Instrumentation and Process

Control
Lecture 4

Lecture 4
Mathematical Models of Chemical Processes

1
 Mathematical Modeling of
Chemical Processes
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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.
 General Modeling Principles
• The model equations are at best an approximation to the real
process.
• Adage: “All models are wrong, but some are useful.”
• Modeling inherently involves a compromise between model
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accuracy and complexity on one hand, and the cost and effort
required to develop the model, on the other hand.
• Process modeling is both an art and a science. Creativity is
required to make simplifying assumptions that result in an
appropriate model.
• Dynamic models of chemical processes consist of ordinary
differential equations (ODE) and/or partial differential
equations (PDE), plus related algebraic equations.
 The rationale for dynamic process models
• Dynamic models play a central role in the subject of process
dynamics and control. The models can be used to:
1.Improve understanding of the process. Dynamic models and
computer simulation allow transient process behavior to be
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investigated without having to disturb the process. Computer

simulation allows valuable information about dynamic and
steady-state process behavior to be acquired, even before the
plant is constructed.
2.Train plant operating personnel. Process simulators play a
critical role in training plant operators to run complex units and
to deal with dangerous situations or emergency scenarios. By
interfacing a process simulator to standard process control
equipment, a realistic training environment is created. This role
is analogous to flight training simulators used in the aerospace
industry.
 The rationale for dynamic process models
(continued.)
3. Develop a control strategy for a new process. A dynamic
model of the process allows alternative control strategies to be
evaluated. For example, a dynamic model can help identify the
process variables that should be controlled and those that
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should be manipulated. Preliminary controller tuning may be

derived using a model, prior to plant start-up using empirical
models. For model-based control strategies, the process model
is an explicit element of the control law.
4. Optimize process operating conditions. It can be
advantageous to recalculate the optimum operating conditions
periodically in order to maximize profit or minimize cost. A
steady-state process model and economic information can be
used to determine the most profitable operating conditions
 The rationale for dynamic process models
(continued.)
For many of the examples cited above – particularly where new,
hazardous, or difficult-to-operate processes are involved –
development of a suitable process model can be crucial to
success. Models can be classified based on how they are obtained:
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a.Theoretical models are developed using the principles of

chemistry, physics, and biology.
b.Empirical models are obtained by fitting experimental data.
c.Semi-empirical models are a combination of the models in
categories (a) and (b); the numerical values of one or more of the
parameters in a theoretical model are calculated from
experimental data.
 The rationale for dynamic process models
(continued.)
Theoretical models offer two very important advantages: they
provide physical insight into process behavior, and they are
applicable over wide ranges of conditions.
However, there are disadvantages associated with theoretical
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models. They tend to be expensive and time-consuming to

develop. In addition, theoretical models of complex processes
typically include some model parameters that are not readily
available, such as reaction rate coefficients, physical properties, or
heat transfer coefficients.
 The rationale for dynamic process models
(continued.)
Although empirical models are easier to develop and to use in
controller design than theoretical models, they have a serious
disadvantage: empirical models typically do not extrapolate well.
More specifically, empirical models should be used with caution
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for operating conditions that were not included in the experimental

data used to fit the model. The range of the data is typically quite
small compared to the full range of process operating conditions.
Semi-empirical models have three inherent advantages:
(i) they incorporate theoretical knowledge,
(ii) they can be extrapolated over a wider range of operating
conditions than purely empirical models, and
(iii) they require less development effort than theoretical models.
Consequently, semi-empirical models are widely used in industry.
  Black box (empirical)
•Large number of unknown parameters
•Can be obtained quickly (e.g., linear regression)
•Dangerous to extrapolate
 Semi-empirical
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•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  c2 x 2
• nonlinear regression

y K 1  e  t /  
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• 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)
Lecture 4
Lecture 5

13
 Table 2.1. 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.
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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. The model should be no more complicated than
necessary to meet the modeling objectives.
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).
 Table 2.1. (continued)
6. Introduce equilibrium relations and other algebraic
equations (from thermodynamics, transport phenomena,
chemical kinetics, equipment geometry, etc.).
7. Perform a degrees of freedom analysis to ensure that the
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model equations can be solved.

