Modeling Dynamic and Static

Behavior of Chemical Processes

Cheng-Liang Chen
PSE
LABORATORY
Department of Chemical Engineering
National TAIWAN University
Chen CL 1
State Variables and State Equations
State Variables:
A set of fundamental dependent quantities whose values
will describe the natural state of a given system
(temperature, pressure, ow rate, concentration )
State Equations:
A set of equations in the state variables above which
will describe how the natural state of a given system
changes with time
Chen CL 2
Principle of Conservation of A Quantity S
S =
_

_
total mass
mass of individual components
total energy
momentum
Chen CL 3

accumulation of S
within a system

time period
=

ow of S
in the system

time period

ow of S
out the system

time period
+

amount of S generated
within the system

time period

amount of S consumed
within the system

time period
Chen CL 4
Total Mass Balance:
d(V )
dt
=

i:inlet

i
F
i

j:outlet

j
F
j
Mass Balance on Component A:
dn
A
dt
=
d(c
A
V )
dt
=

i:inlet
c
A
i
F
i

j:outlet
c
A
j
F
j
rV
Total Energy Balance:
dE
dt
=
d(U +K +P)
dt
=

i:inlet

i
F
i
h
i

j:outlet

j
F
j
h
j
QW
s
Chen CL 5
Mathematical Model
A Stirred Tank Heater
Mathematical model of a process
= state equations with associated state variables
Chen CL 6
Total mass in tank: V = Ah
Total energy of liquid in tank:
E = U +K +P
dU
dt

dH
dt
;
dK
dt
=
dP
dt
= 0
H = Ahc
p
_
T T
ref
_
State variables: h, T
Total mass balance:
d(Ah)
dt
= F
i
F
=c
A
dh
dt
= F
i
F
Chen CL 7
Total energy balance:
d
_
Ahc
p
_
T T
ref
_
dt
= F
i
c
p
_
T
i
T
ref
_
Fc
p
_
T T
ref
_
+Q
T
ref
=0
A
d(hT)
dt
= F
i
T
i
FT +
Q
c
p
A
d(hT)
dt
= Ah
dT
dt
+T A
dh
dt
..
=F
i
F
= F
i
T
i
FT +
Q
c
p
Ah
dT
dt
= F
i
(T
i
T) +
Q
c
p
Chen CL 8
Summary: State equations
A
dh
dt
= F
i
F
Ah
dT
dt
= F
i
(T
i
T) +
Q
c
p
Summary: variables
state variables: h, T
output variables: h, T
disturbances: T
i
, F
i
manipulated variables: Q, F
parameters: A, , c
p
Chen CL 9
Mathematical Model
A Stirred Tank Heater (cont)
Assumed initial steady states:
0 = A
dh
dt
= F
i,s
F
s
0 = Ah
dT
dt
= F
i,s
(T
i,s
T
s
) +
Q
s
c
p
Chen CL 10
Temperature response to a step decrease in inlet temperature:
Dynamic response to a step decrease in inlet ow rate:
Chen CL 11
Additional Element:
Transport Rate Equations
Transport Rate Equations:
To describe rate of mass, energy, and momentum transfer between
a system and its surroundings
Example: a stirred tank heater
heat supplied by steam:
Q = UA
t
(T
st
T)
Chen CL 12
Additional Element:
Kinetic Rate Equations
Kinetic Rate Equations:
To describe rates of chemical reactions taking place in a system
Example: a 1st-order reaction in a CSTR
reaction rate equation:
r = k
0
e
E/RT
c
A
Chen CL 13
Additional Element:
Reaction and Phase Equilibrium Relationships
Reaction and Phase Equilibrium Relationships:
To describe equilibrium situations reached during a chemical
reaction or by two or more phases
Example: a ash drum
temperature of liquid phase
= temperature of vapor phase
pressure of liquid phase
= pressure of vapor phase
chemical potential of component i
in liquid phase =
chemical potential of component i
in vapor phase
Chen CL 14
Additional Element:
Equations of States
Equations of States:
To describe the relationship
among intensive variables
describing the
thermodynamic state
of a system
Example: a ash drum
Ideal gas law for vapor phase:
pV
vapor
= (moles of A + moles of B)RT
=
mass of A + mass of B
average MW
RT
=
mass of A + mass of B
y
A
M
A
+y
B
M
B
RT

