Vous êtes sur la page 1sur 76

1

BATCH REACTOR
Interpretation of rate data
2
Simplest reactor open / closed vessel
Reactants are placed inside the reactor
and allowed to react over time
Products and unconverted reactants are
removed and the process is repeated
Closed system - unsteady state operation
Fitted with a stirrer
May have a jacket / cooling or heating
coils inside the reactor
Generally constant volume / some
designed at constant pressure
Materials of construction different
linings
3
4
Batch Reactor Contd. . . 5
Batch Reactor Animation 6
Batch Reactor Cont. . . 7
Used in variety of applications
Typically for liquid phase reactions that
require long reaction times
Used only when small amount of product is
required
Favored when a process is in developmental
stage or to produce expensive products
Used to make a variety of products at
different times
8
(1) Each batch is a closed system.
(2) The total mass of each batch is fixed.
(3) The reaction (residence) time t for all
elements of fluid is the same.
(4) The operation of the reactor is inherently
unsteady-state; for example, batch
composition changes with respect to time.
(5) It is assumed that, at any time, the batch is
uniform (e.g., in composition, temperature,
etc.), because of efficient stirring.
Characteristics of a Batch Reactor
Batch Reactor Contd ... 9
Advantages:
High conversions can be obtained
Versatile, used to make many products
Good for producing small amounts
Easy to Clean
Dis-advantages:
High cost of labor per unit of production
Difficult to maintain large scale production
Long idle time (Charging & Discharging times)
leads to periods of no production
No instrumentation Poor product quality
GUIDELINES FOR SELECTING BATCH PROCESSES

Production rates:
Sometimes batch process, if the plants have production
capacity less than 10x10
6
lb/yr (5x10
6
kg/hr).
Usually batch process, if the plants have production
capacity less than 1x10
6
lb/yr (0.5x10
6
kg/hr).
Where multiproduct plants are produced using the same
processing equipment.

Market forces:
Where products are seasonal (e.g., fertilizers).
Short product lifetime (e.g., organic pigments).

Operational problems:
Long reaction times (when chemical reactions are slow).
Handling slurries at low flowrates.
Rapidly fouling materials (e.g., materials foul equipment so
rapidly that shutdown and frequent cleaning are required).

11
General Mass Balance Equation:

Input = output + accumulation
+ rate of disappearance
12
General Mass Balance Equation:

Input = output + accumulation
+ rate of disappearance
13
Design Equation
General Mass Balance Equation:

Input = output + accumulation
+ rate of disappearance
0 = 0 + dN
A
/dt + (-r
A
) V
General Design Equation
-(1/ V) dN
A
/dt = (-r
A
)

General Design equation in terms of conversion
(N
Ao
/ V) dx
A
/dt = -r
A

14
Design Eqn. for variable volume batch reactor
C
Ao
/(1+c
A
x
A
) dx
A
/dt = -r
A


Design Eqn. in terms of Total Pressure
(1/oRT) dP
T
/dt = (-r
A
)
Design Eqn. for CVBR
-dC
A
/dt = -r
A


C
Ao
dx
A
/dt = -r
A
in terms of conversion
15
Constant Volume Batch Reactor
}

=
A
A
C
C
A
A
r
dC
t
0

t
}

=
A
x
A
A
A
r
dx
C
t
0
0
Stoichiometric Table Batch Systems
B N
B0
-(b/a)N
A0
x
A
N
B
= N
A0
(M
B
-(b/a)x
A
)
R N
R0
+(r/a)N
A0
x
A
N
R
= N
A0
(M
R
+(r/a)x
A
)
S N
S0
+(s/a)N
A0
x
A
N
S
= N
A0
(M
S
+(s/a)x
A
)
I N
I0
0 N
I
= N
I0

Total N
T0
N
T
= N
T0
+ N
A0
x
A

Where: M
I
= N
I0
/N
A0
= (r/a + s/a b/a 1)
aA + bB rR + sS
For CVBR: C
A
= C
A0
(1-x
A
); C
R
= C
A0
[M
R
+(r/a)x
A
]
Species Initial Change Final moles
A N
A0
-N
A0
x
A
N
A
= N
A0
(1-x
A
)
17
Constant Volume Batch Reactor
-r
A
= -dC
A
/dt = C
A0
dx
A
/dt

