Chemical Engineering Science, 1970, Vol. 25. pp. 3 19-329. Pergamon Press. Printed in Great Britain.

Efkctiveness factor and the structure model of vanadium catalyst

for sulfur dioxide oxidation
B. KADLEC, J. MICHALEK and A. SIMECEK
Department of Inorganic Technology, Institute of Chemical Technology,
Prague 6, Czechoslovakia

(Received 4 July 1969)

Ahstraet-In this publication is studied the simple monodispersed model of a porous structure of
vandium catalyst for sulfur dioxide oxidation. From the comparison of the theoretical and experimen-
tal values of effectiveness factors of three commercial catalysts SVD, ICI, BAV it followed that for
the determination of the relation tortuosity factor r and constriction factor oBruggeman’s equation can
be recommended.

1. INTRODUCTION physical properties of the catalyst and the kinetic

IN OUR previous papers [l-3] we studied the parameters of the reaction
problem of an influence of internal diffusion on
the rate of sulfur dioxide oxidation. The basic km= (h,+C)/(Ah,+B) - kkin for 3 < h,
mass and heat transfer balance equations which < 48% (3)
are solved in these reports, were derived under
the assumption that the kinetics of oxidation A = 8.52518; B = 539.706; C = 503.004 and
of sulfur dioxide can be described by equation
I& = A’ . hp’ - kkln for h, I=-400,
r = &U&o,. ~N.d - N,,/K). (1) (4)
A’ = 3.8299; B’ = -046748,
In this equation
where the dimensionless parameter h, is de-
Sin = reaction-rate constant per unit weight of fined by the relation
catalyst particle,
ZVi= mole fraction of component i (i = SOz, 0,. D* - voV’,/To)- kin pp.
SO,) 9
h,= 4D
. (5)
eff.So!z
K = equilibrium constant.
In Eq. (5)
Based on theoretical calculation of the ef- D = diameter of spherical particle having
fectiveness factor for both isothermal and non- the same ratio (VP/S,) as a particle of
isothermal cases, an equation was proposed, another shape, cm
which expresses the course of the reaction in the VP = total volume of a single catalyst
region of internal diffusion. particle, cm3
The form of this equation is the same as that s, = external area of a single particle of
of the equation describing the rate of sulfur catalyst, cm2
dioxide oxidation in the kinetic region v. = 22 4 14 cmYmole
T, = temperature at outside surface of
r = kditt Ws.02 . ~/(N,, I- NsoJW. (2) particle, “K
To = 273.16 “K
The kaitr values can be calculated from the pP = particle density, g/cm3
319
 B. MDLEC, J. MICHALEK and A. SIMECEK

D &SO2 = effective diffusion coefficient of sulfur where

dioxide cm%.
In the following theoretical solution of the pro-
blem the monodispersed model of a porous
structure of vanadium catalyst was assumed.
This model was derived from the Wheeler’s[4]
classical model using the mean pore radius of
the catalyst 7 = 21/,/S,.
For the model thus defined the effective dif-
fusivity DeH,sOrcan be expressed by equation (5)
D em = (47) - @ . D,,i
where
Dp,i= diffusion coefficient of component
for a straight round pore (F = 2V,lS,),
0 = porosity of catalyst,
(o/r) = (constriction factorltortuosity factor)
WI.
By substituting Eq. (6) and relation
V, *pP we obtain from Eq. (5)
V, = pore volume per unit mass of catalyst,
cm3/g.
In the case of a calculation of the effectiveness
factor (cf. Fig. 1.) or reaction-rate constant kdiff,
respectively, the determination of a ratio (r/u)
causes the greatest difficulties.
Thirty-four years ago Bruggeman [7] presented
the realtion for the calculation of a ratio of the
quantities u and r in the form
(6)
(cr/T) = 01’2. (8)
He derived Eq. (8) from Maxwell’s[8] equa-
i
tion valid for the electric conductivity of spherical
disperse systems.
The aim of this work was to find whether for
the evaluation of the ratio (r/u) of the mono-
dispersed structure model of vanadium catalyst
0 = proposed in this study the Bruggeman’s Eq. (8)
may be recommended.
For the determination of the value (r/u) we
have used the method mentioned in references
[2,3]. Its principle consists in a comparison the

I I I I I I

30 50 (00 200 4006001000

4

Fig. 1. Dependence of the effectiveness factor r) on the dimensionless para-

meter !I. for various y, values. 1, y, = 0.2; 2, y, = 0.5; 3, y8 = 0.9; 4, asymptotic
solution of function r)- h,; 0, check-points calculated from Eqs. (3) and (4).