vapor
=
mass of A + mass of B
V
vapor
= [y
A
M
A
+y
B
M
B
]
p
RT

liquid
= (T, x
A
)
Chen CL 15
Dead Time
Dead Time:
Whenever an input variable of a system changes
there is a time interval (short or long) during which
no eect is obsrved on outputs of the system
dead time, transportation lag, pure delay,
distance-velocity lag
Chen CL 16
Example: liquid through a pipe
A: temperature of inlet changes
B: temperature of outlet response
dead time: d
d =
volume of pipe
volumetric ow rate
=
A L
A U
av
=
L
U
av
T
out
(t) = T
in
(t d)
Chen CL 17
Modeling Diculties
Poorly understood processes
Imprecisely known parameters
Size and complexity of a model
Chen CL 18
Additional Examples of Mathematical Modeling
Continuous Stirred Tank Reactor (CSTR)
Exothermic Rx: A B
Chen CL 19
Total Mass Balance:
d(V )
dt
=
i
F
i
F 0
=c
=
dV
dt
= F
i
F
Mass Balance on Component A:
(r: rate of reaction per unit volume)
dn
A
dt
=
d(c
A
V )
dt
= c
A
i
F
i
c
A
F rV
V
dc
A
dt
+c
A
dV
dt
..
=F
i
F
= c
A
i
F
i
c
A
F k
0
e
E/RT
c
A
V

dc
A
dt
=
F
i
V
_
c
A
i
c
A
_
k
0
e
E/RT
c
A
Chen CL 20
Total Energy Balance:
total energy E = U +K +P = U H(T, n
A
, n
B
) (enthalpy)
dE
dt
=
dU
dt

dH
dt
=
i
F
i
h
i
(T
i
) Fh(T) Q (1)
also
dH
dt
=
H
T
..
V c
p
dT
dt
+
H
n
A
..

H
A
(T)
dn
A
dt
+
H
n
B
..

H
A
(T)
dn
B
dt
note
dn
A
dt
=
d(c
A
V )
dt
= c
A
i
F
i
c
A
F rV
dn
B
dt
=
d(c
B
V )
dt
= c
B
i
F
i
. .
=0
c
B
F +rV

dH
dt
= V c
p
dT
dt
+

H
A
_
c
A
i
F
i
c
A
F rV
_
+

H
B
_
c
B
F rV

(2)
Chen CL 21
(1) = (2) V c
p
dT
dt
=

H
A
_
c
A
i
F
i
c
A
F rV
_

H
B
_
c
B
F rV

+F
i

i
h
i
(T
i
)
. .

i
h
i
(T)
. .
c
A
i

H
A
(T)
+
i
c
p
i
(T
i
T)
F h(T)
. .
c
A

H
A
(T)+c
B

H
B
(T)
Q
=

H
A
c
A
i
F
i
. .
(i)
+

H
A
c
A
F
. .
(ii)
+

H
A
rV
+

H
B
c
B
F
. .
(iii)

H
B
rV +F
i
c
A
i

H
A
. .
(i)
+F
i

i
c
p
i
(T
i
T) Fc
A

H
A
. .
(ii)
Fc
B

H
B
. .
(iii)
Q
=
_

H
A

H
B
_
. .
H
r
rV +F
i

i
c
p
i
(T
i
T) Q
=
i
,c
p
=c
p
i
= V
dT
dt
= F
i
(T
i
T) +
(H
r
)
c
p
. .
J
rV
Q
c
p
Chen CL 22
Summaries:
state var.s: V, c
A
, T
state eqn.s:
dV
dt
= F
i
F
dc
A
dt
=
F
i
V
_
c
A
i
c
A
_
k
0
e
E/RT
c
A
dT
dt
=
F
i
V
(T
i
T) +Jk
0
e
E/RT
c
A

