12.5.
2 The Contact Process 2623
21. K. Vydra, J. Wagner, Erfahrungsaustausch der Chemiker und
Ingenieure des Gasfachs, Rosenheim, 1994.
22. R. B. Klemm, D. D. Davis, J. Phys. Chem. 1974, 78, 1137.
23. N. I. Dowling, J. B. Hyne, D. M. Brown, Ind. Eng. Chem. Res.
1990, 29, 2327.
24. P. A. Tesner, M. S. Nemirovskii, D. N. Motyl, Kinetika i Kataliz
1989, 5, 1015.
25. La Roche Chemicals Information Brochure IC 147 R, 1990.
26. L. Connock, Sulphur 2003, 285, 31.
27. P. D. Clark, N. I. Dowling, M. Huang, Practical Aspects of
Claus Catalysis, Alberta Sulfur Research LTD, Bulletin No.
131, December 2004.
28. M. J. Pearson, Hydrocarbon Process. 1973, 52(2), 81.
29. J. Sames, H. G. Paskall, Sulphur 1984, 172.
30. J. L. Ray, J. F. Chapat, C. Nedez, Comparison of Pure Titanium
and Titanium-Alumina Hybrids Sulfur Recovery Catalysts, Sulfur
Conference, Moscow, October, 2005.
31. P. P. Crevier, N. I. Dowling, P. D. Clark, M. Huang, Sulphur
2005, 298, 28.
32. Sulphur 1990, 211, 27.
33. M. L. Sharp, Discovery Aluminas Seminar, Houston, Texas,
1994.
34. R. P. Eischens, W. A. Pliskin, in Advances in Catalysis
and Related Subjects, D. D. Eley, W. G. Frankenberg, V.
I. Komarewsky (Eds.), Vol. 10, Academic Press, New York,
London, 1958, p. 2.
35. A. V. Deo, I. G. Dalla Lana, H. W. Habgood, J. Catal. 1971,
21, 270.
36. H. Knözinger, P. Ratnasamy, Catal. Rev.-Sci. Eng. 1978,
17, 31.
37. A. Datta, R. G. Cavell, R. W. Tower, Z. M. George, J. Phys.
Chem. 1985, 89, 443.
38. C. C. Chang, J. Catal. 1978, 53, 374.
39. H. G. Karge, I. G. Dalla Lana, J. Phys. Chem. 1984, 88, 1538.
40. F. B. Kasumov, Kinet. Katal. 1992, 33, 374.
41. W. Nehb, Western Research Sulfur Seminar, Lurgi Information
Brochure 1613e, Budapest, 1989.
42. W. Nehb, Western Research Sulfur Seminar, Lurgi Information
Brochure 24e, Budapest, 1992.
43. Sulphur 1988, 195, 24.
44. B. G. Goar, R. Hull, A. D. Bixler, H. L. Vines, Proceedings 66th
GPA Annual Convention, 1987, p. 129.
45. J. Borsboom, J. A. Lagas, 22nd ACHEMA Exhibition Congress,
Comprimo Information Brochure, Frankfurt, 1988.
46. J. Borsboom, B. G. Goar, G. Heijkoop, J. A. Lagas, Sulphur
1992, 220, 44.
47. L. Connock, Sulphur 2003, 287, 31.
48. H. Borsboom, P. van Nisselrooy, ACHEMA Exhibition
Congress, Information Brochure, Frankfurt, 2000.
49. W. Dam, J. A. Hugill, M. L. J. A. Wetzels, Western Research
Sulfur Recovery Seminar, Shell Information Brochure, Budapest,
1990.
50. J. A. Lagas, M. L. J. A. Wetzels, International Conference Sulfur
93, Hamburg, 1993.
51. T. R. Armstrong, J. C. Bourdon, G. N. Tragitt, National
Petroleum Refiners Association Annual Meeting, San Antonio,
Texas, 1985.
52. D. K. Beavon, R. H. Hass, 5th Canadian Symposium on
Catalysts, Calgary, Alberta, 1977, p. 76.
53. International Conference Sulfur 93, Lurgi Information Brochure,
Hamburg, 1993.
54. M. P. Heisel, F. J. Marold, Gas Separ. Purif. 1987, 1, 107.
55. R. Lell, J. B. Nougayrede, Sulphur 1991, 213, 39.
56. Lurgi Information Brochure Sulfreen, 1992.
57. K. Stevens, W. H. Buckhannan, Sulphur 1993, 225, 37.
58. R. E. Heigold, R. G. Holcek, Delta Projects Ltd., Calgary,
Alberta, p. 359.
12.5
Oxidation of Sulfur Dioxide
..
Fritz Naumann∗ and Matthias Schulz
12.5.1
Introduction
The most important industrial application of the catalytic
oxidation of sulfur dioxide is the production of sulfuric
acid. Thus, about 167 million metric tonnes of this basic
chemical, which is even more important than ammonia,
were produced in 2000 [1].
The main use, even though tending to decrease, is the
production of phosphoric acid in the fertilizer industry.
Even today, more than 50% of the total sulfuric acid
production is required for this purpose. In addition,
sulfuric acid is used in practically all fields of chemistry,
such as the synthesis of dyes and the production of
pigments and plastics.
The use of sulfuric acid in the petroleum processing
industry is of increasing importance [2], as is its use in the
extraction of non-ferrous metals. Therefore, the volume of
sulfuric acid production is, even today, one of the criteria
for assessing the economic strength of a country. The
large-scale production of sulfuric acid is today carried out
exclusively by the contact process.
12.5.2
The Contact Process
The first studies of the oxidation of sulfur dioxide on a
platinum wire were carried out around 1831 [3]. From
about 1872, in parallel with the development of dyes, the
demand for sulfuric acid or oleum increased suddenly,
with industrial interest in an efficient production process
increasing correspondingly [4].
It was finally the systematic studies of Knietsch at BASF
which, from 1888, led to the contact process [5] that is used
to the present day, first over a platinum catalyst and later
over vanadium pentoxide [6] (Section 12.5.5). (The lead
chamber process, which between 1910 and 1950 was used
in parallel with the contact process [7, 8], has now been
completely supplanted. Today, it is merely a good example
References see page 2634
∗ Corresponding author.
2624 12.5 Oxidation of Sulfur Dioxide

of homogeneous gas-phase catalysis in which oxides of 100

nitrogen serve to transfer oxygen.)