320
 Structure model of vanadium catalyst for sulfur dioxide oxidation
experimental effectiveness factors qeXl,(when the
rate data of the reactiqn both in the kinetic and
internal diffusion regions are known) with the
theoretical values of Q,. Calculating the theor-
etical value of 7th the value of the ratio (T/V)
has to be systematically changed. The most
probable value of (~/a) is given by the minimum
relative deviation of qeXpfrom qth.
2. EXPERIMENTAL
The validity of the Bruggeman’s equation for
the determination of the ratio (T/U) of the mono-
dispersed structure model of vanadium catalyst
.has been verified by means of the kinetic meas-
urements on two different types of industrial
catalysts.
Experimental data which were obtained for
this purpose on the Czechoslovak industrial
nontabletted catalyst are presented in paper [2].
In this publication some of them will be presented
only there where the aim of the work will require
it.
The method of the determination of the value
(T/U) will be explained for the second measured
catalyst ICI-33-2 only. When this ICI catalyst
was tabletted, pore size distribution function
R (rp) did not contain two expected maxima.
For this reason it is possible to assume the ICI
catalyst to have monodispersed structure (P=
21/,/S,) like the SVD catalyst.
Physical constants of the catalysts
The basic physical properties of the SVD and
ICI catalysts are given in following Table 1.
The specific surface area S, was determined
by the BET method[9] from the nitrogen adsorp-
tion isotherm at 77°K. The pore volume V, was
determined together with the pore size distri-
Table 1. Basic physical constants of
the catalysts
Catalyst S, Vll PP
mZ/g cm% g/cm3
SVD 2.0 0.280 1.17
ICI 21.6 0.326 1.26
321
cPsvd.2sNa2-0
bution curve on a Carlo Erba high-pressure
mercury porometer. The pore size distribution
function for the ICI catalyst obtained from the
desorption curve of the nitrogen isotherm (77°K)
by the Pierce’s method [ lo] had one maximum
only. The character of this curve was practically
the same as the character of the porometer curve.
The small displacement between the functions
remains meanwhile obscure. The particle density
PP was determined pycnometrically with
mercury.
The volume-pressure dependences of the
SVD and ICI catalysts are shown in Figs.
2(a and b). The pore size distribution functions
R (rp) are given in Figs. 3(a and b).
Measurements of rate data in the kinetic and
diffusion regions
To obtain rate data in the kinetic and the inter-
nal diffusion region a differential reactor with
gas recirculation was used [ 11, 121. More detailed
data on the application of this reactor for meas-
urements was presented in the paper [ 131.
Kinetic region. Experimental data were ob-
tained at 460-520°C with an initial content of
7 and 10 per cent SO, and 11 per cent 0, in the
gas mixture for grains of a fraction of 0.8-1-O mm
of the SVD catalyst. The results of these
300 500 700
P dm
Fig. 2(a). Volume-pressure dependence for SVD-
catalyst. 0, fresh catalyst; 0, usedcatalyst.
 B. KADLEC, J. MICHALEK and A. SIMECEK

200 400 600 800 rooo 4200

50 70 fO0 200 500 4000
P ah A ‘P

Fig. 2(b). Volume-pressure dependence for ICI- Fig. 3(b). Pore size distribution function (A) for
catalyst. ICI-catalyst. 1, from mercury porometer; 2, from
desorption isotherm of NZ.

al points for the SVD catalyst and a set of 68

experimental points for the ICI catalyst.
The numerical treatment of the experimental
data was carried out on a digital computer NE
803 B.
Rfr,I The average value of the rate constant of
O-40 Eq. (1) and the mean deviation from this value
were calculated for all temperatures.
From the average rate constants of Eq. (I),
the apparent activation energy and frequency
0.05 factor of the Arrhenius relation were determined
by the least squares method (cf. Fig. 4.). The
numerical values of these quantities are pre-
sented for both catalysts in Table 3. In the case
0
1 I 1
of a determination of the kinetic parameters of
400 200 500 4000 2000 5000 40000
the ICI catalyst we used only the rate data at
A9
380-480°C. At temperatures higher than 480°C
Fig. 3(a). Pore size distribution function (A) for an increasing influence of internal diffusion on
SVD-catalyst. the rate of the process was observed. For this
reason the function log “&,” - l/T cannot be
measurements are presented in the papers [2,3]. expressed by the linear equation (cf. Fig. 4.).
Data obtained for the ICI catalyst at 380-520°C Because the kinetic measurements for the grains
with an initial content of 10 per cent SO, and of the fraction smaller than O-8 was attended by
11 per cent 0, in the gas mixture are given in technical difficulties we have verified our as-
Table 2. These measurements were also carried sumption by the calculation in the last section of
out with grains of a fraction of O-8- 1.0 mm. this work.
Altogether we obtained a set of 56 experiment- Internal difusion region. Experimental rate
322
 Structure model of vanadium catalyst for sulfur dioxide oxidation