Q
c
p
V
output var.s: V, c
A
, T
input var.s: c
A
i
, F
i
, T
i
, Q, F
manip. var.s: Q, F
disturbances: c
A
i
, F
i
, T
i
const. par.s: , c
p
, (H
r
), k
0
, E, R
Chen CL 23
Additional Examples of Mathematical Modeling
An Ideal Binary Distillation Column
Chen CL 24
Assumptions:
constant vapor holdup:
equal molar heats of vaporization for A and B
negligible heat loss
constant relative volativility
100% tray eciency
V = V
1
= = V
N
y
i
=
x
i
1 + ( 1)x
i
neglect dynamics of condenser and reboiler
neglect momentum balance for each tray
leaving liquid = L
i
= f(M
i
), i = 1, , N
liquid holdup = M
i
Chen CL 25
State Equations (1): feed tray (i = f)
total mass:
dM
f
dt
= F
f
+L
f+1
+V
f1
L
f
V
f
= F
f
+L
f+1
L
f
comp A:
d(M
f
x
f
)
dt
= F
f
c
f
+L
f+1
x
f+1
+V
f1
y
f1
L
f
x
f
V
f
y
f
Chen CL 26
State Equations (2): top tray (i = N)
total mass:
dM
N
dt
= F
R
+V
N1
L
N
V
N
= F
R
L
N
comp A:
d(M
N
x
N
)
dt
= F
R
x
D
+V
N1
y
N1
L
N
x
N
V
N
y
N
Chen CL 27
State Equations (3): bottom tray (i = 1)
total mass:
dM
1
dt
= L
2
L
1
+V V
1
= L
2
L
1
comp A:
d(M
1
x
1
)
dt
= L
2
x
2
+V y
B
L
1
x
1
V
1
y
1
Chen CL 28
State Equations (4): ith tray (i = 2, , N 1; i = f)
total mass:
dM
i
dt
= L
i+1
L
i
+V
i1
V
i
= L
i+1
L
i
comp A:
d(M
i
x
i
)
dt
= L
i+1
x
i+1
L
i
x
i
+V
i1
y
i1
V
i
y
i
Chen CL 29
State Equations (5): reux drum
total mass:
dM
RD
dt
= V
N
F
R
F
D
comp A:
d(M
RD
x
D
)
dt
= V
N
y
N
(F
R
+F
D
)x
D
Chen CL 30
State Equations (6): column base
total mass:
dM
B
dt
= L
1
V F
B
comp A:
d(M
B
x
B
)
dt
= L
1
x
1
V y
B
F
B
x
B
Chen CL 31
Relationships:
equilibrium relationships:
y
i
=
x
i
1 + ( 1)x
i
i = 1, , f, , N; B
hydraulic relationships: (Francis weir formula)
L
i
= f(M
i
) i = 1, , f, , N
State Variables:
liquid holdups:
M
1
, M
2
, , M
f
, , M
N
; M
RD
, M
B
liquid concentrations:
x
1
, x
2
, , x
f
, , x
N
; x
D
, x
B
Chen CL 32
Summaries:
2N + 4 nonlinear dierential equations (state eqn.s)
2N + 1 algebraic equations (equilibrium and hydraulic)
example: N = 20 trays
2N + 4 = 2(20) + 4 = 44 nonlinear di. eqn.s
2N + 1 = 2(20) + 1 = 41 algebraic equations
Chen CL 33
Modeling Considerations
for Control Purposes
State-variables model
input-output model (convenient for control)
Degrees of freedom ( df) inherent in the process
extent of control problem to be solved
Chen CL 34
Input-Output Model:
output = f(input variables)
y
i
= f(m
1
, , m
k
; d
1
, , d
t
) i = 1, , m
Chen CL 35
Example: Input-Output Model for CSTR
Assumptions: F
i
= F dV/dt = 0
Chen CL 36
Total Energy Balance:
V
dT
dt
= F
i
(T
i
T) +
Q
c
p
Q = UA
t
(T
st
T)

