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KELOMPOK 2
UNIVERSITAS INDONESIA
DEPOK 2019
Example 10.2
Suppose that a fixed bed reactor is to be designed for oxidation of SO2 using platinum/Al2O3
catalyst. The intrinsic rate equation (g mole / (h)(g catalyst) from experimental rate data is:
1
PSO P1/O 2−(
)P
2
K SO
2 3
r= 2
[0.176+12.9 PSO ] 3
Intra particle transport effects are negligible, but external concentration and temperature
differences may be important. We will assume isothermal conditions at 480 °C in order to
simplify the calculations. The superficial mass velocity of gas through the bed will be 147 lb/
(h)(ft)2. To demonstrate the procedure for accounting for external mass transport limitation,
calculate the global rate at a location in the reactor where the bulk partial pressures are those
given in table below.
Solution:
Density of air:
28.9 273
(
359 480+ 273 )( 790
760 )
=0.0304 lb/ft 3
Schmidt group:
μ 0.09
= =1.21
ρD 0.0304 (2.44)
Equation 10-20:
μ 23
Cb −C s=
rp
ρD ( )
=
0.0956
2
( 1.21 )3
=1.40 x 10−5 lb mol/ ft 3
G 5.12 147
at
ρ
jD ( ) 0.31 (
0.0304 )
So,
( pb− p s )SO =R g T ( C b−C s ) =0.73 [ 1.8 ( 480+273 ) ] ( 1.40 x 10−5 ) =0.0139 atm
2
ps=0.0603−0.0139=0.0464 atm
Calculation for O2
Equation 10-20:
2
μ 3 0.0956
Cb −C s=
ρD
rp
=
( )
2 ( 0.81 )
2
3
=5.4 x 10−6 lb mol /ft 3
G 5.12 147
at
ρ
jD ( ) 0.31
0.0304 ( )
So,
ps=0.201−0.005=0.196 atm
Equation 10-20:
μ 23
Cb −C s=
rp
ρD ( )
G
at
ρ D
j ( )
So,
ps=0.0067+0.0150=0.0217 atm
(0.0217)
0.176+ 12.9¿
¿
¿2
¿
1
r=
2
1
1/ 2
PSO PO −(
K2
=
3
1/ 2
)PSO 0.0464 (0.196) −
73
0.0217( )
[0.176+12.9 PSO ]2 ¿
3
Since this result is close to the assumed value, it is the desired global rate for a location in
the reactor where the conversion is 10%.
Problem 10.3
Predict the global rate of raction for the oxidatation of SO 2 at bulk gas condition of 20%
conversion at 480 oC. Other condition are as given in Prob 10-2. The rate at the catalyst
surface is to be calculated from Eqs. (G) and (H) of Example 9-2. Assume isothermal
condition. The constants in Eqs. (G) and (H) at 480 oC are :
K = Kp = 73 (atm) -1/2
Also calculated the ratio ƴ of the global rate and the rate evaluated at bulk condition.
Solution :
From table problems 10.2 we can get the rp, g mol SO2/ (h) (g catalyst) in term of
Temperature :
To develop an expression for the rate of reaction we must postulate the method of obtaining
adsorbed atomic oxygen. If it is supposed that molecular oxygen is first adsorbed on a pair of
vacant centers and that is product then dissociates into two adsorbed atoms, the process may
be written :
O-O
O2 + 2X → | | → 2O . X
X–X
Since the surface reaction is controlling, the adsorpstion of oxygen must be at equilibrium.
Then the concentration of adsorbed atomic oxygen is given by the equilibrium equation.
2 2
r AO=ko . P o 2 . Ć v −k −o Ć O
1 2
(
r AO=ko . Po 2 . Ć 2v −
Ko O
Ć )
1 2
Where r AO=0 (
0=ko . Po 2 . Ć2v − Ć
Ko O )
1 2
Ć O =ko Po 2 . Ć 2v
Ko
So,
2
Ć O
Ko= 2
Po2 Ć v
(1)
SO2 . X + O . X → SO3 . X + X
r s =k s . C s
1
(
r s =k s Ć so2 Ć0 − Ć Ć
K s so 3 v )
(2)
The concentrations of SO3 and SO2 adsorbed on the catalyst are given by the conventional
equilibrium expressions
SO3 + X → SO3 . X
r AD 2=k SO 3 . P So3 . ĆV −K−So 3 ĆSO 3
1
(
r AD 2=k SO 3 Ć SO 3 ĆV −
K SO 3
Ć so3 )
Where r AD 2=0
1
0=k SO 3 . P So 3 . ĆV − Ć
K SO 3 SO 3
1
Ć SO 3=k SO 3 . PSo 3 . Ć V
K SO 3
Ć SO 3=K SO 3 . P So 3 . Ć V (3)
SO2 + X → SO2 . X
r AD 3=k SO 2 . P So2 . ĆV −K−So 2 Ć SO 2
1
(
r AD 3=k SO 2 Ć SO 2 Ć V −
K SO 2
Ć SO 2 )
Where r AD 3=0
1
0=k SO 2 . P So 2 . ĆV − Ć
K SO 2 SO 2
1
Ć SO 2=k SO 2 . PSo 2 . Ć V
K SO 2
Ć SO 2=K SO 2 . P So 2 . ĆV (4)
The last term is include to take into account the possibility that N 2 may be adsorbed on the
catalyst. Eliminating ĆV from Eq. (2) by introducing Eq (6) :
Ć m
ĆV = 1/ 2 1 /2
1+ K SO 2 . P So2 + K SO3 . PSo 3 + K o Po 2 + K N 2 . P N 2
(6)
1 1
r=
(
k s Ćm2 Ko 2 . K SO 2 P So2 . P o22−
1
.P
K So 3 )
2
(1+ K SO 2 . PSo 2 + K SO 3 . P So 3 .+ K 1o/2 P1/o 22+ K N 2 . PN 2)
(7)
Because the partial pressures of sulfur of sulfur dioxide and sulfur trioxide are both small, the
value of PN 2 will not vary significantly with conversion. Hence K N 2 . PN 2 may be
regarded as a constant in Eq (7). Since conversion was only variable causing the composition
to change PO 2 PSo 2 , and PSo 3 are not independent, but are related to the initial,
constant composition and the conversion. Hence Po 2 in the denominator of Eq. (7) can be
expressed in terms of conversion or, more conveniently, in terms of PSo 3 . Eq (7) may be
simplified to :
[ ]
1 1
r=
k s Ć m2 Ko 2 . K SO 2 P So 2 . Po22− ( K1 ) P So 3
2
( A' +B ' PSo 3 )
(8)
R= A+ Bp so3 (G)
1/ 2
[ ]
1
1
R=
P So2 . P − P 2
o2
K So 3 ( )
r
(H)
Since conversion was the sole variable, individual adsorption equilibrium constants
K o , K SO 2 , K SO 3 , K N 2 cannot be determined. Table 9-1 for Partial pressure from r, g mol
SO2/ (h) (g catalyst).
