Journal of the Air Pollution Control Association

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The Double Contact Process For Sulfuric Acid

Production

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:
10.1080/00022470.1968.10469134

To link to this article: https://doi.org/10.1080/00022470.1968.10469134

Published online: 16 Mar 2012.

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 W. Moeller
K. Winkler The Double Contact Process
Farbenfabriken
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 -
0,4

0,3
1

<q
^98%
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
L
12 Vol. % SO,
the neighborhood of sulfuric acid plants, sufficient oxygen for the ensuing oxida- SO2 concentration entering converter

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

324 Journal of the Air Pollution Control Association


.450°C
•400"
4 6 8 10 12 Vol.'/oSO,
SO, concentration entering converter
Figure 3. Concentration of emitted SO2 as a
function of SO2 before the converter.
Parameter: Degree of reaction
O US contact plants / . . _ .,
. . . . f raw material: Sulfur
U double contact plants
It is better for low SO2 contents of the
starting gas than for high SO2 contents.
With the catalysts normally used today
reasonable reaction speeds can be
reached at temperatures in the range of
440°C. The SO2 content of the starting
gas cannot be kept as low as desired
since this would call for an increase of
equipment dimensions in inverse pro-
portions.
It may be seen from Figure 1 that the
theoretically possible degree of reaction
is approximately 98%. The degrees of
reaction reached in commercial opera-
tions are slightly below those which
would be theoretically possible. In
Figure 2 the percentages emitted by
ten U. S. plants1 are plotted versus the
SO2 concentration of the starting gas.
From 1.5 to 4.4% of the SO2 are emitted;
in other words, the degrees of reaction
are between 95.6 and 98.5%. Figure 3
shows that the concentrations emitted
by these plants are between 0.13 and
0.54% by volume SO2.
In the Bayer double contact process
the reaction is interrupted after approx-
imately 90% SO2 has been reacted to
form SO3 which is removed in a first
absorption stage, the so-called inter-
mediate absorption, and the remaining
SO2/air mixture is once more reacted at
the contacts. By removing the SO3
during the intermediate absorption, the
May 1968 Volume 18, No. 5
AIR FOR SULFUR BURNING
SO, GAS
TO STACK
ABSORBING
TOWER
1 AIR FROM
DRYING TOWER
Figure 4: Flow diagram for sulfur-burning double-contact plant with intermediate
SO3 absorption
state of the remaining gas mixture de-
parts from the equilibrium and permits
further reaction, which means higher
degrees of reaction. The theoretical
proportions are shown in Figure 1.
Theoretically, the double contact pro-
cess allows the degree of reaction to be
increased from approximately 98% for
the contact process to approximately
99.8%, and thus the amount of SO2
emitted is reduced by a factor of ten.
The higher yield of SO2 (and thus of
sulfuric acid) in the Bayer double con-
tact process, in conjunction with the
lower percentage of emitted SO2, is of
course achieved at a cost. The process
calls for an additional heat exchanger
and an additional absorption tower.
Figure 4 shows a schematic diagram of
the process. The two pieces of appa-
ratus on the right of the flow diagram
must be provided as additional fixtures
for the double contact process. A cost
calculation has shown that, in the Fed-
eral Republic of Germany, this extra
investment is made good by the higher
sulfuric acid yield and savings in plant
equipment since the double contact
process permits higher SO2 concentra-
tions in the starting gas resulting in a
higher SO2 throughput, or smaller
equipment dimensions. Thus the
double contact plants in Europe, which
use pyrites as a starting material, today
operate with up to 10% SO2 in the start-
ing gas as compared with the formerly
normal level of 6.5 to 7%. When using
elemental sulfur, commercial-scale trials
with a starting gas mixture of 13.4%
SO2 still gave good degrees of reaction
for the Bayer double contact system;
while the conventional contact process
in such cases only allows gas concen-
trations of approximately 10% SO2.
These high starting concentrations of
SO2 of the double contact process have
been made possible by the intermediate
absorption stage. Assuming a gas to
have 10% SO2 and 11% O2, when using
elemental sulfur in the normal contact
HE= HEAT EXCHANGER
CONVERTER
TOWER FOR
INTERMEDIATE
ABSORPTION
process, it would correspond to O2/SO2
proportions of 1.1. No satisfactory
degree of reaction can be achieved in this
way. While, at first, the same O2/SO2
proportions are, of course, encountered
with the same gas in the double contact
process; the O2/SO2 proportions have,
however, improved to 6.5 after the
intermediate absorption, which is gen-
erally carried out after 90% reaction.
These improved O2/SO2 proportions
after intermediate absorption enable
the operator to use a starting gas mix-
ture of high SO2 content.
A phenomenon discovered after the
first trial run by the double contact
principle was of great importance:
On completion of intermedite absorption
the temperature at which the catalyst
begins to respond was about 50°C
lower than normal. This greatly helps
our efforts at controlling air pollution
since the favorable equilibrium state
cuts down the quantity of emitted SO2
by 50% or more at a temperature which
is 50°C lower.
The first double contact plant has
been commissioned in March 1964.
Eighteen double contact plants were
on stream in May 1967 and another
eight are scheduled to go into produc-
tion by the end of 1967. Further
plants have also been ordered. The
process has come up to expectations and
in particular, the problem of SO2 being
emitted during sulfuric acid production
may be considered solved. The SO2
concentration emitted by the double
contact plant, based on elemental sul-
fur, which is located in the district
supervised by us does not exceed more
than 240 ppm under 20% overload and
as little as 100 to 120 ppm SO2 under
normal load.
References
1. "Atmospheric Emissions from Sulfuric
Acid Manufacturing Processes," U. S.
Dept. of Health.. Ed. and Welfare,
Public Health Service, Div. of Air
Poll., Cincinnati, Ohio (1965).
325