1. Zero Order Reaction:
-r
A
= -dC
A
/dt = k

} }
=
t
C
C
A
dt k dC
A
A
0
0
C
A0
- C
A
= kt
C
A0
x
A
= kt
Strictly homogenous reactions do not follow zero order. Apparently
the reaction order is made zero w.r.t. a reactant.
18
2. First Order Reaction: A Products
-r
A
= -dC
A
/dt = kC
A


} }
=

t
C
C
A
A
dt k
C
dC
A
A
0
0
-ln (C
A
/C
A0
) = kt
-ln(1-x
A
) = kt
-r
A
= k C
A
0.6
C
B
0.4
??
Unimolecular Collision theory ??

Example: N
2
O
5
2NO
2
+ O
2

19
First Order Reaction kinetics
Influence of k
20
3. Second Order Reaction:
2A Products
A + B Products C
A0
= C
B0


-r
A
= -dC
A
/dt = kC
A
2

} }
=

t
C
C
A
A
dt k
C
dC
A
A
0
2
0
1/C
A
1/C
A0
= kt
x
A
/(1-x
A
) = kC
A0
t
21
4. Second Order Reaction:
A + B Products C
A0
= C
B0


-r
A
= -dC
A
/dt = kC
A
C
B

t
K(C
B0
-C
A0
)
kt C C
C C
C C
x
x M
A B
A B
A B
A
A
) ( ln
1
ln
0 0
0
0
=
|
|
.
|

\
|
=
|
|
.
|

\
|

|
|
.
|

\
|
A B
A B
C C
C C
0
0
ln
Example: CH
3
COOC
2
H
5
+ NaOH CH
3
COONa+C
2
H
5
OH
22
5. Third Order Reaction:
3A Products
2A + B Products C
A0
= 2C
B0

A + B + C Products C
A0
= C
B0
= C
C0

-r
A
= -dC
A
/dt = kC
A
C
B
C
C
= k
'
C
A
3

Example: 2NO + H
2
H
2
O +N
2
O
2NO + Cl
2
2NOCl
t k
C C
A A
'
= 2
1 1
2
0
2
23
6. Third Order Reaction:

2A + B Products C
A0
= 2C
B0

-r
A
= -dC
A
/dt = kC
A
2
C
B

2
ln ln
2
0 0
0
kt M
C
M
C
C
C
M
C
C
A A
B
A A
B
=
24
7. Third Order Reaction:

A + B + C Products C
A0
= C
B0
= C
C0

-r
A
= -dC
A
/dt = kC
A
C
B
C
C

) )( (
) / ln(
) )( (
) 1 / 1 ln(
0 0 0 0
0
0 0 0 0
0
C B A B
A B B B
C A B A
A A
C C C C
x M M C
C C C C
x C


+


kt
C C C C
x M M C
A C B C
A C C C
=


+
) )( (
) / ln(
0 0 0 0
0
25
8. n
th
Order Reaction:
nA Products

-r
A
= -dC
A
/dt = kC
A
n

kt n
C C
n
A
n
A
) 1 (
1 1
1
0
1
=

kt n C C
n
A
n
A
) 1 (
1
0
1
=

26
The reciprocal of rate approaches infinity as C
A
0
27
Integrated forms Constant density
28
Note that for a II
order reaction with a
large ratio of feed
components, the order
degenerates to a first
order (pseudo first
order).

29
Differential Method of analysis
C
A
t
-r
A
f(c)
k
) ( ) , ( C f k C k f
dt
dC
r
A
A
= =

=
30
Differential Method of analysis
ln(-r
A
)

ln(C
A
)
ln k
n
A
A
A
C k
dt
dC
r =

=
n
) ln( ) ln( ) ln(
A A
C n k r + =
If r
A
= kC
A
a
C
B
b
, how to use DM?
Use stoichiometric ratio of reactants
Use method of excesses
Use method of least squares

) ln( ) ln( ) ln( ) ln(
B A A
C b C a k r + + =
31
32
33
Integral Method of analysis

Guess the reaction order

Integrate and Derive the equation

Check whether the assumed order is
correct or not by plotting the necessary
graph

