Mathematical Modeling of Chemical Processes: CAB3014 - Chemical Process Dynamics and Control

Process Dynamics and Control
Chapter 2
Mathematical Modeling of
Chemical Processes
07/25/20 CAB3014 - Chemical Process Dynamics and Control 1

Chapter Objectives
End of this chapter, you should be able to:

1. Develop unsteady-state models (dynamic models) of
chemical processes from physical and chemical principles
2. Explain the rationale for dynamic models
3. Explain a general strategy for deriving dynamic models
4. Carry out simulation studies (Solution of the dynamic
models that consist of sets of ODE’s and AE’s)

Mathematical Model (Eykhoff, 1974)
• “a representation of the essential aspects of an

existing system (or a system to be constructed)
which represents knowledge of that system in a
usable form”
• Everything should be made as simple as possible,

but no simpler

Uses of mathematical models
Design:
• Exploring the sizing and arrangement of processing
equipment for dynamic performance
• Studying the interactions of various parts of the
process, particularly when material recycle or heat
integration is used
• Evaluating alternate process and control structures
and strategies
• Simulating start-up, shutdown, and emergency
simulations and procedures.

Uses of mathematical models
Plant operation:
• Troubleshooting and processing problems
• Aiding in start-up and operator training
• Studying the effects of and the requirements for
expansion (bottle-neck removal) projects
• Optimizing plant operation
• It is usually much cheaper, safer, and faster to
conduct the kinds of studies listed above on a
mathematical model than experimentally on an
operating unit.

Principles of Model Formulation
• The model equations are at best an

approximation to the real process.
• Adage: “All models are wrong, but some are
useful”
• Inherently involves a compromise between
– model accuracy and complexity
– the and effort required to develop the
model

Process modeling
• Both an art and a science.

• Requires creativity to make simplifying
assumptions that result in an appropriate
model
• Dynamic models of chemical processes
consist of ODEs and/or PDEs, plus related
algebraic equations

A Systematic Approach for Developing
Dynamic Models
1. State the modeling objectives and the end use of

the model. They determine the required levels of
model detail and model accuracy.
2. Draw a schematic diagram of the process and label
all process variables.
3. List all of the assumptions that are involved in
developing the model. Try for parsimony; the
model should be no more complicated than
necessary to meet the modeling objectives.

Systematic Approach
4. Determine whether spatial variations of process

variables are important. If so, a partial differential
equation model will be required.
5. Write appropriate conservation equations (mass,
component, energy, and so forth).
6. Introduce equilibrium relations and other algebraic
equations (from thermodynamics, transport
phenomena, chemical kinetics, equipment
geometry, etc.).

A Systematic Approach…
6. Perform a degrees of freedom analysis (Section

2.3) to ensure that the model equations can be
solved.
7. Simplify the model.
• Arrange the equations so that the dependent
variables (outputs) appear on the left side and
the independent variables (inputs) appear on
the right side.
• This model form is convenient for computer
simulation and subsequent analysis.
8. Classify inputs as disturbance variables or as
manipulated variables.

Modeling Approaches
Physical/chemical (fundamental, global)

• Model structure by theoretical analysis
–Material/energy balances
–Heat, mass, and momentum transfer
–Thermodynamics, chemical kinetics
–Physical property relationships
• Model complexity must be determined (assumptions)
• Can be computationally expensive (not real-time)
• May be expensive/time-consuming to obtain
• Good for extrapolation, scale-up
• Does not require experimental data to obtain (data
required for validation and fitting)
• Theoretical models of chemical processes are based on
conservation laws.

Mass Balance
Conservation of Mass
 rate of mass  rate of mass  rate of mass 

    (2-6)
accumulation   in   out  (2.1)
Conservation of Component i
(2.2)

Energy Balance
Conservation of Energy
(2.3)

Energy Balance …
• Total energy of a system, Utot
(2.4)
• For the processes and examples considered in

this course, it is appropriate to make two
assumptions:
– Changes in potential energy and kinetic
energy can be neglected
– The net rate of work can be neglected

Energy Balance …
• For these reasonable assumptions, the energy balance in Eq.

