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Journal of the Air Pollution Control Association

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The Double Contact Process For Sulfuric Acid


W. Moeller & K. Winkler

To cite this article: W. Moeller & K. Winkler (1968) The Double Contact Process For
Sulfuric Acid Production, Journal of the Air Pollution Control Association, 18:5, 324-325, DOI:

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W. Moeller
K. Winkler The Double Contact Process
Boyer AG For Sulfuric Acid Production

In the usual contact plants 9 7 - 9 8 % of the SO2 is oxidized to SO3 while the remaining 2 - 3 % nonoxidized SO2
are emitted. The stack gas generally contains 0.2-0.3% by volume SO2. Through changing to the Bayer
Double Contact process, the conversion can be raised to 99.5% or higher. The sulfuric acid can be produced
at the same cost as with the single contact method, since the additional capital investment is compensated by
higher yield and throughput (this applies to Germany). Based on equilibrium considerations, the rates of
conversion obtainable with the contact and double contact processes are shown. The theoretical results
are compared with the values obtained in practical operations. The fundamentals of the process are ex-
plained and the experience so far accumulated is discussed. The first double contact plant was started up
in March 1964. By the end of 1966 as many as sixteen double contact plants were in operation and a
further ten will go into production during 1967. These plants use sulfur, pyrite, zinc sulfide, or sulfates as
raw materials.

The major part of sulfuric acid is SO, in

stack gas
In terms of quantities, sulfuric produced by the contact process - in
0,6 *-96V
acid is by far ahead of all other chemicals the U.S.A. approximately 90% and in Vol. % SO,
with world production running to 72 the Federal Republic of Germany 0,5
million tons (short tons) in 1965. This
means that approximately one million
tons SO2 are being emitted per year by
approximately 85%. Besides other sul-
fur-containing materials, it is primarily
elemental sulfur and pyrites which are
used as starting materials. An SO2 -


sulfuric acid plants and that the share 0,2 As. .....
of the total SO2 emitted to 2 per cent at O2 - N2 gas mixture is formed when ""'A\^
the most. From this it is obvious that burning the sulfur or pyrites with air. 0,1 —° —
the SO2 emitted during sulfuric acid SO2 contents of 7 to 10% by volume — 99
production is not a global problem. In are normal. The gas should still have 2 4 6 8 10
12 Vol. % SO,
the neighborhood of sulfuric acid plants, sufficient oxygen for the ensuing oxida- SO2 concentration entering converter

however, substantial SO2 levels are tion of SO2 to SO3. This oxidation is
effected catalytically on vanadium pen- Figure 2. Emitted percentage of SO2 as a
often found in the air since the emitted function of SO2 concentration before the conver-
gases seldom contain less than 2000 toxide "contacts"; it is a typical
ppm SO2, and sometimes even over equilibrium reaction :
O US contact plants \ . . , c .,
3000 ppm. Dispersion in the atmo- 2SO2 + O2 •=* 2SO3 , , r raw material; Sulfur
sphere is not very good since the waste • double contact plants)
The equilibrium depends very strongly — emission, when the gas reached equilibrium
gas temperature is approximately 60°C on temperature and it is furthermore
and this temperature being relatively influenced by an excess of oxygen:
low results in sulfuric acid waste gases
being encountered on the ground at SO3
SO2 ' The resultant SO3 is then taken up in
short distances from the smokestack concentrated sulfuric acid in absorption
much more frequently than hot waste towers while the nonoxidized SO2
gases. Although high chimneys have passes this absorption tower and is
proved successful with hot waste gases vented through the chimney.
from power stations, our experience has For the purposes of the following-
shown them to be a rather unsatis- considerations let it be assumed that the
factory approach to the problem where starting material is elemental sulfur
sulfuric acid waste gases are concerned. which is burned with air containing 21%
In light of this, research was started by oxygen. The resultant gas mixture is
our company as early as ten years ago to be passed on to the contact in un-
with the aim of materially reducing the diluted form. In Figure 1 the degree
SO2 levels in the waste gases from sul-
0,90 of reaction of SO2 to SO3 has been
furic acid production.
400 420 440 460 480 500 520 540°C plotted for this gas versus the reaction
reaction temperature temperature, assuming that equilibrium
has been reached. The SO2 concen-
Drs. Moeller and Winkler are Figure 1 . Conversion of SO2 to SO3 at equilib-
tration of the starting gas has been
associated with Farberfabriken rium as a function of temperature.
Bayer AG, 509 Leverkusen, Bayer- (SO2 from sulfur combustion)
selected as the parameter. The graphs
werk, Germany. Parameter: show that the degree of reaction in-
SC>2-concentration entering converter creases with decreasing temperature.

