Model reaktor fixed bed

Modeling of Fixed Bed Reactors (Froment and Bischoff, 1990)

 PSEUDOHOMOGENEOUS MODELS
 The Basic One-Dimensional Model
 One-Dimensional Model with Axial Mixing
 Two-Dimensional Pseudohomogeneous
Models
 HETEROGENEOUS MODELS
 One-Dimensional Model Accounting for
Interfacial Gradients
 One-Dimensional Model Accounting for
Interfacial and Intraparticle Gradients
 Two-Dimensional Heterogeneous Models
 THE BASIC ONE-DIMENSIONAL MODEL
d us C A 
  rA  B
dz

 (H )rA  B  4 T  Tr 
dT U
us  g c p
dz dt
dpt  g us
2

  f
dz dp

Tad  T0 (H ) p Ao (H )C Ao

   Runaway criteria
T0 M m pt c pT0  g c pT0
ONE-DIMENSIONAL MODEL WITH AXIAL MIXING

d 2C A dC A
Dea 2
 us  rA  B  0
dz dz
d 2T
 (H )rA  B  4 T  Tr   0
dT U
ea 2  us  g c p
dz dz dt

us C A0  C A   Dea
dC A
For Z = 0 dz
 g us c p T0  T   ea
dT
dz
For Z = L dC A dT
 0
dz dz
TWO-DIMENSIONAL PSEUDOHOMOGENEOUS
MODELS
  2C 1 C  dC A

Der  2  
  us  rA  B  0
 r r r  dz

  2T 1 T  dT
ea  2    u s  g c p  (H )rA  0
 r r r  dz

For Z = 0 C = C0 T = T0

dC A dT
For r = 0  0
dr dr
HETEROGENEOUS MODELS
ONE-DIMENSIONAL MODEL ACCOUNTING FOR
INTERFACIAL GRADIENTS
For the fluid phase:

us
dC A
dz

 k g av C  Css 
us  g c p
dT
dz
 s U

 h f av Ts  T  4 T  Tr 
dt

For a cross section of the bed including soilid and fluid:

 B rA  k g av C  Css 

(H )  B rA  h f av Tss  T 
ONE-DIMENSIONAL MODEL ACCOUNTING FOR
INTERFACIAL AND INTRAPARTICLE
GRADIENTS
For the fluid phase: u s
dC A
dz
 k a
g v C  C s 
s

 h f av Ts  T   4 T  Tr 
dT U
us  g c p s

dz dt
For the solid phase:

 2 dCs 
   s rA Cs , Ts   0
De d
 
 2 d  d 

e d  2 dTs 
     s (H )rA Cs , Ts   0
 d  d 
2
TWO-DIMENSIONAL HETEROGENEOUS MODELS
For the fluid phase:
dC A 1   C 
us
dC A
dz
 ur
dr
  ers
r r 
rD
r 

 g v
k a C  Cs
s 
 T T  1   T 
 f c p u z  ur    r    h a T
f v s T
s

 z r  r r  r 
ers

For the solid phase:

 
k g av Css  C   s (1   ) A R

1   Ts 

k f av T  T f 
s
s
  rer
r r  r 
   s (1   ) ( H A R )
MODELLING FOR PREDICTION OF
RUNAWAY BEHAVIOR
IN NON-ADIABATIC
HETEROGENEOUS
CATALYTIC COMBUSTION
Introduction
 Flow reversal technology is a relatively
new technique for handling exothermic
reaction in fixed bed reactors.
 Flow reversal process is carried out using
two adiabatic reactors connected together
with a heat exchanger placed between
them.
 In this research dynamic cycling state
(including flame out and runaway) were
studied.
Schematic diagram of the experimental set-
up and detailed reactor

Reactor
Mixer System 1.6 cm
30 cm

Filter
Propylene Flow 1 cm
controller
15 cm

Oxygen

Preheater 1.6 cm
Temperature 30 cm
data logger
Catalyst used in the process
 Granulars of catalyst, Platinum and Palladium on
zeolite, developed in the laboratory were used in
the process. The metal (Pt and Pd) on zeolite
catalysts contained 2 to 4 % metal, the metal
being deposited as a shell surrounding the
catalyst particle.

