Theoretical Models of

Chapter 2

Chemical Processes
 Theoretical Models of
Chemical Processes
Contents:
- General modelling principles
Chapter 2

- Dynamic models of representative processes:

• Blending process
• Stirred tank heat exchange process
• The continuous stirred tank reactor
• Distributed parameter Systems (double pipe heat
exchanger)

Textbooks:
• Seborg et al., Process Dynamics and Control, CHAPTER 2
• Stephanopoulos, Chemical Process Control, 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
Chapter 2

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.
 Conservation Law applied to a closed system, but
communicated with the surroundings

S, fundamental quantity:
• Total Mass
• Mass of individual components
Chapter 2

• Total Energy
• Momemtum
 Conservation Laws
Theoretical models of chemical processes are based on
conservation laws.

Conservation of Mass
 rate of mass  rate of mass  rate of mass 
Chapter 2

      (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 
Chapter 2

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)
Chapter 2
 Development of Dynamic Models
Illustrative Example: A Blending Process
Chapter 2

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.
Assumptions?
• The unsteady-state component balance is:
d Vρx 
w1 x1  w2 x2  wx (2-3)
Chapter 2

dt
The corresponding steady-state model (derived in Ch. 1)
0 w1  w2  w (2-4)
0 w1x1  w2 x2  wx (2-5)

For constant density (common approximation for liquids):

dV
 w1  w2  w (2-12)
dt
 d Vx 
w1x1  w2 x2  wx (2-13)
dt
 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
Chapter 2

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
 Dynamic model of the blending process:

dV 1
 w1  w2  w  (2-17)
dt 
dx w1 w2
 1 
x  x   x2  x  (2-18)
dt V  V
Chapter 2

Study on your own:

- Write the model of the blending process using volumetric
flowrates, instead of mass flowrates
Chapter 2 Stirred-Tank Heating Process

Figure. Stirred-tank heating process

Chapter 2 Continuous Stirred Tank reactor (CSTR)

Figure. CSTR
 EXAMPLE OF NON LINEAR DYNAMICS IN CSTR
Parameter Value
Step changes in cooling water temperature from 300 K to
F 100 L/min 305 K and from 300 K to 290 K
Reactor temperature T(t)
CAi 1 mol/L
Increasing the cooling water
Ti 350 K temperature to 305 K induces
an oscillatory response of both
V 100 L
reactor temperature and
r 1000 g/L concentration of the reactant.
Cp 0.239 J/g K The oscillations are
-DHR 5 x 104 J/mol characterized by an apparent
reation run-away with a
E/R 8750 K temperature spike.
k0 7.2 x 1010 min-1
Reactant concentration CA(t) However, when the
UA 5 x 10 J/min K
4
concentration drops to a low
Tc(0) 300 K value, the reactor then cools
until the concentration builds,
CA(0) 0.5 mol/L then, there is another
temperature rise
T(0) 350 K

Exothermic irreversible
1st order reaction
AB
Chapter 2 Tubular Heat Exchanger

Figure. Shell and tube heat exchanger

The temperature of the liquid changes with time and along the axial position
z, from the value T1(t) at the entrance to the value T2(t) at the exit.
Assumption: the temperature does not change along the radius of the pipe.
There are two independent variables, z and t.
 Tubular Heat Exchanger

The energy balance will characterize the liquid temperature.

Chapter 2

Consider the element of length Dz, over a period of time Dt

Enthalphy transferred
Accumulation Flow in of Flow out of
from the steam to the
of energy enthalphy enthalphy
during the = - + liquid, through the
during the during the
wall, during the time
time period Dt time period Dt time period Dt
period Dt
 Check what you have learned

• In what principles are the theoretical models of Chemical processes

based?
• What is the main difference between Dynamic and Steady-sate models?
• Can you differentiate between a fundamental quantity and a state
Chapter 2

variable?
• Can you differentiate between a state variable and a constant parameter?
• Which is the typical independent variable in dynamic models?
• Can you differentiate between coupled and non-coupled set of ordinary
differential equations (ODEs)?
• Define when a mathematical model is linear / non-linear. What is most
common among Dynamic models of chemical processes?