8 SO oxidation catalyst

2
and catalyst beds

Chapter 7 shows that SO2 þ 0.5O2 ! SO3 oxidation is a key step in sulfuric acid man-
ufacture. SO3 is essential for H2SO4 making, i.e., for the reaction:
80-110  C
SO3 ðgÞ þ H2 OðlÞ





! H2 SO4 ðlÞ
in SO3 , O2 , N2 gas in 1:5% H2 OðlÞ, 98:5% H2 SO4 ðlÞ, sulfuric acid in strengthened sulfuric acid

(1.2)
Chapter 7 also shows that V, K, Na, Cs, S, O, SiO2 catalyst is a key ingredient in
ensuring rapid, efficient SO2 oxidation. Without catalyst, SO2 oxidation is slow at
temperatures where SO2 oxidation is thermodynamically efficient.
This chapter describes SO2 oxidation catalyst. It does so in terms of:
(a) catalyst physical and chemical characteristics (Fig. 8.1)
(b) catalyst reaction mechanisms
(c) choice of catalyst chemical compositions for different industrial tasks, e.g., strong SO2
gas, weak SO2 gas (Table 8.1)
(d) industrial catalyst quantity requirements.

8.1 Catalytic reactions

Active SO2 oxidation catalyst consists of a molten vanadium-alkali metal pyrosulfate
film on a porous solid silica substrate. Catalytic SO2 þ 0.5O2 ! SO3 oxidation takes
place with dissolved V, S, O ionic complexes by reactions like:
ðVOÞ2 OðSO4 Þ4 4 ! O2 ðVOÞ2 OðSO4 Þ4 O2 4 (8.1)

ðVOÞ2 OðSO4 Þ4 O2 4 ! SO2 ðVOÞ2 OðSO4 Þ4 O4 þ SO3 (8.2)

ðVOÞ2 OðSO4 Þ4 O4 4 ! SO2 ðVOÞ2 OðSO4 Þ4 SO3 4 (8.3)

ðVOÞ2 OðSO4 Þ4 SO3 4 ! ðVOÞ2 OðSO4 Þ4 4 þ SO3 (8.4)

or, overall:
2SO2 ! O2 2SO3 (8.5)
(Lapina et al., 1999). N2 and CO2 do not react during the SO2 oxidation process.

Sulfuric Acid Manufacture. http://dx.doi.org/10.1016/B978-0-08-098220-5.00008-3

© 2013 Elsevier Ltd. All rights reserved.
92 Sulfuric Acid Manufacture

Figure 8.1 Photograph of SO2 oxidation catalyst pieces, courtesy Haldor Topse
A/S. Rings, star rings, and pellets are shown. The star rings are also referred to as
“Daisy-shape” and “ribbed ring” depending on their manufacturer. This shape maximizes
catalyst surface area and minimizes resistance to gas flow. The pellets give well-distributed
flow in low gas velocity converters. In operation (370-630  C), the catalyst consists
of a molten vanadium-alkali metal sulfate/pyrosulfate film on a porous solid silica
substrate. The outside diameter of the largest piece (far right) is 25 mm.

Reactions (8.1)–(8.4) have smaller activation energies than Reaction (8.5). They
give rapid SO2 oxidation at moderate temperatures.
Rapid reaction between gases and ions requires that the vanadium ion salt be
molten (Christensen and Polk, 2011). Melting at moderate temperatures (350  C)
is obtained by combining high melting point:

vanadium pentoxide (melting point, 670  C)

with low melting point:

potassium (420  C), sodium (400  C), cesium (460  C) pyrosulfates (Fig. 8.2).

8.1.1 Maximizing catalyst activity

Catalyst activity is maximized by:

(a) maximizing V5þ concentration in the molten catalyst

(b) maximizing gas/catalyst film interfacial area
(c) temperature (Fig. 8.3).

V5þ concentration is maximized by:

(a) maximizing V2O5 solubility by optimizing the catalyst’s K, Na, Cs sulfate/pyrosulfate

mix
(b) including a significant amount of cesium in the mix
(c) increasing temperature.

