Lecture (12)

Isothermal Operation

Continuous – Stirred Tank Reactor CSTR

"Back-Mix or Mixed Flow Reactor"

o Operate under steady state

o Flow in is equal flow out
o Reactor composition equal exit stream composition.
o Constant rate of reaction throughout the reactor volume
o Composition ≠ f (Position)
o Composition =f (time) ideal restrictions
o Temperature ≠ f (Position)
o Temperature ≠ f (time)

General Mole Balance

Molar flow rate of A - Molar flow rate of A +Disappearance = Accumulation

fed to the system leave the system

V dN j F j ,o
F jo  F j   r j dV 
dt

F j ,o  Input Feed
F j  Output Stream
dN j Fj
 0 No accumulati on( St.St.Opeartion)
dt
V
Fjo  Fj   rj dV  0

The CSTR is modeled as being well mixed such there are no spatial variations in the rate of
reaction :-
V
 r j dV  Vr j

1
 …Design Reactor Equation

for CSTR

• Consider the general reaction;

Stoichiometry set up of equations with A as basis

b c d 
A    B   C    D
a a a

Molar flow rate of species A 

    moles of A fed    moles of A reacted 
 reacted or consumed     
 FAo X    time  
 moles of A fed 

Molar flow rate of species A  Molar flow rate of species A  Molar flow rate of species A 
 leaves the system   fed to the system   consumed within the system 
     
 FA    FAo    FAo X  

FA  FAo [1  X ]
Where υo entering volumetric flow rate

FAo  FA
V
 rA The composition from the
reactor is identical to the
composition inside the reactor,
then the rate of reaction is
evaluated at the exit conditions
FAo X
V
 rA exit

C Ao  o  C A 
V
 rA 

2
 Plug Flow Reactor
PFR
V V  dV

CA C A  dC A
F jo Fj
X X  dX
FA FA  dFA

o Operate under steady state

o Flow in is equal flow out (constant mass)
o Conversion increases along the length of reactor
o Composition = f (Position , or direction of flow)
o Composition ≠ f (time) at a given position
o Composition ≠ f ( radial position) ideal restrictions
o Temperature = f (Position , or direction of flow)
o Temperature ≠ f (time) at a given position
o Temperature ≠ f (radial position)
o Degree of completion of a reaction depend on
reactor volume

General Mole Balance

Molar flow rate of A - Molar flow rate of A +Disappearance = Accumulation

fed to the system leave the system

V dN j
Fjo  (Fjo  dFj )   rj dV  0
dt
The balance is made over a finite reactor volume, dV , then

Fjo  (Fjo  dFj )  rj dV  0

dF j  r j dV
dF j
dV 
rj

3
Integrating with the limits at V=0,FA=FAo…..at V=V1, FA=FA1

FA1 FA 0
dF j dF j
V 
FAo
rj
V  r
FA1 j

FA  FAo [1  X ]

Reactor Design Equation

Of PFR

FA1 FA 0
dF j dF j
V  rj
V  r
FA1 j
FAo
X
dX
V  FAo 
0
 rj

Constant Volume (Constant Density)   0 (ε=0)

liquid-phase and some of gas phase reaction system fall into this category.

CSTR

FAo X
V 
 rA 
C Aoo X
V 
 rA 
C Ao X

 rA 
space time   V
o

1 1
 rA  rA Area
Area

4
 X CA CAo

V  VC
 Area=   F
Ao
Area= FAo C Ao Ao

Constant Volume (Constant Density)   0 (ε=0)

liquid-phase and some of gas phase reaction system fall into this category.

PFR
X
dX
V  FAo 
0
 rj

V V  X
dX
  
FAo C Ao o C Ao 0  r j

X
dX
  C Ao 
0  rj

1 1
 rA  rA
Area Area

X CA

V  VC Ao
Area=  Area=  
FAo C Ao FAo

5
 First order and Irreversible :-

AB ,  rA  kCA

CSTR PFR

FAo X X
dX
V  V  FAo 
 rA  0
 rA

C Ao
CA  C A  C Ao e  k
1  k

Second order and Irreversible :-

AB ,  rA  kCA2

CSTR PFR
X
FAo X dX
V  V  FAo 
 rA  0
 rj

C Ao  C A 1 1 1  C Ao
k        CA 
C A2 k  C A C Ao  1  C Ao k
,

Bimolecular Reactions
Stoichiometric Table Flow System
Specie Initial Change Remaining Concentration
A FAo -FAo X FA = FAo(1 – X) C A  C A0 1  X 