34
35
Differential Method Integral Method
Easy to use and is
recommended for testing
specific mechanism
Require small amount of
data
Involves trial and error
Cannot be used for
fractional orders
Very accurate
Useful in complicated
cases

Require large and more
accurate data
No trial and error
Can be used for
fractional orders
Less accurate
Generally Integral Method is attempted first and
if not successful, the differential method is used.
36
Method of Excesses
Consider r
A
= kC
A
a
C
B
b
Perform the experiment with C
B0
>> C
A0
and
measure C
A
as a function of t.
r
A
= kC
A
a
C
B
b
= kC
B0
b
C
A
a
= k'C
A
a

Use either differential method or integral
method and evaluate k & a
Perform the experiment with C
A0
>> C
B0
and
measure C
B
as a function of t.
r
A
= kC
A0
a
C
B
b
= k'C
B
b

Use either differential method or integral
method and evaluate k & b
Require multiple experiments
37
Method of Half lives
) 1 ( ) 1 (
1 1
1
0
1
= =

n kt n
C C
n
A
n
A
At t = t
1/2
, C
A
= C
A0
/2
k n
C
t
n n
A
) 1 (
) 1 2 (
1 1
0
2 / 1


=

|
|
.
|

\
|


+ =

k n
C n t
n
A
) 1 (
) 1 2 (
ln ) ln( ) 1 ( ) ln(
1
0 2 / 1
ln(t
1/2
)

ln(C
A0
)
K
(1-n)
Require multiple experiments
For I Order reactions: t
1/2
= ln(2)/k
t
1/2
does not depend on C
A0

38
Check the value of dimensionless rate constant kC
A0
(n-1)
t
for each order at t = t



39
40
Method of Half lives
41
At t = t
1/n
, C
A
= (1- 1/n) C
A0

Method of Fractional lives
The ratio of any two fractional lives is
characteristic of the order.
k n
C
t
n n
A
) 1 (
) 1 2 (
1 1
0
2 / 1


=

k n
C
t
n
n
A
) 1 (
) 1
2
3
(
1
1
0
3 / 1

) 1
2
3
(
) 1 2 (
1
1
3 / 1
2 / 1

n
n
t
t
1
2
3
ln
2 ln
3 / 1
2 / 1
= = n f or
t
t
The half-life, or half-period, of a reaction is the time
necessary for one half of the original reactant to
disappear.

42
43
Method of Initial Rates
The order of the reaction with respect to an individual
component can be determined by making an initial rate
measurement at two different initial concentrations of
this species while holding all other concentrations
constant between the two runs.

Advantage of the initial rate method is that complex rate functions
that may be extremely difficult to integrate can be handled in a
convenient manner. Moreover, when initial reaction rates are used,
the reverse reactions can be neglected and attention can be
focused solely on the reaction rate function for the forward
reaction.

44
Method of Initial Rates
-r
A0
= k (C
A0
)
n
ln(-r
A0
)

= ln(k) + n ln(C
A0
)
(C
A0
)
1

(C
A0
)
2

(C
A0
)
3

Time, t
(-r
A0
)
1
= slope at (C
A0
)
1
, t = 0
(-r
A0
)
2
= slope at (C
A0
)
2
, t = 0
(-r
A0
)
3
= slope at (C
A0
)
3
, t = 0
45
Method of Initial Rates
ln C
A0

ln (-r
A0
)

46
47
C
A
/C
A0

D
A =
kC
A0
n-1
t
Comparison of Different order
Reactions in a Batch reactor
48
Variable Volume Batch Reactor
(

+ = = =
dt
dV
C
dt
dC
V
V dt
V C d
V dt
dN
V
r
i
i i i
i
1 ) ( 1 1
dt
dV
V
C
dt
dC
r
i i
i
+ = Volume Change with time ??
Fractional Change in Volume or Expansion factor(
A
):
fed moles of no Total
completed is reaction when moles of no total in Change
A
.
.
= c
0
0 1
=
= =

=
A
A A
X
X x
A
V
V V
c
Expansion factor can be obtained if we know the initial
volume and the volume at any X. Similarly X can be obtained
given expansion factor.
49
0 0 T
T
N
N
V
V
=
A A A A A
T
A
T
T
x x y x
N
N
N
N
c o o + = + = + = 1 1 1
0
0
0
0
0 A A
y o c =
1 + =
a
b
a
s
a
r
o
Example: A 3R, starting with pure A
Since pure A, y
AO
= 1.
Also = 3/1 -1 = 3-1 = 2.