Table 2. Experimental r values for ICI catalyst (a fraction of Table 2. (conrd.)

0.8-1.0 mm
W/F a b Y r.lOs kkl.
W/F a b Y r.lOJ ki,,
480°C
380°C
0943 0.0998 0.11 0.570 60.34 5.03
0943 0.1002 o-11 0.072 7.65 0.25 1.230 0.0993 0.11 0.610 49.24 464
1.230 0.1002 0.11 0.144 11.70 0.42 1.780 0.0996 0.11 0.677 37.88 4.50
1.780 0.1002 0.11 0.187 10.54 040 6.219 0.09% 0.11 0.847 13.56 444
2.700 0.0995 0.11 0.228 8.41 0.34 0.943 0@998 0.11 0.563 59.61 4.87
6.219 0.1002 0.11 0.383 6.17 0.32 1.230 oQ993 0.11 0601 48.53 4.45
0943 0*1002 0.11 0.072 7.65 0.25 1.780 0.0996 0.11 0.673 3766 4.41
1.230 0.1002 0.11 0.131 10.69 0.38 2.700 0.1018 0.11 0.726 27.36 394
l-780 0*1002 0.11 0.182 10.23 0.39 6.219 00996 0.11 0.844 13.51 3.31
2.700 0.0995 0.11 0.228 8.41 0.34 Average 440
6.219 0*1002 0.11 0.374 6.02 o-31
Average 0.34 5Otw.

400°C 0.943 0.0999 0.11 060 63.57 6.00

1.230 0.0999 0.11 0.636 51.65 5.52
0.943 0~1002 0.11 0.145 15.38 0.56 1.780 0.0999 0.11 0.715 40.12 597
1.230 0.1013 0.11 0.178 1464 0.55 2.700 0.0994 0.11 0.774 28.49 597
1.780 0.1013 0.11 0.215 12.24 0.48 6.219 0.0999 0.11 0.832 13.36 4.53
2.700 0.1013 0.11 0.267 10.01 0.43 0.943 0.0999 0.11 0.597 63.26 5.92
6.219 0.0995 0.11 0.432 6.91 040 1.230 0.0999 0.11 0.633 51.42 5.43
Average 048 1.780 o+l999 0.11 0.729 40.91 6.54
2.700 0.0994 0.11 0.767 28.25 5.67
420°C 6.219 0@99 0.11 0.818 13.14 3.89
Average 5.54
2.700 0.1013 0.11 0443 16.62 097
6.219 0.1013 0.11 0.611 9.96 0.88 520°C
0943 0.1002 0.11 0.248 26.31 1.10
I.230 0.1002 0.11 0.304 24.75 1.13 0943 0.1002 0.11 0.618 6566 6.69
1.780 0.1013 0.11 0.374 21.30 1.09 1.230 0.1002 o-11 0.656 53.47 6.61
2.700 0.1013 0.11 0444 1666 098 1.780 0.1002 0.11 0.737 41.51 7.82
6.219 0.1013 0.11 0.617 10.05 090 2.700 0.1013 0.11 0.7% 29.87 8.87
Average 1.Ol 6.219 0.1013 0.11 0.840 13.68 7.10
0.943 o-1002 0.11 0.623 66.18 7.15
440°C 1.230 0*1002 0.11 0.651 53.00 6.40
1.780 0.1002 0.11 0.728 40.98 7.29
0943 0.1013 0.11 0.360 38.65 194 2.700 0.1013 0.11 0.792 29.73 8.53
1.230 0.1013 0.11 0.414 34.14 190 6.219 0.1013 0.11 0.842 13.72 746
2.700 0.0995 0.11 0.580 21.36 1.76 Average 7.42
6.219 0.0995 o-11 0.712 11.39 1.45
0.943 0.1013 0.11 0.374 40.21 2.07 List of symbols for Table 2. W, mass of catalyst (g); F,
1.230 0.1013 0.11 0.413 34.05 1.89 feed rate (mol.h-I); a, initial molar fraction of sulfur
I.780 0.1013 0.11 0.4% 28.24 1.86 dioxide in gas mixture; b, initial molar fraction of oxygen in
2.700 0.0995 0.11 0.570 2099 1.69 gas mixture; Y, conversion; r reaction rate (mol/gh).
6.219 0.0995 0.11 0.708 11.33 1.42
Average 1.78
data were obtained for cylindrical granules of
460°C
the SVD catalyst of 6 mm dia. and 12 mm
0.943 0@90 0.11 0469 49.24 3.15 average length and for irregular particles 5 mm
1.780 0.0990 0.11 0606 3368 3% dia. obtained from the original granules by crush-
2.700 0.0990 0.11 0.687 25.19 3.01
6.219 OGWO 0.11 0.804 12.80 2.72 ing and sieving. The measurements themselves
1.230 0@90 0.11 0.531 42.74 3.17 were performed using a gas of initial composition
1.780 OGBO 0.11 0601 33.41 299
7 per cent SOz, 11 per cent 0, and 10 per cent
2.700 0.09% 0.11 0686 25.16 3.00
6.219 0@90 0.11 0.799 12.72 260 SOz, 11 per cent 0, at temperatures of 460,
Average 2.96 480,500,52O”C.
323
 B. KADLEC, J. MICHALEK and A. SIMECEK