8. Simplify the model. It is often possible to 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.
9. 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
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 Physical property relationships

• Model complexity must be determined (assumptions)
• Can be computationally expensive
• 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)
 • Conservation Laws
Theoretical models of chemical processes are based on
conservation laws.

Conservation of Mass
 rate of mass  rate of mass  rate of mass 
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      (2-6)
accumulation   in   out 

Conservation of Component i
rate of component i  rate of component i 
   
 accumulation   in 

rate of component i  rate of component i 

   (2-7)
 out   produced 
 Conservation of Energy
The general law of energy conservation is also called the First
Law of Thermodynamics. It can be expressed as:
rate of energy  rate of energy in  rate of energy out 
     
 accumulation   by convection   by convection 
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net rate of heat addition   net rate of work 

   
  to the system from   performed on the system  (2-8)
 the surroundings   by the surroundings 
   

The total energy of a thermodynamic system, Utot, is the sum of its

internal energy, kinetic energy, and potential energy:
U tot U int  U KE  U PE (2-9)
 •Development of Dynamic Models
•Illustrative Example: A Blending Process

An unsteady-state mass balance for the blending system:

rate of accumulation   rate of   rate of 

      (2-1)
 of mass in the tank  mass in  mass out 
 or d Vρ 
w1  w2  w (2-2)
dt
where w1, w2, and w are mass flow rates.

• The unsteady-state component balance is:

d Vρx 
w1 x1  w2 x2  wx (2-3)
dt

The corresponding steady-state model was derived in Ch. 1 (cf.

Eqs. 1-1 and 1-2).
0 w1  w2  w (2-4)
0 w1x1  w2 x2  wx (2-5)
The dynamic model of the blending process in Eqs. 2-2 and 2-3
can be simplified and expressed in a more appropriate form for
computer simulation. For this analysis, we introduce the
additional assumption that the density of the liquid, ρ, is a
constant. This assumption is reasonable because often the density
has only a weak dependence on composition.

Equation 2-13 can be simplified by expanding the accumulation

term using the “chain rule” for differentiation of a product:

d Vx  dx dV
 V  x (2-14)
dt dt dt
Substitution of (2-14) into (2-13) gives:
dx dV
V   x w1 x1  w2 x2  wx (2-15)
dt dt

Substitution of the mass balance in (2-12) for  dV/dt in (2-15)

gives:
dx
V  x w1  w2  w  w1x1  w2 x2  wx (2-16)
dt

After canceling common terms and rearranging (2-12) and (2-16),

a more convenient model form is obtained:
dV 1
 w1  w2  w  (2-17)
dt 
dx w1 w2
  x1  x    x2  x  (2-18)
dt V  V
24
Lecture 6

26
 Degrees of Freedom Analysis

1. To simulate a process, its model equations (differential and

algebraic) constitute a solvable set of relations
2. The output variables (typically the variables on the left side of
the equations) can be solved in terms of the input variables (on
Chapter 2

the right side of the equations).

3. In order for the model to have a unique solution, the number of
unknown variables must equal the number of independent
model equations.

4. where NV is the total number of process variables (distinct

from constant process parameters) and NE is the number of
independent equations.
 Degrees of Freedom Analysis
1. NF = 0: The process model is exactly specified. If NF = 0, then
the number of equations is equal to the number of process
variables and the set of equations has a solution.
2. NF > 0: The process is underspecified. If NF > 0, then NV > NE,
so there are more process variables than equations.
Chapter 2

Consequently, the NE equations have an infinite number of

solutions, because NF process variables can be specified
arbitrarily.
3. NF < 0: The process model is overspecified. For NF < 0, there
are fewer process variables than equations, and consequently
the set of equations has no solution.
 Table 2.2. 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
Chapter 2

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.
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.
Stirred-Tank Heating Process (constant
Holdup)

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

 Stirred-Tank Heating Process (constant
Holdup)
Assumptions:

1. Perfect mixing; thus, the exit temperature T is also the

temperature of the tank contents.
2. The liquid holdup V is constant because the inlet and outlet
flow rates are equal.
3. The density  and heat capacity C of the liquid are assumed to
be constant. Thus, their temperature dependence is neglected.
4. Heat losses are negligible.
For the processes and examples considered in this book, it
is appropriate to make two assumptions:

