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A: GENERAL
ELSEVIER Applied Catalysis A: General 139 (1996) 149-159

Activity of vanadium catalysts with large iron

contents towards oxidation of sulfur dioxide
Piotr Grzesiak a Teresa Gapifiska a Grzegorz Schroeder b.,
Florian D o m k a b
a Institute oflnorganic Chemistry of Gliwiee, Research and Technology Works, R. Maya 1, 62-030 Luboh,
Poland
b Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Pozna~, Poland

Received 19 July 1995; revised 29 November 1995; accepted I December 1995

Abstract

In 1 9 9 2 - 9 3 , a total destruction of vanadium catalysts with large iron contents used for
oxidation of sulfur dioxide took place in three Polish sulfuric acid plants. This paper discusses the
influence that the changes in the active phase of catalyst with great amounts of added iron had
upon the rate of the SO 2 oxidation reaction.

Keywords." SO 2 oxidation reaction; Vanadium catalysts; Sulfuric acid

1. Introduction

In 1992-93, a total physical destruction of vanadium catalysts used in the

sulfuric acid plants (Figs. 1-3) took place [1-3]. All factories were using gas
evolved by roasting copper concentrate and used S C / S A technology (single
conversion SO 2 and single absorption of the sulfur trioxide). The destructed ring
catalysts were of the 04-115 type (cesium-promoted sulfuric acid catalysts), and
of the 04-111 type. The former type was utilised for 4 months on the 4th bed of
the sulfuric acid converter, the latter, 2 years on the 1st bed converter A,B-
streams (fast increase of the pressure drop on the first beds has been observed
after 12 months). Since such a total physical destruction of the catalyst had not

* Corresponding author. Tel. ( + 48-61) 658667, fax. ( + 48-61) 658008, e-mail schroede@chem.amu.edu.pl

0926-860X/96/$15.00 © 1996 Elsevier Science B.V. All rights reserved

SSDI 0 9 2 6 - 8 6 0 X ( 9 5 ) 0 0 3 2 6 - 6
150 P. Grzesiak et al. / Applied Catalysis A: General 139 (1996) 149-159

Converter inlet gas

5.7% SO:
SO: free gas
-

L 420oC

f
/ S

I st~
catatyst ~ ! I! ring s 1
...~. ............. tL.............. ~.............. ~ ........... t, ............ 1~..... 1.7% S02
4.1% S03
552°C

I
Catalyst bed
temperatures

bed °C

1 inlet 420

© 1 outlet 552
I 4 inlet 390

4 outlet 405

T ] V * t1'- [ single-rings[ i ~'

i
I

0~ 0.6% SO:
5.4% SCh
390°C

]~NlystN~i 15 riags I ~ I

[!umP.°f.~ "stl. j.... Converter outlet gas [

I
P (absorptionS03)

~ O I, hot gas exchanger

~1, physical destruction direction

Fig. 1. Converter sulfuric acid plant nr. I, S C / S A technology (single conversion SO 2/single absorption SO3).

been observed before, studies aimed at explaining this phenomenon were taken
up. It was found out that the greatest difference between these catalysts and the
standards was the iron content [4].
 P. Grzesiak et al. /Applied Catalysis A: General 139 (1996) 149-159 151

ConverUx inlet gas

5.5% S02
S03 - free gas
425°C

/ I S
I

1.6% S02
4.0% S03
545°C

2ha II
I~ , ~ o 4 q ! l - n c s

©
I

........
~ r s t ~ 1 !!~gS ]

0 0.6% S02
I
t 5.4% SO~
420°C

cata~stO4-! rings

I Converteroutletgas ]
(absorption SO3)

0 * hot gas exchanger

# 9 physical destruction direction

Fig. 2. Converter sulfuric acid plant nr. II, A stream technology S C / S A (single conversion SO 2/single
absorption SO3).
152 P. Grzesiak et al. / Applied Catalysis A." General 139 (1996) 149-159

Converter inlet gas

5.5% SO2
I S03 - free gas

[ 1 st bed [
catalyst 04-111 rings
....*................~ .................
~ ....................#. .................~,....
1.6% S02
4.0% SO3
550°C

©
I

3rd~ :

0.6% S02
5.4% S03
420°C

Converter outletgas [
) (absorption S03)