12.5.2.1 Thermodynamic Considerations

The first studies on the equilibrium of the catalytic SO2
oxidation were conducted by Knietsch [5].
In the contact process, process gas containing sulfur
dioxide and oxygen is passed over a catalyst, with the
sulfur dioxide being oxidized to sulfur trioxide: 90
1
SO2 + O2 −
−
−−−
− SO3
H = −99 kJ mol−1 (1)
2
This reaction is strongly exothermic and is associated

Conversion / %
with a reduction in volume (this will be discussed further
in the description below of its large-scale application).
P = 7 bar
The sulfur trioxide thus formed is absorbed in 98%
sulfuric acid and reacts with the water therein to give
P = 5 bar
sulfuric acid in accordance with [8–11] 80

SO3 (g) + H2 O(1) −

−
−−−
− H2 SO4 (1)

H = −132.5 kJ mol−1 (2) P = 3 bar

The equilibrium position of Eq. (1) is dependent on

temperature, pressure, and concentration of the reactants
and is, in accordance with the law of mass action,
described as follows:
P (SO3 ) 70
Kp = (3)
P (SO2 ) × P (O2 )1/2
The classical description of the relationship between
P = 1 bar
temperature and equilibrium constant was given by
Bodenstein and Pohl [12]: 700 800 900
5186.5 Temperature / K
log Kp = + 0.611 log T − 6.75 (4)
T
Fig. 1 Equilibrium curves for a gas containing 11% SO2 and 10.9%
Later publications [13, 14] deviate somewhat from this: O2 at various pressures.
4956
log Kp = − 4.678 (5)
T
or Figure 1 shows the dependence of the equilibrium
5022 position on temperature and pressure for a typical process
log Kp = − 4.765 (6) gas containing 11% SO2 and 10.9% O2 , the remainder
T
being N2 .
The relationship between temperature and total pres-
sure p can be derived from the law of mass action:
12.5.2.2 Reaction Mechanisms and Kinetics
1 x 100 − ax The oxidation of SO2 over a vanadium pentoxide
Kp = × × (7)
p 1−x b − ax catalyst was, for many years, regarded exclusively as a
As is usual in practice, the oxygen and sulfur dioxide heterogeneous gas–solid reaction.
concentrations are here given in percent by volume: According to the present state of knowledge, the active
composition, namely a mixture of vanadium pentoxide
2a percent by volume of SO2 with alkali metal sulfates or pyrosulfates is, under
b percent by volume of O2 operating conditions, present as a melt in the pores of
x SO2 conversion the silica support [15, 16]. On the basis of this model,
numerous investigations have been carried out over the
Kp can be determined from any of Eqs. (4–6). past 30 years with the aim of describing the kinetics
 12.5.2 The Contact Process 2625

of the SO2 oxidation sufficiently accurately [17–19]. The Eq. (8) cannot be regarded as rate determining, at least
best-known model for the course of the reaction in the not generally.
melt is that of Mars and Maessen [20]. In accordance with There is a little more known today about the
this, the equilibrium established in the melt is formally composition of the active V4+ and V5+ species than
expressed as was known 30 years ago [22, 23]. Species having only one
vanadium atom, and also those having two vanadium
1
2V5+ + SO2 + O2 −
−
−−−
 4+
− 2V + SO3 (8) atoms, have been discussed in the past. Likewise, various
2
models for the distribution of the melt in the support
The rate-determining step is thought to be the particle were presented some years ago [24, 25]. The
reoxidation of V4+ by molecular oxygen: cluster model [25] of Villadsen and Livbjerg, optimized
1 at BASF by measurements on industrial catalysts [21],
O2 + 2V4+ −−−→ 2V5+ + O2− (9) has been particularly useful in providing simplifying
2
assumptions in respect of both the degree of utilization
It must be noted that the validity of kinetic equations of the melt and the activity of the pores [21, 26].
derived from any reaction model is limited to quite definite Using a modified Thiele modulus for gas and liquid
temperature ranges [8]. In addition, transport processes phases [21] gives
at the gas–liquid phase boundary must always be taken
into account [16]. rv = Z1 × ηL × ηG × (1 − ξ 2 ) × rL (12)
Another interesting point in this context is the reference
to two different species of the V4+ type: one is an active where:
soluble species which participates in the redox reaction; rv = overall reaction rate (mol SO2 cm−3 s−1 )
the other is an inactive, insoluble species [21]. It is now rL = reaction rate in the liquid
assumed that, in irreversible deactivation of the catalyst, ηL = f (Z2 , p(O2 ), p(SO2 ), U, T ) liquid-phase efficie-
the latter species is predominantly formed. ncy factor
Based on the assumption that the reaction itself is first ηG = f (Z3 , Z4 , p(O2 ), p(SO2 ), U, ηL , T ) gas-phase ef-
order with respect to oxygen, the reaction rate rL can be ficiency factor
expressed as (1 − ξ 2 ) = deviation from equilibrium
Z1 , Z2 , Z3 , Z4 catalyst parameters:
P (SO2 ) Z1 = Vp × a × qs /qc
CV2 × KC × 
P (SO3 ) a
rL = kL × P (O2 ) ×
 (10) Z2 =
P (SO2 ) 2 V p qc
1 + KC ×
P (SO3 ) Z3 = f (Rp )
where SO2 is moles of SO2 per cm3 of melt, kL is the Vc
z4 = 
rate constant, CV is the vanadium total concentration a
Sc
(i.e., C4+ 5+
V + CV ), and KC is the equilibrium constant for
1−a

Eq. (8). ξ = 1/q p(O2 ) × Kp
A more empirical expression is given by Boreskov [18]: Vp = carrier porosity (cm3 g−1 )
P (SO2 ) a = fraction of the carrier pore volume filled with liquid
1.25 qs , qc = density of carrier and catalyst, respectively
P (SO3 )
rL = kL × P (SO2 ) × (11) Rp = medium pore radius (cm)
P (SO2 )
1 + 1.25 Vc /Sc = ratio of the particle volume to the geometrical
P (SO3 )
surface of the particle
At higher temperatures (i.e., >770 K), the two equations q = p(SO2 )/p(SO3 )
agree very well with the experimental data, while at lower Figure 2 shows, greatly simplified, the influence of the
temperatures the Boreskov equation is superior. This is amount of active material on the activity of the catalyst
because Eq. (10) does not take into account the formation (SO2 conversion per unit time and catalyst volume).
of insoluble, inactive V4+ , which is only correct at higher Further significant contributions to elucidating the
temperatures [8]. mechanism of SO2 oxidation over industrial vanadium
There are also other points which have not been catalysts have in recent years come from the Institute
completely clarified. For example, it has been found for Catalysis in Novosibirsk, these being based on
that forward and reverse reactions of Eq. (8) under 51 V, 17 O, 29 Si and 27 Al NMR studies [27–31].
certain conditions proceed more slowly than the reac-
tion in accordance with Eq. (9) [18]. This means that References see page 2634
2626 12.5 Oxidation of Sulfur Dioxide

