Problema 1

JUO CHAHUAYLACC, Renzo Eugenio

Industrial scale production of sulfuric acid is dependent on the oxidation of
sulfur dioxide to trioxide in fixed bed catalytic reactor.

SO 2 +0.5 O2 SO 3
Through the years, several catalyst formulation have been employed, but one
of the traditional catalytic agents has been vanadium pentoxide. Calderbank
has indicated that for a catalytic consisting of

V 2 O5

supported by a rate

expression of the form

1

r p=

k 1 pSO p O k 2 p SO pO2
2

1
2
SO2

( A)

That may be regarded as a degenerate form of typical Hougen-Watson kinetics.

The rate constants are given by

ln k 1 =12.07

31000
RT

And

ln k 2 =22.75

53600
RT

Where:
T
R

k1
k2

: Is expressed in degrees Kelvin

: Is expressed in calories per mole-degree Kelvin
: Is expressed in moles per second-gram of catalyst-atmosphere 3/2
: Is expressed in moles per second-gram of catalyst-atmosphere

For our present purposes, the global rate expression may be presumed to be
identical with that of equation (A). The reaction is highly exothermic and must
be regarded as reversible. Consequently, although high temperatures enhance
the initial rate, they limit the conversion that can be archived. This limitation
can be circumvented by cooling a hot effluent to a temperature where the
equilibrium is more favorable, and then contacting this stream with additional
catalyst.

Determine the catalyst requirements for a two stage adiabatic fixed bed
reactor with interstage cooling. Specified production requirements are 50 tons
of

H 2 SO 4 / day

Additional Data and Specifications

Feed
composition
SO2
O2
N2

Mole percent
8
13
79

Total pressure 1 atm

First-stage inlet temperature 370 C
First-stage effluent temperature 560 C
Second-stage inlet temperature 370 C
Overall conversion of SO2 99%
Heat capacities (calories per gram degree Kelvin) 0.250
Heat of reaction at temperature T (kilocalories per gram mole) =24.60+1.99*10-3T for t in degrees Kelvin.
Bulk density of catalyst=0.6 g/cm3
Reactor diameter =6 ft.
Notes:
The first-stage effluent temperature has been limited to 560 C in order to
prevent excessive catalyst activity losses. The heat of reaction data is slightly
inconsistent with the reported activation energies, but use of this expression
demonstrates the ease with which temperature dependent properties may be
incorporated in the onedimensional model.

Solucin:
La reaccin:

1
SO 2 + O2 SO 3
2
El diagrama:

Clculos:
Determinemos

F AO =

50 ton H 2 SO 4 1 da
da
24 h

Determinemos

Ft =

F AO

( )(

1h
3600 s

)(

907.18lb
1ton

)(

1 kmol H 2 SO 4
98 kg H 2 SO 4

)( )

100
3
=5.41110
99

Ft

F AO
=0.0676 kmol /s
0.08

Determinemos el peso molecular promedio

PM prom =0.0864+0.1332+0.7928=31.49

g
kg
o
mol kmol

Del Balance de Energa:

dT H R F AO
=
dx
Ft C p
3
dT (24.60+1.9910 T )(0.08) F AO
=
dx
F AO C p
3
dT (24.60+1.9910 T )(0.08)kcal/molg ( 1000 molg /1 kmol )
=
dx
0.250 cal/ g ( 31.4 g /mol ) ( 1000 mol/1 kmol ) ( 1 kcal/1000 cal )

dT
kcal
=250.70060.0203 T
(1)
dx
kmol
Determinando el rea transversal

Ac=26267.7 cm2
Realizando el Balance de materia

F AO
dz
=
dx cat Ac(r p )

dz
=
dx

5.411103 kmol SO 2 / s

1000 mol SO 2
1 kmol SO 2

0.6 g
26267.7 cm 2 (r p ) mol
3
cm
seg

dz 3.4332104
=
[ cm ] (2)
dx
r p
P=1 atm
pi = y i P
pi= y i

r p=

1
2
O2

k 1 pSO p O k 2 p SO p
2

1
2
SO2

p
ln k 1 =12.07

31000
RT

k 1=exp ( 12.07

31000
)
RT

k 1=exp (12.07 ) . exp (

31000
)
RT

31000/1.987 T

k 1=174555 e

A su similar con K2
9 53600/ 1.987 T

k 2=7.50910 e

Teniendo para gases:

y=

ni
nT

Aplicando estequiometria:
Comp.

Mol.
Inic.

Moles a
X

yi

SO2

8(1-x)

8(1-x)/(1004x)

N2

49

79

O2

13

13-8/2x

SO3

(13-4x)/(1004x)
8x/(100-4x)

8x
100-4x
Uniendo la ecuacin (A) con la ecuacin (2), se tendra:

dz
=
dx

174555 e

31000
1.987T

3.4332104
53600
8 ( 1x )
134 x
8x
9 1.987 T
7.50910 e
1004 x 1004 x
1004 x
0.5
8 ( 1x )
1004 x

)(

)(

134 x
1004 x

Usando el software de Mathcad, con las ecuaciones (1) y (3) obtenemos:

0

643

0.1

666.741

127.012

0.2

690.433

186.716

0.3

714.078

216.76

0.4

737.674

232.922

0.5

761.223

242.247

0.6

784.724

248.101

0.7

808.177

252.282

0.8

831.583

256.471

0.9

854.941

239.539

10

878.252

238.92

0.5

( 3)

Teniendo para nuestro caso que en el primer reactor sale a una temperatura de
833K, por lo cual interpolamos teniendo as que la conversin es de:
X=0.80606
Y el tiempo a dicha conversin:
t=255.4438seg.

Estos clculos son para el primer proceso, para el segundo caso vendra a ser:
Hallando los moles iniciales y los reaccionantes:
Mol.
Comp. Inic.
SO2
1.55152
N2
79
O2
9.77576
SO3
6.44848
Como podemos ver, esa ser la composicin que ingresar al segundo reactor,
en el cual se tiene que la conversin ser de un 99%