Gas/molten catalyst film interfacial area is maximized by maximizing substrate poros-

ity and wettability—i.e., by ensuring that the substrate contains many pores, uniformly
covered by a thin film of molten catalyst (Christensen, 2012).
 Table 8.1 Descriptions, advantages, and uses of Haldor Topse’s sulfuric acid catalysts (Haldor Topse, 2011). Industrial input gas

SO2 oxidation catalyst and catalyst beds

temperatures are somewhat higher than those indicated here (Tables 7.2–7.7 and 19.3). Other manufacturers make similar catalysts (BASF,
2012; Felthouse et al., 2011). Specially formulated catalysts are also used for wet gas sulfuric acid plants, i.e., WSA and SULFOX (Chapter 25).

Catalyst VK38 VK48 VK59 VK69 VK-701

characteristic

Alkali metals K, Na K, Na Cs, K, Na Cs, K, Na K, Na

Vanadium ion High High High
concentration
Ignition 360 360 320 320 310
temperature ( C)
Continuous 400-630 410-550 370-500 370-500 400-500
operating
temperature range
( C)
Advantage High- Strong catalytic activity Low continuous (i) Low continuous gas input Highest catalytic
temperature gas input temperature activity
stability temperature (ii) High catalytic activity
Suggested use All catalyst beds, Last bed before H2SO4 (i) Ignition After H2SO4 making Beds 3 and 4 in
especially first making, i.e., gases with layer in any bed SO2 þ 0.5O2 ! SO3 oxidation for single absorption
and second high SO3/SO2 ratios (ii) Last bed in operation in lean SO2 gases plants
single-contact Bed 3 in 3 þ 1 or
acid plant 3 þ 2 double
absorption plants

93
94 Sulfuric Acid Manufacture

700
670
Temperature (°C) Cs2S2O7 -V2O5

500
460
412
397

344
300

0.333

0.5
100
0 0.2 0.4 0.6 0.8 1
Cs2S2O7 V2O5
Mole fraction V2O5
Figure 8.2 Cs2S2O7-V2O5 phase diagram. The lowest melting point is 344  C, far below
V2O5’s 670  C melting point. After Folkmann et al. (1991).

1000
Conditions: 10% SO2, 10% O2, high conversion

100 VK-701 LEAP5TM

Relative activity

10 VK59

VK48

720 740 760 780 800 820 840 860 °F

1
380 390 400 410 420 430 440 450 460 °C
Temperature
Figure 8.3 Graph showing catalyst activity as a function of catalyst temperature. Details of the
catalysts are given in Table 8.1. Activity increases with increasing temperature. It also increases
with increasing V and Cs contents (Table 8.1). VK-701 LEAP5™ has an optimized substrate
which is well covered (wetted) by molten catalyst (Christensen, 2012).
SO2 oxidation catalyst and catalyst beds 95

8.1.2 Deactivation and reactivation

Catalyst deactivates1 when it is cooled below its solidification temperature.
This happens when a catalyst bed is fed with cold gas or when the acid plant is
shut down.
Fortunately, catalyst solidification and melting are reversible so that the catalyst
reactivates when it is once again heated and remelted. However, care must be taken
to avoid exposing the cooled catalyst to moist air. Catalyst absorbs moisture, which
causes it to weaken and partially disintegrate (MECS, 2011).
Access to moist air is minimized by closing all the catalytic converter’s
inlet and outlet flues. This has the additional benefit of avoiding oxidation of the
catalyst’s sulfur—so that catalyst composition does not change during a plant
shutdown.

8.2 Maximum and minimum catalyst operating

temperatures
Table 8.1 indicates that industrial catalysts operate between:
l
400  C (occasionally lower)

and
l
600  C (occasionally higher).

Operating above 400  C ensures that the catalyst is molten and active.
Operating below 600  C ensures the presence of Reactions (8.1) and (8.2)’s
active ions in the molten catalyst. Temperatures above 600  C cause:
(a) these active ions transform to inactive vanadates (VO4 3 ) (Rasmussen, 2001)
(b) the molten catalyst film and solid substrate to irreversibly react and form a viscous inac-
tive liquid.