A
= (3 - 1)/1 = 2
With 50% inerts: y
AO
= 0.5 & = 3/1 -1 = 2.

A
= (4-2)/2 = 1
= 0.5 (3-1) = 1
50
Variable Volume Batch Reactor
dt
dx
x
C
dt
dx N
x V dt
dN
V
r
A
A A
A A A
A A
A
A
c c +
=

=
1 ) 1 (
1 1
0 0
0
A A
A A
A A
A A A
A
x
x C
x V
x N
V
N
C
c c +

=
+

= =
1
) 1 (
) 1 (
) 1 (
0
0
0
A A
A R A
R
x
x a r M C
C
c +
+
=
1
] ) / ( [
0
A A
A
A
A
x
x
C
C
c +

=
1
1
0 0
0
/ 1
/ 1
A A A
A A
A
C C
C C
x
c +

=
51
CVBR VVBR
}
+
=
A
x
A A A
A
A
x r
dx
C
t
0
0
) 1 ( c
x
A

t / C
A0
}
=
A
A
C
C
A A
r dC t
0
/
1 /-r
A
t
C
A

C
A0

) 1 (
1
A A A
x r c +
52
Variable Volume Batch Reactor
1. Zero Order Reaction:
} }
=
+
t
x
A A
A
A
dt k
x
dx
C
A
0 0
0
1 c
L
n
(
1
+

A
x
A
)


t
k
dt
dx
x
C
r
A
A A
A
A
=
+
=
c 1
0
t k x C
A A A A
c c = + ) 1 ln(
0
t k V V C
A A
c = ) / ln(
0 0
k
A
/C
A0

53
Variable Volume Batch Reactor
2. First Order Reaction:
} }
=

t
x
A
A
dt k
x
dx
A
0 0
1
-
l
n
(
1
-
x
A
)


t
A A
A A
A
A
A A
A
A
x
x C
k kC
dt
dx
x
C
r
c c +

= =
+
=
1
) 1 (
1
0 0
kt x
A
= ) 1 ln(
* Performance equation is similar to that of CVBR
54
Variable Volume Batch Reactor
3. Second Order Reaction:
} }
=

+
t
A
x
A
A A A
dt C k
x
dx x
A
0
0
0
2
) 1 (
) 1 ( c
2
0
2
0
1
) 1 (
1
(

+

= =
+
=
A A
A A
A
A
A A
A
A
x
x C
k kC
dt
dx
x
C
r
c c
t kC x x x
A A A A A A 0
) 1 ln( ) 1 /( ) 1 ( = + + c c
55
Variable Volume Batch Reactor
4. Higher Order Reactions:
} }

+
t
n
A
x
n
A
A
n
A A
dt C k
x
dx x
A
0
1
0
0
1
) 1 (
) 1 ( c
n
A A
A A
n
A
A
A A
A
A
x
x C
k kC
dt
dx
x
C
r
(

+

= =
+
=
c c 1
) 1 (
1
0 0
Analytical integration would be difficult.

Resort to either graphical / numerical integration.
56
Constant Volume Batch Reactor (P
T
vs. t)
) (
1
0
0 0
0
0
0
T T
T A
A A A
A
P P
P dt
d
V
N
dt
dx
V
N
r = =
c
A A
T
T
T
T
x
N
N
P
P
c + = = 1
0 0
(

= 1
1
0 T
T
A
A
P
P
x
c
dt
dP
RT dt
dP
P V
N
dt
dP
P V
N
T T
T
T T
T A
A
0 0 0
0
0 0
0
1
o o c
= = =
Design equation for CVBR in terms of P
T

c
A
Fractional Volume / Pressure Change ??
57
CVBR Concentrations in terms of P
T

