Chemical Engineering Science. Vol. 43, NO. 2. pp. 22 I-226, 1988 0009-2509188 53.00+0.

00
Printed in Great Britain. 0 1988 Pergamon Journals Ltd.

MODELLING OF SO2 OXIDATION RATES BASED ON

KINETIC DATA OF A Cs/V CATALYST AT HIGH PRESSURES
AND CONVERSIONS

F. J. DOERING, M. L. UNLAND and D. A. BERKEL

Monsanto Corporation, 260 SpringsideDrive, Akron, OH 44313, U.S.A.

(Received9 February 1987; accepted 18 May 1987)

Abstract-Various kineticmodels were derivedfrom reactionmechanismswhichhave been proposed in the

literaturefor SO* oxidation. These kineticmodels were used to fit kineticdata of a Cs/V = 3.5 sulfuricacid
catalystat conversionsabove 97 ‘4, pressuresup to 10 atm and temperaturesof 36@4OO”C. The model which
fit the kineticdata the best was derivedfrom the Boreskov associative reaction mechanism. The rate model
was one-half order in 0, and first order in SO, with both SO* and SO3 terms in the denominator.

INTRODUCTION dinuclear V4 + species. Their kinetic equation had to be

Many kinetic equations have been proposed for the
oxidation of SO2 to SO, with vanadium catalysts
(Urbanek and Trela, 1980; Donovan et al., 1983).
Because of recent advances in analytical instruments,
much work has been published on physical measure-
ments of the V,OJK,S,O, catalyst (Doering et al.,
1987), a molten salt dispersed on a silica support at
reaction conditions. These physical measurements
have provided a large amount of evidence on what the
actual SOa oxidation mechanism is. Kinetic equations
have been derived from various postulated reaction
mechanisms and used to fit experimental data on a
particular catalyst under certain reaction conditions.
Mars and Maessen (1968) proposed a two-step mech-
anism and derived a kinetic mode1 which showed that
the oxidation of VA+, the second step, was rate
determining. Boreskov et al. (1967) proposed a kinetic
equation based on experimental data from a commer-
cial BAV catalyst:
R = ~PO,PSO,(~ - (B/&)*)/(Pso,
Both the Mars and Maessen reaction mechanism
and the Boreskov kinetic mode1 have been used in
recent literature to explain the SO, oxidation kinetics.
Herce et rrl. (1977) obtained experimental data at
elevated pressures and analyzed the results with several
known kinetic equations (including (1) and Mars and
Maessen, 1968). It was shown that even though
equation (1) was the best, the kinetic parameters were
significantly dependent upon the total pressure.
Mukhlenov et al. (1979) and Kokhreidze et al. (1979)
modified the Boreskov equation at elevated pressures
by division with P 112. Neth et al. (1980) developed a
kinetic mode1 which took into account both mass
transfer and chemical reaction. They showed that the
Boreskov equation (I) predicted their experimental
data on commerical catalysts better than Mars and
Maessen.
Ivanenko er al. (I 974) proposed a three-step reaction
mechanism and assumed a mole of O2 reacting with a
modified to fit their kinetic data. Villadsen and
Livbjerg (1978) presented a three-step reaction
mechanism that better explained the kinetic differences
between thin film and thick film catalysts. Removal of
SO, fromaV4+ species was shown to be a critical step.
Boreskov et al. (1980) used relaxation (transient re-
sponse) methods to give evidence of a six-step reaction
mechanism. This mechanism could follow two routes
for oxidation of SO, depending on reaction con-
ditions: associative which proceeds without changes in
the vanadium valence state, and redox which proceeds
in the absence of SO,.
Balzhinimaev et al. (1986) derived a kinetic equation
based on an analysis of a detailed reaction mechanism
(Balzhinimaev et al., 1984). This equation described
experimental data for a wide range of reaction con-
ditions (including elevated pressures). Their associative
reaction mechanism included three binuclear com-
plexes of V5+ as intermediates taking part in the
catalysis: a highly reactive peroxide complex was
+ &so,). (1) assumed to react consecutively with two molecules of
SO2 to form a complex with a sulfite ligand. Transfer
of two electrons from the sulfite ligand to oxygen was
the third step needed to form the initial peroxide
complex. The kinetic equation derived from the postu-
lated reaction mechanism was very similar to equation
(1) after a term was added to account for secondary
reactions between the V5 + complexes and SO3
pressure.
In summary, a significant amount of information
has been generated to understand the reaction
mechanism for the oxidation of SOI with K/V catalysts.
Recent researchers are having some success fitting
broader ranges of kinetic data with models derived
from various reaction mechanisms. However, all of the
mechanistic questions have not been answered yet due
to the complex nature of the catalyst. More experimen-
tal information is needed to explain the reaction
mechanism and to give a complete kinetic model.
Our previous work on K/V and Cs/V catalysts at
221
222 F. J.
high conversions (Doering et al., 1987) indicated that
Boreskov’s six-step reaction mechanism could explain
our physical property data very well. Since much of the
catalyst in a sulfuric acid plant converter operates in
the lower temperature range and high SO,/low SO2
gas (greater than 90% conversion), we decided to
evaluate catalysts under these conditions. Kinetic data
of this type is rare (Livbjerg and Villadsen, 1972; Neth
