College of Engineering

Department of Chemical Engineering

CHE 308:
Kinetics and Reactor Design
By
Dr. Naveed Khan
Chapter: Non-Isothermal Reaction
Textbook: Elements of CHE Reaction Engineering( H.S
Fogler) & Chemical Reaction Engineering (O. Levenspiel)

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez 1
Non-Isothermal Reactions

 Consider the following liquid-phase

exothermic
reaction: A
 
The reaction takes place in aBPFR under adiabatic,
non-isothermal conditions
 We need to calculate the volume of flow reactor to
achieve conversion X
 The mole balance: dX

rA
dV FA0

dX kCA0 1 X  1 1
k exp
 E  1 1 
   CA0 1 X
dV  FA  F
0 A
 
 R  T1 T  
0

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)

5, Smith, Dr. M. Anwar Parvez
Energy Balance for Flow Reactors
 Since the reaction is non-isothermal, the temperature will
vary along the reaction length
 The temperature is related to conversion through energy
^
balance equation: dEQ
 For a flow reactor: W
 rateof   Rateof flow   Rateof work 
 Rateof energy   Rateof energy 
         
 Accumulation    of heat to    doneby   added tothe system  leaving the
 of energy the system  
  the system   by mass
system


  flowin  

dE sys • 
 QW  Fin Ein  Fout E
ˆ dt out
.

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Energy Balance for Flow Reactors

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
The Energy Balance equation
 For the following reactions: b
A B C D
c d
a a
n n a
 Fi 0 H i 0  FA0 H A0  FB 0 H B 0  FC 0 H C 0  FD 0 H D 0  FA0  i H i 0
i1 i1
n n

 and FH i i  FA H A  FB H B  FC H C  FD H D  FA0  H i i   i X 

i1 i1

 then
n

F H  F Hn
 FA0
n

 H 
 d H D  c H C bB A
a H   X
i i
i1
i0
0
i
i1 i1
i0
 Hi i  A0
a a
F H
n n n


i1 Fi 0 H i 0  
i1 Fi H i  FA0   H i 0  H i i  H Rx  T
FAo X
i1

 For steady state conditions, the energy balance

•  n
dEˆsys  QW  H i 0  Hi i  H Rx T FAo X  0
A0 
dt F i1

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
1. Adiabatic Reactions with constant CP
•  n
QW  H i 0  H i   H Rx F X
A0 
i T Ao
F i1  0

 For Adiabatic reactor
•
with

negligible shaft
work: Q  0 and W  0 S
 The energy balance equation becomes
n

FA0   H i 0  H i i  H Rx T FAo X  0

i1
T
 But H i 0  H i    C Pi dT  C Pi T T 0
No phase Change and constant C
Pi
n
 Then 

i1  C T  T   H
i Pi  0 Rx X
T
Ti 0
0
 And the temperature is now related to conversion

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
1. Adiabatic Reactions with constant CP

 From energy balance find T at different X

T1  T0
 H rx X
X T -rA -rA/FA0

0 T0

atCeach X
i 0.1
 Find the rate equation Pi 0.2


rA  kCA0 1  X   1   
A0
k exp 1
 R  T1 T 
E Estimate
1 1   FA0/-rA
 C 1 X 
 Plot FA0/-rA versus X
 Find the reactor volume from the
corresponding area
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Example: F P-8-6
 The elementary irreversible organic liquid phase reaction
AB C
is carried out adiabatically in a flow reactor. An equimolar feed in A
and
B enters at 27° C, and the volumetric flow rate is 2 dm3/s and CA0=0.1
kmol/m3.
a) Calculate the PFR and CSTR volume necessary to achieve 85%
conversion.
b) What is the maximum inlet temperature one could have so that the boiling
point of the liquid (550° K) would not be exceeded even for complete
conversion?
c) Plot the conversion and temperature as function of PFR volume.
d) Calculate the concentration achieved in one 500 dm3 and in two 250-dm3
CSTRs in series.
HA°(273)= -20 kcal/mol, HB°(273)= -15 kcal/mol, HC°(273)= -41 kcal/mol
CP,A=CPB=15 cal/mol.K, CP,C=30 cal/mol.K
k = 0.01 dm3/mol.s at 300° K, E =10000 cal/mol
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution Part a:
AB C
 CP=CPC-CPA-CPB=0 HRX =
constant
T  T H

  300 H
rx
H H  
A

B

 C C
C

1 0
C 
X i
PA PB

Pi6000X
T1  300  30  300  200X

 E  1 1  10000  1  1  
k  k 1 exp       0.01exp   
 R  T 1 T    1.987  300 T 

-rA  kC A20 (1

X )2

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution: Part a
 Volume of CSTR equals the area of rectangle
 VCSTR = 0.85 x 206
= 175 dm3
 Volume of PFR equals the entire Area under the curve
~ 305 dm3
 VPFR

