Kinetics and effectiveness factor for SO, oxidation on an industrial

vanadium catalyst
HANS LIVBJERG and JOHN VILLADSEN
Instituttet for Kemiteknik, Danmarks tekniske Hejskole, Lyngby, Denmark

(Received 4 April 197 1)

Abstract-An experimental study of the reaction rate for SO1 oxidation on a commercial V105
catalyst is presented. Results in the purely kinetic region are correlated by means of 12 published rate
expressions. It is concluded that most rate expressions are adequate only in a narrow temperature
and composition range and that probably no single rate expression can be applied in the whole range
of industrial operating conditions. Experiments with large size pellets are used to determine catalyst
effectiveness as a function of temperature and conversion. It is found that a serious transport resist-
ance occurs for T 2 450°C and that the effectiveness decreases somewhat at high conversion. The
effective diffisivity of SO* is determined and finally the tortuosity of the catalyst is calculated. The
results show that the effective diffisivity can be determined on the basis of a gas-phase diffusion
model and that the tortuosity factor falls within the range of previously published values with a slight
increase for high conversion and possibly also for low temperature.

PHYSICAL AND CHEMICAL PROPERTIES OF probably caused by a change of physical prop-

V,O, CATALYSTS
A TYPICAL industrial SO, oxidation catalyst is
manufactured as porous pellets in which the
active components, V,O, and alkali-metal oxides,
are deposited on an inactive silica carrier. It is
well known that the reaction mechanism does
not resemble other oxidation reactions on V,O,
catalysts. The catalytically active components
are completely or partly molten at the tempera-
tures encountered in industrial sulphur dioxide
converters [l, 21, and the oxidation takes place
in a liquid lilm which covers the internal surface
of the solid support. The low melting point of
the catalyst is due to a formation of sulphates
and pyrosulphates which occurs as soon as the
alkali metal oxide of the fresh catalyst is exposed
to the sulphur oxides of the reaction mixture at
elevated temperatures [ 11. The promoting effect
of the alkali metals is ascribed to their ability
to provide a liquid phase solution of vanadium
compounds with much enhanced catalytic
properties. The most frequently used promoter
is K,O (2-4 moles per mole V,Os in most in-
dustrial catalysts), but the K,O may partially
be substituted by other group-l metal oxides
such as Na,O, Rb,O or Cs,O. The variation
of catalytic activity due to such substitutions is
21
erties of the catalyst melt, i.e. viscosity and melt-
ing point[2]. This theory is sustained by the
observation that the highest activity is obtained
for the metal oxides that are able to combine
chemically with more than two SO, molecules to
higher pyrosulphates resulting in a lower melt-
ing point for the catalysts [ 1,2].
The valence shift Y+5 * V+4 seems to play an
important role in the reaction mechanism [ 1,4].
The amount of vanadium reduced to the tetra-
valent state under given reaction conditions is
observed to depend upon the type of promoter
[l]. For this reason it is probable that not only
physical but also chemical properties of the
catalyst melt are influenced by the choice of
promoter [ 31.
The absorbed quantity of SO, and the extent
of reduction of vanadium vary strongly with the
reaction conditions [ 1,4]. The measurements of
Tandy show an abrupt increase of both properties
when the temperature is decreased below about
450°C for a K,O promoted catalyst. For many
industrial catalysts the apparent activation energy
is also much higher in the low temperature range
than in the higher range[4]. The reason for the
pronounced variation of the catalyst properties
at different temperature levels is not clearly
 H. LIVBJERG and J. VILLADSEN

understood. An explanation may be sought in a results may be explained by a rapid establishment

partial solidification of the catalyst melt in the of equilibrium for the liquid phase reaction:
lower temperature range possibly by a precipita-
tion of insoluble vanadium compounds [9. 131. so, + 2v+5 + 02- e so, + 2v+4. (3)
The degree of reduction of vanadium was
measured by Mars and Maessen[4] who observed They considered the reoxidation of V+4
that the quantity K defined by Eq. (1) over a
large range of reaction conditions and catalyst 302+2v+4 -2v+5+0-- (4)
compositions is a function of temperature alone.
to be rate determining for the overall reaction,
and they proposed that the rate for this step
K=g$+ SO2 (1) should be given by

in which [V+4] and [V+5] are the concentrations
of vanadium compounds in the liquid melt and
PsoS and Pso2 are the partial pressures in the gas
phase in contact with the melt.
For a K,O promoted catalyst the experimental
data were well correlated by the function
. (2)
Mars and Maessen have shown that these
r = k’P,,[ v+q*. (5)
A combination of Eqs. (I), (2), and (5) yields
the kinetic expression No. 4 in Table 1. This
expression was found to correlate experimental
rate data very well for K20 and N%O promoted
catalysts except at low temperaturest51, where
the above mentioned change in catalyst properties
probably alters the reaction mechanism.
SimeEek et af.[ 193 have split Eq. (4) into three
elementary steps with a gradually increasing

Table 1. Reaction rate equations for sulfur dioxide oxidation on vanadium and alkali containing catalysts

Forward reaction
No. Author Ref. r+ l/s Notes

Differential reactor,
1 Eklund TR420-554°C.
[ill 2
PD0.67-1_38mm,
KIV3/1

Integral reactor
2 Boreskov t121 2 TR47O"C
K/V= 2/l

Recirculation reactor,
TR:462-522°C
PD0.S1 mm.
3 Boreskov 16 and 131 1 2 Rate expression is
SO found to be best at high
temperatures and
conversions

Differential reactor
KPso,lPs,, - PD 0.5mm. Sodium and
4 Mars and [4 and 51 potassium oxides in
kpo*[l+ (KPso,/Pso,)o~51z
Maessen various concentrations.
where
Rate expression is
K = 2.3 x 10-8exp (27,2OO/R,T) found to be best at
high temperatures

22
 Kinetics and effectiveness factor for SOS oxidation

Table 1 (cont.)