1.0

loa k

4.3 4.4 1.5

‘lT.40S

Fig. 4. Dependence of log k on l/T for ICI-catalyst. 1,

kinetic region; 2, dependence of log k on l/T for grains of a
fraction of 0.8-1.0 mm; 3, diffusion region; 0, experimental Fig. 5. Dependence of reaction rate on conversion
values of k obtained for grains of a fraction of 0.8-1.0 mm; at 400°C. 0, kinetic region; @, diffusion region.
0, theoretical values of khb; @, experimental values of k
obtained for tablets of 6 X 4 mm.

Table 3. Kinetic parameters of the measured 3oI

catalysts

Catalyst A,mol/gh E kcal/mol S, Q

SVD 6.04 x lo9 32.4 00508 0994 20
ICI 3.29 x 108 27.0 0.0855 0994 I-.fOJ
S,, average square relative deviation; Q, correla-
tion coefficient of a function log kkin- l/T.

In the case of the ICI catalyst the rate data f0

were obtained for cylindrical tablets of 6 >A4 mm
using a gas of initial composition 10 per cent
SOz, 11 per cent O2 at temperatures 400, 420,
440,460,480,500,.520”C.
The results of the measurements for the SVD 0.2 0.6 0.8
Y
catalyst are presented in the papers [2,3]; for
Fig. 6. Dependence of reaction rate on conversion
the ICI catalyst they are given in Table 4. In at 420°C. 0, kinetic region; 0, diffusion region.
this publication we do not present the results of
the isotherm at 380°C because of the difficulty intitial composition of the gas mixture, whence
of reproducing results. the experimental effectiveness factor qexp is
given by
Experimental effectiveness factors
The experimentally determined dependences (9)
of the reaction rate on conversion y were plotted
in diagrams (Figs. 5-9) enabling to determine where a, b are the initial molar fractions of sul-
the reaction rate in both the kinetic and diffusion fur dioxide and oxygen in the gas mixture. Thus,
regions at a given temperature, conversion and qexp values were obtained for the SVD catalyst
324
 Structure model of vanadium catalyst for sulfur dioxide oxidation

Table 4. Experimental r values for ICI catalyst (tablets of Table 4. (conrd.)

6X4mm)