2-3 can be written as
(2.5)
U int  the internal energy of   denotes the difference

between outlet and inlet
the system conditions of the flowing

H  enthalpy per unit mass streams; therefore

w  mass flow rate  
-Δ wH = rate of enthalpy of the inlet
Q  rate of heat transfer to the system stream(s) - the enthalpy
of the outlet stream(s)

Black box (empirical)
– Large number of unknown parameters

– Can be obtained quickly (e.g., linear
regression)
– Model structure is subjective
– Dangerous to extrapolate

Semi-empirical
• Compromise of first two approaches

• Model structure may be simpler
• Typically 2 to 10 physical parameters estimated
(nonlinear regression)
• Good versatility, can be extrapolated
• Can be run in real-time
• linear regression y  c0  c1 x  c 2 x 2
• nonlinear regression y  K 1  e 
 t /

Semi-empirical
• Number of parameters affects accuracy of model,

but confidence limits on the parameters fitted must
be evaluated.
• Objective function for data fitting – minimize sum of
squares of errors between data points and model
predictions (use optimization code to fit parameters)
• Nonlinear models such as neural nets are becoming
popular (automatic modeling)

Development of Dynamic Models
Illustrative Example: A Blending Process
An unsteady-state mass balance for the blending system:
(2.1)
or
(2.6)
where w1, w2, and w are mass flow rates.

Blending Process
The unsteady-state component balance is:
(2.7)
The corresponding steady-state model was derived in

Ch. 1 (cf. Eqs. 1-1 and 1-2).
(2.8)

The Blending Process Revisited
For constant ρ, Eqs. 2-6 and 2-7 become:

(2.9)
(2.10)
Equation 2-10 can be simplified by expanding the

accumulation term using the “chain rule” for
differentiation of a product:
(2.11)
Substitution of (2-11) into (2-10) gives:

(2.12)

Blending Process Revisited …
Substitution of the mass balance in (2-9) for in (2-12) gives:
(2.13)
After canceling common terms and rearranging (2-9) and

(2-13), a more convenient model form is obtained:
(2.14)
(2.15)

• The dynamic model in Eqs. 2-14 and 2-15 is in a

convenient form for subsequent investigation based on
analytical or numerical techniques
• Specify the inlet compositions (x1 and x2) and the flow
rates (w1, w2 and w) as functions of time
• Specify the initial conditions for the dependent variables,

V(0) and x(0)
• Determine the transient responses, V(t) and x(t)


Dynamic models of representative
processes
• Stirred-Tank Heating Process
Figure 2.3 Stirred-tank heating process with constant holdup, V.

Stirred-Tank Heating Process
Assumptions:
• Perfect mixing
 The exit temperature T is also the temperature of
the tank contents
• The liquid holdup V is constant because the inlet and
outlet flow rates are equal
• The density ρ and heat capacity C of the liquid are
assumed to be constant
 Temperature dependence is neglected
• Heat losses are negligible
Model Development
• For a pure liquid at low or moderate pressures, the internal
energy, Uint, is approximately equal to the enthalpy, H
• H depends only on temperature
• We assume that Uint = H and where the caret (^) means per
unit mass.
A differential change in temperature, dT, produces a
corresponding change in the internal energy per unit mass,
(2.16)
where C is the constant pressure heat capacity.

The total internal energy of the liquid in the tank is:
(2.17)
An expression for the rate of internal energy accumulation

can be derived from Eqs. (2-16) and (2-17):
(2.18)
• Note that this term appears in the general energy

balance of Eq. 2-5.
Suppose that the liquid in the tank is at a temperature T

and has an enthalpy, Ĥ . Integrating Eq. 2-16 from a
reference temperature Tref to T gives,
(2.19)

Without loss of generality, we assume that Hˆ ref  0 .