Forward reaction
No. Author Ref. r+ 11s Notes

Differential reactor,
- TR 370-450°C
5 Calderbank iI41 uPo,)~s(~so,Y4
V,O,-Na,O
catalyst

Simplified version of
6 Calderbank 1151 kf’o.Ps”o: 1 express. No. 5 for
design purposes

Catalyst of
7 Krichevskaya iI61
k pso,po\
NJ
1 pure vanadium
[ P SO3 1 pentoxide

Recirculation
Kadlec [17 and 181 kP”‘sP,o, 1 reactor.
8 TR 460-520°C
et al.

Rate expression derived

from the Mars and
SimeEek KPso,lPso~ Maessen kinetic theory
9
et al. [191 kpoz 1+ (KPso,/Pso,)05
2 assuming
02- + v4+ = v5+ + 20-
K = 2.3 x 10m8exp (27,2OO/R,T) to be the rate
determining step.
TR 380-480°C

Recirculation

1
Razaev - reactor
10
et al. PO1 kPo, p cw K/V = 2.5/l
[ SOS
Differential
Goldman kf'so,p8;s reactor
11 et al. Pll 1
TR 380-426°C
(1 +(P~op)"*+Pso,Kso,+PsosKso.)'

Collina kPoJ-‘so, Differential and

12
et al.
[221
[1+f’so,Kso,
+PsosKsoJ2 1
Integral reactors
TR 400-550°C
K sot = exp -9.953 + y)
K sos = exp -71.745 +F)

TR: Temperature range; PD: Diameter of catalyst pellets; K/V: Potassium/vanadium ratio (atom/atom).

23
 H. LIVBJERG and J. VILLADSEN

degree of reduction of 0,. They assume that the Under certain conditions a physical inter-
elementary step O,-+ V+4 * V+5 + 20- is rate pretation may be given to the parameter s in (6).
determining, and on this assumption they derive If one single elementary step is rate determining
a rate equation (No. 9 of Table 1) which deviates for the overall reaction (9) s will be the stoichio-
somewhat from Mars and Maessen’s metric number for this step assuming that the
rate
equation. rate of the forward reaction is described correctly
Glueck and Kenney measured the reaction by r, even close to equilibrium. This result is
rate for unsupported catalyst melts [8] and found derived under certain idealised assumptions in
the reaction to be 1st order in SO, and zero Boudart’s textbook[lO] (Chap. 2.6). It is plaus-
order in O2 and with an apparent activation ible that a rate determining step-if existing-may
energy of only 10.8 kcal/mole between 330 and involve one of the following: (a) one oxygen
380°C. Still on unsupported melts the rate of molecule, (b) one oxygen atom, (c) one sulphur
absorption of SO, in Y+5 containing melts and dioxide molecule or (d) one sulphur trioxide
of 0, in I/+’ containing melts has been measured molecule. In the first case s = 4 while s = 1 for
[9]. It is concluded that apparently none of these (b)-(d). These two values of s are consistent with
steps can be rate determining for the SOz oxida- the s-values proposed in the different references
tion. This is not necessarily in contradiction to shown in Table 1.
the result of Mars and Maessen since (4) is an This theoretical interpretation of s is however
overall reaction equation, which consists of based on the existence of a single rate determin-
several elementary steps. Holroyd and Kenney ing elementary step and on r, actually being
[9] conclude that the first step (formation of O,-)the rate of the forward reaction even close to
is not rate determining while Simecek et al. equilibrium. The latter condition must be
propose a second step of (4) to be rate deter- verified experimentally by tracer measurements
mining. or alternatively the expression r, must be
For design purposes a large number of based upon a realistic kinetic model before a
empirical or semi-empirical correlations of
theoretical interpretation of s is justified. These
laboratory data have been proposed. The reviews conditions are only satisfied for a few of the rate
of Mars and Maessen[5], Boreskov et al. [6] and expressions in Table 1 and the form (6) must as
Weychert and Urbanek[7] include a majority yet be considered as an empirical standard form
of these rate expressions. Table 1 includes 12 of introduced for reasons of convenience.
the best known design equations. All equations The different rate equations in Table 1 are
of this table are brought into a standard form seen to be rather conflicting, and it is demon-
strated by Weychert and Urbanek[7] that the
r = r, (1 -p1’s) (6) influence of conversion upon rate of reaction is
predicted very much differently by the extremes
in which p is defined by
among the listed rate expressions. Uncritical
use of the formulas outside the range indicated
PmIK,
p = Ps&P&"2 (7) by the underlying experimental investigations
may consequently lead to very drastic errors.
and the equilibrium constant K, by Some characteristic features are however
common for a majority of the listed rate expres-
sions. Thus the reaction is generally found to be
Kp = (p,>‘:,z)eq = 10500/T-4~743atm-1/2 (8)
first order in oxygen partial pressure. The influ-
ence of SO, and SO, is more conflicting but a
in accordance with the stoichiometric equation product inhibition by SO, is found in most
cases, even far from equilibrium.
so3 ++o, e so3. (9) The use of Hougen-Watson rate expressions
24
 Kinetics and effectivenessfactor for SO2 oxidation
such as Eqs. 11 and 12 of Table 1 is justified
only as far as this type of functional expression
is generally easy to fit to a given set of experi-
mental data. Any interpretation of the parameters
in terms of “adsorption constants” is wholly
unjustified, since the catalyst is in a liquid state
at the reaction conditions.
INTRAPARTICLE DIFFUSION
Recent experimental studies [ 17,18,23] have
shown that pore diffusion restrictions may con-
siderably decrease the reaction rate in industrial
SO, oxidation reactors. A mathematical descrip-
tion of these phenomena seems extremely
complicated due to the existence of a dispersed
liquid phase in the pore structure. Thus liquid
phase diffusion of both catalyst components
and reaction components and blocking of pore
passages under certain reaction conditions may
possibly have to be taken into account besides
the conventional gas phase diffusion phenomena.
Rony [24,25] has treated the general problem
of pore diffusion in supported liquid-phase
catalysts. His pore diffusion model involves a
number of parameters describing the geometrical
shape of the liquid phase in the pore structure.
Some of the parameters in Rony’s model cannot
at present be independently determined, hence
his results cannot as yet be used to full advantage.
Moreover, for the SOZ oxidation catalysts the
liquid phase probably changes its volume with
varying reaction conditions due to the reversible
SO, absorption, which might also affect the
liquid phase diffusion coefficients. For these
reasons the effect of the liquid phase on the pore
di@usion in the SO2 oxidation is still an unsolved
problem, and the experimental diffusion data
are treated with a gas phase model in this as
well as in all previous investigations.
Ivanov et af.[23] and Kadlec et a1.[17.18] have
calculated the effectiveness factor r) and the
effective diffisivity DsoZ for typical industrial
catalysts by measuring the reaction rate on pellets
of varying size produced by crushing industrial
catalyst pellets. The authors report effectiveness
factors between O-99 and 0.20 depending on the
catalyst and the reaction conditions. An experi-
25
mental value of DsoI is determined on the basis
of effectiveness factor measurements and is
related to the pore structure of the catalyst
through the tortuosity factor 7 (Eq. 28) based
on the pore structure of the fresh catalyst. The
results obtained by the authors show T-values of
1.6[ 181 and 1.5[23] for ordinary monodispersed
catalysts and 3 [23] for a bidispersed catalyst.
MEASUREMENT OF THE REACTION RATE
In this study a series of rate measurements for
a Haldor Topsoe vanadium catalyst is presented.
The reaction rate is determined for different
pellet sizes in the region of significant internal
transport restriction as well as in the truly kinetic
region. The laboratory apparatus is a previously
described [ 26,271 recirculation reactor in which
the rate of recirculation is high enough to ensure
complete mixing in the external reaction mixture,
hence giving well defined conditions at the outer
surface of the catalyst pellet. Special care has
been taken to ensure that no measurements were
in error due to failure in reaching a steady state
activity-an important problem for the reaction
system studied, since under certain conditions
very long time may be required to reach a steady
state activity. This is probably caused by the
liquid-phase catalyst which may undergo large
composition changes when the reaction condi-
tions are altered. The long transient period is
especially observed at low temperature (up to
24 hr at the lowest temperature used (416°C))
and generally after changes in reaction tempera-
ture. For this reason all runs with one catalyst
sample have been performed without disrupting
the temperature control of the reactor. In this
way a number of runs have been extended over
night or even longer, and a control of all measure-
ments at the same temperature is obtained by
checking the consistency of the experimental
data, including both long term and short term
runs, on a plot of the measured reaction rate
versus degree of conversion.
CATALYST
The kieselgur supported V,O,/Kc,O Haldor
Topsoe catalyst was supplied as 6 X 6 mm cylin-
 H. LIVRJERG and J. VILLADSEN