0 ) hot gas exchanger

41, ~' physical destruction direction

ff Removal from converter and screening

Fig. 3. Converter sulfuric acid plant nr. II, B stream technology S C / S A (single conversion SO 2/single
absorption SOB).
 P. Grzesiak et al. / Applied Catalysis A: General 139 (1996) 149-159 153

In a previous paper [3], a chemical composition of 'fresh' and used catalysts

as well as the influence of changes in the active phase of the catalysts on the
mechanical resistance were presented. A hypothesis clarifying the causes of the
total destruction of catalysts was proposed.
In order to determine the influence of the chemical composition of the
catalyst, particularly the influence of a large iron content on the activity, the
kinetic studies were conducted using fresh catalysts, samples already used in
converters, and catalysts that underwent the total physical destruction.
This paper, is an attempt to define the influence of iron content on catalyst
activity and the process of physical destruction of the catalyst, based on the
results of the kinetic studies.

2. Experimental

The 'fresh' catalysts with an initial catalyst activity of various times of

employment in contact processes, and samples of destructed catalysts of the
04-115 type (promoted with cesium compounds) and of the 04-111 type
(recovery catalyst) were examined. The former type was utilised for 4 months
on the fourth bed of the converter, and the latter for 2 years on the first beds.
The chemical composition of those catalysts was established using the method
described earlier [5]. The catalytic activity as a function of the reaction rate (W)
against temperature was determined using the method described in [6] on a flow
isothermal apparatus (Fig. 4).

i i i [ i [ ] i i [ i

~z20

M3 F
9.

A3

Fig. 4. The scheme of contact apparatus for determination of rate of SO 2 oxidation reaction. (1) Air
compressor; (2) molecular sieves; (5) flow mixer; (6) gas analysers (SO 2, 0 2 ) ; (7) primary reactor; (8) heater;
(9) research apparatus; (10) absorber (SO 2, SO3). ERG - - electronic regulator; ERG-3 - - flow controller; RT
- - t e m p e r a t u r e regulator; T - - temperature recorder; F - - filter.
154 P. Grzesiak et al. / A p p l i e d Catalysis A: General 139 (1996) 149-159

The reaction mixture with appropriate sulfur dioxide and oxygen content was
generated by mixing sulfur dioxide with air and oxygen-free argon. The gas
flow was controlled using an electronic regulator ERG equipped with a con-
troller ERG-3. The air used for those experiments was dehydrated by means of
molecular sieves 13X. Analysis of SO 2 contents was performed using a mi-
croculometric total sulfur analyser AN SO 2. The measurements were based on
automatic titration of iodine/KI solution (stabilized with acetic acid) and a
mixture containing SO 2 (SO 3 free). The titration was run till the pre-pro-
grammed end-point was reached. The total sulfur content (as % SO 2) was
determined by integration of the total current necessary to regenerate the iodine
used. The electrochemical gas analyser was used simultaneously with the
oxygen content analyser OM 200. The composition was as follows: SO 2 - - 8%
( V / V ) , 0 2 - - 13% ( v / v ) , N N 2 - - 79% ( v / v ) , gas flow 0.3 N m 3 s J
The rate of the oxidation reaction was determined by calculation of the
change of the SO 2 concentration on both ends of the flow reactor (points A2 and
A3) at fixed temperatures (380-600°C) and AT = 20°C. From the concentration
values A2(T) and A3(T), the conversion was calculated using the formula:
X(T) = 10000 × [A2(T) - A3(T)]/[A2(T) × ( 1 0 0 - 1.5A3(T))]
where, A2(T) - - SO 2 concentration at A2 point-inlet of the reactor ( % ( v / v ) )
and A3(T) - - SO 3 concentration at A3 point-outlet of the reactor (%(v/v)).
The reaction rate (W) at the temperature T was calculated according to the
formula:
W(T) = lOOVso2X(r) gM -1
where Vso2 - - SO 2 flow (dm 3 s - l ) , M - - catalyst mass (g), g - - bulk density
(g d m - 3).
The error of the determination of rate constants did not exceed 0.005 (s-1
atm-~).
Taking into account the reaction rate for the systems studied and using the
Borieskov-Ivanov equation [7], the rate constants (k) of the oxidation process
were calculated (Tables 3-6). The dependence of In k and 1/T allowed the
calculation of activation parameters according to the Arrhenius equation.

