TOPIC 7
NON-ISOTHERMAL
REACTORS
Stoichiometry Combine
C A CAO (1 X )
E 1 1 E 1 1
k1 exp C A o (1 X ) k1 exp (1 X )
dX
R T1 T R T1 T
dV FAO O
Plot graph
In general
d c b
H Rx (T ) H D (T ) H C (T ) H B (T ) H A (T )
a a a
n
Q W FAO i ( H io H i) H Rx (T ) FAO X 0
i 1
T
H R T H R (TR ) CP dT
TR
d c b
H R H D H C H B H A
a a a
d c b
C P C PD C PC C PB C PA
a a a
H Rxn
o
(Tref ) H Co2 H 4 (Tref ) H Ho 2 (Tref ) H Co2 H 6 (Tref )
H Rxn
o
(298 K ) 52.28 0 (84.66) kJ / mol
136.94 kJ / mol
Positive heat of reaction : ENDOTHERMIC reaction (needs heat)
H Rxn
o
(Tref ) H CO
o
2
(Tref ) 2 H o
H 2 O (Tref ) H o
CH 4
(Tref ) 2 H o
O 2
(Tref )
o
H CO 2
(298 K ) 390.1 kJ / mol
H Ho 2O (298 K ) 241.8 kJ / mol
o
H CH 4
(298 K ) 74.8 kJ / mol
H Oo 2 ( 298 K ) 0 kJ / mol
H Rxn
o
(298 K ) 390.1 2 241.9 (74.66) 2 (0) kJ / mol
799.1 kJ / mol
Q W s F io Eio |in F i Ei |out 0
Q Ws FAO i C Pi (T Tio ) FAO X H R (TR ) C P (T TR ) 0
Adiabatic operation,
X
C i Pi (T Tio )
Q=0, Ws=0
H R (TR ) C P (T TR )
X [H R (TR )] i CPiTo XCPTR
T
C i Pi XCP
Exothermic ΔH is negative
Endothermic ΔH is positive
At equilibrium,
rA 0
C Be
C Ae
Ke
C A0 X e
C A0 (1 X e )
Ke
Ke
Xe
1 Ke
n C4 H10 i C4 H10
The reaction is to be carried out adiabatically in the liquid phase under high pressure using
essentially trace amount of a liquid catalyst which gives a specific reaction rate of 3.1 h-1 at
360 K. Calculate the PFR volume necessary to process 100,000 gal/day of a mixture of 90
mol % n-butane and 10 mol % i-pentane (inert). The feed enters at 330 K.
k1
• BASIC REACTION: A
k
B
2
dCA
• RATE EQUATION FOR A: rA k1CA k2CB
dt
• STOICHIOMETRY: C A C A0 (1 X A );C B C A0 ( B X A )
WITH B C B 0 / C A0
• AT EQUILIBRIUM,
RATE OF DISAPPEARANCE OF A= RATE OF FORMATION OF B
dC A k1 CB ( B X A )
0 k1C A k 2C B K C
dt k C (1 X )
2 A A
Energy balance :
n
~
Q Ws FA0 i C pi (T Ti 0 ) FA0 X H RX (TR ) Cˆ p (T TR ) 0
i 1
=0 =0 =0
T Ti 0
H RX (TR ) X H RX (TR ) H RX 6900 J / mol A B
n
~
i pi
n
~ ~ ~
iC pi C pA i PC piP
C
i 1
i 1
0.1
141 161
0.9
6900
159.5 J / mol K
T 330 X
159.5
X FA0 1 E 1 1 H RX 1 1
V dX rA kCA0 1 1 X k k (T1 ) exp K C K (T2 ) exp
0 rA K C R T1 T R T2 T
65700 1 1
k 31.1exp
8.31 360 T
6900 1 1
K C 3.03 exp
8 . 31 333 T
6900
T 330 X
159.5 These equations can be solved simultaneously
X FA0
V dX
0 rA X Xe
1
rA kCA0 1 1 X
KC
65700 1 1 V
k 31.1exp
8.31 360 T T
6900 1 1
K C 3.03 exp
8 . 31 333 T
At equilibrium: -rA = 0 V
-rA
1 KC
rA kCA0 1 1 X Xe Max. reaction rate @
KC 1 KC somewhere in the tube
a⇔b•
the highest conversion that can be achieved in
reversible reactions is the equilibrium
conversion. •
for endothermic reactions, the equilibrium
conversion increases with increasing
temperatute up to a maximum of 1. •
for exothermic reactions, the equilibrium
conversion decreases with increasing
temperature.
Heat Transfer to a CSTR
Heat transferred between
coolant and reactor (from
energy balance on the
coolant:
UA(Ta1 Ta 2 )
Q mcCp c (Ta1 Ta 2 )
ln[ (T Ta1 ) /(T Ta 2 )]
Assuming CSTR temperature, T is spatially uniform:
UA
Q mc Cp c (Ta1 T ) 1 exp
(mc Cp c )]
For high coolant flow rates , Ta1 Ta2=Ta and the 2nd order
terms are neglected in the Taylor expansion of exp function.
Therefore:
Q UA(Ta T )
In PFR/PBR the concentration and reaction rates vary
along the reactor length. Q will likely vary too.
A V a = heat exchange
Q U (Ta T ) dA U a (T
a T ) dV area/volume
dQ dQ a
Ua (Ta T ) U (Ta T )
dV dW cat
Equations relating X and T, and Fi and T
In terms of conversion, X
Curve B:
Reaction rate very rapid. Virtual equilibrium reached in
reaction conversion dictated by equilibrium conversion.