drical pellets. Its physical properties are sum-
marized in Table 2 and the pore size distribution
for a fresh sample is shown in Fig. 1. The small
pellets used in the purely kinetic runs were
obtained from the cylindrical pellets by slicing
these with a knife perpendicular to the cylinder
axis and grinding these slices between plane
faces covered with coarse emery cloth into
circular plates of well defined shape and thick-
ness. In some runs irregular unground slices
were used and by comparison of the measured
rate for the two types of catalyst sample it was
ascertained that the grinding process does not
affect the difftrsivity through the external surfaces
of the ground pellets.
The pore volume and the pore size distribution
were measured by a mercury porosimeter for
the small pellets after several weeks under reac-
tion conditions. Part of these measurements
are included in Table 2. A small reduction in
pore volume can be observed for the used
catalyst in comparison with a fresh sample-most
significantly for the catalyst that has been
operated at the lowest temperature 416”C, but
no conclusion concerning the pore structure at
reaction conditions can be drawn from these
measurements, since the catalyst sample was
cooled slowly down to room temperature in a
stream of dry nitrogen which may very well
have eluted a large amount of SO3 from the
catalyst.
EXPERIMENTAL DATA
Five series of runs are shown in Figs. 2-6. The

Table 2. Data for catalyst VK 38 A supplied by Haldor Topsoe.

Type: V,O,, K,O on kieselguhr; VpOs content: 8 wt per cent;
K/V mole ratio: 3.0; effective heat conductivity A - 7.0 x 10e4
Cal/cm sec”C); Pore structure data from mercury porosimeter

Mean pore
Catalyst Pellet Surface radius r
sample density p,, area S, (A) In
used at Wcm3) Porosity 6 W/g) (J%. 30)

416°C 1.49 0.36 2.0 2390

454°C 140 0.39 1.8 3180
454°C 1.31 0.42 1.9 3310
469°C 144 0.37 1.7 3050
Fresh
catalyst 1.33 044 2.1 3190

Pore radius i

Fig. 1. Pore volume distribution for a fresh catalyst measured by

mercury penetration porosimeter.

26
 Kinetics and effectiveness factor for SOI oxidation

I
Series 1 Series 3

90 m 415.9‘C 453.6 ‘C
25.
m L.O.Slmm n 1=0.23mm
V LE 1.03mm V Lz1.03mm

20.

50
1 15.

I
10.

5.

10

0 0,
0 0.5 I 0.6 0.9 1

Degree of conversion Degree of conversion

Fig. 2. Reaction rate for small and large pellets at 415.9”C. Fig.4. Reaction rate at 453.6”C and high conversion. The
The regression curves are calculated on basis of rate equation regression curves are calculated on basis of rate equation
No. 5 of Table 1 (1 /S = 2). No. 3 (l/s = 2).

Series 2 Series 4
453.6 ‘c 4689 ‘C

\ . L=O.Z7mm n L=O.ZOmm

V L; 1.03mm

“i
0.5 1 05

Degree of conversion Degree of conversion

Fig. 3. Reaction rate at 453.6”C. The regression curves are Fig. 5. Reaction rate at 46W“C. The regression curve is
calculated on basis of rate equation No. 12 (l/s = 2). calculated by rate equation No. 12 (l/s = 2).