3. Results and discussion

The chemical composition of catalysts of the 04-115 and the 04-111 types is
collected in Table 1, whereas the composition of these catalysts after 4 months
(04-115) and 2 years (04-111) in the contact apparatus is given in Tables 2 and
3.
The chemical composition of catalysts significantly changes in time. After 4
months, the content of vanadium in the 04-115 catalyst was decreased by 20%,
 P. Grzesiak et al. / Applied Catalysis A." General 139 (1996) 149-159 155

Table 1
The chemical composition of catalysts
Compounds Catalyst
(% m / m ) 04-115 04-111
V205 8.9 7.8
K~O 13.3 15.3
Na~O 0.2 2.5
Cs~O 1.3 0.0
SO 4 34.3 34.4
Fe203 6.8 5.6
Cs/V 0.1 0.0
Fe/V 0.9 0.8

Table 2
The chemical composition of the 04-115 catalyst after a different service time in converter (4th bed)
Service time (% m / m )
V205 K20 Cs20 Fe203 Na20 (SQ) 2
2 months 7.7 11.6 0.8 5.6 0.2 34.5
4 months surface single-rings 7.5 11.5 0.3 5.7 0.1 34.4
bottom of bed lump of catalyst 7.1 11.8 0. I 6.0 0.2 34.8
dust of catalyst 7.6 11.4 1.2 6.0 0.2 34.3

Table 3
Content (% w / w ) of V205, K 2 0 and Fe203 for the 04-111 catalyst after 2 years in converter
Place of catalyst in converter V205 K20 Fe203
I st bed surface 6.24 11.5 5.1
(A) Stream 10 cm from the surface 6.20 14.0 4.5
20 cm from the surface 4.74 10.5 2.2
40 cm from the surface (dust) 7.22 14.1 5.3
1st bed Rings (yellow) 4.68 10.5 2.6
(B) Stream Rings (green) 7.62 14.0 4.9

potassium by 13%, and iron by 16%. After 2 years, the content of vanadium in
the 04-111 type catalysts was decreased by 40%, potassium by 30%, and iron by
60%. The maximum changes in the chemical composition did not exceed 0.3%
for V205, and 0.5% for K 2 0 in the yearly cycle of production.
In both cases the decrease in vanadium and iron contents was greater than the
decrease of the potassium content. This non-typical change of the chemical
content is very characteristic of the surface salting-out of the elements of the
active phase, which was found to occur in the above cases. The characteristic
brown sinter was observed on all the samples except 'fresh' catalysts.
156 P. Grzesiak et al. / Applied Catalysis A: General 139 (1996) 149-159

Table 4
Kinetic parameters of the SO 2 oxidation reaction for the 04-115 'fresh' catalyst and after 2 or 4 months of
utilisation in converter (4th bed)
Temp. (°C) Rate W ( s - 1 ); rate constant k ( s - 1 atm- l )
'Fresh' 2 months 4 months
100XW 100×k 100XW 100× k 100× W 100X k
380 1.986 16.50 1.321 10.00 0.843 6.50
400 3.263 27.35 2.184 18.03 1.675 13.85
420 4.838 43.00 3.708 32.59 3.113 26.76
440 6.852 68.! 5 5.989 60.71 5.678 54.33
460 9.584 108.62 9.066 100.08 8.661 93.91
E a (kJ tool - 1) 93.2 ___1.3 116.0 +_ 1.9 113.7 -I-2.0
A ( s - i atm- i) (46+__ 10)105 (8+_0.6)107 (32_+ 11)108
r 0.999 0.999 0.999

It was noticed that during the oxidation process, vanadium oxide molecules
showed a tendency to migrate to the interior, whereas potassium compounds
became the main components of the surface of the active phase [8,9].
Kaluski et al. [10] studied changes in the vanadium catalysts with an
increased iron content (4.1% w / w ) . They found out that during the exploitation
of the catalyst the promotor (potassium and vanadium) content decreased
together with iron content. Calcium migrated from the beds working at higher
temperatures to the shelves working at lower temperatures. For the catalysts
studied, they also observed changes in the support (SiO 2) structure during the
utilisation.
Chemical changes, salting-out, and the decrease of mechanical resistance
show that the excess amount of iron compounds may cause a different behaviour
of the catalysts studied. Therefore, after 1993, the manufacturer of these type of