Z1 · hL · hG 2200
0.2
2000

1800

Temperature / K
700 Kelvin 1600

0.15 1400

1200
740 Kelvin
1000

0.1 800
6 8 10 12 14 16 18 20
SO2 / vol. %
780 Kelvin

Fig. 3Theoretical sulfur combustion temperature as a function of

combustion gas SO2 concentration (air temperature 350 K, sulfur
0.05
temperature 410 K).

690 K can thus produce steam, which has a substantial

0 influence on the production costs of the sulfuric acid.
0 0.1 0.2 0.3 0.4
a
Fig. 2Influence of liquid loading factor on activity at various
temperatures [21].
12.5.3
Sulfur Dioxide as the Basis of Sulfuric Acid Production
On a large scale, sulfuric acid is produced exclusively
from sulfur dioxide by the contact process. The demand
for sulfuric acid is not always the main driving force:
frequently, it is more a case of the sulfuric acid being
unavoidably obtained as a byproduct, for example, in
metallurgy (French: acide fatale).
Overall, on an industrial scale sulfur dioxide is
obtained from a series of raw materials: elemental sulfur,
pyrite, sulfidic ores of non-ferrous metals, spent acid,
H2 S-containing tail gases from coke ovens, gypsum and
other sulfates, and sulfur-containing tail gases from power
stations.
12.5.3.1 Classical Sulfuric Acid Production
12.5.3.1.1 Sulfur Dioxide from Combustion of Elemental
Sulfur According to Eq. (13), the combustion of sulfur
with air is a strongly exothermic process:
S(rhombic) + O2 (g) −−−→ SO2 (g)
−1

H = −297 kJ mol
The combustion gases therefore leave the sulfur furnace
at high temperatures (Fig. 3). Cooling in the downstream
waste-heat boiler to the reactor inlet temperature of about
0.5 About 34% of the total energy (from sulfur combustion,
SO2 oxidation and heat of absorption of sulfur trioxide)
are recovered here [32].
In the past, the sulfur was burned in horizontal, rotating
cylinders using sucked-in air. To make the combustion
of sulfur as efficient as possible, atomization burners are
used today. These can be either ultrasound atomizers or
rotary burners.
It can be generally said that the production of sulfuric
acid from sulfur is technologically the most advantageous.
The high expenditure for the purification of the SO2 -
containing process gases, required in other processes, is
not needed, so that the capital costs are a maximum of
50% of those for a metallurgical plant.
12.5.3.1.2 Sulfur Dioxide from Roasting of Pyrite Pyrite
has always been widely used as a raw material, although
to a decreasing extent [33]. The sulfur content is generally
between 40% and 50%, with problems sometimes being
caused by the content of other elements such as heavy
metals and arsenic.
The roasting of pyrite proceeds via several stages and
can be described overall as follows:
1
2FeS2 + 1 O2 −−−→ Fe2 O3 + 4SO2
2

H = −1660 kJ mol−1 (14)
As can be seen, the roasting reaction is also strongly
exothermic. It is therefore possible to generate up to
(13)
1.5 metric tons of steam per metric ton of pyrite in a
downstream waste 40 bar heat boiler.
Various roasting techniques exist, but today a flu-
idized bed technology, as was introduced in 1950 by
 12.5.3 Sulfur Dioxide as the Basis of Sulfuric Acid Production
BASF [34, 35], is used almost exclusively. There are several
advantages of this process.
• optimum steam yield by means of direct heat transfer
from the fluidized material
• wide range of tolerable particle sizes (0.2 − 10 mm)
• absolutely uniform temperature distribution and reli-
able temperature control.
However, a high degree of experience and skill is a
prerequisite for the proper operation of a fluidized-bed
furnace.
The bed temperature is normally between 970 and
1170 K. The normal abrasion during fluidization produces
dust which consists mostly of iron oxide. This dust must
be removed by means of a complicated, multistage gas
purification procedure before the SO2 -containing roasting
gas is passed into the contact catalyst stage. In addition, as
in all plants having a gas purification stage, the gas must
be reheated to the catalyst temperature of about 690 K
prior to entering the reactor – hence the name ‘‘cold gas
plants’’.
Fluidized beds, as they are built today (e.g., by Lurgi,
Frankfurt), have a capacity of up to 1000 metric tons per
day. In large plants, two such furnaces are frequently
connected in parallel and supply one sulfuric acid plant
with process gas.
12.5.3.2 Sulfur Dioxide from Metallurgical Plants
Sulfur dioxide from the waste gases of metallurgical
plants (for producing copper, zinc, lead, and nickel)
must be processed further for environmental reasons
to give sulfuric acid. The proportion of total sulfuric acid
production made up by such smelter acid has therefore
continuously increased during the past 40 years. For
example, while in Germany the proportion was only 25%
in the 1970s, by 1992 it had risen to 35% [36].
Some exceptions are still the Chilean copper mines of
Chuquicamata and, in particular, the copper and nickel
industry on the Kola peninsula [37]. The latter emits, to
the present day, 500 000 metric tons of sulfur dioxide per
year into the atmosphere without waste gas purification
by means of downstream sulfuric acid production.
12.5.3.2.1 Copper Smelting As for the other non-
ferrous metals mentioned in the introduction, copper
is also extracted from sulfidic ores (e.g., CuFeS2 ),
giving crude copper, magnetite, and sulfur dioxide via
several intermediate stages such as FeS, elemental sulfur,
and Cu2 S. The various processes for copper extraction
have been considerably improved in recent years, with
energy savings and environmental protection being major
considerations.
2627
Only the most widely used process, the Outokumpu
flash smelting process, will be mentioned here [38]. In this
process the copper concentrate, together with preheated
air (about 870 K), frequently enriched with elemental
oxygen [36], is blown into the reaction shaft. The SO2 -
containing waste gases leave the flash smelting furnace
at temperatures of 1470 K and higher.
12.5.3.2.2 Zinc Blende Roasting Zinc blende (ZnS) is
the most important raw material for zinc production.
The ores, enriched by flotation to a zinc content of
over 50%, are usually roasted in a fluidized-bed furnace.
Atmospheric oxygen here reacts with the zinc sulfide at
temperatures between 1170 and 1270 K to give zinc oxide
and sulfur dioxide which is converted to sulfuric acid after
the usual gas purification step.
12.5.3.2.3 Nickel Sulfide and Lead Sulfide Although
in modern plants, the fluidized-bed process is likewise
used for nickel production (mainly from pentlandite
(Ni, Fe)9 S8 ), lead is extracted either in conventional sinter-
ing plants or, more recently, by the QSL process [39] (Que-
neau–Schumann process, further developed by Lurgi).
Here, the concentrate is continuously introduced into a
horizontal reactor. In the oxidation zone, the lead sulfide
is partially oxidized by blowing in technical-grade oxygen:
5
2PbS + O2 −−−→ Pb + PbO + 2SO2 (15)
2
The lead oxide present in the liquid slag is then reduced
by coal dust in the downstream reduction zone to give
lead. The waste gases leave the reactor at a temperature of
about 1470 K with an SO2 content of 15 to 20%. In each
case the gas is subjected to a complicated purification stage
prior to entering the sulfuric acid reactor and, depending
on the catalysts used, to dilution with air.
12.5.3.3 Sulfur Dioxide from Decomposition of Acid
The reprocessing of spent acid is uneconomical in every
case, and is carried out only for ecological reasons. In this
process, the acid is sprayed from above into a vertical fur-
nace having a refractory lining. In the upper part, several
combustion chambers in which heavy fuel oil or natural
gas is burned are arranged in a circle. The acid is then
thermally decomposed at temperatures above 1270 K:
1
H2 SO4 −−−→ SO2 + H2 O + O2
2