ef al., 1980) and is of great interest to industrial
practice. Thus this paper has two purposes. The first is
to present kinetic data for the first time at conversions
close to equilibrium and at elevated pressures and
temperatures below 400°C. The second purpose is to
compare various kinetic equations and to determine
which equation predicts kinetic data the best under
these conditions.
EXPERIMENTAL METHODS
A pressure reactor system was built to obtain kinetic
data on various catalysts at pressures up to 10 atm
(1 atm = 101.3 kPa). The flow system was similar to
that discussed elsewhere (Doering and Berkel, 1987).
The differences for high pressure operation will be
described here.
The reactor was a 5 in. (12.7 cm) standard Berty type
acquired from Autoclave Engineers, Inc. The entire
vessel was made from 316 stainless steel. A catalyst
basket with a 150 cc volume was positioned in the
center of the reactor cavity so that the impeller could
direct gas flow up around the outside and down
through the catalyst basket. The net result was a
completely internal recycle reactor. Changes were
made in the magnedrive assembly of the Berty reactor
to prevent bearing failures. An additional Purebond
3310 bearing (part No. 107A-0642) was installed on the
upper end of the drive shalt. A stainless steel spring was
added to prevent the bearings from spinning. Stainless
steel spacers were shortened so that the additional
bearing and spring could fit. A 5 scc/min Nz stream was
fed at the bottom of the magnedrive assembly to purge
the bearings during pressure changes only.
Temperature in the reactor was maintained by a
jacketed resistance heater with three heating zones
1100 W each. The three zones were controlled by a
single on-off type temperature controller provided by
Autoclave Engineers. A 7.50 W ring heater was in-
stalled on the base of the reactor vessel to prevent heat
loss through the bottom.
An SO1 saturator tank was used to supply high
pressure SO, to the reactor. The tank was a Whitey one
gallon stainless steel cylinder and it was wrapped with
a silicone insulated heating tape. Nitrogen was bub-
bled through the SO2 in the tank at 40°C. A Brooks
Model 5841 mass flow controller kept the N, feed
constant. Liquid level in the saturator tank was
monitored by a heavy wall sight glass which was
isolated by valves at either end.
After passing through the saturator tank, the
SO,/N, stream was mixed with mass flow controlled
N2 and O2 streams to give the desired feed gas
DOERING et al.
concentrations. Two mass flow controllers were used
to give the desired preconverted gas flow to the reactor.
The Kim I microcomputer (Doering and Berkel, 1987)
automated the selection of the feed gas flows through
and around the preconverter. Different conversions in
the reactor were obtained at each feed gas com-
position, pressure and temperature by varying the total
gas flow to the reactor between SO-500 scc/min. Excess
gas was vented through a back-pressure regulator
which was located immediately before the two mass
flow controllers. A back-pressure regulator im-
mediately after the reactor was heated in a 150°C hot
box to control reactor pressure. The remainder of the
flow and analytical system was the same as that
reported earlier (Doering and Berkel, 1987).
The catalyst was prepared in the same way as
reported elsewhere (Doering and Berkel, 1987). Final
catalyst properties were: 0.0696 gV/g support, 2.03 g
catalyst/g support, and 0.871 g catalyst/cc. The catalyst
support consisted of 4.5 mm by 4.5 mm cylindrical
silica pellets supplied by Houdry (HSC-534). The
support properties were: 1.1 cc/g pore volume,
258 M’/g surface area and the following pore volume
distribution (measured by a mercury penetration po-
rosimeter): 25 “/0of the volume at 900 A or greater pore
diameter, 50”/, of the volume at 100 A or greater pore
diameter and 75 7” at 85 A. The bed volume of catalyst
used for the kinetic measurements was exactly 100 cc.
To insure steady-state measurements, the catalyst
remained at each conversion for eight hours before
changing to the next conversion condition.
CALCULATION METHODS
The rate of reaction for each operating condition
was calculated in the same way as discussed before
(Doering and Berkel, 1987). Various kinetic models
have been derived from proposed reaction mechan-
isms. The 3-step mechanism proposed by Villadsen
and Livbjerg (1978) will give the following rate equa-
tion when oxidation of V4+ is the rate limiting step
(Doering and Berkel, 1987):
R = kp:;p,o$l - BlK,)l(~so, + APSO~
+ CPSO*PS03)~ (2)
k = k, v,, A = l/(K,K,) and C= l/K,. Ki is
the equilibrium constant for reaction step i, ki/k-i.
Kinetic equation (1) can be derived from the reaction
mechanism of Ivanenko et al. (1974) where A = l/K,.
From the first four steps of Boreskov’s six-step mech-
anism (Boreskov et al.,1980) another kinetic equation
can be derived if we assume that the second step
(oxidation of a V,05-SO2 species) is rate determining
and half-order with respect to 0,. Another assumption
that the V205 species concentration is very small when
compared to the other vanadium species was
shown to be possible by Chumachenko er al. (1982).
Incorporation of the various assumptions will give the
following rate equation:
R = kp::::p,02(l - BIK,)I(Pso~ + APSOJ (3)
 Kinetic modelling of Cs/V catalyst 223

