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Ideal Reactors for a Single Reaction

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Ideal Reactors for a Single Reaction

Homogeneous reactions will be considered.


Batch Reactor
dXA

-rA=CA0
-rA=

dt

(constant volume)

CA0

dXA

(volume varies)
from these equations, given conversion vs. time (or some equivalent thereof) we can
get the rate law. Alternatively, the reactor can be designed (volume of reactor, time of running for a given
conversion) can be found given rate law.
1+dyAoXA

dt

Flow Reactors

Space-time and Space-velocity


t is space-time, the time required to process one reactor volume of feed at specified conditions, s is the spacevelocity, number of reactor volumes of feed at specified conditions that can be treated in unit time.
Example, space-time of 2 s means one reactor volume can be processed by given reactor in 2 s.
t and s are defined in terms of the feed stream:
CA0V

V
v0 Note that residence time, which for the case of flow reactors is the average amount of time
v0
spent by molecule inside the reactor is
V
t=
v . The two are equivalent only for constant density systems since in other cases the inlet and outlet
volumetric flow rate are different (expansion factor). A
t=

Space-time is a design variable and its definition arises naturally out of the material balance for CSTRs and
PFRs. It is based on inlet flow and concentration conditions. It is important to note the conditions at which
space-time is defined.
CSTR:

FA0-FA=(-rA)V or
t=
t=

CA0XA
(-rA)

assuming the initial feed stream has unconverted A. If the feed is partially converted,

CA0(XA-XA0)
(-rA)exit

For constant density,


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t=

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CA0-CA
(-rA)

Thus given any three of V,FA0,XA,(-rA) the other one can be easily calculated. Note that the
reaction rate is relatively easily obtained in this case as compared to Batch reactor data (no need for
differentiation here). Graphically, we can represent these equations as:
Simplifications for first and second order reactions:
1. First order reaction
-rA=kCA so
t=

CA0XA
kCA

kt =

XA

1-XA

XA(1+dyAoXA)
k(1-XA)

for constant density systems

2. Second order reaction 2A- > Prodts


t=

CA0XA
kCA2

kCA0t =

XA(1+dyAoXA)2

XA

k(1-XA)2

(1-XA)2

for constant density systems

The dimensionless group formed from k,t,CA0 is called the Damkohler number. Its
numerical value depends only on conversion for the case of isothermal CSTRs:
Reaction Type

Da

Variable Density Constant Density

First order

kt

XA(1+dyAoXA)

Second order, 2A- > Prodts

kCA0t

XA(1+dyAoXA)2

Second order, A+B- > Prodts, CB0=MCA0 kCA0t

XA(1+dyAoXA)2

(1-XA)

(1-XA)2

(1-XA)(M-XA)

XA

1-XA
XA

(1-XA)2
XA

(1-XA)(M-XA)
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nth order reaction -rA=kCAn

kCA0n-1t

XA(1+dyAoXA)n
(1-XA)n

XA

(1-XA)n

Damkohler number is extremely useful in design and scale-up of reactors.


Example Problems

Ex. 5.20 Levenspiel.


CSTR, A- > R, aqueous solution of 100 mmol A/liter is fed to a 1 liter reactor. Outlet concentrations of A
versus flow rates are measured. Determine rate equation. Assume the reactant alone determines the rate.
v, l/min

CA, mmol/l
CA0-CA

4 20

96 80

24

50

50

-rA=v0(CA0-CA)/V, mmol/l/min 96 480 1200


Examining the data above, we see that the rate law is
-rA=24(min-1)CA

Note that in this case 'aqueous solution' gives us the hint that we are dealing with constant density system.
Also, in case the data did not look so perfect as above, we could have used graphical methods we know in
order to evaluate the reaction order and rate constant.
Ex. 5.4 L:

Plan to replace present CSTR with one having double the volume. For same aqueous feed (10 mol A/l) and
same feed rate find the new conversion. The reaction kinetics is given by : A- > R;-rA=kCA1.5 and the present
conversion is 70%.
2CA0v0XA1

kCA01.5(1-XA1)

=
1.5

CA0v0XA2

kCA01.5(1-XA2)1.5

since feed concentration and volumetric flow rate are unchanged.