H = +202 kJ mol−1 (16)
References see page 2634
2628 12.5 Oxidation of Sulfur Dioxide
Downstream of the decomposition furnace are a waste-
heat boiler, a complete gas purification stage, and a
sulfuric acid plant.
In general, this method is only used for processing
spent acids the impurities of which burn without leaving
any residue. Even the water content must not exceed a
certain level (at most 40%), as otherwise the additional
energy requirement is too high. For a 70% acid, for
example, 46% of the total dissociation energy is required
to vaporize the water and the acid, 31% for the actual
dissociation process. The overall energy requirement is
6.4 × 106 kJ per metric ton of H2 SO4 [40].
12.5.3.4 Sulfur Dioxide from Combustion of H2 S
Sulfur is recovered from gases containing high concen-
trations of hydrogen sulfide (e.g., from desulfurization
of natural gas), by means of the Claus process (see
Section 12.4).
In the case of smaller waste gas streams having a lower
H2 S content, preference is given to burning the hydrogen
sulfide and the other sulfur-containing components such
as COS and mercaptans. This applies, in particular, to
waste gases from coke ovens.
In an excess of air, H2 S combustion proceeds according
to
2H2 S + 3O2 −−−→ 3SO2 + 2H2 O

H = −518 kJ mol−1 (17)
The SO2 concentration of the combustion gas naturally
depends on the initial concentration of H2 S and is, at
most, 6 to 7%.
Owing to the high water content, care must be taken in
the downstream waste-heat boiler that the temperature of
the moist gas does not drop below the dewpoint before it
enters the sulfuric acid plant.
12.5.3.5 Sulfur Dioxide from Sulfates
.. ..
12.5.3.5.1 Decomposition of Gypsum (M uller–K uhne
Process) The Müller–Kühne process [41] is based on
the thermal decomposition of gypsum under reducing
conditions. In this process, the calcium sulfate is de-
composed at about 970 K in the presence of coal to give
calcium sulfide and carbon dioxide. The calcium sulfide
reacts at 1170 K with additional calcium sulfate to give cal-
cium oxide and sulfur dioxide, so that the overall reaction
is described by Eq. (18):
4CaSO4 + 2C −−−→ 4CaO + 4SO2 + 2CO2 (18)
The calcium oxide thus formed is used in the cement
industry.
Particularly massive amounts of gypsum are formed
in the production of phosphoric acid. (In the USA, and
there predominantly in Florida, 35 million metric tons are
produced annually and stored in the open. The gypsum
mounds, which are visible from afar, have now exceeded
600 million tons (!) and, because of the possible danger
to the environment of traces of uranium compounds, are
causing considerable annoyance among the population.)
Reprocessing by the above, or another, modified
process [42], has hitherto failed because of the high energy
costs. Nevertheless, there are several sulfuric acid plants in
operation worldwide which use gypsum as raw material.
12.5.3.5.2 Decomposition of Iron Sulfate Iron sulfate
is an undesired byproduct of the production of titanium
dioxide by the acid process. It is obtained as heptahydrate
(FeSO4 · 7 H2 O), and has attained a certain degree of
notoriety as a result of its dumping in the North Sea
(green vitriol). Every ton of TiO2 results in 3 to 4 tons of
green vitriol, that is, between 5 and 7 million metric tons
per year in the Western hemisphere.
Today, the dissociation is principally carried out at
1120 K in a fluidized bed [43]. Here too, a subsequent
complicated gas purification procedure must be carried
out before the sulfur dioxide is further processed into
sulfuric acid.
12.5.3.6 Sulfuric Acid from Sulfur Dioxide in Tail Gases
from Power Stations
The catalytic oxidation of sulfur dioxide in the waste
gases of relatively small power stations makes sense in
certain cases, and is also practiced. Examples are Block
II and III of the municipal power stations in Münster,
Germany [44]. Since the SO2 content of the waste gas
is only about 2000 mg m−3 , the final product is an acid
having a concentration of at most 70%, which can be
used, for example, in the fertilizer industry (manufacture
of superphosphate).
12.5.4
The Contact Process: Practical Application
12.5.4.1 Fundamentals
12.5.4.1.1 Single Absorption Catalysis According to
Eq. (1), the equilibrium of the SO2 oxidation is shifted
to the right at lower temperatures, that is, in favor
of SO3 formation. This means, first, that the reaction
should be carried out at temperatures which are as low as
possible, with the lower limit being set by the minimum
temperature of the catalyst bed. In practice, therefore, the
heat liberated in the strongly exothermic reaction must
 12.5.4 The Contact Process: Practical Application 2629

