Alessandro Cozzani

Reaction Engineering Notes I

30.12.2000
__________________________________________________________________________________
REACTION ENGINEERING
Batch operation: Small scale
Continuous operation: Large scale
MASS BALANCE (ISOTHERMAL):

,
_

,
_

,
_

,
_

t
on Accumulati
t
Converted Mass
t
Output Mass
t
Input Mass
Where Mass Converted =
( )( ) t V r
r = rate of disappearance (mol V
-1
s
-1
)
BATCH REACTORS
Unsteady state process: all variables change with time.
Concentration and temperature assumed constant.
Volume may change with time.
( ) ( ) ( ) t V r M N M N M
R A A t t A A t A A

+

( ) ( ) ( ) t V r N N
R A t t A t A

+
[M
A
]

dt V r dN
R A A

[Lim t0]

dt
dN
V
r
A
R
A
1

(1) and
dt
dN
V
r
B
R
B
1

Where N
A
= N
A
(t) = no. of moles of A at time t
r
A
= r
A
(t) = net reaction rate of A at time t.
DEFINE CONVERSION X
A
AT TIME T :
0
0
A
A A
A
N
N N
x

or
( )
A A A
x N N 1
0
or
0
1
A
A
A
N
N
x

0 A
A
A
N
dN
dx
Time for achieving a given degree of reaction from N
A0
to N
A
. Integrate (1):
1
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________


A
A
N
N
A
A
R
t
r
dN
V
dt
0
1
0

A
x
A
A A
R
r
N dx
V
t
0
0
1


A
x
A
A
R
A
r
dx
V
N
t
0
0
CONTINUOUS TUBULAR REACTOR:
PLUG FLOW
PLUG FLOW ASSUMPTION (PFA):
- Axial mixing (convection or diffusion) neglected. Realistically when L/D>50
- Flow rate and fluid properties (P, T, composition) assumed uniform over any
cross-section (piston)
- Good radial mixing assumed at high flow rates: Re 10
4
- Isothermal reaction
- Axial temperature gradients do NOT violate PFA.
MASS BALANCE:
( ) ( ) ( ) 0
+ R A A V V A A V A A
V r M n M n M

( ) ( ) ( ) 0
+ R A V V A V A
V r n n
[M
A
]

0
R A A
dV r dn
[Lim t0]

R
A
A
dV
dn
r
and
R
B
B
dV
dn
r
Volume of reactor from n
Ao
to n
A
:


V n
n
A
A
R
A
A
r
dn
dV
0
0
2
V
n
A0
n
Ae
n
AV
n
AV+V
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________


A
A
n
n
A
A
R
r
dn
V
0
For constant volume:
T A A
v C n
( )
A
T
A
T
A
x
v
n
v
n
1
0

( )
A A A
x C C 1
0
For reaction A B:
T
A
A A
v
n
k kC r
Define Residence Time in PFR:
T
R
v
V

[s]
CONTINUOUS STIRRED TANK
REACTOR (CSTR)
ASSUME:
- Mixing is complete: properties of reaction mixture are uniform (if fluid not
viscous)
- Reaction equal to properties at exit stream
- Rate of reaction is constant (evaluated at product stream T, P, x)
MASS BALANCE:
( ) ( ) ( ) 0
0

R A A A
V r n n

A
A A
R
r
n n
V

R
A A
A
V
n n
r

0
3
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
COMPARISON OF REACTION RATES:
PFR vs. CSTR
PFR CSTR
T UA Q

T
Q
UA

for both systems

( ) ( )
CSTR PFR
UA UA <
CSTR: requires larger heat transfer area (UA) for same amount of heat transferred.
Lower concentration driving force
Lower average rate of reaction
Lower conversions for comparable V
R
V
T
must be larger for given output
Advantageous to have several small CSTRs in series to reduce bypassing and
increase conversion
Ease of construction and low cost
Easy temperature control
Ease of maintenance
For an infinite number of CSTRs in series, conversion approaches that of a PFR.
4
t
C
A
C
A,exit
C
A,in
t
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
TUBULAR REACTORS IN DETAIL
aA bB + dD
n
A A
kC r (n order of reaction)

e A
A
n
n
A
A
R
r
dn
V
,
0

e A
A
n
n
A
A
R
kC
dn
V
,
0

( )

e A
A
n
n
n
T A
A
R
v n k
dn
V
,
0
since
T
A
A
v
n
C
, where v
T
= vol.
flow rate

e A
A
n
n
n
A
A
n
T
R
n
dn
k
v
V
,
0
(*)
If constant volumetric flowrate v
T
, then:
( )
A
T
A
T
A
x
v
n
v
n
1
0