series comprise measurements at varying degree and (2) small catalyst plates produced as
of conversion at different temperature levels for described above. All runs are at one atmosphere
different catalyst pellet sizes: (1) 6 X 6 mm pellets total pressure and the composition of the feed
27
 H. LIVRJERG and J. VILLADSEN

will be inversely proportional to the ratio between

s*rM 5
20. volume and external surface of the catalyst
464.0 ‘C
m L*O.ZOmm pellets at otherwise identical reaction conditions
V L=l.O3mm [28]. This is not the case in Figs. 2-6, hence it
may a priori be concluded that at least the small
15. pellets are outside the region of strong diffusion
restrictions. By the calculation procedure
described below the mean value of the effective-
ness factor within each series is found to be 0.%,
10.
O-95, O-94 and 0.94 for the small pellets in series
1, 2, 3 and 5 respectively. In each series the
effectiveness factor for the small pellets is
5. independent of conversion (Yat least within the
accuracy of measurement. Accordingly only
negligible errors are introduced by considering
the small pellet data to be purely kinetically
0
controlled.
0 0.5

Degree of conversion An Arrhenius plot of the measured reaction

rate is shown in Fig. 7 with the large pellet data
Fig. 6. Reaction rate at 484*O°C.The regression curves are included for comparison. It is evident from Fig. 7
calculated on basis of rate equation No. 12 (l/s = 2). that the temperature dependence of the reaction

was held constant at 11 per cent OZ, 7 per cent

SO, and 82 per cent Nz by volume. The composi-
tion of the reaction mixture can then be expres-
sed by a single parameter CX,the degree of
conversion. By variation of the feed rate a
corresponding variation of (Ybetween the limits
0 < a! c (Y,~is obtained. The mole fractions of
the reaction components are obtained in terms
of (Yand the inlet mole fractions by Eqs. (10-12)

* _ Y&(1 -4
so, - (10)
1- kqOa .g -5.5.
ii
Y& - 3qon
yo*= I- *qo*
(11) E .

f .
a -6.0.
ayiO* 2 .
Y (12)
so3= 1 -_baY;o* *
i:
-I
‘8
KINETICS -6.5
1.35 1.40 1.45
The influence of intraparticle transport l/T lo-''K"
restrictions is demonstrated by the difference
between the curves for different pellet sizes in Fig. 7. “Arrhenius plot” of measured reaction rate for small
and large pellets at different conversion levels. The numbers
Figs. 2-6. In the region of strong intraparticle on the curve segments are values of the “‘apparentactivation
transport restrictions the measured reaction rate energy” (Kcallmole) calculated from the slope of the lines.

28
 Kinetics and effectiveness factor for SOS oxidation

rate is quite complicated. The apparent activa-
tion energy E calculated from the kinetic data in
Fig. 7 changes from - 65 kcal/mole to - 16
k&/mole in the temperature range 416-484”C.
Consequently the reaction rate can only in a
very limited temperature range be described with
any accuracy by an Arrhenius expression of the
form
temperature within each series 5 is a function of
(r only and is calculated by Eqs. (7), (8) and
(10-12).
With the experimental technique described in
[27] the error of the reaction rate measurements
is not constant, but can be considered approxi-
mately proportional to the reaction rate. A sum
of weighted squared residuals is accordingly

r=k,,exp -& ~(Po*,Psoa,Pso,). (13) (SSR), = i (y)’ (15)

( B > f=l

To study the influence of partial pressures on
the reaction rate a weighted least squares method
is used to determine the “rate constant” k for
each rate expression in Table 1. This analysis
is performed for each series separately, which
seems the most reasonable procedure in view of
the irregular temperature dependence of the
reaction rate shown in Fig. 7. Any of the rate
expressions in Table 1 can be written as
r = k Xf(Po,,Pso,,P soarT)(l --P19 = k5
f is independent of temperature except for
Eqs. Nos. 4, 9, 11 and 12 of Table 1 and in
these cases the explicit temperature depend-
ence off as given by the authors is inserted in
(14). k is the proportionality constant to be
determined in the following statistical analysis.
For a given rate expression and for constant
in which ri is the measured reaction rate for
(Y= Q and & is the corresponding value of 5.
The minimum value of (SSR), is obtained for
(16)
The results of the calculation are shown in
Tables 3-7. To study the intluence of the back-
wards reaction the two values 1 and fr for the
(14) parameter s (Eq. 6) are included for each rate
expression. Within each series the goodness of
fit for the various regression curves can be
judged by comparing the mean relative error
E given by
E= (1‘7)
Large differences in E for the various rate

Table 3. Rate constants, Series 1415.9”C

l/s= 1 l/s = 2
Rate Eq.
No. Rate constant Mean error Rate constant Mean error
k lin% k c in %

I 8.8 x 10-B 38 8.1 x 1OP 34

2 17.7 x 10-B 68 15.4 x 10-B 64
3 25.0 x 10-B 58 21.9 x 10-e 53
4 12.9 x 10-B 18 12.2 x IO-6 12
5 16.2 x 10-O 8 15.7 x 10-6 7
6 39-l x 10-B 16 37.1 x 10-B 11
7 2.52 x 1O-s 34 2.34 x 10-S 30
8 119 x 10-s 58 103 x 10-e 53
9 5.55 x 10-a 58 4.91 x 10-a 54
10 7.51 x 10-a 26 7.06 x 10-e 22
11 2.65 x lo-* 59 2.32 x lo-” 53
12 2.88 x lo-* 83 2.45 x lo-* 80

29
 H. LIVBJERG and J. VILLADSEN

Table 4. Rate constants, Series 2 453*6”C

l/s= 1 l/s = 2
Rate Eq.
No. Rate constant Mean error Rate constant Mean error
k ein% k E in %

1 6.9 x lO-5 7 6.5 x lO-5 11

2 9.6 x lo-+ 29 .8.5 x 10-s 23
3 14.4 x 10-S 15 13.0 x 10-S 6
4 15.9 x 10-J 6 14.9 x 10-S 12
5 14.9 x 10-S 24 14.4 x 10-S 29
6 34.0 x 10-S 17 32.7 x lO-5 22
7 2.05 x 10-S 8 1.93 x 10-s 13
8 68.3 x lO-5 15 61.8 x 10-S 6
9 7.1 x 10-S 22 6.4 x 1OF 16
10 6.5 x l(r” 11 6.2 x lo+ 17
11 4.06 x 10-z 9 3.74 x 10-2 4
12 3.57 x 10-Z 9 3.29 x lo+ 3

Table 5. Rate constants, Series 3 453.6”C

l/s= 1 l/s=2
Rate Eq.
No. Rate constant Mean error Rate constant Mean error
k E in % k E in %