k = k2 K/(1 + &h A = l/(K,K,(l +K4)) and

K, = K,K,KJ. Chumachenko et al. (1982) did a
similar derivation except they assumed that the oxi-
dation of the V205-SO2 species was first-order in O2
and the reverse reaction could be ignored (less than
80% conversion of SO,).
Even though other kinetic models can be derived
from proposed reaction mechanisms, we will analyze
our kinetic data with models (lE(3) and the “power
law” model:

R = kp”,Zp:o,ll - BIKPVPO~O,. (4)

Equation 4 has been used by many earlier workers for
SO, oxidation modeling (eq. (1) of Urbanek and Trela,
1980). The main features of the four models are shown
in Table 1. Earlier work (Livbjerg and Villadsen, 1972)
showed an effectiveness factor for pore diffusion
restrictions approaching one at high conversions and
416°C. Since our reaction conditions were all below Fig. 1. Reaction rate vs conversion at 380°C. Feed gas: 1 1 “/,
400°C and very close to equilibrium, the effectiveness so, (+ 0.4 “/,), 9.9 “/, o* ( f 0.2 “/,).
factor was assumed to be one for the single pellet size
evaluated in this study.
Since we studied conversions very close to equilib- Table 2. Experimental design for kinetics
rium, the correct term for the equilibrium constant, K,,
Gas composition Temperatures (“C) Pressures (atm)
had to be used. Donovan et al. (1983) compared five
sources of equilibrium data and showed some vari- 380 10, 7.5, 5, 2.5
ation in the data. Our experimental results gave the 395 10, 2.5
following least squares fit: 365 10. 2.5
13% SO& 14% 02 395 10; 2.5
log K, = (4921/T) - 4.6658. (5) 380 5
365 10, 2.5
Equation (5) is very close to Boreskov’s equation cited 9 “/, SO2, 14 o/, 0, 395 10, 2.5
elsewhere (Donovan et al., 1983). Equilibrium conver- 380 5
sions were obtained from the kinetic data by expand- 365 10, 2.5
9% SO*, 8% 02 395 10, 2.5
ing plots like Fig. 1 above 99 “/0 conversions and 380 5
reading the conversion at R = 0. All of our kinetic data 365 10, 2.5
were fitted by a non-linear regression analysis method 11 y0 soz, 10% 0, 380 5, 10
(Doering and Berkel, 1987). To improve the fitting of
the data, the rate constant k was centered about 380°C
(653°K) in the following way:
insure perfect internal mixing and differential
k = A, exp(E/Rc (l/T- l/653)) (6) conditions.

