UNIT-1

Process Modeling Simulation

Mathematical Modeling
Modeling is representation of construction and working of a system. A model is
similar to the system in question and reflects the effect of change done to the
system. A model should be real enough to understand and complex enough to
incorporate all the salient features of the practical system.

In other words, Mathematical Modeling is a representation of the system with the

help of fundamental laws such as mass, energy and component balance etc.

Model is verified by simulating it under known conditions and then comparing the
results with experimental outputs. The model intended for simulation is generally a
mathematical model and it can be classified as :

• Deterministic – input and output variables have fixed values.

•Stochastic – At least one of the input or output variable is probabilistic.
•Static – Time is not taken into account.
•Dynamic – Time varying interactions among the variables are taken into account.
•Most simulation models are stochastic and dynamic.
Types of Models
1. Physical model – These are scale representation of a physical quantity. They
are used to study limited set of behavioral characteristics of the system for
amendment of large scale projects.
2. Mathematical model – The components are represented and interrelated by
mathematical equations. These equations are developed either by extensive
scientific studies, or lab testing, or derived by fitting real data in an expression
and then calculating error.
3. Simulation model – These models are the subsets of the physical and
mathematical models. System conditions are changed and model is run to
simulate the effect of that change.
 
Simulation is the operation of the model; it evaluates the performance of the
proposed system under various conditions over real time periods. Simulation is
done to optimize the system performance, reduce the chance of failure in the actual
system and reduce the squandering of resources.
Uses of Mathematical Models
Mathematical Models can be useful in all phase of chemical engineering, from
research and development to plant operations and even in business & economic
studies.

1.) Research and Development: - Mathematical Modeling used in R & D in terms

of determining chemical kinetics mechanisms and parameters from laboratory or
pilot plant reaction data; for optimization purposes and scale up calculations.

2.) 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
alternative process and control structures and strategies; simulating start-up,
shutdown, and emergency situations and procedures.

3.) Plant Operation: Troubleshooting control and processing problems; studying

the effects of and the requirements for expansion (bottleneck-removal)
projects; optimizing plant operation.
Continuity Equation (Mass Balance)
The law of conservation of mass when applied to a dynamic system implies that
flow of mass into the system minus flow of mass out of the system equals to the
time rate change of mass inside the system.

The unit of this equation s mass per unit time.

Example:
Consider the tank of perfectly mixed
Liquid shown in figure. into which flows a
liquid stream at a volumetric rate of F 0 ( m3 /
min) and with a density of (kg/ m3 ). The
volumetric holdup of liquid in the tank is V
(m3 ) and its density is (kg/ m3 ). .The
volumetric flow rate from the tank is F, and
the density of the out flowing stream is the
same as that of the tank’s contents.
The system for which we want to write a
total continuity equation is all the liquid
phase in the tank. We call this a
macroscopic system, as opposed to a
microscopic system, since it is of definite
and finite size.
Mass Balance
First we have to set the assumption for the system, for this tank system assumption
are:
1.) system is operated under isothermal condition.
2.) Volume of the tank is assume to be constant.
3.) density of the liquid is constant through out the process.

Now write the mass balance for the system:

Degree of Freedom: DOF is obtained as

Number of variables minus Number of
equations. It always must be equal to zero
to obtain a solution.
Here t is the only independent variable
and one mass balance equation so DOF is
equal to zero.
Component Continuity Equation(Component Balance)
Similarly Continuity Equation (Mass balance), the Component Continuity
Equation
involves movement of components in and out of the system. The component
balance Implies that if a chemical reaction occur inside a system, the number of
moles of individual components will increase if it is a product of the reaction or
decrease if it is a reactant. Therefore, component balance for system is written as:

The units of this equation are moles of jth component per unit time.
The flows in and out can be both convective (due to bulk flow) and molecular
(due to diffusion). We can write one component continuity equation for each
component in the system. If there are NC components, there are NC
component continuity equations for any one system.
Component Continuity Equation(Component Balance)
Example: -

Consider the tank of perfectly mixed liquid that we used in previous

example except that a chemical reaction takes place in the liquid in the tank. The
system is now a CSTR (continuous stirred-tank reactor) as shown in Fig.
Component A reacts irreversibly and at a specific reaction rate k to form product,
component B.

Let the concentration of component A in the inflowing feed stream be C A0

(moles of A per unit volume) and in the reactor C A . Assuming a simple first-
order reaction, the rate of consumption of reactant A per unit volume will be
directly proportional to the instantaneous concentration of A in the tank.