W/F a b Y I-- 103 k,,,

W/F a b Y r* 10s kkln

400°C 500°C

2.830 0*1002 0.11 0.230 8.15 0.33 2.830 0.1003 0.11 0.564 19.98 168
3.700 0.1002 0.11 0.261 7.06 0.30 3.700 0~1003 0.11 0,592 16.05 1.47
5.338 0*1002 0.11 o-314 590 0.27 5.338 O-0996 0.11 0.638 1190 1.28
8.116 0~1002 0.11 0.419 5.18 O-29 8.116 o-0996 o-11 0.703 8.63 1.22
18.610 0.0988 0.11 0.610 3.24 0.29 18.610 0.1003 0.11 0.793 4.27 1.02
2.830 0.1002 0.11 0.219 7.76 0.31 2.830 0.1003 o-11 0.561 19.88 166
8.116 0.1002 0.11 0.407 5.02 0.28 3.700 O-1003 o-11 0.582 15.79 1.41
Average O-30 5.338 0.09% 0.11 0.644 12.02 1.33
8.116 o+l996 0.11 0.707 8.68 1.25
420°C 18.610 0.1003 0.11 0.793 4.27 l-02
Average l-33
2.830 0.0988 0.11 0.311 IO.84 0.51
3.700 0.0988 0.11 o-349 9.33 0.47 520°C
5.338 0.0988 0.11 o-433 8.01 0.47
8.116 0.0988 0.11 0.541 6-59 0.49 3.390 0.1002 0.11 0645 19.06 2.25
18.610 0.0988 0.11 o-706 3.75 046 5.830 0.0987 o-11 o-713 12.07 1.99
2.830 0.0988 0.11 0.311 10.84 0.51 10.820 0.0994 0.11 Q-767 7.04 164
8.116 0.0988 0.11 0.534 6.50 O-48 14.930 OX)994 0.11 0.824 5.49 2.28
18.610 O-0988 0.11 0.703 3.73 0.45 Average 2.04
Average 0.48
List of symbols forTable 4 is the same as that for Table 2.
440°C

2.830 0.0988 o-11 0.397 13.86 0.76

3.700 0.0996 0.11 0443 1 l-93 0.71
5.338 0.0988 o-11 0.529 9.79 0.71
8.116 0+996 0.11 0.633 7.76 0.75
18.610 O-0982 o-11 0,774 4.09 0.70
2.830 O-0988 o-11 0,397 13.86 0.76
3.700 0.0996 o-11 0.433 11.65 0.68
5.338 O-0988 0.11 0.528 9.77 0.71
8.116 0.0996 0.11 0.626 7.68 0.73
18.610 0.0982 0.11 0.774 4.08 0.70
Average 0.72

460°C

2.830 O-0984 0.11 0.438 15.24 O-92

3.700 O-0991 0.11 0.474 12.69 0.82
5.338 0*0991 o-11 0.545 IO-11 0.76
8.116 O-0991 0.11 0646 7.89 0.81
18.610 0.0991 0.11 0.786 4.19 0.80
2.830 O-0984 0.11 0.422 1466 0.85 O-2 o-4 O-6 04 "10
18.610 0.0991 o-11 0.781 4.16 0.77 Y
Average 0.82
Fig. 7. Dependence of reaction rate on conversion
at 440°C. 0, kinetic region; 0, diffusion region.
480°C

2.830 0.09% 0.11 0.501 1764 1.23

for gas 7 per cent SOz + 11 per cent 0, and 10
3.700 0.1003 o-11 0.573 15.52 1.30
5.338 0.1010 0.11 0.622 11.76 1.14 per cent SO, + 11 per cent O2 in the range of y
8.116 0.0996 o-11 O-691 848 1.07 from O-4 to O-9 (cf. the papers [2,3]) and for
18.610 0.1003 0.11 O-785 4.23 0.85
the ICI catalyst for gas 10 per cent SO,+ 11
2.830 0.09% 0.11 0.493 17.36 1.19
3.700 0.1003 o-11 0.581 15.74 l-35 per cent 0, in the range of y from 0.1 to 0.9
Average 1.16 (cf. Table 5.).
325
 B. K_~DLEC, J. MICHALEK and A. SIMECEK

60

40

r. 4tP

20

0.4 0.6 0-6 br-0 o-4 O-6 O¶ 3 to

Y Y
Fig. 8. Dependence of reaction rate on conversion Fig. 9. Dependence of reaction rate on conversion
at 460°C. 0, kinetic region; 8, diffusion region. at 480°C. 0, kinetic region; 0, diffusion region.

