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TUGAS TEKNIK REAKSI KIMIA LANJUT

EXAMPLE 10.2 & PROBLEM 10.3

KELOMPOK 2

ANDRE FAHRIZ PERDANA HARAHAP (1406605843)

ANYA PRILLA AZARIA (1806153990)

SYARIFAH NADIRATUZZAHRA (1806243506)

DEPARTEMEN TEKNIK KIMIA

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)

For 10% conversion, r p = 0.0956 gmol/(h)(g) and am = 5.12 ft2/lb then,

Calculation for SO2

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

For oxygen, r p = 0.0956/2 g mol/(h)(g catalyst);

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,

( pb− p s )O =R g T ( C b−C s ) =0.73 [ 1.8 ( 480+273 ) ] ( 5.4 x 10−6 ) =0.0054 atm


2

ps=0.201−0.005=0.196 atm

Calculation for SO3

For oxygen, r p = 0.0956/2 g mol/(h)(g catalyst);

Equation 10-20:

μ 23
Cb −C s=
rp
ρD ( )
G
at
ρ D
j ( )
So,

( pb− p s )SO =Rg T ( C b−C s ) =0.0130 atm


3

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 :

A = -127 (atm)3/2 (h)(g catalyst)/g mol

B = 15,3 (atm)1/2 (h) (g catalyst)/g mol

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 :

T (oC) 400 420 440 460 480 500


rp, g mol SO2/ (h) 0,02397 0,0344 0,0514 0,0674 0,0898 0,122
(g catalyst)

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)

Where Ć o represents the consentration af adsorbed atomic oxygen and Ć v represents


the consentration of vacant centers. Solving this expression for Ć o yields :
1/ 2 1 /2
Ć o = K o P o 2 Ć v
The surface-raction step is represented by :

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)

Subtituting the values of Ć o , Ć SO 3∧Ć SO 2 :


1
(
r s =k s K SO 2 . P So2 . ĆV . Ko 1/ 2 . P1/o 22 . Ć V − K SO 3 . PSo 3 . Ć V . ĆV
Ks )
K SO 3
(
r s =k s Ko1/ 2 . K SO 2 . P So2 . P 1/o 22−
Ks )
. PSo 3 ĆV 2 (5)

The total concentration of centers is the summation :


Ćm =ĆV + Ć SO 2 + Ć SO 3 + ĆO + Ć N 2
1/ 2 1 /2
Ćm =ĆV +¿ K SO 2 . P So 2 . ĆV + K SO 3 . P So3 . Ć V + K o . Po 2 . Ć v +
K N 2 . PN 2 . Ć V

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)

Subtituting ĆV from Eq(5) :


2
K Ć m
(
r s =k s Ko . K SO 2 . P So2 . P − SO 3 . PSo 3
1/ 2 1/ 2
o2
Ks )( 1 /2 1/ 2
1+ K SO2 . PSo 2+ K SO 3 . P So3 + K o Po 2 + K N 2 . PN 2 )
1/ 2
K SO 3
Noting that Ko . K SO 2 , = K, may we write :
Ks

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)

Combining the constants and rearranging leads to the linier from

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).

r, Partial pressure (atm) at catalyst surface


gmoll/(h)(g
catalyst) SO3 SO2 O2
0,02 0,0428 0,0255 0,186
0,04 0,0331 0,0352 0,19
0,06 0,0272 0,0409 0,193
0,08 0,0236 0,0443 0,195
0,10 0,0214 0,0464 0,196
0,12 0,0201 0,0476 0,197

We must interpolate data to partial pressure in r = 0,0898 , interpolated from excel we get :

r, Partial pressure (atm) at catalyst surface


gmoll/(h)(g catalyst) SO3 SO2 O2
0,0898 0,0225 0,0453 0,1955
Where :

A = -0,127 (atm) 2/3 (h) (g catalyst)/ g mol

B = 15,3 (atm)1/2 (h) (g catalyst)/ g mol

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

r = 0,4179 g mol / (h) (gr catalyst)

Rate-Reaction at Bulk rate condition

Firstly, we find the density of the air from this equation :


Air density 273 K P
x x
Molal volume∈STP T ( C ) +273 K Patm

28,9 lb /lbmol 273 K 790 atm


x x = 0,0304 lb/ft3
359 ft 3 /lbmol 480 C+273 K 760 atm

The molecular diffusivity of SO2-air is 2,44 ft2/h.

Then the Schmidt group :

µ 0,09
=
ρ D (0,0304)(2,44)
= 1,21

T, ◦C 350 360 380 400 420 440 460 480 500


rp, gmol
0,004 0,0078 0,0144 0,0239
SO2/(h)(g 0,0344 0,0514 0,0674 0,0898 0,122
9 8 3 7
catalyst)

For 20% conversion, rp = 0,0898 lbmol/(h)(lb) and at = 5,12 ft2/lb.

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 :

πdp2 = πdL + πd2/2

πdp2 = (3,14)(1/96)(1/96) + (½)(3,14)(1/96)2 = 0,0005 ft2

dp = 0,0128 ft

The Reynold number is,

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

Substituting all these results in Eq. (10-20) yields

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

kmam = 11280,6442 ft3/lb(h)

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

rp = (11280,6442 ft3/lb(h)) x (7,9605 x 10-6 lbmol/ft3)

rp = 0,0898 lbmol/(h)(lb catalyst) = 0,0898 gmol/(h)(gr catalyst) which is impossible

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

Mean rp, g moles SO2/ Pb (atm)


conversion of (h)(g catalyst) SO2 SO3 O2
SO2
0.1 0.0956 0.0603 0.0067 0.201
0.6 0.0189 0.0273 0.0409 0.187

The interpolation of Table 10-2

rp , Partial pressure (atm) at bulk


gmol/(h)(g catalyst) SO3 SO2 O2
0.0898 0.0135 0.0537 0.1982

So we can conclude that the bulk partial pressure are,

Pb(SO3) = 0,0135 atm

Pb(SO2) = 0,0537 atm

Pb(O2) = 0,1982 atm

Then, we can input the value of bulk pressure of each spesies,

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) ]

r b=¿ 3,7486 gmol/(h)(gr catalyst)

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

Surface Rate Reaction


Ratio γ =
Bulk Rate Reaction
gmol
(0,4179 )
h gr catalyst
Ratio γ =
gmol
(3,7451 )
h gr catalyst

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.