( )
A A A
x C C 1
0
Changes in v
T
neglected if liquid phase reaction.
Returning to (*) with constant v
T
:

e A
A
n
n
n
A
A
n
T R
kn
dn
v V
,
0
But k not constant unless isothermal process, since RT
E
A
k

exp
.
Assume constant and first order reaction n = 1:

e A
A
n
n
A
A T
R
n
dn
k
v
V
,
0

,
_

0
,
ln
A
e A
T
R
n
n
k
v
V

,
_

e A
A T
R
n
n
k
v
V
,
0
ln
5
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
For n 1:

'

,
_

1
0
1
,
1 1
1
1
n
A
n
e A
n
T
R
n n
n k
v
V
VOLUME CHANGE IN PFR (ISOTHERMAL)
A 2S
T
A
A A
v
n
k kC r
Hence:

e A
A
n
n
n
A
A
n
T
R
n
dn
k
v
V
,
0
(*)
Accounting process:
A A To T
A A S S
I I
A A A A
x n n n
x n n n
n n
x n n n
0
0 0
0
0 0
2
+
+

Assume gas mixture obeys perfect gas law
RT n Pv
T T

:

,
_

P
RT
n v
T T

( )

,
_

+
P
RT
x n n v
A A T T 0 0
by substituting previous result for n
T
.
Hence substituting back into (*):
( )

,
_

+
e A
A
n
n
A
A
A Ao T R
n
dn
k P
RT
x n n V
,
0
1
0

( )
( )
( )

,
_

+

e A
A
n
n
A A
A A A
A Ao T
R
dx n
k P
RT
x n n
x n n
V
,
0
0
0 0
0
1
since
( )
A A A
A A A
dx n dn
x n n
0
0
1


Limits arise from
( )
A A A
x n n 1
0
:
e A A e A A
A A A
x x n n
x n n
, ,
0
0


Neglect P unless very high pressures (10-20 bar) used and P large:

e A
x
A A
A A A
A A T
R
dx n
x n n
x n n
Pk
RT
V
,
0
0
0 0
0 0

e A
x
A
A
A A T
R
dx
x
x n n
Pk
RT
V
,
0
0 0
1
[n
A0
]

'

2
,
1
,
0
0
0
0
1 1
I
x
A
A A
A
I
x
A
A
T R
e A e A
x
dx x
n
x
dx
n
Pk
RT
V
(**)
6
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
Integrating I
1
and I
2
:
( ) x
x
dx
I
x

1 ln
1
0
1
( ) x x dx
x
dx
x
x
dx
x
x
I
x x x

,
_

1 ln
1
1
1
1
1 1
1
0 0 0
2
Now substitute back into (**):
( ) [ ] ( ) [ ] { }
e A A e A T R
x x n x n
Pk
RT
V
, 0 , 0
1 ln 1 ln +

( ) [ ] ( ) [ ] { }
e A A T e A T R
x x y n x n
Pk
RT
V
, 0 0 , 0
1 ln 1 ln +
since
0
0
0
T
A
A
n
n
y

( ) ( ) { }
e A A Ae n A e A T R
x y x y x n
Pk
RT
V
, 0 , 0 , 0
1 ln 1 ln

( ) ( ) { }
Ae n A Ae n A T R
x y x y n
Pk
RT
V
, 0 , 0 0
1 ln 1 +

( )

'

,
_

+
Ae n A
Ae n
A T R
x y
x
y n
Pk
RT
V
, 0
,
0 0
1
1
ln 1
NOTE:If H
r
significant, energy and mass balance solved simultaneously
V = 0 for liquid phase reactions.
7
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
CSTR IN DETAIL
NO VOLUME CHANGE ON REACTION:
A Products
A A
kC r
A
A A
R
r
n n
V

A
A A
R
kC
n n
V

0
T
A
A A
R
v
kn
n n
V

0
Perfect mixing assumption: fluid is instantaneously mixed.
Total volume required for same conversion ALWAYS greater than for Batch or PFR.
VOLUME CHANGE UPON REACTION:
A 2S A p A
p k r
[k
p
=mol/m
3
.s.bar]
A
A A
R
r
n n
V