dT
dt
+
_
F
i
V
+
UA
t
V c
p
_
. .
a1/+K
T =
F
i
V
..
1/
T
i
+
UA
t
V c
p
. .
K
T
st

dT
dt
+aT =
1

T
i
+KT
st
SS: 0 +aT
s
=
1

T
i,s
+KT
st,s

d(T T
s
)
dt
+a (T T
s
)
. .
T

=
1

(T
i
T
i,s
)
. .
T

i,s
+K (T
st
T
st,s
)
. .
T

st

dT

dt
+aT

=
1

i
+KT

st
T

(t) = c
1
e
at
+
_
t
0
_
1

i
+KT

st
_
dt
initial: T

(t = 0) = 0 c
1
= 0
T

(t) =
_
t
0
_
1

i
+KT

st
_
dt
Chen CL 37
Block Diagram: inputs (T

i
(t), T

st
(t)) output (T

(t))
This example: output variables = state variables
Chen CL 38
Distillation: output variables = state variables!
State variables:
liquid holdups:
M
1
, M
2
, , M
f
, , M
N
; M
RD
, M
B
liquid concentrations:
x
1
, x
2
, , x
f
, , x
N
; x
D
, x
B
Output variables:
distillate rate and composition: F
D
, x
D
bottom rate and composition: F
B
, x
B
Chen CL 39
DOF: Degree of Freedom
Degrees of Freedom (DOF):
# of independent variables that must be specied in order to dene
a process completely
DOF = (# Var.s) (# Indep. Eq.s)
Chen CL 40
Example: stirred tank heater
mathematical model: # of eq.s = 2
A
dh
dt
= F
i
F
Ah
dT
dt
= F
i
(T
i
T) +
Q
c
p
# of variables = 6 (h, T
i
, T, F, F
i
, Q)
DOF = 6 - 2 = 4
specify T
i
, F
i
, F, Q h(t), T(t)
in order to specify a process completely
the # of DoF should be zero
Chen CL 41
Example: binary distillation column
DOF = (4N + 11) (4N + 5) = 6
Chen CL 42
Degrees of Freedom of A Process
f = DOF = V E = (# Var.s) (# Indep. Eq.s)
Case 1: DOF = 0
unique values of the V variables
the process is exactly specied
Case 2: DOF > 0
multiple solutions result from the E equations
can specify arbitrarily f of the V variables
the process is underspecied by f equations
Case 3: DOF < 0
no solution to the E equations
the process is overspecied by f equations
Chen CL 43
DOF and Process Controllers
An under-specied process with DOF = f > 0
Q: how to reduce DOF to zero
to specify system completely with unique behavior ?
from external world: disturbances
to add control loops
Control loop:
additional equation between MV and CV
additional variable: set-point
same: DOF
dierence: specify MV specify set-point
Chen CL 44
Example: stirred tank heater with two control loops
DOF = 4 DOF = 0 if we specify
T
i
, F
i
from external world ( disturbances)
set-points of the two controllers
Chen CL 45
Example: binary distillation column ( DOF = 6)
specication of disturbances (external world):
feed rate (F
f
) and feed composition (c
f
)
DOF = 6 DOF = 4
specication of control objectives ( set-points):
(I) for products:
x
D
: distillate composition
x
B
: bottom stream composition
(II) for operational feasibility:
M
RD
: liquid holdup in reux drum
M
B
: liquid holdup at base of column
four control loops
DOF = 6 DOF = 4 DOF = 0
Chen CL 46
Note: other alternative control objectives
(1) keep at desired F
D
, x
D
, M
RD
, M
B
(2) keep at desired F
B
, x
B
, M
RD
, M
B