be removed, since otherwise the reaction would stop after
the first, adiabatic reaction step.
The reaction is therefore divided into several stages
(in general four or five), that is, into adiabatic substeps
between each of which cooling is carried out (Fig. 4). SO2
conversions between 97.5% and 98.5% are achieved in
this way, depending on the volume ratio oxygen: sulfur
dioxide in the process gas. Although, on the basis of
stoichiometry, an O2 : SO2 ratio of only 0.5 : 1 would be
required according to Eq. (1), the proportion of oxygen is
considerably higher in practice (in general at least 1 : 1) to
achieve conversions which are as high as possible.
After the last catalyst layer, the sulfur trioxide formed
up to this point is absorbed in approximately 98% sulfuric
acid in a brick absorption tower packed with ceramic
rings.
The gas temperature upstream of the absorption tower
is adjusted to 430–460 K by means of heat exchangers,
Gas composition
SO2 = 10.50 vol.%
O2 = 10.40 vol.%
although the optimum absorption temperature is
substantially lower, namely about 330 K. However, to
minimize corrosion, this temperature cannot be set first;
that is, the gas is deliberately fed ‘‘too-hot’’ into the
absorber and then cooled by means of appropriately pre-
cooled absorber acid to the ideal absorption temperature.
In the absorption itself, the sulfur trioxide reacts with the
water in the 98% acid in accordance with
SO3 + H2 O −−−→ H2 SO4

H = −132.5 kJ mol−1 (19)
to give sulfuric acid.
The achievable degree of absorption is over 99.9%,
depending on a series of additional details governed by
the construction.
The single absorption catalysis described here is still
practiced in many countries today. Due to the maximum
achievable final conversion of 98 to 98.5%, the emissions
of sulfur dioxide are, however, comparatively high; for
example, more than 2000 ppm by volume for an initial
concentration of 10%.

12.5.4.1.2 Double Absorption Catalysis Sulfuric acid

plants operating according to the single absorption
ed
100 4.B catalysis principle are still approved and built today,
for example in North Africa or South America. In the
ed

Theor. equilibrium
3.B

long term, however, processes giving far higher final

conversions and thus considerably lower emissions will
become established. The leading process of this type is
double absorption catalysis [45].
It can be seen from Eq. (1) that, besides temperatures
which are as low as possible, the intermediate removal of
ed
2.B

the sulfur trioxide formed up to a certain stage increases

the overall SO2 conversion. In practice, an additional
absorption tower is therefore installed as an intermediate
Conversion / %

absorber.
50 The main configurations used nowadays are:

• System 2 + 2 converter with four beds – the intermedi-

ate absorber is located after the second bed; conversion
up to this point is about 88%, final achievable conver-
sion is about 99.7%.
• System 3 + 1 converter with four beds – here, the SO3 -
containing gas is passed through the intermediate
absorber after the third bed (Figs. 5 and 6). The prior
conversion at this point in time is already 95 to 97%;
final achievable conversion is about 99.8%.
• System 3 + 2 converter with five beds – in recent years,
ed
1.B

a series of plants have been built according to this

0
700 800 900 system, particularly in Western Europe. This process
Temperature / K makes possible high final conversions of more than

Fig. 4 Stage diagram for four adiabatic catalyst layers. References see page 2634
2630 12.5 Oxidation of Sulfur Dioxide

Gas composition 99.8%, and may be used wherever particularly low SO2
SO2 = 10.50 vol.% emissions are prescribed.
O2 = 10.40 vol.%

The inlet and outlet temperatures, conversions and

concentrations for a four-bed converter, system 3 + 1
ed After intermediate
100 4.B absorption are summarized in Table 1. The process gas used in
ed

the example is a typical gas produced by combustion

3.B

Theor. equilibrium
90 of sulfur, i.e. SO2 and O2 concentrations add up to
20.9%, corresponding to the oxygen content of the
combustion air.
80

12.5.4.1.3 Pressure Catalysis The obvious suggestion of

70
ed

carrying out the catalytic oxidation of SO2 under pressure

2.B

was made over 70 years ago [46] (Fig. 1).

Conversion / %

60 To date, however, only two such plants have been

built. Of these, the smaller one has almost never been
50 operated under pressure because of various problems
with the compressors, although it was designed for
2.65 × 105 Pa. It is now still operated in a conventional
40
way in Canada and produces about 200 metric tons of acid
per day.
30 The plant built 10 years earlier (in 1973), has a capacity
of about 560 metric tons per day, is located in the vicinity
20 of Lyon, and still operates today at a pressure of about
4 × 105 Pa. The combustion air (the plant uses sulfur as
10
raw material) is compressed after the drier to the intended
operating pressure. After the combustion furnace, the
ed

process gas is cooled from about 1470 K to about 710 K via

1.B

0 a waste-heat boiler and is passed through the first catalyst

700 800 900
Temperature / K
stage. The SO2 content here is between 11% and 12%.
In contrast to a conventional converter having four
Fig. 5 Improvement of the SO2 conversion by intermediate catalyst beds, the individual stages are separate here, being
absorption after the third pass. arranged as four miniconverters. The cooling between

Sulfur

S–combustion Converter
chamber
To stack

Sulfuric Air
acid

Air-drying tower Final absorber Intermediate absorber

Fig. 6 A very greatly simplified scheme of a sulfuric acid plant having an intermediate absorption step after layer 3.
 12.5.4 The Contact Process: Practical Application 2631

Tab. 1 Operating data for a sulfuric acid converter system 3 + 1

Layer Cumulative Temperature K SO2 vol.% SO3 vol.% O2 vol.%

conversion %

1 In 0 703 10.0 0.0 10.9

Out 64.1 887 3.71 6.76 7.88
2 In 64.1 713 3.71 6.76 7.88
Out 89.9 787 1.06 9.60 6.61
3 In 89.9 698 1.06 9.60 6.61
Out 96.8 718 0.34 10.37 6.26
4 In 96.8 678 0.38 0.00 6.98
Out 99.8 689 0.02 0.36 6.82

the individual stages is carried out by means of heat
exchangers or economizers.
There is an intermediate absorption step installed after
the third bed, and the final absorption is carried out after
bed 4. The waste gas is subsequently decompressed via a
turbine and passes to the stack. The conversion of SO2 to
SO3 is in the region of 99.8%.
In principle, pressure catalysis process has two
advantages process has two advantages:
It is usually reckoned that about three conventional
catalyst beds can be replaced by a fluidized-bed reactor.
If the gas is subsequently passed first through an
intermediate absorber and then over a conventional fixed
bed as a final layer, final conversions of over 99.7% can
be achieved (Fig. 7) [47].
The theoretical advantages of this process are impres-
sive at first sight:

