• Tuesday 13 Feb 2007 class will be replaced

• Attend IChemE education workshop on Mass

and Energy Transfer
• Wed 10am
• Thu 11am

• Improve understanding of the process • Theoretical Model

• Transient process; computer simulation – dynamic and steady state • Using principles of chemistry, physics and biology

• Train plant operating personnel • Empirical Model

• Simulator – realistic training environment • By fitting experimental data

• Develop a control strategy for a new process • Semi-Empirical Model

• Identify controlled variables, manipulated variables • Numerical value of one of the parameters in a theoretical model are calculated from
experimental data
• Optimise process operating conditions
• Recalculate the optimise operating conditions

)
$
*! ) + $
! $
!" # !
$ $ ,!
$ !
$ -! . $ $
$ ! /
!
! + $ !
$ % 0! $
$ ! 1
!
& ' ( 2! $ "
" '# #!
!

1
 )
$ $ !
3! 1 Conservation of Mass
"
% rate of mass rate of mass rate of mass
!#! = − (2-6)
accumulation in out
4!
$ ! Conservation of Component i
5! 1
$ " # rate of component i rate of component i
$ " # =
accumulation in
! $
!
6! $ rate of component i rate of component i
$ ! − + (2-7)
out produced

Conservation of Energy 1
8
% $
$ 7 . %
!1 8
!
rate of energy rate of energy in rate of energy out %
= −
accumulation by convection by convection $ !
7 ' ! ,95

net rate of heat addition net rate of work dU int

+ to the system from + performed on the system (2-8) dt
(
= −∆ wH + Q ) (2-10)

the surroundings by the surroundings U int = the internal energy of ∆ = denotes the difference
the system between outlet and inlet
conditions of the flowing
H = enthalpy per unit mass streams; therefore
% 8
w = mass flow rate - ( ) wH = rate of enthalpy of the inlet
U tot = U int + U KE + U PE (2-9) Q = rate of heat transfer to the system stream(s) - the enthalpy
of the outlet stream(s)

The analogous equation for molar quantities is, ' 8 :

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

2
The unsteady-state overall balance is:
Equation 2-13 can be simplified by expanding the accumulation term
d (V )
= w1 + w2 − w (2-2) using the “chain rule” for differentiation of a product:
dt
where w1, w2, and w are mass flow rates. d (Vx ) dx dV
ρ = ρV + ρx (2-14)
dt dt dt
The unsteady-state component balance is:
Substitution of (2-14) into (2-13) gives:
d (V x )
= w1 x1 + w2 x2 − wx (2-3)
dt dx dV
ρV + ρx = w1 x1 + w2 x2 − wx (2-15)
dt dt
The corresponding steady-state model is:
Substitution of the mass balance in (2-12) for in (2-15) gives:
0 = w1 + w2 − w (2-4)
dx
0 = w1 x1 + w2 x2 − wx (2-5) ρV + x ( w1 + w2 − w) = w1x1 + w2 x2 − wx (2-16)
dt

For constant ρ , Eqs. 2-2 and 2-3 become: ' ,!*8 %

dV
ρ = w1 + w2 − w (2-12)
dt
ρ d (Vx )
= w1 x1 + w2 x2 − wx (2-13) *;2<<% ( ,;,<<% (
dt =*;<!0 =,;<!42
After canceling common terms and rearranging (2-12) and (2-16), a more >;6<<% ( - >;6<<% ( -

convenient model form is obtained: -

?;,

dV 1
= ( w1 + w2 − w ) (2-17)
dt ρ
" # $ @
dx w1 w
= ( x1 − x ) + 2 ( x2 − x ) (2-18)
dt V ρ Vρ