Table 5
Kinetic parameters of the SO z oxidation reaction for the 'fresh' catalyst and after 4 months of utilisation in a
converter (4th bed)
Temp. (°C) Rate W (S- 1 ); rate constant k ( s - 1 a t m - 1)
04-115 Catalyst 04-111 Catalyst
'Fresh' 4 months 'Fresh' 4 months
100×W 100×k 100XW 100×k 100×W 100×k 100×W 100×k
380 1.986 16.50 0.843 6,50 0.936 7.44 0.893 7.00
400 3.263 27.35 1.675 13.85 1.572 12.77 1.545 12.51
420 4.838 43.00 3.113 2@76 2.745 23.27 2.572 21.59
440 6.852 68.15 5.678 54.33 4.414 39.89 4.203 37.67
460 9.584 108.62 8.661 93.91 6.588 65.07 6.290 61.35
E a (kJ mo1-1 ) 93.2+ 1.3 113.7+2.0 109.1 +2.0 108.5_+0.8
A (s i tool l) (46_+ 10)105 (32_+ 1 l)108 (38 +_ 10)106 (32 +_0.5)106
r 0.999 0.999 0.999 0.999
 P. Grzesiak et al. /Applied Catalysis A: General 139 (1996) 149-159 157

Table 6
Kinetic parameters of the SO 2 oxidation reaction for the 04-111 "fresh' catalyst and after 2 years of utilisation
in a converter (A stream)
Temp. Place of catalyst in converter
(°C) "Fresh' Surface 10-311 cm from 3 0 - x cm from
the surface the surface

100× W 100× k 100× W lOOXk IOOXW lO0×k lOOxW lOOxk

400 1.558 12.66 0.906 7.192 0.378 2.95 0.271 2.10
420 2.588 21.83 1.508 12.22 0.856 6.78 0.572 4.48
440 4.445 40.22 2.558 21.53 1.555 12.63 1.371 11.06
460 7.244 73.64 4.361 39.29 2.752 23.35 2.548 21.45
480 11.009 133.84 6.588 65.08 4.090 36.47 4.030 35.89
500 12.448 164.33 7.398 75.76 4.776 43.77 4.712 43.116
520 13.839 197.69 8.391 89.83 5.525 52.17 5.187 48.38
540 13.799 197.36 8.301 88.62 5.268 52.72 5.521 52.211
560 13.651 194.98 8.234 87.69 5.521 52.29 5.495 51.93
580 13.541 194.69 8.157 86.79 5.491 51.94 5.455 51.53
600 13.397 195.25 8.036 85.46 5.458 51.65 5.421 51.19

For 400-
480°C
E,~ 124.9_+3.7 117.5_+2.8 132.5+_5.8 153.1 +_6.3
A (5.9_+3.7)10 ~ (8.9±4.1)107 (6.1 _+5.8)10 ~ (I .6+- 16)10 I11
r 0.999 0.999 0.997 0.998

For 520-
600°C
E~ - 1.1 ±0.4 - 3 . 5 ±0.2 - 1.0 ±0.6 3.0+-2.7
A 1.6 ± 0.1 0.53 +_0.01 0.45 ± 0.39 0.79 ± 0.31
r 0.852 0.996 0.694 0.536

catalysts clearly specifies that the iron contents in the 04-110, 04-111, and
04-115 type catalysts should be on a trace level [11].
The kinetic studies of iron-doped catalysts are illustrated in Tables 4 - 6 . The
04-115 cesium catalyst shows great and systematic decrease of its catalytic
activity defined as a decrease of the oxidation rate constant vs. utilisation time at
temperatures below 420°C. For the utilisation time studied at 380°C, this
decrease reached 40% after 2 months, and 55% after 4 months. At 420°C, the
decrease was between 7 and 22% (Table 4). At higher temperatures the
oxidation rate constants decreased less significantly.
Additionally, we studied changes of the reaction rate for the ring catalyst
04-111 after 4 months of the utilisation time, which was loaded on the same bed
on which the 04-115 type catalyst had worked. Additionally, the working
temperature of this bed was set to 420°C. The results of the kinetic experiments
are compared with those obtained using the 04-115 type catalyst for the
utilisation time of 4 months. The results are collected in Table 5.
These results show only small decreases of the oxidation reaction rate (less
than 5% over the studied temperature range). This decrease is related to the
158 P. Grzesiak et al./Applied Catalysis A: General 139 (1996) 149-159