• As a result of the displacement of the chemical • Lower capital costs, higher energy yield (steam)
equilibrium of the SO2 oxidation, the process requires • Almost unlimited high SO2 concentrations in the
smaller amounts of catalyst than are normally used, process gas, as long as the O2 : SO2 ratio is correct.
namely about 100 L per metric ton per day of sulfuric
acid instead of 170–180 L per metric ton per day.
• Owing to the smaller gas volume, the whole plant is 100
also significantly smaller; hence, the capital costs are 12% SO2
lower. 9% O2
These advantages are counteracted by some disadvan-
tages: 90

• Owing to the higher consumption of electric power, the

Conversion / %

operation of the plant is significantly more expensive,

which is barely acceptable at present energy costs.
• In addition, material costs are today substantially higher 80
because of the stricter safety regulations (pressure
operation) compared with over 30 years ago.

On balance, sulfuric acid plants using pressure catalysis

70
are today no longer practical from the point of view of
operating economics. In addition, final conversions of
99.8% are just as achievable using conventional means
(e.g. 3 + 2 system).
60
675 700 725 750 775 800 825 850 875
12.5.4.1.4 Fluidized-Bed Technology If it is possible, in Temperature / K
contrast to the adiabatically operated multistage reactor,
effectively to remove the heat directly at the point where it Fig. 7 Achievable conversion using pseudoisothermal operation
is produced (i.e., directly at the catalyst particle) and thus in a single stage.
finally to operate isothermally, then high conversions
could be achieved in a single stage only. References see page 2634
2632 12.5 Oxidation of Sulfur Dioxide
This aspect is becoming increasingly important in
non-ferrous metallurgy [36].
However, the whole process either stands or falls on the
basis of the abrasion resistance of the catalyst used.
On the one hand, as in the conventional fixed-bed
catalyst, particular pore volumes or a specific pore
distribution are required. On the other hand, the catalyst,
the particle size of which has been between 0.3 and
1 mm in experiments to date, would have to survive
the fluidization process without damage for as long
as possible (maximum acceptable abrasion is 5% per
year).
This problem has still not been solved, despite
promising initial success. The first, still relatively small,
pilot plant was replaced as early as 1971 by a production
plant having a capacity of about 110 metric tons of SO3
per day [40]. In the mid 1970s, this was followed by
a substantially larger plant having a capacity of about
250 metric tons of SO3 per day. After the fluidized
bed (diameter 6.4 m), an intermediate absorption stage
was installed followed by a conventional fixed-bed
converter having two layers. The final conversion was
over 99.7%.
This plant was shut down some years ago and
the fluidized-bed catalysis project was stopped, as had
also occurred at BASF in Ludwigshafen somewhat
earlier.
Fig. 8 The sulfuric acid plant, 1914. (Reproduced with kind permission of BASF AG.)
12.5.5
The Catalyst
During the early years of industrial sulfuric acid
production, platinum on asbestos was still used as
catalyst [5].
The main advantage of platinum, namely to give good
conversions even at relatively low temperatures, was
counteracted by a whole series of disadvantages. These
included, in particular, the high price and the operating
life, which was much too short as a result of its extreme
sensitivity to catalyst poisons such as heavy metals (and
particularly traces of arsenic).
For these reasons, an intensive search for an alternative
to the precious metal catalyst was conducted in many
places, with the result that in 1913 the then Badische
Anilin & Soda Fabrik in Ludwigshafen was granted a
patent for a vanadium pentoxide catalyst [6], which in
principle is still used today (Fig. 8).
This catalyst is not only largely insensitive to catalyst
poisons, but is also substantially cheaper to produce.
Disadvantages are the operating temperatures, which are
320 K higher than with platinum, and the correspondingly
lower SO2 conversions.
However, this gap has now been significantly re-
duced by the use of new types of promoter, such
as cesium sulfate. Such additives lower the melting point
of the active components and thus make the reactions

described in Section 12.5.2.2 possible, in accordance with
Eqs. (8) and (9) at temperatures above 650 K. (For com-
parison, the minimum temperature for a conventional
catalyst without cesium is above 680 K, depending on the
gas composition.)
12.5.5.1 Catalyst Production
Worldwide, about 8500 metric tons of sulfuric acid catalyst
are produced annually. This amount results both from
the replacement of screening losses (see below) and spent
(i.e., deactivated) catalysts in existing plants, and from the
requirement for new sulfuric acid plants.
In the production of the catalyst, the individual
components such as vanadium pentoxide, alkali metal
sulfates and silica as support are usually mixed with one
another and subsequently made into a paste. The final
catalyst shape can have many variations, with the well-
proven extrudates (diameter 6 or 8 mm, length about
10 mm) having been joined by, in particular, rings and
star rings (BASF) in recent years (Fig. 9).
The dimensions are approximately comparable: internal
diameter from 4 to 5 mm, external diameter about
10 mm, length at most 15 mm. The shaped bodies are
subsequently dried, calcined at temperatures between
770 and 870 K, sieved, and packed.
The V2 O5 content of modern sulfuric acid catalysts is in
the range 6 to 8% by weight and the alkali metal:vanadium
ratio is between 2.5 : 1 and 3.5 : 1, depending on the
converter layer in which the catalyst is subsequently to
be used.
Up to the end of the 1970s, sulfuric acid catalysts were
still supplied in partially sulfated form, because these
are less moisture-sensitive. Since, on the other hand, the
alkali metal compounds are present as pyrosulfates under
the reaction conditions, the following reaction took place
Fig. 9 Various catalyst shapes. (Illustration courtesy of BASF AG.)
12.5.5 The Catalyst 2633
when the catalyst was put into service:
K2 SO2 + SO3 −−−→ K2 S2 O7