' ,!*8 %
*;2<<% ( *;,<<% (
=*;<!0 =*;<!42
>;6<<% ( - >;6<<% ( -

?;, -
*;2<< 0<<% ( *;,<<% (
=*;<!0 =*;<!42
>;6<<% ( - >;6<<% ( -

d (V x ) ?;, -
= w1 x1 + w2 x2 − wx (2-3)
dt
) <= * *+ , , −
+ " # "#
= * * , ,

2<< <!0 + ,<< <!42

=
"2<< + ,<<#

3
 ' ,!*8 %
*;,<<% (

*;2<< 0<<% ( =*;<!42

>;6<<% ( -
=*;<!0
>;6<<% ( -
?;, -
*;2<< ,;,<<

=*;<!0 =,;<!42
>;6<<% ( - >;6<<% ( -

d (V x ) ?;, -
= w1x1 + w2 x2 − wx (2-3)
dt
? ?ρ + = * * + , ,

?ρ +
" # "#
$ + = * * , ,

"6<<#",# "0<<#"<!0# + ",<<#"<!42#

+ =
0<< + ,<< 0<< + ,<<

- + = <!2*4

' ,!*8 %
*;2<<% ( *;,<<% (
=*;<!0 =*;<!42
>;6<<% ( - >;6<<% ( -

?;, -
*;2<< *;,<<% (
=*;<!0 <!3 =*;<!42
>;6<<% ( - >;6<<% ( -

?;, -
?ρ +
+ = * * , ,

"6<<#",# "2<<#"<!0# + "*<<#"<!42#

+ =
2<< + *<< 2<< + *<<
" # "#
- + = <!025

Stirred-Tank Heating Process

(using heating fluid flowing in coil)
*;2<<% ( *;,<<% (
=*;<!0 =*;<!42
>;6<<% ( - >;6<<% ( -

?;, -

?ρ +
+ = * * , ,

"6<<#",# "2<<#"<!3# + ",<<#"<!42#

+ =
2<< + ,<< 2<< + ,<<

- + = <!3,2

Stirred-tank heating process with constant holdup, V.

4
 Model Development
9' :
Assumptions:
• Energy balance
1. Perfect mixing; thus, the exit temperature T is also the D
=
B
=
(ρ?BC) = ρ (?BC) = C −
B C+A
B
temperature of the tank contents.
2. The liquid holdup V is constant because the inlet and outlet
flow rates are equal. • Constant , V and specific heat, C
3. The density ρ and heat capacity C of the liquid are assumed to ρ?
( )= ( − )−
ρ
( − )+ A
be constant. Thus, their temperature dependence is neglected.
4. Heat losses are negligible.
• Constant V, then wi = w
ρ?
( )= ( − )+ A

? 9' : ? 9' :
• Energy balance Continuity balance • Constant , specific heat, C but variable V
(ρ?BC) = C −
B C+A
B ρ
(? ) = − ρ? +ρ ( − ) −
= ( − )− ( − )+A
ρ
• Constant , specific heat, C but variable V ρ? + − − + = − − + +A
ρ
(?BC) = C −
B C+A
B
ρ? = ( − )+ A
ρ ρ
ρ ?
(BC) + BC ?
= C − C+A
B B
= ( − )+ A
ρ? ρ?
−
ρ? +ρ ( − ) = ( − )− ( − )+A
ρ

Group Exercise Group Exercise

: ) %B

$
" # $
" #? $ $
" # $ ( )= ( )+ A
dV 1 ρ? −
= ( w1 + w2 − w ) (2-17)
dt ρ " #? $
dx w1 w = ( − )+ A
= ( x1 − x ) + 2 ( x2 − x ) (2-18) ρ? ρ?
dt V ρ Vρ

5
 Stirred-Tank Heating Process
(electrically heated)
? 9' :
• Energy balance over the system
D
=
(ρ?BC) = C −
B C+A
B

= − + ( − )

= ( − )+ ( − )
A
• Energy balance over the heating element
D
=A −A

=A − ( − )

Stirred-tank heating process with constant holdup, V.

? 9' : ? 9' :
,
*
• Rearrange (2.47) = ( − )+ ( − ) • Substitute dTe/dt = + ,
− −

= ( − ) =A − ( − )
− = = ( − )
= +

• Express Te * ,
*
+ − − =A − + = ( − ) −
= ( ρ− ) , ρ
= +

,
+ + + + = + +A
• Differentiate Te with reference to time, t ,

,
*
= + ,
− −

' ,!0
? 9' :
• m/w=10min
• Divide the equation with WC • meCe/wC=0.5min
,
A
,
+ + + + = + + A
• meCe/heAe=0.5min
A • 1/wC=0.05oCmin/kCal
• If thermal capacitance MeCe of the heating element is small ρ

compared to MCρ • Calculate nominal steady state temperature

• It reduces to 1st order ODE (same as eq. 2.36) • If Q change from 5000 to 5400 kCal/min, plot temperature
response
ρ? = ( − )+A • If meCe/heAe=0.5min is relatively small, calculate the
response T(t)