1 6.3 x 1OF 9 5.3 x 10-S 16

2 11.6x lo+ 4 9.6 x 1OW 4
3 16.4 x lo+ 7 13.5 x 10-S 2
14.1 x 10-J 5 11.8 x 10-E 12
5 9.5 x 10-S 16 8.1 x 10-S 23
6 25.1 x 1O-J 12 21.4 x lo+ 19
7 1.79 x 10-S 10 1.51 x 10-S 17
8 78.0 x lo+ 7 64.0 x 10-S 2
9 8.4 x 10-S 4 6.9 x lO-5 4
10 5.2 x lO-5 13 4.43 x 10-S 20
11 4.30 x lo-* 5 3.54 x 10-Z 3
12 3.81 x lO+ 5 3.13 x 10-a 3

Table 6. Rate constants, Series 4 468.9”C

l/s= 1 l/s= 2
Rate Eq.
No. Rate constant Mean error Rate constant Mean error
k E in % k E in %

1 1.02 x lo-’ 17 0.94 x lo-’ 14

2 1.38 x lo-’ 43 1.21 x 10-d 38
3 2.09 x 10-d 18 1.90 x 10-a 10
4 2.82 x lo-’ 8 2.62 x lo-’ 5
5 2.36 x lO-4 20 2.27 x lo-’ 25
6 5.3 x lo-’ 12 5.06 x 10-a 18
7 0*302x 1O-4 14 0.281 x 10-a 12
8 9.9 x 10-d 18 9.0 x lo-’ 10
9 1.38 x 10-d 37 1.22 x lo-’ 31
10 0.97 x IO-4 10 o-91 x 10-d 12
4.00 x l&2 8 3.70 x 10-Z 4
:: 446 x IO-3 9 4.12 x 10-a 3

30
 Kinetics and effectiveness factor for SOP oxidation

Table 7. Rate constants, Series 5 4WO”C

l/s= 1 l/s=2
Rate Eq.
No. Rate constant Mean error Rate constant Mean error
k c ill % k rin%

1 1.26 x lo-’ 19 1.16x 1O-4 17

2 1.63 x lo-’ 45 1.40 x 10-d 39
3 2.57 x lo-’ 16 2.32 x 1O-4 7
4 4.20 x lo+ 13 3.85 x 10-d 9
5 3.14 x 10-d 18 3.03 x 10-d 24
6 6.95 x 1O-4 11 6.63 x lo-’ 18
7 0.379 x 10-d 16 0.350 x 10-d 15
8 12.2 x lo-’ 16 11.0x 10-a 8
9 2.18 x 1O-4 39 1.88 x lo-’ 33
10 1.23 x lo-” 13 1.15 x 10-d 15
11 3.53 x 10-p 3.27 x lo-* 5
12 5.17 x 10-S ; 4.76 x lo+ 3

expressions are indicated in Tables 3-7. It Table 8. Apparent activation energy for selected rate
appears that some of the expressions completely constants
fail to correlate the experimental data, especially E (Cal/mole)
Rate Eq.
at the lowest temperature in Series 1. Only Mars No.
and Maessen’s rate expression (No. 4) gives a 415.9-453.6”C 453.6-484.O”C

relatively small error in all 5 series. Apart from 3 47,000 22,000

No. 4 it appears that those rate expressions which 4 70,000 36,000
5 62,000 27,000
fit the data well at temperatures 454-484”C 6 64,000 26,000
(Nos. 3, 8, 11 and 12) give very large errors at 11 - -4,900
the lowest temperature, and conversely that 12 - 14,100
Nos. 5 and 6 which are appropriate at the low
temperature give large errors at the higher
temperatures. The influence of s is best obtained in this study compares well with the results
from the data in Series 3 where (Yis high and obtained for example by Ivanov et al. [13,23],
for the highest temperature in Series 5. In these but it cannot be considered a general character-
series s = 3 seems to give a somewhat smaller istic of V,O, containing SO, oxidation catalysts
error than s = 1 for the rate expressions which since a regular Arrhenius behaviour of k is
fit the data best. observed in the same temperature range by
An examination of the temperature depend- Mars and Maessen [5] and by Simicek [3]. The
ence of the calculated k values confirms that latter study does however show that the apparent
none of the “rate constants” obey an Arrhenius activation energy is very sensitive to changes in
law in the experimental temperature range. For catalyst composition.
some of the “rate constants” a mean apparent
activation energy is shown in Table 8. These INTRAPARTICLE MASS AND HEAT
values deviate somewhat from the values cal- TRANSPORT
culated from Fig. 7 mainly because some of the To treat the experimental data for the large
rate expressions contain other temperature pellets a mathematical model describing the
dependent parameters besides k. This is espec- combined effect of chemical reaction and
ially noted for Eq. (11) in which the calculated transport processes in the porous pellets was
k-value decreases with increasing temperature. developed in [31]. The model assumes that the
The irregular temperature dependence found heat and mass fluxes can be expressed by
31
 H. LIVBJERG and J. VILLADSEN

position-independent transport coefficients. The by Eq. (22) will never exceed 2.X. The energy
equation of continuity for each of the three balance has been included in the calculations,
reaction components and the equation of energy but as indicated by the small temperature rise
provide four coupled differential equations, only a minor numerical correction to an iso-
which take the following form for regular pellet thermal model is needed. The assumption of
symmetries: constant transport coefficients and of constant
cT is amply justified by the small temperature
d rise.
PdR Ra-%zTDSOpdYso
dR p +pPr = 0 (18)
> The effective diffusivities DsoI, DSOaand Do,
are to be derived from the numerical treatment
R l--o_
d +- of the experimental data. However, the ratio
:pp’= 0 (19)
dR between these quantities may be estimated from
the ratios between corresponding diffusivities
Rt-a-
d Ra-lc D Goa in a straight cylindrical capillary with cross
T SOa do -pPr = 0 (20)
dR > sectional dimensions corresponding to the pore
size of the catalyst. Calculations show[26] that
with
the values in Eqs. (23) and (24) will be almost
constant for all the experimental conditions used,
Y,=Y, for R=R, and z=O for R=O
and they are furthermore approximately in-
dependent of pore size and pore size distribution.
and