H = −159 kJ mol−1 (20)
The heat generated in this reaction, in addition to the
heat of reaction of the likewise exothermic SO2 oxidation,
required an exceptional amount of delicate ‘‘feel’’ and
experience in the first use of the catalyst. In fact, there
have been a series of cases in which the catalyst charge,
at least 100 metric tons in a relatively large plant, was
completely or partially destroyed by over-heating.
This risk no longer exists today, as sulfuric acid catalysts
from reputable manufacturers are, in principle, supplied
fully sulfated and can be put into service without any
special precautions.
12.5.5.2 Catalyst Requirements
The operator of a sulfuric acid production plant demands a
number of things from the catalyst: operating life, energy
savings, and activity are of particular importance.
The operating life – that is, the interval between
necessary shut-downs of the sulfuric acid plant due
to deactivation of the catalyst – is an important cost
issue. This is particularly the case if the plant serves to
process SO2 -containing waste gases from the production
of non-ferrous metals (Section 12.5.3.2). In an unplanned
shutdown of the sulfuric acid plant, all upstream units
would likewise have to be stopped, which could cost in
the order of a million dollars.
The most important factors influencing the operating
life of the catalyst are its mechanical stability (i.e., it
must not break down even under unfavorable operating
conditions) and as low as possible a sensitivity to dust in
the process gas.
Under certain conditions, for example when using rich
process gases from the combustion of sulfur, high thermal
stability is additionally required. This mainly applies to
the first layer, where temperatures of up to 900 K can
occur in the catalyst bed. Furthermore, in the screening
of the catalyst required after operating times of various
lengths the losses should be as small as possible. They are,
depending on previous stresses in operation and catalyst
quality, of the order of magnitude of at most 10%.
The requirement for energy savings relates to the
pressure drop caused by the catalyst. The pressure drop in
modern plants is lower by at least a factor of two compared
with that of about 15 years ago; hence, the saving of blower
energy is considerable. This has been made possible by
the introduction of new shapes, for example of star rings
in place of the classic pellets or even spheres. Figure 10
References see page 2634
2634 12.5 Oxidation of Sulfur Dioxide
1000
500
delta p / mm WC
Extrudates 6 mm
100
50
Rings 10 mm
Star rings 10 mm
10
0.1
Gas velocity / m s−1
Fig. 10 Pressure drop of various catalyst shapes per meter bed
depth, as a function of the gas velocity (standard m s−1 ).
shows the dependence of the pressure drop per unit bed
depth on the gas velocity for various catalyst shapes.
Catalyst activity determines the achievable SO2 con-
version for a given plant. In practical operation, low-
temperature activity is demanded; that is, the ability to
effect conversion in the temperature range below about
690 K. This is generally of particular importance for the
last catalyst layer, where the decisive fractions of a per-
cent of SO2 must be converted. For example, while the
final conversion of a sulfuric acid plant still operating
the single absorption catalysis process is at most 98.5%,
this figure can be increased to 99.2 to 99.3% by use of
a cesium-promoted, highly active sulfuric acid catalyst. A
decisive factor here is the possible lowering of the gas
temperature before the last layer, from 693 K to about
658 K. The corresponding emissions of sulfur dioxide are
thereby reduced (to ca. 50%).
Good activity in the lower temperature range is
achieved by the use of suitable support materials such
as diatomaceous earth having an appropriate, accurately
defined porosity, and also by the addition of certain
promoters. In particular cases, cesium sulfate has been
used for this purpose for some years [36], but this does
make the catalyst considerably more expensive.
12.5.5.3 Disposal of Spent Catalyst
Despite continually increasing specific space velocities,
the catalysts from reputable manufacturers have a long
lifetime. Under favorable conditions, this can be 20 years,
particularly in the lower reactor layers.
However, when the catalyst finally has to be replaced,
there arises the question of how to dispose of the
spent catalyst in a manner appropriate to the prevailing
environmental conditions. Since vanadium pentoxide is
toxic and the catalyst has possibly been additionally
contaminated during ongoing operation, this increasingly
presents a problem to many plant operators.
Landfill, which until a few years ago was still
customary even in a few Western European countries, in
favorable cases after preceding immobilization of soluble
constituents, is no longer as possible.
Most environmental authorities require proof of
complete recycling of the catalyst. Technically, this
problem has now been solved, and reprocessing is
practised in many plants. However, the costs of this
process are quite considerable: between US 300 and
500 dollars per metric ton, including transport to the
0.5 1 reprocessor, have to be taken into account.
References
1. B. Suresh, K. Yagi, Chemical Economics Handbook, Report
Sulfuric Acid, SRI International, Meulo Park, 2003.
2. N. Edmonson, Sulphur 1994, (230), 16–20.
3. P. Phillips, Bristol, British Patent 6096, 1831.
4. C. Winkler, Dinglers Polyt. J. 1875, 218, 128.
5. R. Knietsch, Ber. Deutsch. Chem. Gesell. 1901, (34), 4069.
6. German Patent 291 792, 1913.
7. B. Waeser, Die Schwefelsäurefabrikation, Vieweg, Braun-
schweig, 1961.
8. H. J. Becker W. Gösele, N. Neth, J. Adlkofer, Chem Ing.-Tech.
1979, 51, 789.
9. A. Urbanek, M. Trela, Catal. Rev.-Sci. Eng. 1980, 21, 73.
10. W. Heck Praxis der Naturwissenschaften – Chemie 1990, 1/39,
2.
11. U. Sander, U. Rothe, R. Kola, Ullmann’s Encyklopädie der
Techn. Chemie 1982, 21, 117.
12. M. Bodenstein, W. Phol, Z. Elektrochem. Angew. Phys. Chem.
1905, 11, 373.
13. J. K. Dixon, J. E. Longfield, Catalysis P. H. Emmett (Ed.),
Reinhold, New York, 1960, Vol. 3, p. 322.
14. Inorganic Sulphur Chemistry, G. Nickless (Ed.), Elsevier,
Amsterdam, 1968, p. 543.
15. N. Neth G. Kautz, H.-J. Huster, U. Wagner, Chem. Ing.-Tech.
1979, 51, 825.
16. C. N. Kenney, Catalysis 1980, 3, 125.
17. P. Mars, J. G. H. Maessen, Proceedings 3rd International
Congress on Catalysis, Amsterdam, 1964, 266.
18. G. K. Boreskov, G. M. Polyakowa, A. A. Ivanov, V. M.
Mastikhin, Kinet. Katal. (USSR), 1973, 210, 626.
19. J. Villadsen, H. Livbjerg Catal. Rev.-Sci. Eng. 1978, 17, 203.
20. P. Mars, J. G. H. Maessen. J. Catal. 1968, 10, 1.
21. M. Appl, N. Neth, Proceedings British Sulphur Corp. 3rd
International Conference on Fertilizers, London, 1979, Paper
XX.
22. Y. Kera, K. Kuwata, Bull Chem. Soc. J. 1977, 50, 2831.
23. F. P. B. Holroyd, C. N. Kenney, Chem. Eng. Sci. 1971, 26, 1971.
24. P. R. Rony, Chem. Eng. Sci. 1968, 23, 1021.