2XA1

XA2
=8.52=
(1-XA1)1.5
(1-XA2)1.5 Solving this non-linear equation, we get the new conversion to be 79.4%.

3. The kinetics of a 'simple isothermal homogeneous fluid reaction A + ... -> products' has been measured in
a CSTR by changing the residence time. (Separation method: the concentrations of the other components are
kept constant). The data is: CA,0 = 1 (mol/l)

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tau (sec) 0.1 0.5 2 12 90

C(mol/l) 0.92 0.73 0.5 0.25 0.1

Calculate: conversion of A, reaction rate r(A), reaction order concerning A, and rate constant.
Answer: The reaction is of second order and has a rate constant of 1 (l/mol sec)
Plug Flow Reactor:
-rA=FA0

dXA
dV

or since FA0 is constant,


XAf

t = CA0
0
For constant density systems:

CAf

t=C

A0

dXA

(-rA)

dCA

(-rA)

Simplifications for known rate law:


1. Zeroth Order: kt = CA0XA
2. First Order Irreversible: kt = -(1+dyAo)ln(1-XA)-dyAoXA
constant density: kt = -ln(1-XA)
Note that the equation describing the space-time for PFR is identical in form to the equation describing time
in batch reactor in case of constant density systems.
Example problems:

1. Derive the expression for a Damkohler number for PFR for first order reversible reaction A rR with
CR0/CA0=M and -rA=k1CA-k2CR and equilibrium conversion of XAe.
At equilbrium,
k1CA0(
k2=k1(

1-XAe

1+dyAoXAe
1-XAe

)=k2CA0(

M+rXAe

1+dyAoXAe

) or

)
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M+rXAe

XA
(1+dyAoXA)dXA

t = CA0
0 k1CA0(1-XA)-k2CA0(M+rXA)

M+rXAe XA
(1+dyAoXA)dXA
t=
0 (1-XA)(M+rXAe)-(M+rXA)(1-XAe)
k1
X
M+rXAe A (1+dyAoXA)dXA
k1 t =
M+r 0
XAe-XA

k1t =

M+rXAe
M+r

(1+dyAoXA)ln(

XAe

XAe-XA

)-dyAoXA

Note that to solve PFR problems, integration is required, much like batch reactor systems.
E.g. 5.3 Levenspiel:
Elementary liquid phase reaction A+2B R with rate equation

-rA=-rB/2=[(12.5l2/mol2/min)CACB2-(1.5min-1)CR]mol/l/min

is to take place in a 6 l steady-state mixed flow reactor. Two feed streams, one containing 2.8 mol A/l and the
other containing 1.6 mol B/l are to be introduced at equation volumetric flow rates into the reactor. 75%
conversion of the limiting reactant is desired. What should be the flow rate of each stream? Assume constant
density.
Solution:

When the feed streams are mixed, volume is 2 liters. The number of moles of A and B are 2.8 and 1.6 moles
respectively. Therefore
CA0=1.4mol/l
CB0=0.8mol/l
CR0=0
The limiting reactant in this case has to be B, based on the initial concentrations and the stoichiometric
coefficients.
CB=0.8mol/l(1-0.75)=0.2mol/l

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CA=1.4-0.75*0.8/2=1.1mol/l
CR=0.3mol/l
Therefore,
-rA=0.1mol/l/min
-rB=2(-rA)=0.2mol/l/min
v0=(-rB)V/(CB0-CB)=2l/min
2. P4.3 Fogler: Zeroth order reaction A- > 3B, gas-phase, isothermal. Initial concentration of A is 2 mol/l,
there are 40% inerts in the feed. Specific rate constant is 0.1 mol/l/min and activation energy is 40kJ/mol.
Final conversion required is 80%. in case of flow reactors, the volumetric flow rate to be used is 2 l/min.
Calculate
(a) Time required in a constant volume batch reactor:
t=CA0XA/k=16min

