+
=
generation
accumulation
Component balance on material A:
Rate of flow of A into the reactor = 0
Rate of flow of A out of the reactor = 0
Rate of generation of A due to chemical reaction = rA V
where V is the reactor volume.
Rate of accumulation of A =
dNA
dt
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Summary
Examples
Examples
Batch Reactor
Hence,
dNA
= rA V
dt
1 dNA
d(NA /V )
dCA
=
=
= rA
V dt
dt
dt
Since the equation is a first-order reaction,
rA = kCA
(38)
(39)
(40)
where the negative sign indicates that component A is being

consumed.
Finally,
dCA
= kCA
dt
(41)
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Summary
Examples
Examples
Continuous Stirred Tank Reactor

The continuous flow stirred-tank reactor (CSTR) is a common type of reactor in chemical engineering. The following
figure shows a CSTR:
Fi
CAi
V
CA
CB
Fo
CA , CB
Consider the following first-order reaction:

k
B
A
Find how the concentration of reactant A changes with time.
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Summary
Examples
Examples

Assuming constant density, mass balance gives:
dV
= Fi Fo
dt
(42)
Mole balance on component A:

Rate of flow of A into the reactor = Fi CAi
Rate of flow of A out of the reactor = Fo CA
(assume perfect mixing such that the outlet concentration is
the same as the concentration in the reactor)
Rate of generation of A due to chemical reaction = rA V =
kCA V
Rate of accumulation of A =
d(CA V )
dt
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Summary
Examples
Examples
This gives the following:

d(CA V )
= Fi CAi F0 CA kCA V
dt
dCA
dV
V
+ CA
= Fi CAi F0 CA kCA V
dt
dt
V
dCA
+ CA (Fi F0 ) = Fi CAi F0 CA kCA V
dt
dCA
Fi
= (CAi CA ) kCA
dt
V
(43)
(44)
(45)
(46)
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Summary

Categories of DOF
Set of Equations
Examples
Unsolvable equations?
Have you ever set up a set of equations and discovered
that despite doing all the algebra right you still couldnt get
an answer? Some problems just cant be solved they are
not specified correctly.
Other problems have multiple solutions; and this can also
pose difficulties.
To solve a system of equations, the number of variables
must equal to the number of independent equations.
An equivalent way of stating this condition is to require the
degree of freedom (DOF), NF be zero:
NF = NV NE
(47)
where NV is the total number of variables and NE is the

number of independent equations.
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Summary

Categories of DOF
Set of Equations
Examples
Three categories of DOF

NF = 0: exactly specified process. If NF = 0, this implies
that the number of equations is equal to the number of variables and the set of equations has a unique solution
NF > 0: underspecified process. If NF > 0, then NV > NE ,
i.e., there are more process variables than equations. Consequently, the NE equations have an infinite number of solutions since NF process variables can be specified arbitrarily.
NF < 0: underspecified process. If NF < 0, there are fewer
process variables than equations and the set of equations
has no solution.
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Summary

Categories of DOF
Set of Equations
Examples
Example 1
Consider the following set of equations:
x + 2y + z = 1
2x + y z = 2
y + 2z = 5
Number of variables NV = 3
Number of independent equations NE = 3
NF = 3 3 = 0
Problem is exactly specified. The set of equations has a
unique solution, i.e., x = 6, y = 5, z = 5.
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Summary

Categories of DOF
Set of Equations
Examples
Example 2
x + 2y + z = 1
2y + 4z = 10
y + 2z = 5
NF = 3 2 = 1
Problem is underspecified. The set of equations has no
unique solution. There are infinite number of solutions.
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Summary

Categories of DOF
Set of Equations
Examples
Example 3
x + 2y + z = 1
2x + y z = 2
y + 2z = 5
x +z =3
NF = 3 4 = 1
Problem is overspecified. The set of equations has no unique
solution. It can be solved by an optimization approach (e.g.,
linear least squares) to get the "best answer" that most
closely solves the set of equations.
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Summary