RI-“-&(R”-‘h$)-(-AH)p,r=O (21) Do,= 1.4 (23)

D sot
with
Dsot = 0.9.
(24)
T=T, for R=R, and $=O for R=O. Dsot

The kinetic expression r to be inserted into

(I = 1 for slab symmetry, a = 2 for cylinder
symmetry and a = 3 for spherical symmetry.
R, is the radius of the cylinder or sphere or the
half-thickness of a catalyst slab.
Equations (18-21) may be used for the 6 x 6
mm cylindrical pellets assuming a = 3 and taking
RJ3 to be the ratio of pellet volume to pellet
external surface. As shown by Aris[30] only
negligible errors are introduced by this procedure.
Similarly slab symmetry (a = 1) is an accurate
assumption for the small pellets.
An upper bound for the temperature rise
within the pellet is obtained as
hot (--AN) G.soz
AT,,, =
A *
With an estimated value of 0.06 cm2/sec for
D SOI the maximum temperature rise calculated
Eqs. (18-2 1) is provided by the analysis of the
kinetic data as described for the small pellets
in the previous section. Any of the rate expres-
sions of Table 1 and the corresponding apparent
activation energies from Table 8 may be selected
as long as it agrees reasonably well with the purely
kinetic experiments from the same series. By
algebraic manipulations described in [31] all
but one of the dependent variables can be elimin-
ated and (18-2 1) are reduced to a single second
order. boundary value problem, which is solved
by orthogonal collocation as described by
Villadsen and Stewart[29,32].
As mentioned above the only unknown para-
meter in the final mathematical model is DSOn,
(22) which is presently to be calculated by a com-
bined use of the large pellet and the small
pellet data.
Let F, be the observed reaction rate with large
32
 Kinetics and effectiveness factor for SO1 oxidation

pellets for a given temperature and a given
degree of conversion CX] and let rjcal be the purely
kinetic rate at CQcalculated from the small pellet
data by inserting (Y= (Yein one of the regressional
expressions of Table 1 and Tables 3-7. The
experimental value of the effectiveness factor
r)f at (Yj is calculated by
(25)
A value of DsOp is inserted into Eqs. (18-21)
and these equations are solved as described
above to obtain a predicted value of r) for
(Y= aj. The difference between 7) and r/j is
used to correct DsoZ and the combined problem
(18-2 1) and (25) is solved by iteration until the
predicted value of r) agrees with qj. This is done
for each (Yeused in the runs with large pellets.
Furthermore an “average DsoZ” is calculated by
minimization of the weighted sum of squared
residuals given by:
in which n is the number of runs with large pellets
in one experimental series, i.e. for one tempera-
ture. The least squares value of the sulphur
dioxide effective ditfusivity D,*,* is the value of
D SO29 which generates a vector ql, r/2 . . . qj, . . . r),
by Eqs. (1.8-2 1) so that (SSR), in (26) is mini-
mized. D,*,* is found by a Golden Section opti-
mization technique.
The unknown parameter Dzoz has now been
calculated from the experiments with large
pellets, but with the assumption that rfCal are
truly kinetic data. In a second calculation step
this assumption is removed. Dgol is now used to
calculate an effectiveness factor for each series
of small pellets by means of Eqs. (18-21) modified
for slab symmetry (a = 1). This effectiveness
factor is virtually independent of (Yand the mean
value q* is accordingly used to correct all
kinetic data within each series
(27)
This procedure sets up a second iteration
process between Eqs. (26) and (27) which
however converges to constant q8 within one or
two iterations.
The final values of Dzot are shown in Table 9.
In each series only four rate expressions from
Table 1 (i.e. those that fit the kinetic data best
at the given temperature) have been used. In
this way a convenient measure of the influence
of the choice of rate expression on the calculated
diflusivity is obtained. From the standpoint of
an accurate determination of Dsoz from the
measurements it is indeed gratifying that the
possible model errors play such a minor role
as seen from Table 9, but on the other hand the
results do show that it is very difhcult to dis-
criminate between kinetic models on the basis
of effectiveness factor measurements alone.
In Fig. 8 the experimental effectiveness factor

Table9. Effective diffusion coefficient for SO0 calculated from experimental

data

Series 1 Series 2 Series 3 Series 5

Rate Eq. 415+X 453.6”C 453.6”C 484.O”C
l/S (cm*/sec) (cm*/sec) (cm*/sec) (cm*/sec)

3 2 - 0*0.566 0.0421 0.0540

1 - 0.0555 oXl414 -
4” 2 0.0188 - - 0.0538
5 1 0.0182 - - -
5 2 0.0178 - - -
6 2 0.0187 - - -
11 2 - 0.0567 0.0414 0.0521
12 2 - 0.0554 0.0413 0.0519

33

C.E.S. - Vol. 27 No. 1-C

 H. LIVBJERG and J. VILLADSEN

0 0.5
pore diffusion restrictions may be very important
.
in the last catalyst layer of industrial converters
1.. ". . . . s
even though the temperature is low and the
reaction rate small.

TORTUOSITY FACTOR
.0.6 It is now possible to relate the calculated
effective ditfusivity to the pore structure of the
catalyst. Actually the pore structure at reaction
conditions is not known with any certainty for
reasons given in the second section of this paper.
Accordingly any change of pore structure or
other influence of the liquid phase on the diffi-
0. sion rate is at first neglected and only the pore
t .a4
structure of the fresh catalyst (Table 2 and
34 Fig. 1) is regarded.
2 . 5wm 1 415.9 lc s’
El . Scrims2 453.6'C
For the pore size of Fig. 1 the diffusion takes
.0.2
. %ri*s 3 453.8'C place in the transition region between Knudsen
. 5win 5 484.0'C diffusion and bulk diffusion. A number of methods
t
are available for prediction of effective diffisivity
1 10 in this range. Equation (28)[Ref. 33, Chap. I] is
0.8 0.9
Degree of conversion frequently used
Fig. 8. Measured effectiveness factor for industrial size
6 X 6 mm cylindrical pellets (L = 1.03 mm). The curves show
the effectiveness factor calculated for an effective diffusivity
equal to D.& (Table 9) using the following rate equations:
&o,=f
(-.&+’ >-l.
so2 g&),
(28)

