CHE594

Chemical Reaction Engineering

TOPIC 7
NON-ISOTHERMAL
REACTORS

SITI WAHIDAH BINTI PUASA

PHONE NO: 03-55436327
Reference: Fogler 4th Edition, Levenspeil
3rd Edition
CHE594: CHEMICAL REACTION ENGINEERING
The combined mole balance, rate law, and stoichiometry yield:

 Mole balance  Rate law

dX  rA  E  1 1 
  rA  k1 exp    C A
dV FA0
 R  T1 T 

 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

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Need another relationship relating X and T or T and V

For an adiabatic reaction, the energy  H rx X

T  T0 
balance can be written in the form: C p, A

Set X Calculate T Calculate k

Calculate FAO/-rA Calculate -rA

Plot graph

CHE594: CHEMICAL REACTION ENGINEERING

19
  dEsystem
Q W s   F io Eio |in  F i Ei |out 
dt

CHE594: CHEMICAL REACTION ENGINEERING

Substitute:

General Energy Balance:

Steady state operation:

To determine the flowrate:

For generalized reaction

In general

CHE594: CHEMICAL REACTION ENGINEERING

Heat of reaction at temperature T (if a phase change
takes place):

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

CHE594: CHEMICAL REACTION ENGINEERING

 Heat of Reaction -SUMMARY

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

CHE594: CHEMICAL REACTION ENGINEERING

Example 1: Ethane Cracking C2 H6  C2 H4  H 2

H Rxn
o
(Tref )  H Co2 H 4 (Tref )  H Ho 2 (Tref )  H Co2 H 6 (Tref )

H Co2 H 4 (298 K )  52.28 kJ / mol

H Ho 2 (298 K )  0 kJ / mol
H Co2 H 6 (298 K )   84.66 kJ / mol

H Rxn
o
(298 K )  52.28  0  (84.66) kJ / mol
  136.94 kJ / mol
Positive heat of reaction : ENDOTHERMIC reaction (needs heat)

CHE594: CHEMICAL REACTION ENGINEERING

 Example 2: Methane Oxidation CH 4  2O2  CO 2  2 H 2O

Calculate heat of reaction for the Methane

Oxidation reaction at standard condition

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

Negative heat of reaction : EXOTHERMIC reaction (generates heat)

CHE594: CHEMICAL REACTION ENGINEERING
 Steady state:

 
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  XCPTR
T
 C i Pi  XCP
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

For ΔCp = 0, the equilibrium constant varies with

temperature
Example 8-3:

Normal butane is to be isomerized to isobutane in a PFR.

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.

ΔH RX  6900J/mol butane Activation energy  65.7kJ/mol

C p n-B  141 J/mol  K K C  3.03 at 60 C
C pi-B  141 J/mol  K C A0  9.3g mol/dm 3
C pi-P  161 J/mol  K
 NOTE ON FIRST-ORDER REVERSIBLE REACTIONS

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

M. Lacroix Nonisothermal Reactor Design 18

 C A  C A0 (1  X )
A B Stoichiometry
C B  C A0 X

Mole balance X FA0

Rate law V  dX
(PFR) 0  rA
 CB    1  
FA0
dX
 rA 
 rA  k  C A    rA  kCA0 1  1   X 
dV  KC    KC  
 E  1 1 
k  k (T1 ) exp    
 R  T1 T 
 H RX  1 1 
K C  K (T2 ) exp    
 R  T2 T 

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 piP
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.

Total heat transferred to the reactor:

A V a = heat exchange
Q   U (Ta  T ) dA   U a (T
a  T ) dV area/volume

Heat transfer rate Heat transfer rate

at a given location at a given location
in a PFR: in a PBR

dQ dQ a
 Ua (Ta  T ) U (Ta  T )
dV dW  cat
Equations relating X and T, and Fi and T

Adiabatic CSTR, PFR, Batch, PBR achieve this

CSTR with heat exchanger, UA(Ta-T) and large
coolant flow rate
PFR/PBR with heat exchange:

 In terms of conversion, X

 In terms of molar flow rates, Fi

Curve A:
Reaction rate slow, conversion dictated by rate of
reaction and reactor volume. As temperature increases
rate increases and therefore conversion increases.

Curve B:
Reaction rate very rapid. Virtual equilibrium reached in
reaction conversion dictated by equilibrium conversion.

Optimum Inlet Temperature:

Fixed Volume Exothermic Reactor
Interstage cooling:
CHE594: CHEMICAL REACTION ENGINEERING