Table 5. Experimentally determined effectiveness factors for ICI-catalyst

Temperature Conversion
(“C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

400 O-65 0.66 064 0.66 0.66 0.67 0.67 0.69 0.68
420 - 0.52 0.52 0.51 0.52 0.52 0.52 0.52 0.53

440 - 0.42 0.41 0.41 0.42 0.42 044 0.44 0.44

460 - - - 0.32 0.32 0.32 0.31 0.32 0.32
480 - - - - - 0.27 0.27 0.27 0.26

Determination of the ratio of (r/a) values of V, and S, the following expression

We have used the method described in the
introduction of this publication.
We have calculated for the systematically
changed values of (T/U) the mean relative devia-
tions (in per cent) of the experimental effective-
ness factors from the theoretical values of Q,,.
For calculations of the modulus h, and thus
also of the theoretical isothermal effectiveness
factor the values of the necessary quantities were
computed as follows:
In cylindrical granules the diameter of the
equivalent sphere having the same ratio (VP/S,)
as the cylinder was determined by means of the
relation
D = 6 VJS,.
For irregular crushed grains with unknown
was used for the calculation of D
D=6V”/S,=6V,.N$S,.N,. (11)
In Eq. (11) V, is total volume of catalyst
particles per unit volume and S, (cm-‘) total
area of catalyst per unit volume. For the SVD
catalyst (the mean radius of catalyst pores P=
21/,/S, = 2800 A) the diffusion coefficient of
sulfur dioxide for a straight round pore Dp,so2
was calculated according to the relation [5]
l/&or = l/&-m + l/&o,-, - (12)
In this case the diffusion of the sulfur dioxide
occurs at a total pressure of P = 1 atm in a
transition region between the molecular and
(10) Knudsen diffusion. In Eq. (12) DS02+, is the
coefficient of molecular diffusion of sulfur di-
326
 Structure model of vanadium catalyst for sulfur dioxide oxidation

oxide in reaction mixture and Dp,SOt-Kis the Table 6. Mean relative deviations (%)q,, from 7th for ICI
Knudsen diffusion coefficient of sulfur dioxide catalyst
for a straight round pore. The value Ds,,,-m was r”C T/U 1.3 1.4 1.5 l-6 1.7 l-8 l-9 2.0 2.1 2.2
calculated with the assumption of sulfur di-
oxide-air mutual diffusion. 400 6.1 4-4 2.8 1.9 1.6 2.3 3.7 5.3 6.9 8.5
420 10.6 8.5 6.0 4.2 2.2 0.9 2.0 4.0 6-O 8.0
For the ICI catalyst (the mean radius of cat- 440 11-9 9.1 6.1 3.8 3.0 2.5 4.0 6-5 9-O 11.4
alyst pores P = 2v,lS, = 300 A) 460 13-9 11.0 7.8 5.6 3.0 0.9 2-O 4.4 6.7 9.0
480 10.7 7.5 4.5 1.6 1.6 3.9 8.0 8.9 11.1 13.5
D Pi302 Average 10.6 8.1 5.4 3.4 2.3 2.1 3.9 5.8 7-9 10.1
= DPso,--K =9~7xl03~~(T/M,,*), (13)

where Mso, is the molecular mass of sulfur 3. CONCLUSIONS

dioxide.
The other numerical values of the quantities
necessary for the calculation of the effectiveness
factors vth are presented in Table 1.
The results of the calculations of the mean
relative deviations qeXPfrom qti are given at all
temperatures and at all values of (r/o) for the
ICI catalyst in Table 6. When the mean relative
deviations qeXP from qul were plotted against
(T/V) in a diagram (cf. Fig. IO.), the optimum
(T/(T) value (for which the deviations of the
experiments from theory were the smallest) was
found to be equal to l-73. For the SVD catalyst
it was found (T/U) = l-75, [2,3].
1 1 1
f-3 f-5 1.7 f-9
vk 2-’ 2*3
Fig. 10. Dependence of the average relative
deviation A (%) of experimental effectiveness
factors from theoretical on the (T/U) value for ICI
catalyst.
After determining the numerical ‘values of
(~/cr) for both catalysts investigated, SVD and
ICI, the theoretical function of log kdin- l/T was
computed. The experimental values of (kdiff)f)exp
obtained from the correlation of the rate data for
the region of internal diffusion by Eq. (2) cor-
responded with the theory very well (cf. Fig. 4.).
For the SVD catalyst the average relative de-
viation (in per cent) of (kdifl&, from (kdl&, was
found to be equal to 16.2 per cent; for the ICI
catalyst it was found to be 14.3 per cent. The
same conclusion can be reached for the ICI
catalyst by the comparison of the (kdiff)exp (a
fraction of 08-l *Omm) and the theoretical values
of the (kdi& at temperatures of 500 and 520°C.
The theoretical ok,&, - values were calculated
from the values of the (kdi&, by using Eq. (3).
These values correspond with the theoretical
Arrhenius function log k - l/T very well (cf. Fig.
4). We carried out this calculation to verify
our assumption mentioned in the section “Kin-
etic Region” that at temperatures higher than
480°C internal diffusion influences the rate of the
process for the grains of fraction O-8-1.0 mm.
The aim of this work was to find whether for
the determination of the ratio (r/a) of the mono-
dispersed structure model of vanadium catalyst
proposed in this work Bruggeman’s equation,
Eq. (8) can be used. For this purpose we carried
out the calculations of the (T/U) corresponding to
Bruggeman’s equation, Eq. (8), supposing the
2-s porosity 0 of the catalyst to be known.
From the comparison of these values and the
values of (T/U) presented in the papers [2,3] it
follows that Eq. (8) (cf. Table 7.) correlates the
measurable quantity 0 with the at present non-
327
 B. KADLEC, J. MICHALEK and A. SIMECEK