Series 1. Rate Ea. No. 5 (l/s = 2). Series 2. Rate Ea. No.
12 (l/s = 2), Series 3. Rate’ Eq. No. 3 (l/s = 2) Series 5. _9SOS is the pseudobinary bulk diffusion
Rate Eq. No. 12 (l/s = 2). coefficient for SO, in the reaction mixture. The
reacting components are highly diluted with
(Eq. 25) is plotted versus (Y.The curves show the inert N2 and the net diffusion flux through the
calculated effectiveness factor for an effective pores may be neglected. Furthermore Bsoz may
diffusivity equal to Dzol. For each series the be equated to the binary bulk diffusion coefficient
. .
best “kinetic rate expression” has been used to of SO, m N, (or m au). Bsoz K is the Knudsen
calculate q(a). The results for the lowest tem- diffusion coefficient. T is the tortuosity factor
perature in Series 1 must be regarded with which should be regarded mainly as an empirical
suspicion. The value of D,*,%is much lower for correction factor to allow for the tortuous diffu-
this series than for the other temperatures and sion path and for pore constrictions. It is tacitly
the experimental 7 values are poorly determined assumed in (28) that 7 is independent of the
due to the bad fit of the kinetic data to the rate diffusion mechanism. gio, depends on the pore
expressions at this temperature and to the high radius r’ as
effectiveness of the large pellets, which makes it
difficult to calculate an effective diffusivity with
any accuracy. The calculated decrease of r)
when (Y+ CX,~which is also observed in the
other series is probably qualitatively correct and The pore radius r’ is not constant and the
compares well with corresponding results in in (28) must be based on an average
value of L@too,
[23] and [3 11. This decrease in 7 indicates that pore radius r; which may be calculated in two
34
 Kinetics and effectiveness factor for SOS oxidation

different ways [33] either from the surface area bulk diffusion coefficient of SO, calculated as the
S, and the pore volume VP binary diffusion coefficient of SOL in N2 by the
Chapman-Enskog formula[33] (p. 12). r may
r -3 be calculated from Table 10 by comparing the
rm- & (30) experimental effective diffusivity with 7Dsoz. The
calculated values of r, all based on Johnson and
or from the pore volume distribution Stewart’s pore diffusion model (last column of
Table 10) are shown in Figs. 9-12.

(31)

The pore diffusion model of Johnson and

Stewart[34] takes the varying pore size into
20
I I Scrics 1

account in the computation of Dsop

(IO
1 1
l
D sot = ;
I( -
0 %o* +gfo,(r’) >
-‘f(r’)dr’ (32)

01
in which f(r ‘)dr ’ is the fraction of a cross section 0 0.5 I

occupied by pore voidages with radii between r ’ Degree of conversion

and r ’ + dr ’ . f(r ‘)dr ’ is obtained from the pore Fig. 9. Tortuosity factor calculated from experimentally
size distribution by determined effective difftrsivity at 4159W. The vertical lines
cover the range of values for the four rate equations used in
the analysis of the individual runs with large pellets. The
f(r’)dr’ = p,d(l/,(r’)). (33) horizontal lines show the corresponding range for the “least-
squares” effective diffusivity D&, from Table 9.
D so* may consequently be calculated in three
different ways
(1) Using Eqs. (28), (29) and (30),
(2) Using Eqs. (28), (29) and (3 l),
(3) Using Eqs. (32) and (33).
All three methods will give the same result for
a narrow pore size distribution or if the diffusion
in all pores occurs by bulk diffusion only. Table
10 shows Dsop x T obtained by the three methods.
0 0.5 ,
The results differ very little as could be pre- Degree of conversion
visaged since the transport occurs predominantly
by bulk diffusion. Included in Table 10 is the Fig. 10. Tortuosity factor at 453.6”C.

Table 10. Pore diffusion resistance calculated from pore diffusion models

Bulk diffusion 7x DsoI (cm%ec) calculated by three pore diffusion models

coefficient
Temperature 9 SO*,Nz Eqs. (29.3073 1) Eqs. (29,303 32) Eqs. (32,33)
(“C) (cm2/sec) (ri= 3190A) (r: = 4090 A) (Johnson-Stewart)

415.9 0.558 0.157 0.170 0.163

453.6 0.611 0.168 0.183 0.175
484.0 0.655 0.177 0.193 0.184

35
 H. LIVFUERG and J. VILLADSEN
1 Seri*s 3
‘VDegree of conversion
I consisting of randomly oriented straight pores
Fii. 11. Tortuosity factor at 453~6°C and high conversion.
II
0 0.5
Dcgrerof convsrrion
Fig. 12. Tortuosity factor at 484*O”C.
These figures show the tortuosity factor for
each experiment with large pellets together with
the tortuosity factor obtained with the least
squares difhisivity Dzo,. In every case four
different values are obtained, corresponding to
the four rate expressions used to obtain DSOnand
D,*,. within each series. Ranges which include
all four values are indicated in the figures. Again
the use of different rate expressions provides a
means of estimating the model errors.
The results for Series 1 in Fig. 9 show a large
scatter in the calculated T values, just as Dzo, is
inaccurate for this low temperature. For this
reason no definite conclusion may be derived
from the surprisingly high r values of this series,
although it is tempting to explain the high values
by a partial plugging of pores with viscous, half-
molten catalyst. The results for Series 2 in Fig.
10 and for Series 5 in Fig. 12 are much more
satisfactory with almost all values in the range
2.8 < r < 4 and with almost no dependence of
the degree of conversion.
T must be regarded as a characteristic para-
meter for each individual pore structure. How-
ever, the r values found in Series 2 and 5
compare well with the results obtained for a
number of other catalyst pore structures[34,
351 and [33] (Chap. 1.6) and they are close to the
value 3 to be found in an ideal pore structure
[34]. The independence of temperature and
conversion shows that apparently there is no
change in pore structure with reaction conditions
within the range of the two series. The measure-
ments in Series 3 are obtained closer to equi-
librium than is the case for the other series. The
results in Fig. 11 show that the tortuosity factor
increases as conversion approaches (Y,~. This
trend is rather significant and it might indicate
that the pore structure undergoes a change for
large (Y so that the resistance to pore diffusion
is increased. However, the trend on Fig. 11 may
I
also by explained by a slight inaccuracy in the
ratio between the diffusivities of SO, and SO,
fixed by Eq. (24). Close to equilibrium the
reaction rate is very sensitive to errors in this
ratio, hence at present no definite conclusion
can be drawn from the apparent increase of
r noted in Fig. 11.
Acknowledgements-The authors are indebted to Haldor
Topsee for providing the catalyst and for permission to
publish the pore distribution data in Fig. 1, which were
obtained in the Tops@e laboratories.
NOTATION
symmetry parameter: 1 for slabs, 2
for cylinders, 3 for spheres
total molar concentration of reaction
mixture, g mole/cm3
molar concentration of SO, at external
catalyst surface, g mole/cm3
binary bulk diffisivity, cmz/sec
pseudobinary diffusivity for com-
ponent i in the reaction mixture
Knudsen diffusivity for component
i, cm%ec
36
 Kinetics and effectiveness factor for SOS oxidation