To insure that the rate data from the Berty recircu-

RESULTS
lation reactor was obtained under differential con-
ditions, the blower speed was changed to see what An experimental design was used for proper fitting
effect flow rate had upon measured reaction rates. The of the data to various models. The experimental center
run condition chosen was 4OO”C, P = 10 atm, 11 “/0 point was 38O”C, 11% SO, and 10 y0 0, at P = 5 atm.
SO*, 10 “/, O2 and 97 “/, conversion for the 100 cc of the The experimental design is given in Table 2. For each
Cs/V catalyst because this condition produced the gas composition, pressure, and temperature, four to six
highest rate of reaction in this kinetic study. The conversions between 97 “/0and equilibrium were run. A
reaction rate was measured at blower speeds of 300, total of 135 experimental data points were obtained for
750 and 1500 rpm. The same rates were obtained at 750 the regression analyses. The data for all run conditions
and 1500 rpm. All runs were made above 1000 rpm to except those in Fig. 1 are given in Table 3. The data at
380°C for 11 “/, SO1, 10% O2 are given in Fig. 1. The
curves were drawn to show trends only. Two import-
Table I. Main features of the kinetic models ant observations can be made from the results in Fig. 1.
Equation p;,
The first is that the reaction rate is not a linear function
Pnso* (B/Kp)“’ Denominator terms
of SO2 concentration. As SO2 content increases (con-
(1) m=l n= 1 s=f PSO,? pso, version decreases), the relative rate drops off indicating
(2) m=f n= 1 s=l that terms for pso and/or pso, yill be necessary in the
pso,, PSO,l Pso, Pso,
(3) ??I=$ n= 1 s=l PSO,? Pso, denominator of aAy rate equation. The second obser-
(4) m n s=l P”s0, vation is that doubling the pressure does not double
224 F. J. DOERING et al.

Table 3. Kinetic data

Run T (“C) P(atm) u/oSO2 ‘;/,O, ‘XX Rate x lo5 Run T (“C) P(atm) %SOz %O, %X Ratex lo5