Categories of DOF
Set of Equations
Examples
Steps in Degree of Freedom Analysis

1. List all the known constants or parameters that can be fixed,
e.g., known physical properties.
2. Identify the number of equations NE . The solution of the
equations are usually the output variables.
3. Identify the number of process variables, NV . These are
usually input variables, e.g., feed flow rate, inlet temperatures.
4. Calculate the number of degrees of freedom, NF = NV NE .
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Summary

Categories of DOF
Set of Equations
Examples
DOF Analysis: Example 1

Analyse the DOF of the system represented by (5), the
surge tank problem.
Fi
V
Fo
The above system can be modelled as:
A
dh
= Fi Fo
dt
(48)
36 / 40

Summary

Categories of DOF
Set of Equations
Examples

Fixed parameter: A
Number of variables NV = 3 (Fi , Fo , V )
Number of equations NE = 1.
(The solution of (48) will give V )
Degree of freedom NF = 3 1 = 2
Hence the inputs Fi and Fo must be specified to solve the
problem.
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Summary

Categories of DOF
Set of Equations
Examples

Analyse the DOF for the system represented by (36) and
(37).
Ti
Fi
V
Q
Heater
T
F
The above system can be modelled as:

dV
= (Fi F )
dt
dT
Fi
Q
= (Ti T ) +
dt
V
VCp
(49)
(50)
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Summary

Categories of DOF
Set of Equations
Examples

Fixed parameters: , Cp
Number of variables NV = 6 (V , Fi , F , Ti , T , Q)
Number of equations NE = 2
Degree of freedom NF = 6 2 = 4
V and T can be selected as the model outputs, hence the
remaining 4 variables are the inputs, i.e., must be specified.
This means that, we must know Fi , F , Ti and Q to be able
to solve the system.
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Summary
Summary
Develop chemical process models from fundamentals

Apply constitutive relationships in process modelling
Analyse the degree of freedom for a system
40 / 40

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KKEK 3152 Modelling of Chemical Processes

Week 3: Model Development

Lecturer: Tan Chee Keong

Refresh of Previous Lecture

Refresh of Previous Lecture

Refresh of Previous Lecture

If Ni is used to represent the moles of component i in a

Refresh of Previous Lecture

Refresh of Previous Lecture

Liquid Surge Tank

Refresh of Previous Lecture

Liquid Surge Tank

Refresh of Previous Lecture

Liquid Surge Tank

Refresh of Previous Lecture

Figure 2: A blending system

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(assuming constant density)

(assuming perfect mixing)

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Substitute (8) into (11):

Refresh of Previous Lecture

Refresh of Previous Lecture

Ideal Gas Law

Process systems containing a gas will normally require a

represents the molar volume.

Refresh of Previous Lecture

Consider the following reaction:

where rA is the rate of reaction of A (mol A/volume*time), k

Refresh of Previous Lecture

The minus sign indicates that A is consumed in the reaction.

We can also express the rate of reaction with respect to

Refresh of Previous Lecture

Refresh of Previous Lecture

The rate of heat transfer through a vessel wall seperating

Refresh of Previous Lecture

Refresh of Previous Lecture

Stirred Tank Heating System

Figure 3: Stirred tank heater

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Stirred Tank Heating System

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Stirred Tank Heating System

Assume perfect mixing such that the outlet temperature is

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Stirred Tank Heating System

Cp (T Tref )(Fi F ) + VCp

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Stirred Tank Heating System

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In a batch reactor, a given amount of material (reactant) is

Develop a model which describes the concentration of component A as a function of time.

Refresh of Previous Lecture

into the system

Refresh of Previous Lecture

where the negative sign indicates that component A is being

Refresh of Previous Lecture

Continuous Stirred Tank Reactor

Consider the following first-order reaction:

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Continuous Stirred Tank Reactor

Mole balance on component A:

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Continuous Stirred Tank Reactor