effective diffusivity for component i,

Di SP total surface of catalyst pellets,
cm%ec m21g
eo, average effective ditbrsivity for a
given temperature, cm+ec
(SW, sum of weighted squared residuals
T temperature, “K
E apparent activation energy, cal/gmole T, temperature at external surface of
-AH heat of reaction, - 23.270 cal/gmole catalyst pellets, “K
K “equilibrium constant” defined by V&7 cumulative pore volume function
Eq. (1) (i.e. volume of pores with radius
k,k’ rate constants 5 r ‘), cm3/g
ko frequency factor VP pore volume, cm3/g
KP equilibrium constant given by Eq. (8), Y* molefraction of component i in reac-
atrn-l/O tion mixture
L length parameter for catalyst pellet YfS molefraction of component i at the
defined as the ratio between pellet external surface of catalyst pellets
volume and pellet external surface, YfO molefraction of component i in
mm reactor feed
Mi molecular weight of component i,
glgmole tireek symbols
pi partial pressure of component i, (Y degree of SO, conversion
atm ffi measured degree of conversion for
R, gas constant, cal/“C/gmole the ith run
R spatial coordinate in catalyst pellet %Q degree of conversion at equilibrium
R, external pellet dimension used in P defined by Eq. (7)
Eqs. (18-21) cm E mean relative error
r reaction rate, gmole SO,/(g cat.)/sec 5 reaction rate expression divided by
r+ rate of forward reaction rate constant (Eq. (14))
ri measured reaction rate for run i 5 calculated for (Y= (Y~
Fj measured reaction rate for large pellets effectiveness factor
Cd
r5 reaction rate calculated by a rate effectiveness factor for run No.j
expression for (Y= (Ye average value of effectiveness factor
W’ 1 Corr. calculated reaction rate for small for the small pellets at a given
pellets corrected for diffusional temperature.
effects porosity
r’ pore radius (A) effective heat conductivity of catalyst
r; mean pore radius calculated by either pellets, cal/cm/sec/T
Eq. (30) or (3 1) <A> density of catalyst pellets, g/cm3
s kinetic parameter defined by Eq. (6) tortuosity factor

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37
 H. LIVBJERG and J. VILLADSEN

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Resume- Les auteurs presentent une etude experimentale de la vitesse de reaction pour l’oxydation
de SO,, lorsqu’on utilise un catalyseur de V*O,. Les resultats obtenus pour la region cinetique sont mis
en correlation a l’aide de douze expressions de la vitesse pub&s darts la litterature. On conclue que
la plupart des expressions de vitesse sont adequates uniquement dans un intervalle t&s Ctroit de la
temperature et de la composition et qu’il est probablement impossible d’appliquer une seule expres-
sion de vitesse a toute la gamme des conditions doperation industrielles. Des experiences avec de lar-
ges grains ont permis de determiner comment I’efficacitt du catalyseur est fonction de la temperature
et de la conversion. On trouve qu’une resistance importante au transport a lieu quand T 2 450” et
que l’efficacite du catalyseur diminue un peu quand la conversion est Clevte. La ditfusivite de SO,
est determinee et on calcule enfin la tortuositt de catalyseur. Les r&hats montrent que la diffisivitd
peut &tre determinCe a partir du mod&e de diffusion de la phase gazeuse et que le facteur de tortuosite
se trouve &re dans la gamme de valeurs deja publites, avec toutefois une leg&e augmentation quand
la conversion est grande et probablement aussi pour les temperatures basses.

Zusanunenfassung - Es wird eine experimentelle Untersuchung der Reaktionsgeschwindigkeit fur

die SO*-Oxydation an einem handelsiiblichen V,Os Katalysator dargelegt. Die Ergebnisse im rein
kinetischen Bereich werden mittels 12 veroffentlichter Geschwindigkeitsausdriicke in Beziehung
gebracht. Es wird festgestellt, dass die meisten Geschwindigkeitsausdriicke nur in einem engen
Temperatur und Zusammensetzungsbereich hinreichend sind, und dass wahrscheinlich kein einzelner
Geschwindigkeitsausdruck im Gesamtbereich der industriellen Betriebsbedingungen anwendbar
ist. Versuche mit grossen Platzchen werden verwendet, urn die Wirksamkeit des Katalysators als
eine Fur&ion der Temperatur und Umwandlung zu bestimmen. Es wird festgestellt, dass fiir
T > 450°C ein emsthafter Transportwiderstand auftritt, und dass bei hoher Umwandlungs gesch-
windigkeit die Wirksamkeit etwas abnimmt. Das effektive DifFusionsvermGgen von SO, wird bestimmt
und schliesslich wird die Kriimmung des Katalysators errechnet. Die Ergebnisse zeigen, dass das
effektive Diffisionsvermogen auf der Grundlage eines Gasphase-Diffisionsmodells bestimmt werden
kann, und dass der Kriimmungsfaktor in den Bereich friiher veriiffentlichter Werte fdlt, wobei eine
leichte Erhohung ftir Umwandlung und mijglicherweise such fur niedrige Tempemturen auftritt.

38