Development of Dynamic Models

Illustrative Example: A Blending Process

Chapter

An unsteady-state mass balance for the blending system:

rate of accumulation  rate   rate of  (2-1)
  of
   
of mass inthe tank mass in mass out
1
     

2
 o d Vρ
dt  w1  w2  w (2-2)
where w1, w2, and w are mass flow rates.

The unsteady-state component balance is:

d  Vρ x   w  w  wx (2-3)
x x
1 1 2 2
dt
The corresponding steady-state model was derived in Ch. 1 (cf.
Eqs. 1-1 and 1-2).
0  w1  w2  (2-4)
w

3
 0  w1x1  w2  wx (2-5)
x2
Chapter

4
 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
accuracy and complexity on one hand, and the cost and
Chapter

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.

5
 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.
2. Draw a schematic diagram of the process and label all
Chapter

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.
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
 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 (Section 2.3)
Chapter

to ensure that the 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.
7
 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

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.
8
 Conservation Laws
Theoretical models of chemical processes are based on
conservation laws.

Conservation of Mass
 rate of mass  rate of mass rate of (2-6)
mass
    
Chapter

accumulation in   
     out 

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

rate of component i rate of component (2-7)

i   
out produced
9
   

1
 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
     
Chapter

net rate of heat addition  net rate of work 

 to the system from  performed on the (2-8)
system
   
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:

Utot    (2-9)
Uint UKE UPE
1
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
dUint �
dt 
 wH   (2-10)
  denotes the difference
Q
Uint  the internal energy of
between outlet and inlet
the system conditions of the flowing
�
H  enthalpy per unit streams; therefore
mass �
of the outlet 1
 w  mass flow
rate
 
-∆ wH = rate of enthalpy of the
inlet
Q  rate of heat transfer to the stream(s) - the enthalpy
system
Chapter

of the outlet 1
The analogous equation for molar quantities is,
dUint
dt

  w-   (2-11)
H- Q
where H- is the enthalpy per mole and is the molar flow rate.
w-

In order to derive dynamic models of processes from the general

energy balances in Eqs. 2-10 and 2-11, expressions for Uint and Hˆ
or H- are required, which can be derived from thermodynamics.

The Blending Process Revisited

For constant , Eqs. 2-2 and 2-3 become:
dV  w  w  (2-12)
 w
1
 1 2
dt
d w w  wx (2-13)
x x
Vx
1 1 2 2
dt
Chapter

1
Equation 2-13 can be simplified by expanding the accumulation
term using the “chain rule” for differentiation of a product:
d dx
Vx   
dVx (2-14)
V
dt dt dt
Substitution of (2-14) into (2-13) gives:
dx
V 
dVx  w  w x  wx (2-15)
x
1 1 2 2
dt dt
Substitution of the mass balance in (2-12) for dV/dt in (2-15)
gives: dx
V  x w1   w w1x1  w2  wx (2-16)
dt w2  x2
After canceling common terms and rearranging (2-12) and (2-16),
a more convenient model form is obtained:
dV 1
 w  w
  w (2-
2
dt  1
 w1   x   w2   x 
dx (2-18)
x x
dt V  1 V 2 11
Chapter
Chapter Stirred-Tank Heating Process

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

1
 Stirred-Tank Heating Process (cont’d.)

Assumptions:

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

the temperature of the tank contents.
Chapter

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.

1
 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 i  where the
nt Hˆ
caret (^) means per unit mass. As shown in Appendix B, a
differential change in temperature, dT, produces a corresponding
change in the internal energy per unit mass, dUˆ ,
int

dUˆ int   (2-29)

dHˆ CdT

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

constant). The total internal energy of the liquid in the tank is:
1
 Uint  (2-30)
VUˆint
Chapter

1
 Model Development - II
An expression for the rate of internal energy accumulation can be
derived from Eqs. (2-29) and (2-30):
dUint  VC
(2-31)
dT
dt dt
Note that this term appears in the general energy balance of Eq. 2-
10.
Suppose that the liquid in the tank is at a temperature T and has an
enthalpy, Hˆ . Integrating Eq. 2-29 from a reference temperature
Tref to T gives,
ˆ
H H ˆ C T 
ref (2-32)
ref  T
where Hˆ ref is the value Hˆ at T . Without loss of generality,
ref
of we
1
 assume that Hˆ  0 (see Appendix B). Thus, (2-32) can be
ref
written as:
 Tref
ˆ
H C T  (2-33)

Chapter

1
 Model Development - III
For the inlet stream

Hˆ i  C  Tref  (2-34)
 Ti
Substituting (2-33) and (2-34) into the convection term of (2-10)
gives:
   
 w C  Tref   w C T  Tref   (2-35)
wHˆ  Ti
   

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

1
 dT
V C  wC T  (2-36)
dt T Q
i
Chapter

1
 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

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
2
 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
Chapter

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.
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:
substrate cells
 more cells + products (2-90)
• Yield Coefficients:

YX / S mass of new cells formed

 mass of substrated consumed to form new cells (2-91)

2
 YP / mass of product formed
Chapter S  mass of substrated consumed to form product (2-92)

2
 Fed-Batch Bioreactor

Monod Equation
rg   X
Chapter

(2-93)

Specific Growth Rate

S
  max (2-94)
Ks  S

Figure 2.11. Fed-batch reactor

for a bioreaction.

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.
Chapter

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 rg is given by the Monod equation in
(2- 93) and (2-94).

2
 Modeling Assumptions (continued)
7. The rate of product formation per unit volume rp can
be expressed as
r p  YP / X (2-95)
rg
Chapter

where the product yield coefficient YP/X is defined as:

YP / X  mass of product formed

(2-96)
mass of new cells formed

8. The feed stream is sterile and thus contains no cells.

General Form of Each Balance

2
Rate of accumulation  rate in rate of formation (2-97)

2
 Individual Component Balances

Cells: d ( XV )
V rg (2-98)

dt

d  PV
Chapter

Product:  (2-99)
 dt Vrp

Substrate: d( SV ) 1 Vr  1 Vr
FSf  g P (2-100)
 YX / S YP /
dt S

Overall Mass Balance

Mass:
2
d (V )
 F (2-101)
dt