8.3 Composition and manufacture

Compositions and methods of manufacturing commercial catalysts are proprietary.
Roughly, however, commercial catalysts contain (mass%):
l
4-10% V2O5
l
15-20% potassium sulfate/pyrosulfate (SO4/S2O7)
l
2-5% sodium sulfate/pyrosulfate
l
5-15% cesium sulfate/pyrosulfate
l
55-70% porous diatomaceous (silica) substrate.

1
Permanent deactivation can occur when the catalyst is poisoned by arsenic or fluorine or damaged due to
exposure to moisture or high gas temperatures.
96 Sulfuric Acid Manufacture

8.3.1 Manufacture
The catalyst is made by:

(a) mixing vanadium oxide, alkali metal oxides, and diatomaceous earth (SiO2) powders in
specified proportions
(b) forming a paste of these components by mixing them with water and inorganic/organic
binding additives
(c) extruding the paste into ring- or pellet-shaped rods
(d) chopping the extrudates into rings or pellets
(e) baking the rings and pellets in an SO2/SO3 atmosphere to:
l
remove water
l
add strength
l
form alkali metal sulfates and pyrosulfates.

(e)’s SO2/SO3 atmosphere is adjusted to give the manufacturer’s specified sulfate/

pyrosulfate (SO4/S2O7) ratio.

8.3.2 Price
In 2012, the price of K-, Na-promoted catalyst is estimated to be 6000 US$ per cubic
meter. The price of K-, Na-, Cs-promoted catalyst is estimated to be 10,000 US$ per
cubic meter.

8.3.3 Installation and plant startup

Purchased rings and pellets are carefully shipped in sealed barrels or in 1-m 
1-m  1-m fiberglass bags. They are carefully loaded by hand or with pneumatic
conveying equipment (VIP, 2012) onto the acid plant’s catalytic converter “trays.”
The catalytic converter is then closed up and SO2 oxidation is begun as described in
Section 7.6.1.

8.3.4 Chemical change and melting

Flow of  400  C SO2-bearing gas around the loaded catalyst causes it to form a mol-
ten vanadium oxide-K, Na, Cs sulfate/pyrosulfate film on the surfaces of the catalyst’s
porous silica substrate.
It is in this melt that catalytic SO2 þ 0.5O2 ! SO3 oxidation occurs.
The steady state in situ composition of the catalyst melt is affected by the compo-
sition of the gas that is passing around the melt. It varies down the catalyst beds.

8.4 Choice of size and shape

Catalyst pieces are sold in the form of star rings, simple rings, and cylindrical pellets
(Fig. 8.1).
SO2 oxidation catalyst and catalyst beds 97

Star rings have the largest surface area and lowest resistance to gas flow (Felthouse
et al., 2011). Pellets have the smallest surface area and highest resistance to flow. Sim-
ple rings are intermediate.
Industrial data (Tables 7.2–7.6) suggest that star rings and rings are equally
favored. Pellets are seldom used.

8.5 Catalyst bed thickness and diameter

Tables 7.2–7.6 gives measured industrial:
l
catalyst bed thicknesses (m)
l
catalyst bed (converter) diameters (m)
l
converter input gas rate (Nm3/h).

This section discusses these values.

8.5.1 Bed thicknesses

Figure 8.4 shows industrial catalyst bed thicknesses. Average bed thicknesses are:

First (feed gas) catalyst bed 0.62 m

Second catalyst bed 0.72 m
Third catalyst bed 0.84 m

with a scatter of 0.2 m each.

1.2
Average bed thickness (m) = 0.11∗bed number + 0.51
Bed thickness (m)

0.8

0.4

0
1 2 3
Feed gas
Catalyst bed
Figure 8.4 Industrial first, second, and third catalyst bed thicknesses. They are from Tables 7.2
to 7.6. They increase from bed 1 through bed 3.
98 Sulfuric Acid Manufacture

Bed 2 is thicker than bed 1 to provide a longer gas residence time (Fig. 8.6). This is
necessary because bed 2 input gas contains:
l
less SO2 and O2
l
more SO3

than bed 1 feed gas. These changes all tend to slow SO2 oxidation. Bed 2’s longer
residence time offsets them.
Bed 3 is thicker than bed 2 for the same reason.