1 403.4 10 10.92 10.02 99.2 1 2.083 70 395.6 2.5 8.99 14.07 98.63 2.504
2 403.6 10 10.93 10.06 98.95 3.435 71 395.4 2.5 9.42 14.05 98.08 4.37
3 403.7 10 10.90 10.01 98.53 5.658 72 392.5 2.5 9.17 14.24 96.74 7.688
4 403.5 10 10.97 10.04 97.68 10.32 73 393 2.5 9.18 14.21 95.60 10.69
5 403.6 10 11.02 10.05 96.81 14.69 74 392.7 2.5 9.4 1 14.25 94.24 14.10
6 395 2.5 10.92 10.02 98.51 1.844 75 392.6 10 8.87 8.0 99.40 0.558
7 395 2.5 10.91 10.05 98.32 2.936 76 392.7 10 8.81 8.02 99.27 0.883
8 394.4 2.5 11.01 10.08 97.19 5.171 77 393.1 10 8.86 7.95 99.21 1.12
9 365.5 10 10.86 10.11 99.67 0.205 78 393 10 8.86 7.91 98.86 2.67
10 365.8 10 10.93 10.06 99.66 0.406 79 393.2 10 8.85 7.90 98.50 4.025
I1 365.3 10 11.15 10.12 99.52 0.834 80 393 10 9.14 7.89 98.12 5.469
12 365.6 10 10.92 10.12 99.05 1.519 81 394.3 2.5 8.52 7.98 98.92 0.50
13 365.4 10 11.14 10.04 97.74 3.593 82 394.9 2.5 8.47 7.91 98.74 0.935
14 369 2.5 10.83 10.05 99.14 0.209 83 395 2.5 8.64 7.88 98.57 1.401
15 369.3 2.5 10.78 10.03 99.26 0.440 84 393 2.5 8.40 7.97 97.99 2.657
16 369.8 2.5 10.83 to.05 98.32 0.798 85 394 2.5 8.48 7.97 97.40 3.972
17 395 10 13.08 t4.07 99.70 0.737 86 394 2.5 8.73 7.99 96.60 5.017
18 395.6 10 12.78 14.09 99.48 1.421 87 379 5 8.48 8.01 99.47 0.133
19 395 10 13.24 14.05 99.34 2.548 88 379.5 5 8.54 7.84 99.36 0.285
20 394.3 10 13.23 14.06 98.74 5.166 89 379.5 5 8.42 7.89 99.23 0.599
21 394.6 2.5 13.35 14.03 99.06 1.299 90 380.2 5 8.41 7.90 98.95 1.269
22 393.7 2.5 13.18 14.03 98.84 2.213 91 380 5 8.53 7.84 98.64 1.912
23 396 2.5 12.90 13.94 98.67 2.444 92 379.6 5 8.74 7.86 98.24 2.531
24 395 2.5 13.34 13.94 97.89 5.123 93 365 10 8.52 7.96 99.57 0.103
25 395.4 2.5 13.21 13.92 96.93 7.716 94 363.5 10 8.43 7.87 99.51 0.550
26 396.7 2.5 13.58 13.83 96.12 9.556 95 363.7 10 8.49 7.86 99.00 1.215
27 377.5 5 13.01 14.23 99.70 0.120 96 363.5 10 8.50 7.83 98.59 1.813
28 378.1 5 12.76 14.29 99.67 0.414 97 363.5 10 8.58 7.79 97.92 2.245
29 378.9 5 13.04 14.28 99.61 0.775 98 364.7 2.5 8.14 8.22 99.56 0.156
30 378.6 5 12.86 14.31 99.32 1.846 99 364.7 2.5 8.30 8.05 99.35 0.312
379.3 5 12.71 14.30 99.04 2.637 100 365.4 2.5 8.21 8.14 99.02 0.603
:: 378.5 5 12.93 14.10 98.50 3.649
33 361.7 10 12.99 14.31 99.86 0.033
34 362.4 10 12.98 14.3 1 99.87 0.054 Table 4. Kinetic data at lower conversions
35 362.9 10 12.90 14.36 99.86 0.135