B FBo = FAo B -(b/a)FAo X FB = FAo[B –(b/a)X]  b 

CB  C A0   B  X 
 a 
C FCo = FAo C +(c/a)FAo X FC = FAo[C +(c/a)X]
CC  C A0   C  X 
c
 a 
D FDo = FAo D +(d/a)FAo X FD = FAo[D +(d/a)X]  d 
CD  C A0   D  X 
 a 
I FI = FAo  FI = FAo I C Io

FTo = FAo i FT = FTo +FAoX

i = Fio/FAo = Cio/CAo= yio/yAo  = (d/a) + (c/a) – (b/a) - 1

6
 Variable Volume (Variable Density, but with Constant T and P )

  0 (1   X )

– Concentration (CSTR, PFR): C  F j  Pj

j
 Z j RT j

FT P
– Total Concentration CT  
 ZRT
Fo Po
– At entrance to the reactor concentration Co  
 Z o RTo
 FT  T  P0  Z 
  0     
 FT 0  T0  P  Z 0 

with constant temperature and pressure, and the compressibility factor will not
change significantly during the course of the reaction ,

 FT 
  0  
 FT 0 
 F  F j 
C j   To  
 0  FT 
 Fj 
C j  CTo  
 FT 
n
Total molar flow rates FT=FA+FB+FC+FD+……= F
j 1
j

 FT 
FT = FTo +FAoX sub in   0  
 T0 
F

 FTo  FAo X 
  0  
 FT 0 

  0 1  y Ao X 

  0 1  X 


Molar flow rate of species j is Fj  FA0  j   j X 

7
Stoichiometric Table Flow System

Concentration at variable volume or density

Specie
N  FA0 1  X  FA0 1  X  C A0 1  X 
CA   A    
 V   o (1  X ) (1  X )

N  FA0   B - (b/a) X  FA0   B - (b/a) X  C Ao   B - (b/a) X 

CB   B    
 V   o (1  X ) (1  X )

N  FA0  C  (c/a) X  FA0  C  (c/a) X  C Ao  C  (c/a) X 

CC   C    
 o (1  X ) (1  X )
 V 

N  FA0   D - (d/a) X  FA0   D  (d/a) X  C Ao   D  (d/a) X 

CD   D    
 V   o (1  X ) (1  X )

N  FA0  I FA0  I C Ao  I
CI   I    
V    o (1  X ) (1  X )

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 Non-Isothermal Operation Reactor

CSTR

Although the CSTR is well mixed and the temperature is uniform throughout the reaction
vessel , these conditions do not mean that the reaction is carried out isothermally.
Isothermal operation occurs when the feed temperature is identical to the temperature of
the fluid inside the CSTR.

FAo , To

Energy Balance in CSTR

FA , T , X Ta

FA , T , X

Heat Accumulated
Heat Flow Heat Flow Heat Generated by Heat Removal by
in
- out
+ Reaction
- wall
= by Reaction

No accumulation in CSTR (steady state operation) then:-

FAo   i C piT   tion

FAo  i C piTio tion
tion H r T   (rAV )  UA(T  Ta )  0

FAo  i C pi Tio  T    H r T  (rAV )  UA(T  Ta )  0

 H r T  (rAV )  UA(T  Ta ) ………………1

T  Tio 
FAo  i C pi

9
 FAo X
For CSTR design equation V
 rA 

sub for FAo X  rAV in energy balance equations then :-

FAo   i C pi T  Tio   UA (T  Ta )
X 
 H r T  ………………2

PFR

V V  V
Q
F jo Fj
 Fi H i  Fi H i

Tubular reactor with heat gain or loss

Consider a tubular reactor in which heat is either is add or removed through the cylindrical
walls of the reactor ,we assume that there are no radial gradients in the reactor and that the
heat flux through the wall per unit volume or reactor is shown in figure above.

 Fi H i V   Fi H i V V  Q  0

Q  UATa  T 

11
 Ta= ambient temperature K ,T =reactor temperature K

Taking the limit V  0 , we get:-

d  Fi H i
UATa  T   0
dV

 dFi
UATa  T  
dH i
H i   Fi  0 ……………………………….3
dV dV

dFi
From mole balance of species i ,  ri   i (ri ) …………………..4
dV
T
Enthalpy of each species i , H i  H TR    Cpi dT  H io TR   Cpi T  TR 
i
o

TR

dH i dT
Differentiating enthalpy equation with respect to V :  Cpi …5
dV dV

Sub equation 4 and 5 in 3

UATa  T   i H i (ri )   Fi Cpi

dT
0
dV

UATa  T   H R (ri )   Fi Cpi

dT
0
dV

dT UATa  T    H R (ri ) Heat Heat


dV  Fi Cpi generated removed

dT  H R (ri )  UAT  Ta 

dV  Fi Cpi

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