8.5.2 Bed diameters

Figure 8.5 shows industrial catalytic converter (hence catalyst bed) diameters as a
function of measured first catalyst bed feed gas volumetric flow rates. Bed diameters
are between 8 and 16 m. They increase with increasing input gas flow rate. They are
predicted well by the trendline equation on the graph.

8.6 Gas residence times

Nominal residence times of gas in a converter’s catalyst beds are calculated
from measured bed thickness, converter diameter, and converter gas input rate.
The equation is:
Bed thickness ðmÞ
Nominal gas residence time in catalyst bed ðsÞ ¼  !
Converter gas input rate Nm3=s
p  ðconverter diameter, mÞ2
4

20
Diameter = –7.45 ⫻10–5∗(gas rate)2 + 6.45 ⫻10–2∗(gas rate) + 3.25
Converter diameter (m)

15

10

0
0 100 200 300 400
Converter gas input rate (1000 Nm3/h)

Figure 8.5 Measured industrial catalytic converter diameter as a function of measured

converter gas input rate. Diameter increases with increasing flow rate. This keeps catalyst bed
residence times roughly constant (Fig. 8.6).
SO2 oxidation catalyst and catalyst beds 99

3
Average nominal residence time (s) = 0.26∗bed number + 1.19

Nominal residence time (s)

2

0
1 2 3
Catalyst bed
Figure 8.6 Industrial first, second, and third catalyst bed gas nominal residence times. They
increase with increasing bed number. This is due to the increase in bed thickness with increasing
bed number (Fig. 8.4). The points have been calculated from Tables 7.2 to 7.6 industrial catalyst
bed thicknesses, converter diameters, and converter input gas flow rates.

Figure 8.6 plots values calculated from the data of Tables 7.2–7.6. Residence times
are seen to be 1.5 or 2 s, increasing with bed number.

8.7 Catalyst bed temperatures

Figure 8.7 shows industrial catalyst bed input gas temperatures (Tables 7.2–7.6).
There is considerable spread in the data because various catalysts are being used.

Average inlet gas temperature (°C) = 8.3∗bed number + 417

460
Gas inlet temperature (°C)

440

420

400

380
1 2 3
Catalyst bed
Figure 8.7 SO2-bearing gas temperature at the inlet of each catalyst bed. The higher
temperatures in beds 2 and 3 are chosen to increase catalyst activity (Fig. 8.2) as SO2-
and O2-in-gas concentration decreases and SO3-in-gas concentration increases.
100 Sulfuric Acid Manufacture

However, input gas temperature increases slightly from bed to bed. This is designed
to increase catalyst activity (Fig. 8.2) to offset declining reaction rates caused by:

(a) decreasing SO2- and O2-in-gas concentrations

(b) increasing SO3-in-gas concentration.

8.8 Catalyst bed maintenance

Over time, catalyst beds (especially bed 1) become clogged with dust. This gradually
increases the pressure that must be applied to push gas through the beds. Eventually,
this pressure becomes too high and the dust must be screened out of the catalyst.
Screening entails removing the catalyst from its converter tray, passing it across vibrat-
ing screens, and loading the screened catalyst back into the tray with a small amount of
new catalyst makeup (Louie, 2008). It is done every year or two, most frequently for the
first catalyst bed. It is done as quickly as possible to minimize acid production loss.
The interval between screenings can be extended by using large star-shaped cata-
lyst pieces atop the first catalyst bed (Felthouse et al., 2011). This allows the dust to
pass further down the beds instead of forming a dense layer atop the first bed.

8.9 Summary
SO3 is a key ingredient in making H2SO4(ℓ). It is produced rapidly and efficiently by
oxidizing SO2 to SO3 in a molten V, K, Na, Cs, S, O catalyst film, 400-600  C. The
molten film is supported on a solid, porous silica substrate.
SO2 and O2 dissolve in the molten catalyst. They then react with V, S, O cations to
form and exsolve SO3. The reactions are rapid at temperatures (400-600  C) where
SO2 þ 0.5O2 ! SO3 oxidation is thermodynamically efficient.
The process is carried out industrially in 0.5- to 1-m-thick beds of 10- to 12-mm
catalyst rings or star rings (Fig. 8.1). Reaction times are 1.5-2 s.