Thus, (2-19) can be written as:
(2.20)
For the inlet stream: (2.21)
Substituting (2-20) and (2-21) into the convection term

of (2-5) gives:
(2.22)
Finally, substitution of (2-18) and (2-22) into (2-5)

(2.23)

Define deviation variables (from desired operating/set point)
y  T T T is desired operating point

u  ws  ws ws (T ) from steady state
V dy H v H v V
 y  u note that  K p and  1
w dt wC wC w
dy
note when 0 y  K pu
dt
dy
1   y  K pu
dt
General linear ordinary differential equation solution: sum of exponential(s)
Suppose u  1 (unit step response)
  
t
y (t )  K p 1  e 1 
 
 

Example 1:
Ti = 40o C, T = 90o C, Ti = 0o C  V 2 104 kg

   2hr
w 104 kg hr
w s =0.83 106 g hr
H v =600 cal g H v 600(cal/g)
Kp   4
C=l cal g o C wC 10  10 3 (g/hr)  1 (cal/g o C )
4  6  10 5 ( o C hr/kg)
w=10 kg hr
 =103 kg m 3
y  T T
3
V=20 m u  ws  ws
V  2  104 kg
Steady-state balance: The dynamic model is

dy
wC(T -Ti )=ws ΔH v 2 = -y + 6 10-5 u
dt

Example 1:
Step 1: at t=0 double ws
T(0) = T y(0) = 0
ws
u = +0.83  10 6 g hr
5
ws
K pu  6  10  0.83  10 6
t=0
 50
2
dy
dt
= -y + 50 
y = 50 l - e -0.5t 
Final T = yss + T = 50 + 90 = 140o C

Example 1:
Step 2: Maintain T = 140o C / 24 hr New steady

state
Step 3: Then set u = 0, ws = 830 kg hr

dy
2 = - y + 6 10 -5 u , y (0) = 50
dt
Solve for u = 0 y = 50e -0.5t

as t  , y0
How long to reach y = 0.5 ?
Self-regulating, but slow

Example 1:
Step 4: How can we speed up the return from 140°C to

90°C?
ws = 0 g/hr u = -0.83 x 106 g/hr

dy
2 = - y - 50
dt

y = - 50 l - e -0.5t 
At steady state with ws =0, y  -50°C T  40°C
Now, find the time to reach y = 0.5?
Definitely much quicker

than the case u = 0

Process Dynamics
• Process control is inherently concerned with unsteady

state behavior, i.e., "transient response", "process
dynamics"
Stirred tank heater: Assume a "lag" between heating element

temperature Te, and process fluid temp, T.
Heat transfer limitation = he A(Te – T)

Energy balances
dT
Tank: wCTi  he A(Te  T )  wCT  mC
dt
dT
Heating element: Q-he A(Te -T)=meCe e
dt
dT dTe
At steady state :  0, 0
dt dt
Process Dynamics
Specify Q  Calculate T, Te
2 first order equations  1 second order equation in T
Relate T to Q (Te is an intermediate variable)
y=T- T u=Q-Q Ti fixed
m me C e d 2 y  me C e me C e m  dy 1
2
 
   
  y  u
he Ae dt  he Ae wC w  dt wC
Note Ce  0 yields 1st order ODE (simpler model)

Liquid storage systems
1
q= h Rv: line resistance
Rv
linear ODE
If P  p  gh
q=Cv P-Pa Pa : ambient pressure
Non-linear
ODE
Degrees of Freedom Analysis
1. List all quantities in the model that are known constants

(or parameters that can be specified) on the basis of
equipment dimensions, known physical properties, etc.
2. Determine the number of equations NE and the number
of process variables, NV. Note that time t is not
considered to be a process variable because it is neither
a process input nor a process output.
3. Calculate the number of degrees of freedom, NF = NV -
NE.

Degrees of Freedom
4. Identify the NE output variables that will be obtained

by solving the process model.
5. Identify the NF input variables that must be specified
as either disturbance variables or manipulated
variables, in order to utilize the NF degrees of freedom.