Properties

Surface area 2.01 x 105 m2/kg

Bulk density 1.8 x 103 kg/m3
Total pore volume 2.4 x 10-4 m3/kg
Feedstock

 Technical grade CO was used as

feedstock. This grade had a minimum
purity of 99.0%, toxic, no odour, fire and
inhalation hazards.

 A technical grade of oxygen with 99 %

purity was used as oxidizing agent.
MATHEMATICAL MODEL
 MATHEMATICAL MODEL
Packing zones
Solid phase:
 T s k esax  2 T s k esr  1    T s  
= +   r  
t  s Cp s  Z 2  g Cp s  r r  r  

h av
- (T s -T g )
 s Cp s (1 -  )
Gas phase:
T g k egax  2 T g k egr  1    T g  
= +  r 
t 
 g Cp g  Z 2  g Cp g  r r  r  

h av T g
- (T g - T s ) -V
 s Cp s (1   ) Z
Catalyst zone
Solid phase:
 T s k esax  2 T s k esr  1    T s  
= +  r  
t  s Cp s  Z 2  g Cp s  r r  r  
h av (-H)(- r c )
- ( T s - T g )+
 s Cp s (1 -  ) Cp s
Gas phase:

T g k egax  2 T g k egr  1    T g  
= +  r 
t  g Cp g  Z 2  g Cp g  r r  r  

h av T g
- ( T s - T g ) -V
 g Cp g  Z
 Mass balance:
Gas phase:
Cg 2 C g  1    C g 
= D eax + D er  r 
t Z2  r r  r  
  

k g av C g
- (C g - C s ) - V
c Z
Solid phase:

 C s k g av
t
=
c
 
C s - C g -  s (- r c )
The boundary conditions are :
z = 0 (inlet)
T g
V  g Cp g T o = V  g Cp g T g - k egax
Z

k esax
T s
Z

= h T s -T g 
z =
L1 and z = L2

     
(1 -  p ) k esax T s  = (1 -  c ) k esax T s 
 Z  p  z  c

 T g   T g 
 p   g Cp g V T g - k egax  =  c   g Cp g V T g - k egax 
 Z p  Z c
 For radial direction:
h wg ( T g - T w )+ h ws ( T s - T w ) = hc ( T w - T c )
T s
k esr = h ws ( T s - T w )
r
T g
k egr = h wg ( T g - T w )
r

For packing zones 1 and 2:

k insul
h wg ( T g - T w ) + h ws ( T s - T w ) = ( T w - T amb )
 x insul
The equation for reaction rate is :

k K CO K O PCO PO
(- r c ) = 2 2
- - - mol/h - kg - cat
1 + K CO PCO + K O PO 
2
2
2

k = 1.5792 x 10^10 exp (-20158.507/RT)

KCO = 1.8 exp (5451.197/RT)
KO2 = 2.1 x 10-5 exp (11205.4/RT)
 Results of mathematical modeling
500
Temperature distribution (C)

400

300
Experiment
Model
200

100

0
0 20 40 60 80
Reactor length (cm)

Example of the predicted axial temperature profiles along the reactor system
 320
Temperature distribution (C)

295
1 min
3 min
270
5min
15min
245

220
25 30 35 40 45 50
Catalyst bed (cm)

Temperature distribution in the reaction zone at the end of 15th cycle

Results of dynamic
cycling state
 Excessive cooling
300 Temperature
Temperature distribution (C)

250 distribution
200 1st cycle after 15 min
5th cycle
150
10th cycle
100 15th cycle

50

0
0 20 40 60 80
Reactor length (cm) Temperature distribution (C) 275

250
1 min
3 min
225
5min
15min
200

Temperature distribution
in the reaction zone 175
25 30 35 40 45 50

at the end of 1st cycle Catalyst bed (cm)

Runaway
700

600
Temperature (C)

500
1%
400
2%
300
5%
200

100

0
25 30 35 40 45 50
Catalyst bed (cm)

Effect of propylene concentration on the temperature profile

Maximum temperature (C) 1000
900
800
1%
700
2%
600
2.50%
500
3.00%
400
300
200
1 3 5 7 9 11 13 15
Cycle number

Effect of propylene concentration on the maximum temperature

Temperature distribution (C) 1000
900
800
1 min
700
3 min
600
6 min
500
10 min
400
300
200
25 30 35 40 45 50
Catalyst bed (cm)