36 362.7 10 12.99 14.31 99.71 0.740 Run T (“C) P(atm) ‘x SO, % 0, “/, X Rate x lo5
37 363.3 10 12.93 14.30 99.59 1.164
38 363.4 10 13.25 14.26 99.41 1.696 a 381 2.5 11.0 10.0 97.79 2.45
39 364.1 2.5 13.16 14.13 99.75 0.072 b 381 2.5 11.0 10.0 94.30 1.24
40 364.6 2.5 13.36 13.99 99.75 0.113 c 366 2.5 8.2 8.0 98.19 1.24
41 365 2.5 13.51 13.52 99.68 0.205 d 366 2.5 8.2 8.0 96.63 1.64
42 365.3 2.5 12.72 13.25 99.39 0.740 e 366 2.5 8.2 8.0 94.29 1.55
43 364.6 2.5 12.48 13.39 98.99 1.24
44 365.5 2.5 12.04 13.62 98.59 1.545
45 391.6 10 9.08 14.14 99.51 1.404 the reaction rate. In fact, at 97.5 “/0conversion the rate
46 390.8 10 9.08 14.13 99.42 2.251 is approximately proportional to P I/‘.
47 390.6 10 9.06 14.15 99.18 3.922
Another important observation is that as conver-
48 390.8 10 9.13 14.19 98.55 7.414
49 391.6 10 9.14 14.08 97.98 10.44 sions were decreased below 97 0/0 for a given tempera-
50 392.2 10 9.43 14.01 97.12 14.30 ture, pressure and gas concentration, the rate of
51 376.6 5 8.78 14.16 99.84 0.048 reaction would actually drop instead of increase.
376.7 8.94 14.23 99.72 0.223 Several examples of this occurrence are shown in
:: 377.1 : 8.85 14.22 99.64 0.537
5 1.252 Table 4. Since a change in the vanadium catalyst
54 376.6 8.96 14.19 99.42
55 377 5 8.87 14.24 99.19 1.94 properties apparently occurred at conversions below
56 378.9 5 9.31 14.10 98.93 2.594 97”/0, we did not attempt to fit data at any lower
57 364.3 10 9.37 14.24 99.63 0.064 conversions.
58 364.4 9.58 14.21 99.61 0.220
The regression analyses of the various kinetic
59 364.6 :: 9.54 14.23 99.55 0.561
60 364.3 10 9.64 14.21 99.35 1.305 models are shown in Table 5. The results can be
61 363.9 IO 9.68 14.26 99.12 1.924 summarized as follows:
62 363.9 10 9.91 14.16 98.89 2.614
63 364.5 2.5 9.02 14.13 99.57 0.109 (1) The best fit was given by eq. (3). Equation (2)
64 364.8 2.5 9.02 14.08 99.47 0.275 reduced to (3) because parameter C was statisti-
65 365.7 2.5 8.95 13.70 99.31 0.583 cally insignificant.
66 365.5 2.5 8.92 13.74 98.89 1.204
(2) Equation (1) gave a poor fit of the data when OZ
67 366.6 2.5 8.81 13.78 98.51 1.769
68 366.9 2.5 2.549 was first order. O2 went to half-order when m was
9.25 13.88 97.97
69 395.3 2.5 9.16 14.15 98.88 1.541 used as a parameter to fit the data.
 Kinetic modelling of Cs/V catalyst 225