25. H. Livbjerg, B. Sorensen, J. Villadsen, Adv. Chem. Ser. 1974,
133, 242.
26. N. Neth, G. Kautz, H.-J. Huster, U. Wagner Germ. Chem. Eng.
1980, 3, 44.
27. V. M. Mastikhin, O. B. Lapina, V. N. Krasilnikov, A. A. Irakin,
React. Kinet. Catal. Lett. 1984, 24, 119.
28. V. M. Mastikhin, O. B. Lapina, L. G. Simonova, React. Kinet.
Catal. Lett. 1984, 24, 127.
29. V. M. Mastikhin, O. B. Lapina, L. G. Simonova, React. Kinet.
Catal. Lett. 1984, 26, 431.
30. V. M. Mastikhin, O. B. Lapina, B. S. Balzhinimaev, L.
G. Simonova, L. M. Karnatovskaya, A. A. Ivanov, J. Catal. 1987,
103, 160.
31. B. S. Balzhinimaev, A. A. Ivanov, O. B. Lapina, V. M.
Mastikhin, K. I. Zamaraev, Faraday Discuss. Chem. Soc. 1989,
87, 133.
32. Sulphur 1988, 197, 26.
33. Sulphur 1984, 175, 24.
34. W. Pfannmüller, Die Technik des Wirbelschichtröstverfah-
rens, Monograph 21, DECHEMA, 1952.
35. A. Johannsen, W. Danz, Chem. Ing.-Tech. 1957, 29, 563.
36. J. Adlkofer, E. Dieckmann, E. Winkler, Sulphur 1993, 229, 50.
37. Sulphur 1993, 225, 29.
38. B. Andersson, P. Hanniala, S. Härkki, CIM Bull. 1982,
75(845), 172.
39. Fischer, Metall 1982, 36, 296.
40. U. Sander, G. Daradimos, Chem. Eng. Process 1978, 74, 57.
41. W. J. Müller, Angew. Chem. 1926, 39, 169.
42. Sulphur 1993, 224, 39.
43. U. Sander, U. Rothe, R. Gerken, Winnacker Küchler, Chemische
Technologie 4th edn., Carl Hauser Verlag, Munich, 1982, Vol.
2, pp. 26–27.
44. Sulphur 1990, 211, 23.
45. German Patent 1 136 998, 1960, (Farbenfabriken Bayer AG).
46. P. Askenasy, O. Merkel, German Patent 640 626, 1932.
47. W. Becker, Sulphur 1982, 1958, 30.
48. M. Tacke et al., DE-A-4217317, 1992.
12.6
..
M uller–Rochow Synthesis: The Direct Process
to Methylchlorosilanes
Wilfried Kalchauer∗ and Bernd Pachaly
12.6.1
Introduction
The ‘‘Direct Synthesis’’, also called the ‘‘Direct Pro-
cess’’ by Müller and Rochow, is the copper-catalyzed
reaction of silicon with organic chlorides by which
organochlorosilanes are formed. It is the only solid-
catalyzed gas–solid reaction applied in the chemical
industry. Of commercial interest is only the reaction
of silicon with chloromethane as the basic process to
produce methylchlorosilanes; of minor importance is
∗ Corresponding author.
12.6.2 Formation of Methylchlorosilanes 2635
the reaction with chlorobenzene to phenylchlorosilanes.
Methylchlorosilanes are the monomeric intermediates
used to prepare the remarkable number of silicone prod-
ucts based on siloxanes (see Section 12.6.3). The reaction
of silicon with organic chlorides can be summarized by
the simple equation:
Si + 2RCl −−−→ Rx SiCl4−x (1)
where x = 1 to 4, and R = CH3 , C2 H5 , or C6 H5 .
The reaction with R = CH3 was first discovered by
Rochow in the United States [1], and independently by
Müller in Germany [2] around 1940, and is therefore
also termed the Müller–Rochow Synthesis. The historical
background is well described by Liebhafsky [3]. For the
interested reader, the classical basis of the reaction is
available in Voorhoeve’s book, Organosilanes: Precursors to
Silicones [4], the importance of silicones is described in
Noll’s book Chemistry and Technology of Silicones [5], and
a summary covering catalyzed direct reactions of silicon
was edited by Lewis and Rethwish [6].
During the more than 60 years since its discovery, the
Müller–Rochow synthesis has become utilized worldwide
in the rapidly growing area of silicones. Silicone
products – mainly fluids, elastomers, and resins – are
used in many different applications on the basis of their
unique properties.
12.6.2
Formation of Methylchlorosilanes
The reaction of silicon with chloromethane to form
dimethyldichlorosilane does not necessarily need a
catalyst. For instance, it was reported as early as 1966
that pyrophoric silicon reacts with chloromethane at
473 K in the absence of any catalyst under generation
of methylchlorosilanes [7]. In addition, Maier studied the
reaction mechanism of dimethyldichlorosilane formation
in the system of silicon atoms and methyl halides at
10 K in an argon matrix, also without any catalyst [8, 9].
However, for a suitable reaction rate a technical grade
silicon and a catalyst system is needed. The lowest mea-
sured onset temperature for an activated technical grade
silicon–copper system is 376 K [10], and on an industrial
scale the reaction is usually carried out at temperatures
between 540 and 590 K. This leads to a complex mixture
of different monomeric methylchlorosilanes, plus minor
amounts of hydrogen, hydrocarbons, oligomeric silanes,
siloxanes, and carbosilanes. The product mixture of this
reaction is referred to as ‘‘crude silane’’. The reaction is
exothermic, with approximately 2300 kJ kg−1 crude silane
being released. A first-order dependence of reaction rate
References see page 2644