Temperature distribution in the catalyst bed during runaway

Identification of
flame out and runaway
 In the non-adiabatic flow reversal experiments,
runaway and flame out can occur after several
cycles.
 The slowness of these two process means that
remedial action can be taken if flame out and
runaway behavior can be identified.
 Three approaches seem possible based on the
results presented :
1) ratio temperature difference to the cycle difference
(RTC),
2) ratio temperature difference over time (RTT), and
3) temperature gradient in the bed front.
Calculation of the change of maximum
measured temperature at the end
of half cycle by the cycle repetition
using the following equation :

Tmax (Tmax ) i  (Tmax ) i 1

RTC  
cycle (cycle) i  (cycle) i 1
When the runaway occurs, RTC is positive and
much greater than zero while RTC is negative
when the system is extinguished and finally
becomes to zero.
100
80
60
40 Basecase
RTC

20 Flameout
0 Runaway

-20
-40
-60
0 5 10 15 20
Cycle number
Calculation of change of maximum
measured temperature at the end of
half cycle within a cycle
Tmax (Tmax ) i  (Tmax ) i 1
RTT  
t ti  ti 1
Identification of unstable behavior using the second
method can only be applied for runaway since there
is moving wave within cycling for flame out behavior.
When runaway occurs, RTT increases with increasing
time. For stable operation, the RTT should go to zero
with increasing time.
 20

15

Runaway
RTT

10
Stable

0
0 5 10 15 20
Time (min)

Effect of time within cycle on ∆Tmax/∆t

for runaway and stable operation
By calculating the temperature gradient
in the bed front as follows
T32.5  T30
Gradient 
32.5  30
Cycle Temperature gradient

Steady Flame out Runaway

cycling
2nd cycle 21.2 17.4 40.1

3rd cycle 21.7 9.5 116.9

Contoh
 Disosiasi katalitik gas A menjadi gas B dan C
dijalankan dalam fixed bed reaktor skala
laboratorium secara isothermal pada suhu 310 oC.
Gas umpan terdiri dari 95 % A dan 5 % inert dan
kecepatan reaksi dalam mgmol / j gkat adalah:
 PB .PC 
k  PA  
(r )  
K 
1  K A .PA 
 Konstanta – konstantanya adalah: k = 79 mgmol /j
gkat, KA = 3.75 (atm)-1, and K = 0.75 atm
 Berat katalis yang digunakan adalah 16.94 gram,
dan tekanan total adalah 1 atm.
Pertanyaan
 Gambarkan grafik hubungan antara W/F dan x
(0, 0.1, 0.2, 0.3, 0.4)
 Hitung nilai maximum dari x
Basis 1 mol umpan
 Umpan terdiri dari 95 % 0.95  x 0.95  x
mol of A dan 5 % inert PA  Pt 
1 x 1 x
A = 0.95 – x x x
B= x PB  PC  Pt 
1 x 1 x
C= x
 PB .PC 
I = 0.05 k  PA  
(r )  
------------------------------ K 
Nt = 1 + x 1  K A .PA 

 0.95  x 1  x 
2

79    
 1 x 0.75  1  x  
(rc )   
 0.95  x 
1  3.75 
 1 x 
  0.95  x 
1  3.75 
1 x 
x x
W

dx
  dx
F 0 (rc ) 0  0.95  x 1  x 
2

79    
 1 x 0.75  1  x  
 
x
W 1

F 79 0 Idx

x  0, I 0  4.802
Integral Simpson’s
x  0.1, I1  5.100
W 1  I 0  I1  1  4.802  5.1 
  (0.1)   (0.1)  0.0063
F 79  2  79  2 
x  0.2, I 2  5.68
W

1 1
4.802  4(5.10)  5.68(0.1)  0.0131
F 79 3
W
x  0.3, I 3  6.68,  0.0209
F
W
x  0.4, I 4  8.70,  0.0305
F
 0.04

0.03
W/F

0.02 Series1

0.01

0
0 0.1 0.2 0.3 0.4 0.5
Conversion (x)
 Konversi maksimum dapat dicapai pada saat
reaksi pada kondisi keseimbangan (-rc )= 0

 0.95  x 1  x 
2

79    
 1 x 0.75  1  x  
(rc )    0
 0.95  x 
1  3.75 
 1 x 
x  0.63
Autothermal reactor

Catalyst bed

Exchanger

Product
Feed