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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The Southern African Institute of Mining and Metallurgy Sulphur and Sulphuric Acid Conference 2009

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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The Southern African Institute of Mining and Metallurgy 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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The Southern African Institute of Mining and Metallurgy 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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The Southern African Institute of Mining and Metallurgy Sulphur and Sulphuric Acid Conference 2009

H Rosenberg
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. Unit cost WSA-DC Cons./ Annual prod. per costs, hour 7.36 t 2,355,000 1250 kWh 500,000 34 t 95 m3 4.1 m
3

DCDA Cons. / prod. per hour 7.36 t 1400 kWh 25 t 930 m3 3.3 m
3

40 /t 0.05 /kWh 8 /t 0.03 /m3 0.50 /m

3

Annual costs, 2,355,000 560,000 -1,600,000 223,200 13,200 1,551,400 8.6

-2,176,000 22,800 16,400 718,200 4

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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