(b) Time required in a constant pressure batch reactor


-

1 dNA
=k and N =N (1-X ) and V=V (1+(3-1)*0.6X )=V (1+1.2X )
A
A0
A
0
A
0
A
V dt

So,

X
dXA
CA0 A
CA0
ln(1+1.2XA)=11.2min
t=
=
k 0 (1+1.2XA) 1.2k

(c) Volume required of a CSTR


V=FA0XA/k=v0CA0XA/k=32l
(d) Volume required of a PFR
V=

v0CA0
k

0XAdXA=32l

Flow Reactors in Series:

Often, more than one reactor is used to perform the reaction. The merits and demerits of this can be analysed
fairly easily for simple reactions.

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Consider two CSTRs in series. Inlet molar flow rate into the first reactor is FA0, the conversion out of the first
reactor is X1 and this is the feed into the second reactor. The exit flow rate and conversion are FAe and Xe
respectively. If the rate equation is known (or if a graph of 1/-ra vs. Xa is given), we can calculate the
volumes of the two CSTRs through our material balance equations:
V1=FA0(

V2=FA0(

-rA1
1

-rAe

)X1

FA1-FAe+rAeV2=0 but FA1=FA0(1-X1) and FAe=FA0(1-Xe) therefore,

)(Xe-X1)

Thus, knowing the rate of the reaction at conversions corresponding to X1 and Xe, the
volume of the reactors can be found. If we were to use one single CSTR for converting to Xe,with
everythingelse the same, the volume of this reactor would be
V=FA0(

-rAe

)Xe

We can see that V V1+V2. This is easy to figure out graphically. Note that the depending
on whether reaction is positive or negative order in the reactant, and depending the intermediate conversion
required, the sum of the volumes of two CSTRs in series could be less than or more than volume of one
reactor achieving all the conversion.
Similarly for PFRs in series,
V1=FA00X1

dXA

(-rA)

V2=FA0X1Xe

V=FA00XAe

dXA

(-rA) but in this case volume of a single reactor to achieve this conversion
dXA

(-rA)

=V1+V2

and this fact is independent of the order of the reaction.

Other situations, such as CSTR followed by PFR and so on can be analysed in a similar manner through the
use of proper material balance equations.
Example problems.

1. n-Tanks In Series Model:

Consider a first order reaction in a series of n CSTRs of same volume. Develop a relationship between final
conversion and Damkohler number

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t1=
X1=
C1=

C0X1
-r1

kt1

1+kt1

X1

k(1-X1)

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or

and

C0

1+kt1 Mole balance on reactor 2:

F1-F2=v0(C1-C2)=(-r2V2) or
t2=
C2=

Cn=

C1-C2
kC2

C1

1+kt2

or
=

C0

(1+kt1)(1+kt2) Extending to n-reactors, we get


C0

(1+kt1)(1+kt2)...(1+ktn) If all reactors are of same size and have same volumetric flow rate,
Cn=

C0

(1+kt)n

Or, exit conversion,


X=1-

(1+kt)n

Plotting X vs. Da, we find that when Da> >1, 90% conversion is achieved in 2-3 reactors.
Reactors in Parallel:

For reactors in parallel, V/FA0 is equal for each parallel stream, assuming no mixing occurs before the final
outlet. Two CSTRs in parallel:
V1=FA01XA/(-rA); V2=FA02XA/(-rA) so the total volume of the two reactors is V=FA0XA/(-rA). Clearly, this
is the volume we would have required of a SINGLE CSTR to get to the same conversion.
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Recall that the same result was obtained for PFRs in series. Thus, for CSTRs in parallel and PFRs in series,
we can analyse by replacing the reactor network with one large reactor. Looking at this from the other angle,
if we replace two CSTRs in series with a large CSTR of volume equal to the sum of volumes of the two
CSTRs, then the conversion obtained will be different. Likewise for two PFRs in parallel.
File translated from TEX by TTH, version 3.11.
On 24 Jan 2003, 11:41.

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