CHEE 321: Chemical Reaction Engineering
4. Reactor Design Complications (Single Reactions)
4a. Multiple Reactors (Fogler 2.5, 4.3, 8.5)
Reversible Reactions (Fogler 3.2.3, examples in Ch 4 and 8)
CSTR in series
CA0
X=0
v0
V1 ; k1
CA1
CA2
X=X1
X=X2
V2 ; k2
Liquid-phase (v = v0), first-order reaction
Mole Balance on CSTR-1
Mole Balance on CSTR-2
FA0 FA
v [C C A1 ]
V1 =
= 0 A0
k1C A1
(rA ) at X = X 1
V2 =
1k1 =
[C A0 C A1 ] C A0
=
1
C A1
C A1
C A1 =
C A0
1 + 1k1
Fogler 2.5, 4.3.2
v [C C A 2 ]
FA1 FA 2
= 0 A1
k 2C A 2
(rA ) at X = X 2
2 k2 =
[C A1 C A 2 ] C A1
=
1
C A2
C A2
C A2 =
C A2 =
C A1
1 + 2k2
C A0
[1 + 1k1 ][1 + 2 k 2 ]
n-Equal Sized CSTR in series
CA0
X=0
v0
CAn
CA n-1
V
=
v0
C A1 =
C A0
1+ k
C A2 =
X=Xn
All CSTRs are operated at same temperature
[ k is same in all reactors]
C A1
1+ k
C An
Fogler 4.3.2
X=Xn-1
C A3 =
C A2
1+ k
C An =
C An 1
1+ k
C A0
C A0
=
=
n
n
(1 + k )
(1 + Da)
CSTRs: Damkohler Number (Da)
Da is a dimensionless number that can provide a quick estimate of the
degree of conversion in continuous flow reactors.
( rA0 ) V
Da =
FA0
First-order reaction
rA0 V V (kC A0 )
Da =
=
= k
FA0
v0C A0
Note: rate is calculated
at inlet conditions
Second-order reaction
rA0 V V (kC A2 0 )
Da =
=
= k C A0
FA0
v0C A0
Da 0.1 usually results in conversion less than 10%
Da 10 usually results in conversion greater than 90%
n-Equal Sized CSTR in series
n Equal-sized CSTRs - Which is a better configuration?
Parallel or Series
v0/n
CA1
X=X1
v0/n
CA2
CA0
X=0
v0
If you had n-equal sized reactors
available and had the option of
setting them in series or parallel,
which configuration would you
choose to achieve maximum
conversion for a first-order reaction
occurring in liquid phase?
X=X2
v0/n
CA3
v0/n
Fogler 4.3.3
X=X3
X = Xmix
-See Fogler 4.3, Ex. 4-2
-Remember your Levenspiel plots
CAn
X=Xn
Why run reactors in parallel?
Reaction Rates for Reversible Reactions
Reaction:
aA + bB cC + dD
Reaction rates for reversible reactions. Whats so special about them?
The reaction occurs in both the forward and reverse directions
The rate law must have expressions for both forward and reverse
reactions
The rate must be thermodynamically consistent. That is, rate laws (if
expressed in terms of concentration) must reduce to thermodynamic
relationship relating reacting species concentrations at chemical
equilibrium.
KC =
CCc ,eq CDd ,eq
C Aa ,eq CBb ,eq
Strictly speaking - All reactions are reversible !!
Thermodynamics: Equilibrium Constant
aA + bB cC + dD
KC =
c
d
CC,eq
CD,eq
a
b
CA,eq
CB,eq
Units are (mol/L)d+c-a-b
See Fogler Appendix C for a discussion of chemical equilibrium. Various
forms of reaction equilibrium constant are used in literature:
K or Reaction Equilibrium Constant (in terms of activities)
Kp or Pressure Equilibrium Constant
KC or Concentration Equilibrium Constant
For ideal gas system, concentration can be expressed in terms of partial pressure Ci =
KC =
c
d
pC,eq
pD,eq
a
b
pA,eq
pB,eq
pi
RT
( RT )( c d + b + a )
= K P ( RT )( a )
Fogler 3.2.3
Reversible Reactions and Reaction Rate
kB
2 C 6 H 6 C12 H10 + H 2
k B
Benzene Diphenyl
Let B = C6H6, D=C12H10
Define reaction rates wrt Benzene
Rate of disappearance of B
Rate of formation of B
rB ,rev = k B CD CH 2
rB , for = k B CB2
Net rate of B formation:
rB = k B CB2 + k B CD CH 2
At equilibrium: rB = 0 = k B CB2 ,eq + k B CD ,eqCH
2 , eq
k B CD ,eq CH 2 ,eq
=
= KC
2
k B
CB ,eq
Therefore,
2 CD CH 2
rB = k B CB
K
C
Note: rD= 0.5 rB
Fogler 3.2.3
Example: CSTR, constant volumetric flow
The elementary liquid-phase reaction
k1
R +S
A + B
k2
is to take place in a 120 L steady-state mixed reactor. Two feed
streams, one containing 2.8 mol-A/L and the other containing 1.6
mol-B/L, are to be introduced in equal volumes into the reactor, and
75% conversion of the limiting component is desired. What should
be the flow rate of each stream? Assume a constant density
throughout, with k1= 7 Lmol-1min-1 and k2= 3 Lmol-1min-1 .
Adiabatic Operation & Equilibrium Conversion
For a reactor operating adiabatically, the maximum conversion that
may be achieved is the equilibrium conversion.
How can we calculate this ?
Reaction
:
A+ B C +
Equilibrium
Step-1: Calculate Xe as a function of T
c/a
d /a
CCe
C De
KC = [ 1 b / a ]
C Ae C Be
But Kc=f(T)
c
c
d
{C A0 ( C + X e )}a {C A0 ( D + X e )} a
a
a
]
KC = [
b
b
{C A0 (1 X e )} {C A0 ( B X e )}a
a
Fogler 8.5
Adiabatic Operation & Equilibrium Conversion
Step-2: Calculate XEB as a function of Temperature from Steady State Energy
Balance Equation
X EB
=
i
pi
Equilibrium
(T T0 )
H Rxn (T )
The above equation is obtained by
substituting Q =0 and Ws=0 in the
general EB equation below
n
Q Ws FA0 [ i C pi dT ] [ FA0 X H Rxn (T ) ] = 0
i =1 T0
Assumptions made?
Fogler 8.5
Adiabatic Operation & Equilibrium Conversion
Equilibrium
Increasing the inlet
temperature results
in shifting of the
EB equation to the
RIGHT
Xe
Adiabatic Temperature
T01
T02
For an example of how to construct
this plot, see Fogler E8-6
Fogler 8.5
Exothermic Reactions: Achieving Higher
Conversion by Inter-stage Cooling
For an example of how to construct
this plot, see Fogler E8-7
Endothermic Reaction and Adiabatic Conversion
Equilibrium
Increasing the inlet
temperature results
in shifting of the
EB equation to the
RIGHT
Xe
Adiabatic Temperature
T01
T02
Endothermic Reactions: Achieving Higher
Conversion by Inter-stage Heating
Xe
X3
X2
X EB =
X1
~
i C pi (T T0 )
H Rxn (T )
