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ERT 210/4

Process Control & Dynamics

DYNAMIC BEHAVIOR OF
Chapter 2

PROCESSES :
Theoretical Models of Chemical
Processes

MISS. RAHIMAH BINTI OTHMAN


(Email: rahimah@unimap.edu.my)
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Chapter 2

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Course Outcome 1 (CO1)
Ability to derive and develop theoretical model of chemical
processes, dynamic behavior of first and second order processes
chemical and dynamic response characteristics of more complicated
processes.
1. Introduction Concepts
Chapter 2

Introduction to Process Control:


Theoretical Models of Chemical Processes
Apply and derive unsteady-state models (dynamic model)
of chemical processes from physical and chemical principles.
2. Laplace Transform
3. Transfer Function Models
4. Dynamic Behavior of First-order and Second-order
Processes
5. Dynamic Response Characteristics of More Complicated
Processes
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Process Dynamics
a) Refers to unsteady-state or transient behavior.
b) Steady-state vs. unsteady-state behavior;
i.Steady state: variables do not change with time
c) Continuous processes : Examples of transient behavior:
Chapter 2

i. Start up & shutdown


ii. Grade changes
iii. Major disturbance;
e.g: refinery during stormy or hurricane conditions
iv. Equipment or instrument failure (e.g., pump failure)
d) Batch processes
i. Inherently unsteady-state operation
ii. Example: Batch reactor
1.Composition changes with time
2.Other variables such as temperature could be
constant.
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Process Control
1. Objective:
Enables the process to be maintained at the desired operation
conditions, safely and efficiently, while satisfying environmental
and product quality requirements.
Chapter 2

2. Control Terminology:
Controlled variables (CVs)
- these are the variables which quantify the performance or quality of
the final product, which are also called output variables (Set point).
Manipulated variables (MVs)
- these input variables are adjusted dynamically to keep the
controlled variables at their set-points.
Disturbance variables (DVs)
- these are also called "load" variables and represent input variables
that can cause the controlled variables to deviate from their
respective set points (Cannot be manipulated).
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Development of Dynamic Models
Illustrative Example: A Blending Process
Chapter 2

Figure 2.1. Stirred-tank 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
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or d V
w1 w2 w (2-2)
dt
where w1, w2, and w are mass flow rates.
Chapter 2

The unsteady-state component balance is:

d Vx
w1x1 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)

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Conservation Laws
Theoretical models of chemical processes are based on
conservation laws.
Conservation of Mass
Chapter 2

rate of mass rate of mass rate of mass


(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
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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)
by the surroundings
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)

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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.
Chapter 2

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
streams; therefore
H enthalpy per unit mass
w mass flow rate

- wH = rate of enthalpy of the inlet
stream(s) - the enthalpy
Q rate of heat transfer to the system of the outlet stream(s)
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The analogous equation for molar quantities is,
dU int
dt

wH Q (2-11)

where H is the enthalpy per mole and w is the molar flow rate.
In order to derive dynamic models of processes from the general
Chapter 2

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

The Blending Process Revisited


For constant , Eqs. 2-2 and 2-3 become:
dV
w1 w2 w (2-12)
dt
d Vx
w1x1 w2 x2 wx (2-13)
dt 11
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:
Chapter 2

dx dV
V x w1x1 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
1
x x x2 x (2-18)
dt V V 12
Chapter 2 Stirred-Tank Heating Process

Figure 2.2 Stirred-tank heating process with constant holdup, V.


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Stirred-Tank Heating Process (contd.)
Case 1: Constant Holdup, V
Assumptions:
Chapter 2

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.

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Model Development
1. 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.
Chapter 2

2. Consequently, in the subsequent development, we assume


that Uint = H and U int H where the 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,dU int ,

dU int dH 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:
Uint VU int (2-30)
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Model Development (contd.)
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
Chapter 2

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, H . Integrating Eq. 2-29 from a reference temperature
Tref to T gives,

H H ref C T Tref (2-32)
where H ref is the value of H at Tref. Without loss of generality, we
assume that H ref 0 (see Appendix B). Thus, (2-32) can be
written as:

H C T Tref (2-33)
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Model Development (contd.)
For the inlet stream


H i C Ti Tref (2-34)
Chapter 2

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


gives:


wH 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
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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 18
Stirred-Tank Heating Process (contd.)
Case 2: Variable Holdup, V
Tank holdup vary with time, based on four assumptions;
Assumptions:
Chapter 2

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.

