** 12-1 Single reaction in a PFR with Heat Exchange, Butane isomerisation

Problem Description
n C 4 H 10 ↔ iC 4 H 10

Or simply A ↔ B

Reactor info
Ten PFRs in parallel each of volume 5 m3
U = 5,000 kJ/m3 h K
MAXIMUM temperature allowed in any reactor at any point is 325 K

Reactor feed info

The feed to be divided across the ten reactors is 163 kmol/h
of a mixture 90 mol % n-butane and 10 mol % i-pentane.
CA0 = 1.86 mol/L
CpA = 141 kJ/kmol.K
Cp0 = ∑ θ i C Pi = 159 kJ/kmol.K
T0 = 305 K

Reaction info

The rate law is (

−r A =k C A −
CB
KC )
Kc = 3.03 at 60 oC
k = 31.1 h-1 at 360 K
Ea= 65.7 kJ/mol
o
∆ H Rx = -34,500 kJ/kmol
Heat capacity of the product isomer is the same as the reactant so ΔCp=0.

Heat transfer info

Mass flow rate of coolant to each reactor is 500kg/hr
Inlet temperature, T1=315 K
Heat capacity CpC=28 kJ/kg K

Questions

Plot X, Xe, T, T, –rA down the length of the reactor for

a) Co-current heat exchange

b) Countercurrent heat exchange
c) Constant ambient temperature T

1
d) Adiabatic Operation

Solution
a) Co-current heat exchange

The feed molar flow is 163 kmol/hr but this includes 10 mol % pentane (P)

kmol
F A 0=0.9∗163=147
hr

The feed is split between 10 reactors

kmol
F A 0=0.1∗147=14.7
hr

Mole Balance

dX −r A
=
dV F A 0

The rate law is

(
−r A =k C A −
CB
KC )
Let’s substitute in expressions for CA and CB

C A=C A 0 (1−X )

C B=C A 0 X

Substituting these two into the rate law and rearranging we get

( {
−r A =k C A 0 1− 1+
1
KC
X
})
Let’s substitute in expressions for k and Kc

k =k ( T ref ) exp
( (
Ea 1
−
R T ref T
1
))
=31.1exp
65700 1
−
8.31 360 T
1
( ( )) 1h
( ( )) [ )]
o

K c =K C ( T ref ) exp
∆ H Rx 1
R
−
T ref T
1
=3.03 exp ⁡
−34500 1
−
8.31 333 T
1
(
Substituting these into the rate law and rearranging we get

2
 ( 360 T )
( − ) C
({ })
1 1 1
−r A =31.1 exp 7906 1− 1+ X

[ )]
A0

(
3.03 exp ⁡ −4149.6
1
−
333 T
1

So the mole balance is

( ( ))
({ })
1 1 1
31.1exp 7906 − C A 0 1− 1+ X

dX
360 T
[ (
3.03 exp ⁡ −4149.6
1
−
333 T
1
)]
=
dV FA 0

Note that usually we have to take into account the temperature dependence of the heat of
reaction, given by the equation
o
∆ H Rxn (T )=∆ H Rxn ( T R )+ ∆ C p (T −T R )

However that is not necessary here as ∆ C p=0 because the products and the
reactants have the same heat capacity, therefore the heat of reaction is constant.

Equilibrium Conversion

Because this is a reversible reaction we need an expression for Xe

C Be CA 0 Xe Xe
By definition K c = = =
C Ae C A 0 (1−X e ) 1− X e

KC
Rearranging to isolate Xe X e=
1+ K C

Energy Balance

Use the energy balance equation for a PFR with co-current heat exchange

dT r A ∆ H Rx−Ua(T −T a ) r A ∆ H Rx −Ua(T −T a )
= =
dV F A 0 ∑ θi C Pi F A 0CP0

o
∆ H Rx =∆ H Rx + ∆C P ( T −T ref )
o
Since ∆ C P =0 ∆ H Rx =∆ H Rx

dT r A (−34500)−5000(T −T a)
=
dV (14.7)(159)

Energy balance on the heat transfer fluid

Use the energy balance for co-current heat transfer fluid in the lecture notes

3
 d T a Ua(T −T a )
=
dV ṁC C PC

d T a 5000(T −T a)
=
dV (500)(28)

Enter these equations into an ODE solver to solve the coupled ODEs. This problem has three
simultaneous ODEs.

Use the differential equations solver, enter the 3 ODEs (mole balance, reactor energy
balance and heat transfer fluid energy balance). Then enter the explicit equations, k, K c, Xe,
FA0, rA and finally enter the constant values. Set initial conditions of conversion and inlet
temperatures.

The temperature rose above 325 K, so the problem requirement is not satisfied (note the graphs in
the example are wrong, these are correct and agree with the code from the Fogler website)

4
b) Counter-current heat exchange

In this case we adapt the heat transfer fluid energy balance by multiplying RHS by -1.

d T a −Ua(T −T a )
=
dV ṁC C PC

Co-current is easier because the entrance condition at V=0 is that T= 315 K, so it is easy to
solve. For counter-current the entrance condition is unknown, only the exit condition is
known as the exit temperature is 315K. So we solve by trial and error.

We guess T at the entrance, V=0 expecting it must be higher than the inlet value of
315 K (Why?)

We repeat this guess until T at the outlet V=5 is 315 K, the known exit condition.

5
6
c) Constant T
Set dT/dV in the heat transfer ODE to _____ to force T to remain constant.

7
d) Adiabatic reactor
Set ____ to zero so there is no heat transfer

8
Conclusions

 Cooling increases the conversion achieved in the reactor because of equilibrium

conversion limitations, therefore the reactors with counter-current flow and
constant T have the highest conversions while the adiabatic has the lowest.
 The rate of reaction is highest at high temperature so there is a balance to be struck
between getting high conversions and not using excessive reactor lengths.

Questions to consider
1) What would happen if the heat of reaction increased?
2) What would happen if the activation energy increased?
3) What would happen if the equilibrium constant increased?
4) What would happen if the feed flowrate increased?
5) What would happen if this was an endothermic reaction?