A p
A A
R
p k
n n
V

( )
A p
A A A A
R
p k
x n n n
V
0 0 0

[sub
( )
A A A
x n n 1
0
]

A p
A A
R
p k
x n
V
0

A p
A A T
R
p k
x y n
V

0 0
(*) [since
0 0 0 A T A
y n n
]
Accounting:
A A T T
A A S S
I I
A A A A
x n n n
x n n n
n n
x n n n
0 0
0 0
0
0 0
2
+
+

Inert used for: - Slowing reaction down (e.g. if very exothermic)
- Heat storage (e.g. for endo/exothermic reactions)
8
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
Re-express partial pressure in terms of p and conversion:
T
T
A
A
p
n
n
p

( )
T
A A T
A A
A
p
x n n
x n
p
0 0
0
1
+

( )
A A T T
T A A
A
x y n n
p x n
p
0 0 0
0
1
+

( )
( )
A A T
T A A
A
x y n
p x n
p
0 0
0
1
1
+

( )
( )
A A
A T A
A
x y
x p y
p
0
0
1
1
+

Sub back into (*):

,
_

,
_

A
A A
T A p
A A T
R
x
x y
p y k
x y n
V
1
1 1
0
0
0 0

,
_

,
_

A
A A
T p
A T
R
x
x y
p k
x n
V
1
1
0 0
NOTE:v
T
and p
A
are both properties of the EXIT stream.
TUBULAR PFR WITH RECYCLE
Behaviour of PFR can be made approach CSTR by placing it inside recycle loop (to
reactor inlet).
Practical uses: - Maintain control of reaction temperature
- When needed to improve mass transfer in reactor (catalytic reactors)
Fraction of product stream recycled to reactor inlet =
PICTURE
9
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
CONVERSION PER PASS:
Ai
Ae Ai
pass A
n
n n
x

, [First order, constant mass density]

TOTAL CONVERSION FOR SYSTEM :
( )
0
0
1
A
Ae A
n
n n

Where n
A0
. = moles of A reacted in system per unit time
For reaction:
A S
Accounting:
( )
( )
( )
0 ,
0 0 ,
0 0 ,
1
1
1
T e T
A S e S
A A e A
n n
n n n
n n n

+

Mole balances:
e A A i A
n n n
, 0 ,
+
(1)
( )
0 0 ,
1
A A e A
n n n
(2)
pass Ae i A i A e A
x n n n
, , , ,

(3)
From (3):
e A
e A
i A
x
n
n
,
,
,
1

Into (1):
e A A
e A
e A
n n
x
n
, 0
,
,
1
+

0
,
,
1
1
A
e A
e A
n
x
n

,
_

( )

e A
A
e A
x
n
n
,
0
,
1 1
Sub into (2):
( )
( )
( )

1
1 1
1
0
,
0
A
e A
A
n
x
n
10

n
A0
(1-).n
Ae
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________

( )
( )
( )

1
1 1
1
,e A
x

( )
( )

e A
x
,
1 1
1
1

( ) ( )
( )
e A
e A
x
x
,
,
1 1
1 1
1

( ) ( )( )
( )
e A
e A e A
x
x x
,
, ,
1 1
1 1 1 1

( )
e A
e A
x
x
,
,
1 1

Now solve for x

A,e
:
( )
e A e A
x x
, ,
1 +

( ) 1
, , e A e A
x x

( ) ( ) 1 1
,e A
x

( )
( )

1
1
,e A
x
VARIABLE RECYCLE RATIO, :

e A
i A
n
n
A
A
R
r
dn
V
,
,

e A
x
A
A
i A R
r
dx
n V
,
0
, [since A i A A
dx n dn
,

]

e A
x
A p
A
i A R
p k
dx
n V
,
0
, (*)
Assume ideal gas law:
( )
i T
A i A
i T
A
A
n
p x n
p
n
n
p
,
,
,
1

,
_

[since
( )
A i A A
x n n 1
, ]
Plug back into (*):
( )

e A
x
e A
A
p
i T
R
x
dx
p k
n
V
,
0
,
,
1

,
_

e A p
i T
R
x p k
n
V
,
,
1
1
ln
(1)
(1) can be restated in terms of , and n
T0
since:
e T T i T
n n n
, 0 , ,
+
(a)
11
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
( )