Table 5. Comparison of kinetic models

Regression
Equation coefficients -40 E m n Others %Rz D

(1) 2 341 23140 *A = 0.7 85 1.11

4 333 20923 0.50 1.06 +A = 0.7 98.3 0.38
104 23965 ZC = 0.25 A = 0.25 98.6 0.35
(:; 4 250 2353 1 0.52 0.97 +A = 0.7 98.4 0.36
6 1207 22054 A = 3.5 98.1 0.40
z 104 23615 A = 0.25 98.6 0.35

‘4) 4 271 2385 1 to.5 0.91 0.9”1 98.5 0.35

4 k = 913 @ 395°C 0.33 1.16 0.86 98.4 0.52
t 4 k = 238 @ 380°C 0.52 0.88 0.69 96.3 0.27
8 4 k = 381@ 365°C 0.67 1.11 1.24 90.3 0.28

+ Not used as a parameter for the regression analysis.

$ Statistically insignificant.
QUsed (B/K,,)*.

(3) The term B/K, raised to the first power gave a
better fit than when the second power was used.
This is shown by comparing the second and third
results for eq. (3).
(4) The power law eq. (4) showed an increase in M and
a decrease in the statistical fit as temperature was
decreased.
(5) The power law eq. (4) gave the same value of 0.91
for the SO2 and SO, exponents.
DISCUSSION
Earlier work (Doering and Berkel, 1987) showed
that the activation energy for Cs/V catalysts ap-
proximately doubled when the reaction temperature
was below 400°C. Only atmospheric pressures and
conversions above 90 0/0were evaluated. Increased SO,
gas concentrations caused lower vanadium catalyst
activity indicating that vanadium was being reduced to
an inactive state. Thermal and EPR studies (Doering et
al., 1987) on the K/V and Cs/V catalysts found little
V4+ precipitation in the Cs/V molten salts; however,
an inactive V4+ compound was forming which ap-
parently caused the break on the Arrhenius plots at
400°C and this compound remained soluble in the
Cs/V molten salt.
The following compares the kinetic results for our
Cs/V = 3.5 catalyst at high pressures with the atmos-
pheric pressure results (Doering and Berkel, 1987).
(9 The activation energy from 36CL4OO”C was found
to be 24 kcal/mol- 1 (in Table S) which is the same
as that found above 400°C at atmospheric
pressure.
(ii) Oxygen to the approximately one-half power was
found to be essential for both cases.
(iii) A term for pso in the denominator of the kinetic
equation also &as important.
(iv) The rate equation (2) for both cases reduced to (3)
when all the data were fitted. So eq. (3) gave the
best fit of all the data.
The only important difference between the high and
low pressure conversion data was the activation energy
under 400°C.
Data on K/V catalysts at various pressures
(Balzhinimaev et al., 1986) showed that crystallization
of V4 + began occurring at significantly lower tempera-
tures when pressures were elevated. Our results with
the Cs/‘V catalyst also show little formation of inactive
V4 + down to 360°C if conversions remain above 97 %_
The drop in reaction rates at conversions below 97 y0
with elevated pressures apparently occurs for the same
reason as with atmospheric pressure (Doering et al.,
1987): an inactive V4+ complex forms at temperatures
below 400°C and decreases the amount of V5+
available for SO, oxidation.
Because we made very large changes in oxygen
pressure during our experiments (Table 2) and our
regression analyses gave excellent fits of the data
(Table 5), we are convinced that the reaction for our
conditions is half-order in oxygen. We also found that
the reaction at a given temperature, conversion and gas
composition is half-order in total pressure. This result
indicates that eq. (3) with Pg2’Pso in the numerator
and P,, and/or P,, terms in the dinominator makes
sense. Oihers (Mukdlenov et al., 1979; Kokhreidze et
al., 1979) had to divide eq. (1) by Pl” to obtain a good
fit of their data at elevated pressures. Oxygen was
assumed to be first-order. Equation (4) fit the data well
at the high conversions apparently because pso was
very small compared to pso,. Note that the expohents
on P and P were both close to one; thus, eq. (4)
agreetO&ith eqsy1).
CONCLUSIONS
(1) The Cs/V = 3.5 kinetic data is best explained by
the model
R = b$,‘f~,,~(l - WK,MP,,~+ AP,,).
(2) An activation energy of 24 kcal mol - ’ at tempera-
tures between 36G4OO”C indicates that little inac-
tive V4 l formed on the Cs/V = 3.5 catalyst under
high pressures and conversions above 97 “A.
(3) The unexpected result that the reaction rate is half-
order in oxygen for the Cs/V = 3.5 catalyst in-
dicates that similar kinetic studies for the K/V
catalyst should be undertaken for comparison.
226 F. J. DQER~NG et al.

NOTATION Kin&. Caral. Lett. 14, 25-29.

Chumachenko, V. A., Balzhinimaev, B. S., Karnatovskaya, L.
A pre-exponential constant for k
M., Matros, Yu. Sh. and Oruzheinikov, A. I., 1982,
A, C kinetic parameters Nonsteady-state kinetic model of sulfur dioxide oxidation
B kinetic parameter = pso/( pso&*) on. vanadium catalysts, React. Kinet. Catal. Left. 20,
D residual standard deviation 145-150.
Doering, F. J. and Berkel, D. A., 1987, Comparison of kinetic
E activation energy, cal/mol
data for K/V and Cs/V sulfuric acid catalysts, J. Catal. 103,
k rate constant, mole SO2 conv./l cat. s 126-139.
atm Doering, F. J., Yuen, H. K., Berger, P. A. and Unland, M. L.,
K,, K2. etc. equilibrium constants 1987, Investigation of the SO2 oxidation rate limiting
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