The Southern African Institute of Mining and Metallurgy

Sulphur and Sulphuric Acid Conference 2009

H Rosenberg

WSA-DC NEXT GENERATION TOPSE WSA

TECHNOLOGY FOR STRONGER SO2 GASES AND VERY HIGH
CONVERSION
Helge Rosenberg
Haldor Topsoe
Up to now, Topse WSA (Wet gas Sulphuric Acid) plants have been in operation for
almost 30 years, and close to 80 plants have been sold. In spite of its unique features and
ability to treat gases without any prior drying, the WSA technology has had certain
restrictions with regards to SO2 concentration in the feed gas, and the overall conversion
of SO2 by catalytic means has been limited to approx. 99.7%.
In commercial scale sulphuric acid production on the basis of elemental sulphur and
metallurgical off-gases, there is a demand for higher SO2 conversion and treatment of
gases with a higher content of SO2. Therefore Topsoe has further developed its WSA
technology to cope with these demands.
This paper will explain more about the principles of such new development and leave the
delegate with a better understanding of the potentials of the new generation of the WSA
technology from Topsoe.
Background
During the last 15 years the Topse WSA (Wet gas Sulphuric Acid) technology has
gained a strong foothold for cleaning of gases with low to medium SO2 contents (up to 67 vol%) by production of sulphuric acid. More than 80 plants have been contracted
worldwide primarily in the following industries:
Oil refining
Coking and coal chemicals
Coal gasification
Viscose fibre production
Metallurgical industry
The plants range from very small units treating e.g. an H2S stream from a coking plant, to
very big units treating flue gases from combustion of sulphur-rich fuel in a steam and
3
power plant in an oil refinery. Process gas flows range from 2,000 to 1,200,000 Nm /h
and sulphuric acid productions from 4 to 1140 MTPD.
The WSA technology is characterised by being a wet process, i.e. the process gas is not
dried, and all the water vapour in the feed gas and the water vapour produced by
chemical reactions remain in the gas. The SO3 is not absorbed in sulphuric acid as in the
conventional dry processes, but hydrated to H2SO4 vapour that is condensed as
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H Rosenberg
concentrated sulphuric acid in an air cooled tubular condenser.
WSA process description
A typical WSA plant treating a H2S gas from an oil refinery is shown in Figure 1. The
process comprises three major steps:
a. Combustion of the H2S gas with air and subsequent cooling of the combustion products
to produce a process gas with around 6 vol% SO2 at 400C.
b. Conversion of the SO2 to SO3 in a three-bed catalytic converter with Topse VK-W
series catalyst, and cooling by steam generation after each bed. In the last cooling step,
the majority of the SO3 reacts with H2O in the gas to form H2SO4 vapour.
c. Cooling of the process gas in a condenser, whereby the acid vapour is condensed to
form 98 wt% H2SO4 which is cooled and pumped to storage. The cleaned gas passes to
the stack. The condenser is a heat exchanger with vertical glass tubes. The glass tubes
are cooled on the outside by atmospheric air.

Figure 1
Advantages and limitations of the WSA technology

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The Southern African Institute of Mining and Metallurgy

Sulphur and Sulphuric Acid Conference 2009

H Rosenberg
The WSA technology as known today has some inherent advantages and some inherent
limitations when compared to conventional sulphuric acid technologies. The most
pronounced advantages are described below:
1. Energy efficiency

The WSA process has a very high energy efficiency because not only the heat of SO2
oxidation but also the heat of reaction between gas phase SO3 and H2O (to form H2SO4
vapour), the heat of condensation of H2SO4 vapour and the cooling duty of the process
gas to approx. 100C are made useful. These energi es are recovered partly in the form
of high pressure steam and partly in the form of hot air that can be used e.g. as
combustion air. Only the cooling duty of the produced sulphuric acid is lost with
cooling water.
2. No by-products
Since the process gas does not have to be dried in the WSA process, there is no loss of
sulphuric acid and no generation of sour waste water.
The limitations of the WSA technology are:
A. Limited SO2 content in feed
Because of considerations concerning construction materials in the WSA condenser,
is not possible to handle gases with sulphuric acid dew points higher than around
260C. This corresponds to a content of SO2 inlet to the SO2 converter of some 6 - 7
vol%. This limitation of course can be overcome by dilution of the gas with
atmospheric air, but this will increase the process gas volume and thereby the
dimensions of the plant.
B. Limited conversion efficiency
Being a single-contact process, the SO2/SO3 equilibrium curve limits the conversion to
typically 99.4 - 99.7%. This limitation can be overcome by scrubbing the tail gas with
caustic or hydrogen peroxide, but this means additional investment and operating
costs.
Introduction of WSA-DC
In recent years the market has demanded the advantages of the WSA technology also in
the fields where the limitations of the technology has hitherto made its use less obvious.
That is why Topse now introduces the WSA-DC technology. DC means Double
Condensation. The WSA-DC technology combines the advantages of the WSA
technology, primarily the high energy efficiency, with the high conversion efficiency of
the double-contact principle. This is illustrated in Figure 2. At the same time a modest
change in the design of the intermediate WSA condenser makes it possible to accept feed
gases with SO2 concentrations of 13 vol% or higher.
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The Southern African Institute of Mining and Metallurgy