Table 7. Results of the comparison of (r/a) values given Table 8. Rate constants kk,,, of Eq. (1) calculated for
by Bruggeman’s equation with those obtained by means given values of rkinof BAV [ 13]-catalyst
of the experimental effectiveness factors
485°C 522°C
V” 9.. (T/U) (T/U)
Catalyst (cm3ig) (g/cm”) i-l;2 from exp. A% Y km . 103 ~II Y rkln . 103 kkb

SVD 0.280 1.17 1.747 1.75 0.2 0.176 4266 2.15 0.288 60.59 3.68
ICI 0.326 l-26 1.561 1.73 9.1 0.235 40.07 2.20 0.360 54.18 3.76
BAV 0.400 1.00 1.581 166 4.8 0.294 3744 2.26 0.432 47.88 3.87
0.353 34.88 2.33 0.503 41.04 394
0.412 3190 2.38 0.575 34.63 4.09
0.471 29.30 2.47 0648 27.79 4.26
measurable value of (Q-/U) very well. For this 0.529 26.35 2.55 0.720 21.42 4.62
reason Eq. (8) can be recommended for the 0.588 23.00 2.61 0.791 13.68 4.86
0647 1966 2.69 0.863 5.47 5.47
determination of (T/U) of the monodispersed 0.705 16.34 2.80
structure model of vanadium catalyst with the 0.764 12.96 2.95
mean radius of catalyst pores P = 2VJS,. 0.823 9.65 3.26
0.882 4.82 3.10
The same conclusion follows from the results
of the kinetic measurements of the authors A.A. Average 260 Average 4.28
Ivanov, G. K. Boreskov and V. S. Beskov[l4].
In this case we obtained from the dependence of
the reaction rates T on conversion y (cf. Fig. 3 of to the relation (12). The comparison of the
the work[ 131 the values of the reaction rates values of nexp with the theoretical values of
rdirf and rkjn at the temperatures 485°C and 522°C 7)th was performed in two variants. At the first
and at a given conversion. The experimental variant we used the effectiveness factors q,_
effectiveness factors qexp obtained from these obtained for the conversions from 20 per cent to
values were afterwards compared with the near from the equilibrium. At the second variant
theoretical values of Q,,. For calculations of the we assumed the effectiveness factors to be prac-
modulus h, and thus also of Q, the values of the tically independent of conversion and equal to
necessary quantities were computed as follows: 0.64 at 485°C and 0.52 at 522°C (cf. the paper
For given values of rkin the reaction- rate [141).
constants k,&, of Eq. (1) were calculated at given The authors found that the experimental
conversions and initial composition of the gas effectiveness factors far from equilibrium were
mixture (cf. Table 8). At the both temperatures practically independent of conversion. Only at
485°C and 522°C a small dependence of the approach to equilibrium were the effectiveness
reaction-rate constant kkrn (on conversions y factors slightly diminished. The authors proved
was observed. Because in both cases the average this experimental fact by calculating the theor-
deviation of the reaction-rate COnStantS kkin)from etical effectiveness factor r),, assuming the kinet-
the values of kkin amounted to 10.9 per cent the ics of sulfur dioxide oxidation to be described
kinetic data may be expressed by Eq. (1) very by the equation presented in the publications
well. [15, 161.
The characteristic dimension D was calculated The results of the calculations of the relative
for cylindrical granules of the BAV catalyst deviations qeXP from qul are given at the both
(4.5 X 4.5 mm) from the relation (10). temperatures and variants as the function of
The next data which are presented in the paper (T/U) in Table 9. From the graphical presenta-
[14] for the monodispersed type of the BAV tion of these functions (cf. Fig. 11) (when for
catalyst are given in Table 7. the values at the both temperatures the mean
The value of D,,,, for a straight round pore value was taken) it followed that the smallest
(P= 2Vg/S, = 1600 A) was calculated according deviations of the experiment from the theory will
328
 Structure model of vanadium catalyst for sulfur dioxide oxidation