324 Journal of the Air Pollution Control Association








Figure 4: Flow diagram for sulfur-burning double-contact plant with intermediate

SO3 absorption

state of the remaining gas mixture de- process, it would correspond to O2/SO2
parts from the equilibrium and permits proportions of 1.1. No satisfactory
further reaction, which means higher degree of reaction can be achieved in this
degrees of reaction. The theoretical way. While, at first, the same O2/SO2
proportions are shown in Figure 1. proportions are, of course, encountered
Theoretically, the double contact pro- with the same gas in the double contact
cess allows the degree of reaction to be process; the O2/SO2 proportions have,
4 6 8 10 12 Vol.'/oSO, increased from approximately 98% for however, improved to 6.5 after the
SO, concentration entering converter the contact process to approximately intermediate absorption, which is gen-
Figure 3. Concentration of emitted SO2 as a
99.8%, and thus the amount of SO2 erally carried out after 90% reaction.
function of SO2 before the converter. emitted is reduced by a factor of ten. These improved O2/SO2 proportions
Parameter: Degree of reaction The higher yield of SO2 (and thus of after intermediate absorption enable
O US contact plants / . . _ ., sulfuric acid) in the Bayer double con- the operator to use a starting gas mix-
. . . . f raw material: Sulfur ture of high SO2 content.
U double contact plants tact process, in conjunction with the
lower percentage of emitted SO2, is of A phenomenon discovered after the
course achieved at a cost. The process first trial run by the double contact
It is better for low SO2 contents of the calls for an additional heat exchanger principle was of great importance:
starting gas than for high SO2 contents. and an additional absorption tower. On completion of intermedite absorption
With the catalysts normally used today Figure 4 shows a schematic diagram of the temperature at which the catalyst
reasonable reaction speeds can be the process. The two pieces of appa- begins to respond was about 50°C
reached at temperatures in the range of ratus on the right of the flow diagram lower than normal. This greatly helps
440°C. The SO2 content of the starting must be provided as additional fixtures our efforts at controlling air pollution
gas cannot be kept as low as desired for the double contact process. A cost since the favorable equilibrium state
since this would call for an increase of calculation has shown that, in the Fed- cuts down the quantity of emitted SO2
equipment dimensions in inverse pro- eral Republic of Germany, this extra by 50% or more at a temperature which
portions. investment is made good by the higher is 50°C lower.
It may be seen from Figure 1 that the sulfuric acid yield and savings in plant The first double contact plant has
theoretically possible degree of reaction equipment since the double contact been commissioned in March 1964.
is approximately 98%. The degrees of process permits higher SO2 concentra- Eighteen double contact plants were
reaction reached in commercial opera- tions in the starting gas resulting in a on stream in May 1967 and another
tions are slightly below those which higher SO2 throughput, or smaller eight are scheduled to go into produc-
would be theoretically possible. In equipment dimensions. Thus the tion by the end of 1967. Further
Figure 2 the percentages emitted by double contact plants in Europe, which plants have also been ordered. The
ten U. S. plants1 are plotted versus the use pyrites as a starting material, today process has come up to expectations and
SO2 concentration of the starting gas. operate with up to 10% SO2 in the start- in particular, the problem of SO2 being
From 1.5 to 4.4% of the SO2 are emitted; ing gas as compared with the formerly emitted during sulfuric acid production
in other words, the degrees of reaction normal level of 6.5 to 7%. When using may be considered solved. The SO2
are between 95.6 and 98.5%. Figure 3 elemental sulfur, commercial-scale trials concentration emitted by the double
shows that the concentrations emitted with a starting gas mixture of 13.4% contact plant, based on elemental sul-
by these plants are between 0.13 and SO2 still gave good degrees of reaction fur, which is located in the district
0.54% by volume SO2. for the Bayer double contact system; supervised by us does not exceed more
In the Bayer double contact process while the conventional contact process than 240 ppm under 20% overload and
the reaction is interrupted after approx- in such cases only allows gas concen- as little as 100 to 120 ppm SO2 under
imately 90% SO2 has been reacted to trations of approximately 10% SO2. normal load.
form SO3 which is removed in a first These high starting concentrations of
absorption stage, the so-called inter- SO2 of the double contact process have References
mediate absorption, and the remaining been made possible by the intermediate 1. "Atmospheric Emissions from Sulfuric
SO2/air mixture is once more reacted at absorption stage. Assuming a gas to Acid Manufacturing Processes," U. S.
Dept. of Health.. Ed. and Welfare,
the contacts. By removing the SO3 have 10% SO2 and 11% O2, when using Public Health Service, Div. of Air
during the intermediate absorption, the elemental sulfur in the normal contact Poll., Cincinnati, Ohio (1965).

May 1968 Volume 18, No. 5 325