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Model Development
The overall mass balance;
d (V )
wi w (2-37)
dt
Chapter 2

The energy balance for the current stirred-tank heating system


can be derived from Eq. 2-10 in analogy with the derivation of
Eq. 2-36. We again assume that Uint = H for the liquid in the tank.
Thus, for constant ;
d (U int ) dH d ( VH ) d (VH ) (2-38)

dt dt dt dt

From the definition of and ( wH ) Eq. 2-33 and 2-34, it follows


that;
( wH ) wi H i wH wiC (Ti Tref ) wC (T Tref ) (2-39)
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Model Development (contd.)
where wi and w are the mass flow rates of the inlet and outlet
streams, respectively. Substituting (2-38) and (2-39) into (2-10)
gives;
d (VH ) (2-40)
wiC (Ti Tref ) wC (T Tref ) Q
Chapter 2

dt
Next we simplify the dynamic model. Because is constant,
Eq (2-37) can be written as;
(2-41)
dV
wi w
dt
The chain rule can be applied to expand the left side of (2-40)
for constant C and ;
d (VH ) dH dV (2-42)
V H
dt dt dt
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Model Development (contd.)
From Eq. 2-29 or 2-33, it follows that dH /dt CdT/dt .
Substituting this expression and Eq. 2-33 and 2-41 into Eq. 2-42
gives;
d (VH ) dT (2-43)
C (T Tref )(wi w) CV
Chapter 2

dt dt
Substituting (2-43) into (2-40) and rearranging give;
dT
C (T Tref )( wi w) CV wiC (Ti Tref ) wC (T Tref ) Q (2-44)
dt
Rearranging (2-41) and (2-44) provides a simpler form for the
dynamic model;
dV
( wi w) (2-45)
dt
dT w Q
i (Ti T ) (2-46)
dt V CV
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Chapter 2 Liquid Storage Systems

Figure 2.5 A liquid-level storage process.


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Model Development
A typical liquid storage process is shown in Fig. 2.5, where qi and
q are volumetric flow rates. A mass balance yields:
d ( V )
qi q (2-53)
Chapter 2

dt

Assume that liquid density is constant and the tank is


cylinderical with cross-sectional area, A. Then the volume of
liquid in the tank can be expressed as V = Ah, h is the liquid level
(or head). Thus, (2.53) becomes;

dh
A qi q (2-54)
dt

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Continuous Stirred Tank Reactor (CSTR)
Chapter 2

Fig. 2.6. Schematic diagram of a CSTR.


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CSTR: Model Development
Assumptions:
1. Single, irreversible reaction, A B.
2. Perfect mixing.
3. The liquid volume V is kept constant by an overflow line.
4. The mass densities of the feed and product streams are equal
Chapter 2

and constant. They are denoted by .


5. Heat losses are negligible.
6. The reaction rate for the disappearance of A, r, is given by,
r = kcA (2-62)
where r = moles of A reacted per unit time, per unit volume, cA
is the concentration of A (moles per unit volume), and k is the rate
constant (units of reciprocal time).
7. The rate constant has an Arrhenius temperature dependence:
k = k0 exp(-E/RT ) (2-63)
where k0 is the frequency factor, E is the activation energy,
and R is the the gas constant.
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CSTR: Model Development (continued)
Unsteady-state mass balance

(2-64)
Chapter 2

Because and V are constant,


(2-65)

Unsteady-state component balance

(2-66)

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Assumptions for the Unsteady-state Energy Balance:
8.

9.

10.
Chapter 2

11.

12.

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CSTR Model: Some Extensions
How would the dynamic model change for:
1. Multiple reactions (e.g., A B C) ?
2. Different kinetics, e.g., 2nd order reaction?
Chapter 2

3. Significant thermal capacity of the coolant liquid?


4. Liquid volume V is not constant (e.g., no overflow line)?
5. Heat losses are not negligible?
6. Perfect mixing cannot be assumed (e.g., for a very
viscous liquid)?

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