References
BASF, 2012. Corporate website. Retrieved from http://www.catalysts.basf.com/p02/USWeb-
Internet/catalysts/en/content/microsites/catalysts/prods-inds/process-catalysts/sulfuric-
acid on May 23, 2012.
Christensen, K., 2012. Meeting Future Emission Challenges with Topse’s New VK-701
LEAP5™ Sulphuric Acid Catalyst. Haldor Topse A/S: Kgs. Lyngby, Denmark. Retrieved
from http://www.topsoe.com/business_areas/sulphuric_acid/sulphuric_acid_catalysts//
media/PDF%20files/Sulphuric_acid/Meeting_future_SO2_emissions_with_VK_701_
LEAP5_apr_2011pdf.ashx on May 23, 2012.
Christensen, K., Polk, P., 2011a. SO2 emission reduction by Topse’s new VK-701 LEAP5™
catalyst. Sulfuric Acid Today 17 (1), 23–24.
SO2 oxidation catalyst and catalyst beds 101

Felthouse, T.R., DiGiovanni, M.P., Horne, J.R., Richardson, S.A., 2011a. Improving sulfuric acid
plant performance with MECS’ new GEAR catalysts. Sulfuric Acid Today 17 (2), 16–18.
Folkmann, G.E., Hatem, G., Fehrmann, R., Gaune-Escard, M., Bjerrum, N.J., 1991. Conductiv-
ity, thermal analysis, and phase diagram of the system Cs2S2O7–O5. Inorg. Chem. 30,
4057–4061.
Lapina, O.B., Bal’zhinimaev, B.S., Boghosian, S., Eriksen, K.M., Fehrmann, R., 1999. Progress
on the mechanistic understanding of SO2 oxidation catalysts. Catal. Today 51, 469–479.
Louie, D.K., 2008. Handbook of Sulphuric Acid Manufacturing, second ed. DKL Engineering
Inc, Toronto.
MECS, 2011. General Start-up/Shutdown Instructions for a Sulfur Burning Sulfuric Acid Plant
Converter Containing MECS Catalyst. MECS Inc., St. Louis, MO. Retrieved from www.
mecsglobal.com/Startup%20-%20Shutdown%20Procedure%20for%20SB%20Plants.pdf
on May 22, 2012.
Rasmussen, S.B., 2001. Multidisciplinary investigation of SO2 oxidation catalyst. Ph.D. Thesis,
Technical University of Denmark, 64.
Haldor Topse, 2011. VK Series Sulphuric Acid Catalysts. Haldor Topse A/S: Kgs., Lyngby,
Denmark. Retrieved from http://www.topsoe.com/business_areas/sulphuric_acid//media/
PDF%20files/Sulphuric_acid/vk_series_sulphuric_acid_catalysts_maj2011.ashx on May
23, 2012.
VIP, 2012. Catalyst Handling. VIP International Inc., Baton Rouge, LA. Retrieved from http://
www.vipinc.com/catalyst.asp on May 23, 2012.

Suggested reading
Christensen, K., 2012b. Meeting Future Emission Challenges with Topse’s New VK-701
LEAP5™ Sulphuric Acid Catalyst. Haldor Topse A/S: Kgs. Lyngby, Denmark. Retrieved
from http://www.topsoe.com/business_areas/sulphuric_acid/sulphuric_acid_catalysts//
media/PDF%20files/Sulphuric_acid/Meeting_future_SO2_emissions_with_VK_701_
LEAP5_apr_2011pdf.ashx on May 23, 2012.
Christensen, K., Polk, P., 2011b. SO2 emission reduction by Topse’s new VK-701 LEAP5™
catalyst. Sulfuric Acid Today 17 (1), 23–24.
Felthouse, T.R., DiGiovanni, M.P., Horne, J.R., Richardson, S.A., 2011b. Improving sulfuric acid
plant performance with MECS’ new GEAR catalysts. Sulfuric Acid Today 17 (2), 16–18.