) 1 ( ) 1 ( ) 1 (
0
0
0
0
0 A
A
A
A
A A A
x
RT
p
x
V
N
x C C = = =
(

= 1
1
0 T
T
A
A
P
P
x
c
) ( ) (
1
0
0
0
0
0
0 0 0 T T
A
A
T T
T A
T A A A
P P
y
y
P P
P
P y x p = =
o c
o / ) (
0 T T
P P =
0
0 0
0
0
] / ) [(
) 1 (
RT
P P p
x
RT
p
C
T T A
A
A
A
o
= =
0
0 0
] / ) [(
RT
P P
a
b
p
C
T T B
B
o
=
58
CVBR Complex reactions:
1. First Order Reversible Reaction:A R
) ( ) 1 (
0 2 0 1 2 1 0 A A A A R A
A
A A
x M C k x C k C k C k
dt
dx
C r + = = =
2
1
0
0 Re
) 1 (
) (
k
k
x C
x M C
C
C
K
Ae A
Ae A
Ae
C
=

+
= =
) (
) (
) 1 (
) 1 (
1
1 A
Ae
Ae
A
A
x M
x M
x k
x k
dt
dx
+
+

=
t k
x M
M
x x
x
Ae A Ae
Ae
1
) (
) 1 (
ln
+
+
=

Integrating:
59
CVBR Complex reactions:
2. Irreversible Reactions in parallel:
A B
A C
A A A
A
A
C k k C k C k
dt
dC
r ) (
2 1 2 1
+ = + =

=
t k k
C
C
A
A
) ( ln
2 1
0
+ = Integrating:
A
B
B
C k
dt
dC
r
1
= =
A
C
C
C k
dt
dC
r
2
= =
2 1
/ k k
dC
dC
C
B
=
2
1
0
0
k
k
C C
C C
C C
B B
=

K
1
/k
2

C
C
C
B

t
C
C

C
B

C
A

60
61
CVBR Complex reactions:
3. Homogenous Catalytic Reactions:
A R
A + C R + C
C A A
A
A
C C k C k
dt
dC
r
2 1
+ =

=
t k t C k k
C
C
obs C
A
A
= + = ) ( ln
2 1
0
Integrating:
t
k
obs

k
2


k
1

C
C

k
obs

0
ln
A
A
C
C

62
CVBR Complex reactions:
4. Auto Catalytic Reactions:
A + R R + R
) (
0 A A R A
A
A
C C kC C kC
dt
dC
r = =

=
) ln( ln
0
0
A
A
A
C C
C
C
+
Integrating:
t
kC
0


C
A
= C
R
=0.5 C
0

-r
A

t kC
C C C
C C C
A A
A A
0
0 0
0 0
) (
) (
ln =

=
63
CVBR Complex reactions:
5. Irreversible Reactions in series:
A B C C
B0
= C
C0
= 0


C
B, max
and t
opt
- ??
C
A
/C
A0

C
C
/C
A0

C
B
/C
A0

64
A
A
A
C k
dt
dC
r
1
=

=
t k
A A
A
A
e C C or kt
C
C
1
0
0
) ( ln

= = Integrating:
( )
t k t k
A
B
e e
k k
C k
C
2 1
1 2
0 1

=
B A
B
B
C k C k
dt
dC
r
2 1
= =
t k
A B
B
e C k C k
dt
dC
1
0 1 2

= +
Solving:
B A A C
C C C C =
0
1 2
1 2
) / ln(
0
k k
k k
t
dt
dC
opt
B

= =
) (
2
1
0
max ,
1 2
2
k k
k
A
B
k
k
C
C

|
|
.
|

\
|
=
If k
1
= k
2
, find t
opt
and C
R, max

65
Consecutive I-order reactions
Conc. vs. time for various ratios of k
2
/k
1

66
Consider the irreversible reactions in series: A R S
Concept of Rate Determining Step (RDS)
A
A
A
C k
dt
dC
r
1
=

=
R A
R
R
C k C k
dt
dC
r
2 1
= =
R
S
S
C k
dt
dC
r
2
= =
I. When k
1
>> k
2
|
.
|

\
|

|
|
|
|
.
|

\
|

|
.
|

\
|
= = =

dt
dC
e
k k
k
e
k k
k
e
dt
dC
C k
dt
dC
r
R
t k t k
t k
R
R
S
S
~ 1
1 2
1
1 2
1
1 2
2
2
Overall rate of product formation is dominated by reaction - 2
II. When k
2
>> k
1
|
.
|