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution: Part a Using Excel
X T k CA -rA FA0/-rA VCSTR VPFR
VPFR
 Volume of CSTR at X 0 300 0.01 0.1 1.00E-04 2000 0 0 0
0.05 310 0.02 0.095 1.55E-04 1290 64 82.25 82

V CSTR  FA0 X  FA0 X 0.1 320 0.03 0.09 2.31E-04 865 87 53.88 136
r A r A 0.15 330 0.05 0.085 3.32E-04 602 90 36.69 173
0.2 340 0.07 0.08 4.61E-04 434 87 25.92 199
0.25 350 0.11 0.075 6.18E-04 324 81 18.95 218
 Volume of PFR at X 0.3 360 0.16 0.07 8.03E-04 249 75 14.32 232
0.35 370 0.24 0.065 1.01E-03 198 69 11.18 243
dV PFR  FA0 dX 0.4 380 0.34 0.06 1.23E-03 163 65 9.02 252
r A 0.45 390 0.48 0.055 1.45E-03 138 62 7.51 260
F X F 0.5 400 0.66 0.05 1.66E-03 121 60 6.46 266
 PFR  r
A0
 rA0 X 0.55 410 0.90 0.045 1.82E-03 110 60 5.76 272
V A A
 X has to be small 0.6 420 1.21 0.04 1.93E-03 104 62 5.33 277

0.65 430 1.59 0.035 1.95E-03 102 67 5.15 282

X 0.7 440 2.08 0.03 1.87E-03 107 75 5.23 288

0.75 450 2.68 0.025 1.68E-03 119 89 5.65 293
V PFR   V PFR
0.8 460 3.42 0.02 1.37E-03 146 117 6.64 300
0
0.85 470 4.32 0.015 9.71E-04 206 175 8.80 309
0.9 480 5.40 0.01 5.40E-04 371 334 14.41 323

0.95 490 6.68 0.005 1.67E-04 1197 1137 39.19 362

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Reactor Volume versus Conversion

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution : Part b
What is the maximum inlet temperature one could have so that the
boiling point of the liquid (550 K) would not be exceeded even for
complete conversion?

T  T0  H rx  X 
T0
200X
 PC
i
i

T0,max  550  200 * X max  550  200 *1  350

K

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Part c:
Plot the conversion and temperature as function of PFR volume.

1 600

0.9

500
0.8

0.7
400

0.6
T

X
0.5 300

T
0.4

200
0.3

0.2
X 100

0.1

0 0
0 50 100 150 200 250 300 350 400
VPF
R

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Part d
Calculate the concentration achieved in one 500 dm3 and in two 250-
dm3 CSTRs in series.
V CSTR  FA0 X  F A0 X  F A0 X
kC A0  1  x
2
r A  E  1  1 C
k 1 exp  R  T 
2
 1

A0
  1 T  x

 F A0 X
E  1 1
k 1 exp     C 2
1  x 
 A0
 R  T 1 .300  200 X 
 For 1
CSTR
V CSTR
0.2
X  500 ,  X  0.92
 10000  1
  1  0.1 2 1  x 
0.01 exp 
 1.987  300 300  200 X 
 For 2 

CSTRs 0.2
V CSTR ,1  FA0 X 1  X 1  250  X1 
r A
 10000  1   0.1
2
1  X  0.881
0.01 exp   1

1 1.987  300 300  200 X 1 


VCSTR ,2

FA0  X 2  X1   0.2
X2
 250  X 2  0.97
r 0.01 exp 10000  1    0.1  1 
A 2
2
  1 1.987  300 300  200 2  X

X

CHE 308 : Kinetic and Reactor Design (NK) Dr. M. Anwar Parvez
CHE 203: Chemical Engineering Thermodynamics I, Chapter # 5, Smith,
Steady State Reactors with Heat Exchange
 We have studied the operation of reactor under adiabatic
condition
 In many cases we need to introduce heat or remove heat from the
reactor
.
 Let Q be the heat added to the reactor Q  UA T  a
T
 
The energy Balance around differential volume V:
Coolant
.
Ta FA
Q  FH 0 T
 i i V   Fi H i V FA0 V
 V
 Q  U  A Ta  T  U a  V  Ta 
T0
T
 A
where a is heat exchange area per unit volume of the reactor,a = V