We must interpolate data to partial pressure in r = 0,0898 , interpolated from excel we get :
K = Kp = 73 (atm) -1/2
With these values the rate equation from Eq (G) and (H) is :
[ ]
1 1
r=
2 2
k s Ć m Ko . K SO 2 P So 2 . P − 2
o2 ( K1 ) P So 3
2
( A' +B ' PSo 3 )
1
r=
2
PSo 2 . P −
o2 ( K1 ) P So 3
2
( A ' + B' P So 3 )
r=
0,0453(0,1955)1 /2− ( 731 ) 0,0225
2
[−0,127+15,3(0,0225)]
0,019721
r=
0,047197
µ 0,09
=
ρ D (0,0304)(2,44)
= 1,21
At 480◦C, the viscosity of air is about 0,09 lb/(h)(ft) and superficial mass velocity is 350 lb/(h)
(ft2) The particle diameter to employ is the diameter of the sphere with the same area as that of
the cylindrical pellets. Hence πdp2 will equal the sum of the areas of the lateral and end
surfaces of the cylinder :
dp = 0,0128 ft
0,09 lb /(h)(ft)
dp G ¿
µ = (0,0128 ft )(350
lb
) = 49,7
( h ) ( ft 2 )
¿
Then we can substitute the void fraction of the bed which is 0,43 and Reynold number to
Equation 10-10,
−0,407
(0,458) d p G
JD = ( )
εB µ
−0,407
(0,458)
JD = (49,7)
(0,43)
JD = 0,2173
µ 2/ 3
Cb - C s =
rp
ρD( )
G
at
ρ D( )
J
0,0898 lbmol 2 /3
( ) (1,21 )
( h ) ( lb )
( )
lb
Cb - C s =
(5,12
ft 2
)
( 350
( h )( ft 2 ) )
(0,2173)
= 7,9605 x 10-6 lbmol/ft3
lb lb
0,0304
ft 3
Because that we evaluated the rate of reaction in bulk, so we can assume that C s~0, so Cb is
7,9605 x 10-6. At first, the rate equation of transport reactant to the catalyst surface is in
Equation 10-1,
rp = kmam(Cb - Cs)
But, because we assume that reactant haven’t reacted at the catalyst surface and the reaction-
rate constant k is very much greater than kmam, so Cs~0, in Equation 10-3 which is,
rp = kmamCb
To find the value of rp we have to solve the kmam value by Equation 10-9,
km ρ am 2/ 3
JD = ( )( )( )
G at
µ
ρD
J DG at
2/3
kmam = µ
ρ( )
ρD
lb ft 2
kmam =
(
(0,2173) 350
( h )( ft 2 ) )
(5,12
lb
)
lb 2 /3
(0,0304 ) ( 1,21 )
ft 3
We can substitute the value of kmam and Cb to Equation 10-3, to solve the value of rate-reaction
in bulk condition.
rp = kmamCb
But, the value of the bulk reaction is less than the surface reaction and it’s impossible.
Because the value of bulk rate reaction should be greater than value of surface rate reaction.
Because the limiting reaction is surface rate reaction which is the slowest reaction. And the
bulk rate reaction should be faster than surface reaction. So we can try another way with
interpolation.
Table 10-2
r b=
PbSo 2 . Pbo22 − ( K1 ) Pb So 3
2
( A ' + B' Pb So 3)
r b=
0,0537 (0,1982)1 /2− ( 731 ) 0,0135
2
[ −0,127+15,3( 0,0135) ]
The value of bulk rate reaction in this calculating is 3,7486 gmol/(h)(gr catalyst) which is
greater than the value of surface rate reaction which is 0,4179 g mol /(h) (gr catalyst).
Ratio γ
1
Ratio γ = 0,126 ~
9
We assumed that the γ ratio in this problem is the comparation of the surface rate reaction with
the bulk rate reaction. And we solve that the value of γ is 0,126 and the value of bulk rate
reaction is 9 times faster than the value of surface rate reaction. That makes sense, because the
theory that the bulk rate reaction will be much faster than the surface rate reaction.