Table 9. Mean relative deviations (%) nexp from nth

for BAV-catalyst

t “C r/a 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0

485 8.1 6.2 4.3 3.0 2.8 3.3 4.3 5.4 i

522 12.2 9.8 7.5 5.2 3.8 3.6 4.2 5.3 ‘5
>
Average 10.1 8.0 5.9 4.1 3.3 3.4 4.3 5.4
485 4.0 2.1 0.1 1.8 3.7 5.6 7.5 9.4 Z

AvEige 6.5
9.0 4.3
6-6 4.2
2.2 l-8 O-6
2-l 2.9
4.3 6.4
5.2 7.4
8.4 .j3

be achieved for (T/U) = 1.73 (variant I) and for

(T/U) = 1.59 (variant II). The mean value of
(T/U) = 1.66 is given in Table 6. This Table
contains the results of the comparison of (~/a)
values given by Bruggeman’s equation with those Fig. 11. Dependence of the average relative de-
viation A (%) of experimental effectiveness factors
obtained by means of the experimental effective- from theoretical on the (T/U) value for BAV
ness factors. catalyst. l , variant I; 0, variant II.
REFERENCES
HI KADLEC B. and REGNER A., Colln Czech. them. Commun. 1968 33 2388.
PI KADLEC B., REGNER A., VOSOLSOBE J. and POUR V., Paper No. 20, Symp. III, Novosibirsk, 4th Int. Gong. on
Catal., Moscow 1968.
[31 KADLEC B. and POUR V., Colln Czech. them. Commun. 1968 33 2526.
[41 WHEELER A., Advances in Catalysis III, p. 246. Academic Press 1950.
[51 SATTERFIELD CH and N. SHERWOOD T. K., The Role of Diffusion in Catalysis, Addison-Wesley 1963.
El PETERSEN E. E., Chemical Reaction Analysis. Prentice-Hall 1965.
[71 BRUGGEMAN D. A. G.,Annln Phys. 1935 24 636.
[S] MAXWELL J. C., A Treatise on Electricity and Magnetism, 2nd Edn., Vol. L. Oxford University Press 188 1.
[9] BRUNAUER S., EMMETT P. H. andTELLER B.,J. Am. them. Sot. 1938 60 309.
[lo] PIERCEC.,J.phys. Chem. 195357 149.
[ 111 MICHALEK J., Thesis. Instifute of Chemical Technology, Prague 1966.
[ 121 VOSOLSOBE J. and MICHALEK J., Colln Czech. them. Commun. 1966 312646.
[13] KADLEC B., Thesis, Institute of Chemical Technology, Prague 1966.
[14] IVANOV A. A., BORESKOV G. K. and BESKOV V. S., Paper No. 21, Symp. III, Novosibirsk, 4th Int. Congr. on
Catal., Moscow 1968.
[15] BORESKOV G. K., BUJANOV R. A. and IVANOV A. A., Kinet. Katul. 1967 8 153.
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KINA L. D., Kin&. Katal. 1968 9 561.

R&sum4- Cet article &die le modble simple a monodispersion dune structure poreuse de catalyseur
de vanadium pour l’oxydation de l’anhydride sulfureux. De la comparaison des valeurs theoriques
et experimentales des facteurs d’efficacite des trois catalyseurs commerciaux SVD, ICI et BAV,
il s’ensuit que l’tquation de Bruggeman peut etre recommandte pour determiner la relation du facteur
de tortuosite 7 et du facteur de construction o.

Zusammenfassuug-In diesem Bericht wird das einfache monodispergierte Model1 einer porijsen
Struktur von Vanadium-Katalysator fur die Schwefeldioxyd-Oxydation untersucht. Der Vergleich
der theoretischen und experimentellen Werte der Wirkungsgrades von drei kommerziellen Kataly-
satoren SVD, ICI, BAV ergab, da8 die Bruggeman-Gleichung zur Bestimmung der Verhltnisses
Windungsfaktor T/Zusammenziehungsfaktor o empfohlen werden kann.

329