Catalyst 04-111 - rings

1.00
0.90
0.80
~ 0.70
0.80
0.~)
~ 0.40
0.30
0.20
0.10
0.00
fresh surface 10to30 30fox
I st bed depth [cm]

Fig. 5. Lower bed activity profile.

change of the composition of the active phase. The chemical composition of the
'fresh' catalyst (including the degree of initial sulfurization) and the catalyst
after 4 months of utilisation was as follows:
'fresh' after 4 months
V205 (% w / w ) 6.8 6.6
K20 (% w / w ) 11.0 10.8
Fe203 (% w / w ) 4.6 4.2
The kinetic studies of the oxidation process using the 04-111 type catalysts
taken from the first beds (A,B streams) after 2 years of utilisation showed that
the catalytic activity over all the temperature ranges studied decreased signifi-
cantly (Table 6).
Catalyst taken from the surface of the first bed (A stream) showed 40%
activity as compared with the 'fresh' catalyst. Even a greater decrease was
found for the catalyst taken from the reactor bed depth. For the larger 10-30 cm
from the surface this decrease amounts to 65%, whereas in bed depth (30-x) it
exceeds 65% (at initial temperatures of 400-420°C it reaches even 80%) (Fig.
5). This non-typical deactivation suggests that there must be an other deactiva-
tion mechanism.
The kinetic studies of the average catalyst sample with purified active surface
taken from the first bed of stream B showed slight increase of activity for this
catalyst as compared with the catalyst taken from various depths of the first bed
of stream A. A characteristic of these changes leads to the conclusion that the
deactivation mechanism is related to the changes in the active phase of the
catalyst.
For the 04-115 type catalyst (working at 380-460°C) the activation energy
value (Table 4) decreases along with the utilisation time, and it is higher (20 kJ
mo1-1) than for the 'fresh' catalyst. For the 04-111 catalyst (Table 5) after 4
months of utilisation a small (0.6 kJ tool 1) decrease of the activation energy is
observed as compared to the 'fresh' catalyst.
 P. Grzesiak et al. / Applied Catalysis A: General 139 (1996) 149-159 159

After 2 years a bend on the Arrhenius plot is observed at 500°C (Table 6) for
the 04-111 catalyst (A, B streams). There is no dependence of the rate constants
and temperature at 500-600°C, whereas at 400-480°C the value of activation
energy increases significantly with the depth of the catalyst bed. In the bed,
depth is taken for measurements, which is a measure for the activation energy.
To sum it up, we have reached the conclusion that a high iron content in the
catalyst utilised in extremal conditions (high temperature and high partial
pressure SO 3) causes high decrease of the catalytic activity as a consequence of
active phase changes. Similar changes have not been observed for the catalyst
with smaller iron contents.

References

[I] P. Grzesiak, T. Gapifiska, A. Wo;~niak and T. Hlyfi, Report no. 3809, Institute of Inorganic Chemistry of
Gliwice, Poland, 1992.
[2] P. Grzesiak, T. Gapifiska, A. Wo~niak and T. Hlyfi, Report no. 3841, Institute of Inorganic Chemistry of
Gliwice, Poland, 1993.
[3] P. Grzesiak, T. Gapifiska, G. Schroeder and F. Domka, Chemik (Poland), 9 (1995) 258.
[4] T. Gapifiska and A. Skubiszewski, Report no. 1221, Institute of Inorganic Chemistry of Gliwice, Poland,
1982.
[5] Z. Kowalewski, P. Grzesiak and T. Gapifiska, Report no. 1632, Institute of Inorganic Chemistry of
Gliwice, Poland, 1975.
[6] Z. Kowalewski and P. Grzesiak, Report no. 2607, Institute of Inorganic Chemistry of Gliwice, Poland.
1982.
[7] Sulfuric Acid, Handbook PWNT Warszawa, 1975.
[8] K. Richtier, I.P, Muchlienow, E.I. Dobkina, S.M. Kuzniecowa and A.M. Larionow, Z. Prikl. Chim., I
(1984) 49.
[9] W.A. Markow, I.P. Dobkina and S.M. Kuzniecowa, Z. Prikl. Chim., 11 (1991) 2417.
[10] K. Kalucki, W. Abramczyk, A. Morawski and J. Kmita, Przem Chem. (Poland), 10 (1993) 400.
[11] J. Adlkofer, E. Dieckmann and E. Winkler, Sulphur, 229 (1993) 50.