Degrees of Freedom Analysis
for the Stirred-Tank Model
Parameters (3): V ,  , C Variables (4): T , Ti , w, Q
Equation (1) : Eq. 2-23 NF = 4 – 1 = 3
The process variables are classified as:

Output variable: T Input variables : Ti, w, Q
For temperature control purposes, it is reasonable to classify

the three inputs as:
Disturbance variables : Ti, w
Manipulated variable : Q
Conclusion!
• Need for mathematical modeling

• Types of mathematical models
• A systematic approach
• Blending example – revisited
• Tank heater example – model developed
• Second-order system
• Linear and nonlinear systems
• Degrees of freedom

For Chapter 3
• Go through Laplace Transform

• Xerox Laplace Transform Table 3.1
page 54-55, Seborg Book

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Process Dynamics and Control

07/25/20 CAB3014 - Chemical Process Dynamics and Control 1

End of this chapter, you should be able to:

07/25/20 CAB3014 - Chemical Process Dynamics and Control 2

• “a representation of the essential aspects of an

• Everything should be made as simple as possible,

07/25/20 CAB3014 - Chemical Process Dynamics and Control 3

07/25/20 CAB3014 - Chemical Process Dynamics and Control 4

07/25/20 CAB3014 - Chemical Process Dynamics and Control 5

• The model equations are at best an

07/25/20 CAB3014 - Chemical Process Dynamics and Control 6

• Both an art and a science.

07/25/20 CAB3014 - Chemical Process Dynamics and Control 7

1. State the modeling objectives and the end use of

07/25/20 CAB3014 - Chemical Process Dynamics and Control 8

4. Determine whether spatial variations of process

07/25/20 CAB3014 - Chemical Process Dynamics and Control 9

6. Perform a degrees of freedom analysis (Section

07/25/20 CAB3014 - Chemical Process Dynamics and Control 10

Physical/chemical (fundamental, global)

07/25/20 CAB3014 - Chemical Process Dynamics and Control 11

 rate of mass  rate of mass  rate of mass 

07/25/20 CAB3014 - Chemical Process Dynamics and Control 12

07/25/20 CAB3014 - Chemical Process Dynamics and Control 13

• Total energy of a system, Utot

• For the processes and examples considered in

07/25/20 CAB3014 - Chemical Process Dynamics and Control 14

• For these reasonable assumptions, the energy balance in Eq.

U int  the internal energy of   denotes the difference

07/25/20 CAB3014 - Chemical Process Dynamics and Control 15

– Large number of unknown parameters

07/25/20 CAB3014 - Chemical Process Dynamics and Control 16

• Compromise of first two approaches

07/25/20 CAB3014 - Chemical Process Dynamics and Control 17

• Number of parameters affects accuracy of model,

07/25/20 CAB3014 - Chemical Process Dynamics and Control 18

Illustrative Example: A Blending Process

An unsteady-state mass balance for the blending system:

where w1, w2, and w are mass flow rates.

The unsteady-state component balance is:

The corresponding steady-state model was derived in

07/25/20 CAB3014 - Chemical Process Dynamics and Control 20

For constant ρ, Eqs. 2-6 and 2-7 become:

Equation 2-10 can be simplified by expanding the

Substitution of (2-11) into (2-10) gives:

07/25/20 CAB3014 - Chemical Process Dynamics and Control 21

Substitution of the mass balance in (2-9) for in (2-12) gives:

After canceling common terms and rearranging (2-9) and

07/25/20 CAB3014 - Chemical Process Dynamics and Control 22

• The dynamic model in Eqs. 2-14 and 2-15 is in a

• Specify the initial conditions for the dependent variables,

07/25/20 CAB3014 - Chemical Process Dynamics and Control 23

07/25/20 CAB3014 - Chemical Process Dynamics and Control 24

• Stirred-Tank Heating Process

Figure 2.3 Stirred-tank heating process with constant holdup, V.

07/25/20 CAB3014 - Chemical Process Dynamics and Control 25

where C is the constant pressure heat capacity.

An expression for the rate of internal energy accumulation

• Note that this term appears in the general energy

Suppose that the liquid in the tank is at a temperature T

07/25/20 CAB3014 - Chemical Process Dynamics and Control 28

Without loss of generality, we assume that Hˆ ref  0 .