Sulphur and Sulphuric Acid Conference 2009

H Rosenberg
The WSA-DC technology is not the most obvious choice for applications where the water
vapour content of the gas is not controllable. In case of a H2S gas with a high content of
water vapour, hydrogen and/or hydrocarbons, it is not possible to avoid a high H2O/SO2
ratio, and that would result in production of acid of lower concentration in a WSA-DC
plant. On the other hand, most gases are of such a nature that it is possible to adjust the
H2O/SO2 ratio to around 1.05 - 1.10. This is also the case with sulphur-based plants,
where H2O has to be added in any case.
The WSA-DC technology is not intended to replace the WSA technology, but to
supplement it. In many cases where the initial SOX content is low, the traditional WSA
process may be better suited than WSA-DC, particularly when the H2O/SO2 ratio is too
high relative to the desired acid concentration.
Figure 2

Advantages of WSA-DC
The WSA-DC technology is characterised by the following advantages:
High energy efficiency (even higher than that of todays WSA technology)
In the WSA-DC technology, like in the WSA technology, the heat of SO2 oxidation, the
heat of SO3 hydration and the heat of acid condensation are utilised. In WSA-DC the
amount of cleaned gas will be smaller because the feed gas does not have to be diluted
with air. This gives lower heat loss. Further, in the WSA-DC process most of the acid is
produced at 150C compared to 260C in the WSA process, so even less heat is lost in
cooling the product acid.

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The Southern African Institute of Mining and Metallurgy

Sulphur and Sulphuric Acid Conference 2009

H Rosenberg
High inlet SO2 concentration
Since the flow pattern in the 1st WSA condenser of the WSA-DC plant is arranged in
such a way that the tube plate in the inlet (upper) end of the condenser can be kept free of
liquid sulphuric acid, the limitation of the gas dew point to 260C has disappeared.
Therefore gases with much higher SO2 content can be accepted than in a WSA plant.
High conversion of SO2
Because the WSA-DC process is a double contact process, higher conversion can be
reached in the two conversion stages than in the one stage of a WSA plant.
High acid concentration
Since the H2O/SO2 is controlled, very strong acid can be produced. The WSA-DC
technology has potential for production of oleum.
Low cooling water consumption
Since almost all process heat is recovered for steam production, there is only very little
heat to be removed by cooling water, namely the enthalpy of cooling the product acid
from 150C to 40C. Even this heat can in some cas es be utilised.
WSA-DC process description
A typical sulphur-based WSA-DC plant is illustrated in Figure 3. The process plant
consists of four main steps:
Sulphur burner with boiler
Catalytic SO2 converter in 3+1 configuration
Intermediate WSA condenser
Final WSA condenser

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Sulphur and Sulphuric Acid Conference 2009

H Rosenberg

Figure 3
The sulphur burner uses preheated, humidified air for the combustion and gives a gas
with approx. 11 vol% SO2. The SO2 gas is cooled in the high pressure steam boiler to
around 400C which is the optimal temperature for the SO2 to SO3 conversion catalyst of
the Topse VK-W series. The VK-W catalysts are specially developed for use in humid
process gases. The top layer of catalyst in the first bed consists of 25 mm daisy shaped
particles which provide good capacity for accumulation of dust without creating
excessive pressure drop. The remaining catalyst consists of either 9 mm or 12 mm
daisies. Due to the exothermal reaction, the outlet temperature from the first bed is
around 600C. The gas is cooled by superheating of high pressure steam and the gas
flows to the second bed. After the second bed the gas is cooled again by superheating of
high pressure steam and the conversion is continued in the third bed. At the outlet of the
third bed the conversion has reached 95%. The gas is then cooled to around 310-320C
by production of high pressure steam, whe reby part of the SO3 reacts with H2O to
form H2SO4 vapour.
The partly converted gas is passed to the intermediate WSA condenser where it enters at
the top and flows down through a number of vertical glass tubes which are cooled on the
outside by humidified atmospheric air. During the cooling, the rest of the SO3 reacts with
H2O to form H2SO4 and the H2SO4 vapour is condensed. At the bottom outlet of the glass
tubes, the gas and the produced acid have been cooled to 150C. The H2O content of the
gas is controlled carefully by injection of water in the cooling air circuit to achieve a
H2O/SO2 ratio of 1.05 - 1.10. In this way the acid product does not absorb any significant
amount of H2O and is therefore of high concentration, typically 99%. The cooling of the
intermediate condenser takes place in a circulation loop of atmospheric air. Part of the hot
air leaving the loop is used as combustion air in the sulphur burner, and part is added to
the gas after the intermediate condenser to provide additional oxygen and water vapour.
The remaining hot air is cooled by preheating of boiler feed water and further cooled by
injection of water. The injection of water serves not only for cooling of the air but also
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Sulphur and Sulphuric Acid Conference 2009