Similarly, First we have to set the assumption for the system, for this tank system
assumption are:
1.) system is operated under isothermal condition.
2.) Volume of the tank is assume to be constant.
3.) density of the liquid is constant through out the process.
4.) A first order chemical reaction is takes place.
Component Continuity Equation(Component Balance)

Here the minus sign comes from the fact that A is being consumed, not produced.
The units of all these terms must be the same: moles of A per unit time. And the
plus sign before the generation term since B is being produced by the reaction.
Here t is the only independent variable and one component balance equation for
each component so DOF is equal to zero.
Energy Balance
According to the first law of thermodynamics energy can neither be created or
nor be destroyed. The first law of thermodynamics puts forward the law of
conservation of energy. Hence law of conservation of energy for an open system
can be written as:

Example:
The CSTR system of previous example will be considered again, this time with a
cooling coil inside the tank that can remove the exothermic heat of reaction
(Cal/g. mol of A reacted). We use the normal convention that is negative for
an exothermic reaction and positive for an endothermic reaction. The rate of
heat generation (energy per time) due to reaction is the rate of consumption of
A times
Energy Balance
Similarly, First we have to set the assumption for
the system, for this tank system assumption are:

1.) Volume of the tank is assume to be constant.

2.) density of the liquid is constant through out
the process.
3.) A first order chemical reaction is takes place.
4.) The rate of heat generation (energy per time)
due to reaction is the rate of consumption of A
times

Now write the energy balance for the system:

Energy Balance
Where: U0 = internal energy (energy per unit mass)
K0= kinetic energy (energy per unit mass)
Φ0= potential energy (energy per unit mass)
W= shaft work done by system (energy per time)
P = pressure of system
P0= pressure of feed stream
= specific volume (m3/kg), reciprocal of
density.

The enthalpy is defined as : H or h = U + PV

We will use h for the enthalpy of liquid stream and

H for enthalpy of vapor phase. Thus equation
given above becomes:

Here for liquid phase PV term is negligible compared to the U term and we use
Rate of change of enthalpy instead of internal energy of system. The DOF is
zero because there is equal number of variable and equations.
Equation of Motion
Newton's law of motion says that force is equal to the mass times acceleration
for a system with constant mass M. In other word, force is equal to the
product of mass and acceleration due to gravity.

where F = force, lbf

M = mass, lbm
a = acceleration due to gravity, m/s2
gc= conversion constant needed when English engineering units are
used to keep units consistent = 32.2 lbm.ft/lbf.sec2

When mass varies with time this above relation is termed as:

where vi = velocity in the ith direction,

Fji= jth force acting in the ith direction
Equation of Motion
Equation described above says that the time rate of change of momentum in the
ith direction (mass times velocity in the i th direction) is equal to the net sum of the
forces pushing in the ith direction. It can be thought of as a dynamic force balance.
Or more eloquently it is called the conservation of momentum.
In the real world there are three directions: x, y, and z. Thus, three force balances
can be written for any system. Therefore, each system has three equations of
motion (plus one total mass balance, one energy equation, and NC-1 component
balances).
Instead of writing three equations of motion, it is often more convenient (and
always more elegant) to write the three equations as one vector equation.
Equation of Motion and Transport Equations
Equation described above says that the time rate of change of momentum in the
ith direction (mass times velocity in the i th direction) is equal to the net sum of the
forces pushing in the ith direction. It can be thought of as a dynamic force balance.
Or more eloquently it is called the conservation of momentum.
In the real world there are three directions: x, y, and z. Thus, three force balances
can be written for any system. Therefore, each system has three equations of
motion (plus one total mass balance, one energy equation, and NC-1 component
balances).
Instead of writing three equations of motion, it is often more convenient (and
always more elegant) to write the three equations as one vector equation.

Transport Equations:

There are three important transport mechanisms:

1.) Mass Transfer
• Fick’s law of diffusion
2.) Heat Transfer
• Fourier law of heat conduction
• Newton's law of cooling for heat convection
3.) Momentum Transfer
• Newton’s law of viscosity
Chemical Kinetics
Chemical Kinetics is branch of science which deals with rate of reaction and
mechanism of reaction.

A.) Arrhenius Equation (Temperature dependence): - The effect of temperature

on the specific reaction rate k is usually found to be exponential:

K=K0exp(-EA/RT)
Where:
K = specific reaction rate
K0 = preexponential factor
EA = activation energy; shows the temperature dependence of the reaction rate,
i.e., the bigger EA, the faster the increase in K with increasing temperature
cal/g.mol)
T = absolute temperature
R = perfect gas law constant = 1.99 cal/gmol.K

B.) Law of Mass Action: - it define an overall reaction rate R as the rate of
change of moles of any component per volume due to chemical reaction divided
by that component’s stoichiometric coefficient.
Thank You
Any Query?