0 d   Fi Hi 
U a  V Ta  T    Fi   Fi H i
V V
V  0
Hi U a Ta  T  
 dV
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Steady State Reactors with Heat Exchange
Ta
 Expanding the energy balance equation: Coolant
V FA
T
FA0
T0 T

d  F H  0
i i

U a T  T 
a
dV
 We get: 
dF 
dH
U a Ta  T   i
dV H i
 i FdV
i  0

 The PFR mole Balance equation:
dFi
A 
dV  r i   i r
 Differentiating the enthalpy equation with respect to V:
d  C p dT
dHi i
dT
 
dV C dV Pi
dV
 Substituting into the expanded energy balance equation:
H  Rx

 i i dT rA H Rx U a T  Ta
U a TP  T    H r    FC dV  dV 
a A i

dT
i

  FCi
P i

0 
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez

Steady State Reactors with Heat Exchange
 The design equation for PFR with heat exchange:
Heat Removal
H
eat Ta
dT Coolant
A
H rRx at U a T Ta
 Gr ene V FA

 
T
 Note: dV   FC FA0
T0
ion
  i P
i

  i X C P  i C P X   F   C
A0 i P  C P X
 F i C P   F A 0  i
i

i

 F A 0   i C Pi
i i
 And the “friendly” form of the design equation becomes: i

dT rA H R x U a T T a 
dV  C P X
F A 0   i C P
 i

 For PBR, W=V b and the design equation becomes i

U
dT rA' H Rx   a T Ta
 b
 C P X
FA 0  i C P
dW  i

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith,
i
Dr. M. Anwar Parvez
Solving CRE Problem for Reactors with Heat Exchange
 The Differential Equation describes the change in T
along the reactor
dT U
rA' H Rx   a T Ta
r H R x U a T T a  or dT
 A  C P X  b
 C P X
F A 0   i C P
dV  i

i
dW FA 0   i C P 
i

 Must be coupled with mole balance equation: i

'
dX or dX 
rA rA

dW FA 0
 Ifthe coolant
dV temperature
F varies down the reactor we
A0

must add coolant balance:

U
d Ta U a T T a dT a B a T Ta 
dV  . 
mc CP dw .
mc CP
c
 c

 This set of equation must be solved simultaneously

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Non-Isothermal Reactor Design: Example
 The elementary irreversible organic liquid phase reaction
AB C
is carried out in a flow reactor. An equimolar feed of A and B
enters at 27° C. The volumetric flow rate is 2 dm3/s and CA0 =
1. kmol/m3.
a) Plot the conversion and temperature as function of PFR volume when a
heat exchange is added, Ua = 20 cal/m3.s.K, and the coolant temperature
is constant at Ta= 450 K
b) Repeat for a coolant flow rate of 50 g/s and CPc = 1 cal/g.K and inlet
cooling temperature of Ta0 = 450 K
c) Vary the cooling rate between 1-1000 g/s
HA°(273)=-20 kcal/mol, HB°(273) = -15 kcal/mol, HC°(273) =-41 kcal/mol
CP,A= CP,B =15 cal/mol.K, CP,C= 30 cal/mol.K
k = 0.01 dm3/mol.s at 300° K, E =10000 cal/mol
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution: Part A
 Reaction Kinetic Data: AB 
 -rA = C Coolant
Ta

 CA0 = mol/dm3 V
FA
T

 CB0 = mol/dm 3 FA0

T0

 v0 =
 T0 =
 k1 = ; T1=
 E=

?
 Thermal Data
 (Hrx)273=
 CP = XA T
 Heat Exchange Data
 Ua =
 Ta =
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
VPFR
Chemical Reaction Engineering
Solution Cont.:
 Mole Balance: dX
dV 
dT

 Energy Balance: dV

 Stoichiometry: CA  ; CB 

 FA0 

 rA 

E 1 1 
 kT1  k exp   
 R  T1 T  

 H rx  
T

=
 i C Pi
 Solve the two differential equations using Polymath
CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Polymath Solution:

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Polymath Solution:

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution: Part A

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Solution Cont.:
 Mole Balance: dX rA
dV 
FA0
rA   Rx
 Energy Balance: dT
 H T U a T  Ta
 CP X

FA0  i C Pi i

dV 
 Stoichiometry: C A  C A0 1 X  C B  C A0 1 X   C A
 FA0  CA0 v0  0.1x2  0.2 mol / s ;
 E  1 1  2
 rA  f X ,T  kCA  k 1exp
2

 R  T1 T  C 0 1 X
 A


  6000 cal / mol.
H rx  T  H rx 273 K 2
 = A C PA  B C PB  C C PC  30 cal / mol.K
 i C Pi
 C P,i   i C P,i C P,C  C P, A  C P,B  0

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez
Tutorial 1

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez 27
Tutorial 2

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez 28
Tutorial 3

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez 29
Tutorial 4 (11-5 Self Assign)

CHE
CHE 308
203: : Kinetic
Chemical and
Engineering Reactor Design
Thermodynamics I, Chapter #(NK)
5, Smith, Dr. M. Anwar Parvez 30