1. Changes in potential energy and kinetic energy can be

neglected because they are small in comparison with changes
in internal energy.
2. The net rate of work can be neglected because it is small
compared to the rates of heat transfer and convection.
For these reasonable assumptions, the energy balance in
Eq. 2-8 can be written as
dU int 
dt
 
  wH  Q (2-10)
 denotes the difference
U int the internal energy of
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)
 Model Development - I
For a pure liquid at low or moderate pressures, the internal energy
is approximately equal to the enthalpy, Uint H, and H depends
only on temperature. Consequently, in the subsequent
development, we assume that Uint = H and Uˆ int Hˆ where the
caret (^) means per unit mass. A differential change in
temperature (dT) produces a corresponding change in the internal
energy perdU ˆ mass,
int ,
unit

dUˆ int dHˆ CdT (2-29)

where C is the constant pressure heat capacity (assumed to be

constant). The total internal energy of the liquid in the tank is:

U int VUˆ int (2-30)

 Model Development - II
An expression for the rate of internal energy accumulation can be
derived from Eqs. (2-29) and (2-30):
dU int dT
VC (2-31)
dt dt
Suppose that the liquid in the tank is at a temperature T and has an
enthalpy, Ĥ . Integrating Eq. 2-29 from a reference temperature
Tref to T gives,

Hˆ  Hˆ ref C T  Tref  (2-32)
where Hˆ ref is the value of Ĥ at Tref. Without loss of generality, we
assume that Hˆ ref 0. Thus, (2-32) can be written as:


Hˆ C T  Tref  (2-33)
 Model Development - III
For the inlet stream


Hˆ i C Ti  Tref  (2-34)

Substituting (2-33) and (2-34) into the convection term of (2-10)

gives:

    
  wHˆ w  C Ti  Tref   w  C T  Tref 
    (2-35)

Finally, substitution of (2-31) and (2-35) into (2-10)

dT
V C wC Ti  T   Q (2-36)
dt
 Degrees of Freedom Analysis for the Stirred-Tank
Model:
3 parameters: V , ,C

4 variables: T , Ti , w, Q
1 equation: Eq. 2-36
Chapter 2

Thus the degrees of freedom are NF = 4 – 1 = 3. The process

variables are classified as:
1 output variable: T
3 input variables: Ti, w, Q

For temperature control purposes, it is reasonable to classify the

three inputs as:
2 disturbance variables: Ti, w
1 manipulated variable: Q
Stirred-Tank Heating Process (variable
Holdup)

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

 Stirred-Tank Heating Process (variable
Holdup)
Assumptions:

1. Perfect mixing; thus, the exit temperature T is also the

temperature of the tank contents.
2. The density and heat capacity C of the liquid are assumed to be
constant. Thus, their temperature dependence is neglected.
3. Heat losses are negligible.
An overall mass balance is needed, because the holdup is not
constant. The overall mass balance is:

The energy balance for the current stirred-tank heating system can
be derived from Eq. 2-10
Assume that Uint = H for the liquid in the tank. Thus, for constant
ρ,
 Model Development - I
From the definition of −Δ(wH) and Eqs. 2-33 and 2-34, it follows
that

where wi and w are the mass flow rates of the inlet and outlet
streams, respectively. Substituting Eq. 2-38 and Eq. 2-39 into Eq.
2-10 gives

Next we simplify the dynamic model. Because ρ is constant, Eq.

2-37 can be written as
 Model Development - II
The chain rule can be applied to expand the left side of Eq. 2-40
for constant C and ρ:

From Eq. 2-29 or 2-33, it follows that dĤ /dt = CdT/dt.

Substituting this expression and Eqs. 2-33 and 2-41 into Eq. 2-42
gives

Substituting Eq. 2-43 into Eq. 2-40 and rearranging gives

 Model Development - III
Rearranging Eq. 2-41 and Eq. 2-44 provides a simpler form
for the dynamic model:

Equations 2-45 and 2-46 provide a model that can be solved

for the two outputs (V and T) if the two parameters (ρ and C)
are known and the four inputs (wi, w, Ti, and Q) are known
functions of time.