\
|

|
.
|

\
|
= =

dt
dC
e
k k
k
dt
dC
dt
dC
r
A
t k k
A S
S
~ ) 1 (
) (
1 2
2
2 1
Overall rate of product formation is dominated by reaction - 1
Overall rate of a reaction is always governed by the slowest
step, which is known as the rate determining step (RDS).
67
6. Reactions with shifting order:
A R
A
A A
A
C k
C k
dt
dC
r
2
1
1+
=

=
t k C C k C C
A A A A 1 0 2 0
) ( ) / ln( = +
The order shifts from low to high (zero to one)
as the reactant concentration drops.
t/(C
A0
-C
A
)


C
A

-r
A

k
1

k
2

68
7. Reactions with shifting order:
A R
A
A
A
C k k
dt
dC
r
2 1
+ =

=
t k
C k k
C k k
A
A
2
2 1
0 2 1
ln =
+
+
The order shifts from high to low (one to zero)
as the reactant concentration drops.
C
A

-r
A

k
1

k
2

t
C
A

69
Guggenheim's Method for First-Order Reactions

A special method to obtain the rate constant for a
first-order reaction when an accurate value of the
initial reactant concentration is not available.
Requires a series of readings of the parameter used
to follow the progress of the reaction at times t
1
, t
2
,
t
3
, etc. and at times t
1
+ , t
2
+ , t
3
+ etc.
The time increment should be two or three times
the half life of the reaction.

For a I order reaction: ln(1-x
A
) = -kt x
A
= 1 - e
-kt
At t
1
and t
1
+ , (x
A
)
t1
(x
A
)
t1+
= e
-kt1
(1-e
k
)

Similar equations are valid at times t
2
, t
3
, etc. In all cases,
the right side will be a constant, since the time increment
is a constant.

70
applicable to systems that give apparent first-order
rate constants.
also applicable to irreversible first order reactions in
parallel and reversible reactions that are first-order in
both the forward and reverse directions.
the technique provides an example of the advantages
that can be obtained by careful planning of kinetics
experiments instead of allowing the experimental design
to be dictated entirely by laboratory convention and
experimental convenience.
Guggenheim's technique can also be extended to other
order reactions, but the final expressions are somewhat
cumbersome.
71
Example:

Note that k can be determined without a knowledge of the
dilatometer readings at times zero and infinity.

72
Batch reactors are charged with reactants, closed, and
heated to the reaction temperature, maintained
isothermally for the duration of the reaction. After the
reaction is completed, the mixture cooled, and the reactor
opened, the product is discharged and the reactor is
cleaned for the next batch. In industrial operations, the
cycle time is constant from one batch to the next.

The time required for filling, discharging, heating, cooling,
and cleaning the reactor is referred to as the turnaround
time (t
t
).

The total batch cycle time t
b
is the reaction t
r
time plus
the turnaround time t
t
.
t
b
= t
r
+ t
t

The total batch cycle time t
b
is used in batch reactor
design to determine the productivity of the reactor.

73
dt
dx
V
N
dt
dN
V
r
A A A
A
0
1
=

=
Design of Batch Reactor
How can you call the above equation as
Design equation of a Batch Reactor ??
Can we Design the Batch Reactor using the
Above equation ??
What do you mean by Design ??
74
Design Problem
The reaction 2A R takes place in a batch
reactor. Pure A is to be taken initially in the
reactor. It is required to produce 3 tons of R per
day. The molecular weight of R is 120. The
density of A is 0.8 kg/lit. The expected
conversion of A is 75%. A time of 30 min must be
allowed for filling the reactor and 45 min for
discharging and cleaning the reactor. Kinetic
calculations show that a reaction time of 4hr 45
min is needed for the required conversion.

What size reactor must be used??
75
Solution
Total batch time = + + 4 = 6 hrs.
Number of batches / day = 4
Required production /batch = tons = 750kg
750 kg of A is required, if x
A
=

100%
For 75% conversion:
Amount of A to be fed /batch = 750/0.75
= 1000kg
Volume of 1000 kg of A = 1250 lit.
Size of the vessel = 1250 lit.
What is the use of the Design equation ??
Is the above Design always valid ??
76
ANY CLARIFICATIONS ?
Gauss, Karl
I have had my results for a long time;
but I do not yet know how I am to arrive at them.

Vous aimerez peut-être aussi