H Rosenberg
provides water vapour required for the formation of the sulphuric acid. The air taken out
of the cooling loop is compensated for by adding hot cooling air leaving the final WSA
condenser.
The gas leaving the intermediate WSA condenser passes through a filter, removing
droplets of acid. Hot, humid air is added, and the gas is preheated to approx. 380C in
two steps, first with boiler feed water and then by superheated steam, before it enters the
fourth conversion step. The catalyst in the fourth conversion step is a special Cspromoted low temperature catalyst, ensuring that a conversion after the fourth catalyst
bed of 99.95% is achievable. At the outlet of the fourth catalyst bed, the gas is cooled to
240C by preheating of boiler feed water before it passes to the final WSA condenser.
During the cooling, most of the SO3 reacts with H2O to form H2SO4 vapour.
The gas enters the final WSA condenser at the bottom and flows up through vertical glass
tubes which are cooled on the outside by atmospheric air. During the cooling, the
remaining SO3 reacts with H2O to form H2SO4, and the H2SO4 vapour is condensed to
H2SO4 liquid, which runs down the tubes counter-currently with the hot gas. The acid is
collected at the bottom of the condenser as concentrated acid, and the gas leaving the top
of the condenser can be sent directly to the stack.
The acid product from the two WSA condensers is mixed, cooled in a cooling circuit, and
pumped to storage. The concentration of the acid product is typically 99 wt%.
The heat recovery system of the WSA-DC plant is designed in such a way that the steam
is exported at approx. 80 bar g and 500C, making it p erfectly suited for power
generation.
Performance, consumption and production figures of WSA-DC
Table 1 shows typical performance figures of a WSA-DC plant based on molten sulphur
in comparison with WSA and a typical conventional dry technology (DCDA):
Sulphur-based plants
SO2 conversion, %
SO2 emission, vol ppm
SO3 emission, vol ppm
Acid concentration, wt%

WSA-DC
99.95
50
5
99

WSA
99.6
250
10
98

DCDA
99.92
80
5
99

Table 1. Typical performance figures of WSA-DC,

WSA and conventional dry sulphuric acid plants
Table 2 shows typical consumption and production figures of a WSA-DC plant based on
molten sulphur in comparison with a typical conventional dry technology (DCDA):
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H Rosenberg
Unit
cost

540 MTPD
sulphur-based
plants
Sulphur consumption
Electricity
consumption
HP steam production
Cooling water
consumption
Process water
consumption
Annual costs
(8,000 h/y)
Cost per ton H2SO4,
, approx.

40 /t
0.05 /kWh

WSA-DC
Cons./
Annual
prod. per
costs,
hour

7.36 t
2,355,000
1250 kWh
500,000

DCDA
Cons. /
prod. per
hour
7.36 t
1400 kWh

Annual
costs,

2,355,000
560,000

8 /t

34 t

-2,176,000

25 t

-1,600,000

0.03 /m3

95 m3

22,800

930 m3

223,200

16,400

3.3 m

0.50 /m

4.1 m

13,200

718,200

1,551,400

8.6

Table 2. Typical operation costs of WSA-DC and conventional dry sulphuric acid
plants
Costs not mentioned in the table, such as labour, maintenance and catalysts are largely the same
for the two types of technologies. Investment cost for the WSA-DC plant is typically slightly less
than for a corresponding DCDA plant.

Applications of WSA-DC
The WSA-DC technology offers a superior solution in cases where the SO2 concentration
in the gas is high and where the demands to SO2 conversion and energy efficiency are
high. These are predominantly metallurgical SO2 gases and sulphur burning.

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The Southern African Institute of Mining and Metallurgy

Sulphur and Sulphuric Acid Conference 2009

H Rosenberg
The Author

Helge Rosenberg, Haldor Topse A/S, Sales Manager

Helge Rosenberg holds a master degree in Mechanical Engineering and a bachelor degree
in business administration. He has been responsible for sales and marketing of Topsoes
environmental technologies for the last eight years and before joining Topsoe,
he worked for more than ten years within the power industry.

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The Southern African Institute of Mining and Metallurgy

Sulphur and Sulphuric Acid Conference 2009

H Rosenberg

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