1
1
0
, 0 ,
T
e T T e T
n
n n n (b)
(a) becomes:

,
_

+
1 1
0 0
0 ,
T T
T i T
n n
n n
(1) can then be rewritten as:

,
_

,
_

e A p
T
R
x p k
n
V
,
0
1
1
ln
1
1
(2)
Now define dimensionless volume N
R
:
0 T
p R
R
n
p k V
N
And apply to (2):

,
_

e A
R
x
N
,
1
1
ln
1
1

( ) ( ) [ ] 1 exp 1
, R e A
N x
Substituting the previous result for x
A,e
:
( )
( )
( ) [ ]

1 exp
1
1
1
R
N

( )
( )
( ) [ ]

+
1 exp
1
1
R
N

( )
( ) [ ]

1 exp
1
1
R
N
( ) ( ) [ ] 1 exp 1 1
R
N
( ) [ ] ( ) [ ] 1 exp 1 exp 1
R R
N N
( ) [ ] ( ) [ ] { } 1 exp 1 1 exp 1
R R
N N

( ) [ ]
( ) [ ]

1 exp 1
1 exp 1
R
R
N
N
[ 1 0 ]
For = 0, the above expression becomes:
( )
R
N exp 1
With = x
e
expression for PFR without recycle
As 1:
( ) [ ]
( ) [ ]
R
R
R
R
N
N
N
N
+

1
]
1

1 1 exp 1
1 exp 1
Lim Lim
1
1

i.e. approaches that of a CSTR with volume V

R
ad total feed rate n
T0
.
12
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
UNSTEADY STATE OPERATION (CSTR
with Accumulation)
MASS BALANCE
( ) ( ) ( ) { }
t
A
t t
A R A A A
N N t V t r t n t n
+
0
Where:
A A
kC r
R A T A A
V N v n C
T R
v V
V
R
= constant
V
T
= constant
As t dt:
dt
dN
V r n n
A
R A A A

0
[where
T
A
R A
v
n
V N
]

dt
dn
v
V
V kC n n
A
T
R
R A A A

0

dt
dn
V kC n n
A
R A A A

0

dt
dn
V
v
n
k n n
A
R
T
A
A A

0
0 A A
T
R
A
A
n n
v
V
k n
dt
dn
+ +

0 A A A
A
n n k n
dt
dn
+ +

0
1
A
A
A
n
k n
dt
dn

,
_

+ +
[ ]
Starting point is CSTR at steady-state:
Define:
1
]
1

+ k

0 A
A
A
n
n
dt
dn
+ (*)
Now:
t
comp A
C n

exp
1 , 2 ,
C n
part A

where part A comp A A
n n n
, ,
+
13
n
A0,ss
n
A0
t
0
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
Sub n
A,part
into (*):

0
2
0
A
n
C +

0
2
A
n
C

0
1
exp
A t
A
n
C n +

Now sub initial conditions, ss A A
n n t
,
0
:

0
1 ,
A
ss A
n
C n +

0
, 1
A
ss A
n
n C

0 0
,
exp
A t A
ss A A
n n
n n +

,
_

[where
k + 1
]
Now calculate new steady-state value of exit stream:

k
n n n n
n n
A A A t A
ss A
t
A
t
+

1
]
1

,
_

1
exp Lim Lim
0 0 0 0
,
For 007 . 0 exp exp 5
5

t t
t
After 5 residence times should approach steady-state.
OVERVIEW: ADVANTAGES OF CSTR
a) Easy temperature control
b) Easy maintenance and cleaning
c) Good heat transfer from tank surfaces and possible use of heating/cooling coils
d) Better heat and mass transfer due to good stirring within tank
e) Good dispersion of reactants in different phases
SPECIAL APPLICATIONS:
Auto-catalytic Reactions
Products increase the rate of reaction, i.e. catalyse the reaction. Possible to operate
CSTR at point of highest rate of reaction CONTINUOUSLY and thus arrive at
smaller reactor volume than PFR.
Reversible Adiabatic Operation with Exothermic Reaction
( )
A A
C t k r
Heat gained by the reaction drives the temperature to high levels, increasing the rate
constant k. This compensates for concentration drop of CSTR, provided the reaction is
NOT reversible.
14
y
eq
T
x
CSTR
Eq. line
Alessandro Cozzani
Reaction Engineering Notes I
30.12.2000
__________________________________________________________________________________
15