6
 ' ,!0 ' ,!0
• m/w=10min • Steady state temperature
• meCe/wC=0.5min = ( − )+ ( − ) <= ( − )+ ( − )
• meCe/heAe=0.5min ( )
=A − ( − ) <=A − −
A • 1/wC=0.05oCmin/kCal
• Ti=100oC
• Substitute
A
• Qin=5000kCal/min ( − )=A
( )+ A
ρ
• Energy balance over system <= −
= ( − )+ ( − )
<=
*
*<< − ( ) + 2<<<
• Energy balance over heating element <!<2
=A − ( − )
• Combine both balances
,
+ + + + = + +
A • Rearrange = -2<
,

' ,!0 ) B ) %
• Apply eq. 2.49 and substitute values
,
A
,
+ + + + = + +

,
"<!2#"*<# ,
+ (<!2 + <!2 + *< ) + = < !2 + *<< + "20<<#"<!<2#

,
2 ,
+ ** + = -4<

• Apply general solution of ODE

' $
= ( − )+ ( − )

' $
= ( − )− ( − )

) B ) % Degrees of Freedom Analysis

qi
−
= $ E 1. List all quantities in the model that are known constants (or
ρ
parameters that can be specified) on the basis of equipment
+
ρ
−
dimensions, known physical properties, etc.
V h q = $ E 2. Determine the number of equations NE and the number of
ρ
process variables, NV. Note that time t is not considered to be a
process variable because it is neither a process input nor a
&$ (ρ? ) = ρ −ρ
= $ E
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.

7
 Biological Reactions
Degrees of Freedom for the Stirred-Tank Model
3 parameters: V , ρ,C
• Biological reactions that involve micro-organisms and enzyme
4 variables: T , Ti , w, Q catalysts are pervasive and provide the basis for production of a wide
variety of pharmaceuticals and healthcare and food products
1 equation: Eq. 2-36 ρ? = ( − )+A
• Important industrial processes that involve bioreactions include
Thus the degrees of freedom are NF = 4 – 1 = 3. The process fermentation and wastewater treatment.
variables are classified as: • Chemical engineers are heavily involved with biochemical and
biomedical processes.
1 output variable: T
• Are typically performed in a batch or fed-batch reactor (semi-batch)
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

• Bioreactions: • Modelling Assumptions

cells
substrate → more cells + products (2-90)
1. The exponential cell growth stage is of interest.
• Yield Coefficients: 2. The fed-batch reactor is perfectly mixed.
mass of new cells formed
YX / S = (2-91) 3. Heat effects are small so that isothermal reactor operation can be
mass of substrated consumed to form new cells assumed.
mass of product formed
YP / S = (2-92) 4. The liquid density is constant.
mass of substrated consumed to form product
5. The broth in the bioreactor consists of liquid plus solid material, the
• Monod equation: mass of cells. This heterogenous mixture can be approximated as a
homogenous liquid.
rg = µ X (2-93)
6. The rate of cell growth rg is given by the Monod equation in (2-93)
• Specific growth rate: and (2-94).
S
µ = µmax (2-94)
Ks + S
Fed-batch reactor for a bioreaction.

7. The rate of product formation per unit volume rP can be expressed

as: • General Form of Each Balance

rp = YP / X rg (2-95) { Rate of accumulation} = {rate in} + {rate of formation} (2-97)

where the product yield coefficient YP/X is defined as: • Individual Component Balances
d ( XV )
mass of product formed • Cells: = V rg (2-98)
YP / X = (2-96) dt
mass of new cells formed
d ( PV )
• Product: = Vrp (2-99)
dt
8. The feed stream is sterile and thus contains no cells.
• Substrate: d( SV ) 1 1
= F Sf − V rg − V rP (2-100)
dt YX / S YP / S
• Overall Mass Balance

• Mass:
d (V )
= F (2-101)
dt

8
 . & + $
• Ability to model process dynamics of simple unit operations
• Ability to solve 1st and 2nd order ODE dynamic model