The wet sulfuric acid process (WSA process) is a gas desulfurization process. After Danish company Haldor Topsoe introduced this technology in 1987, it has been recognized as a process for recovering sulfur from various process gases in the form of commercial quality sulfuric acid (H2SO4) with the simultaneous production of high-pressure steam. The WSA process can be applied in all industries where sulfur removal presents an issue.
The wet catalysis process is used for processing sulfur-containing streams, such as: [1]
The energy released by the above-mentioned reactions is used for steam production. Approximately 2–3 tons of high-pressure steam are produced per ton of acid.
Industries where WSA process plants are installed:
The acid gas coming from a Rectisol-, Selexol-, amine gas treating or similar unit installed after the gasifier contains H2S, COS and hydrocarbons in addition to CO2. These gases were previously vented to the atmosphere, but now the acid gas requires purification in order not to affect the environment with SO2 emission. The WSA process provides a high sulfur recovery and recovers heat for steam production. The heat recovery rate is high, and the cooling water consumption is low, which saves resources. [2]
Example 1:
Example 2: A sulfur plant in China will be built in connection with an ammonia plant, producing 500 kilotons/year of ammonia for fertilizer production [3]
The WSA process can also be used for the production of sulfuric acid from sulfur burning or regeneration of the spent acid from e.g., alkylation plants. Wet catalysis processes differ from other contact sulfuric acid processes in that the feed gas contains excess moisture when it comes into contact with the catalyst. The sulfur trioxide formed by catalytic oxidation of the sulfur dioxide reacts instantly with the moisture to produce sulfuric acid in the vapor phase to an extent determined by the temperature. Liquid acid is subsequently formed by condensation of the sulfuric acid vapor and not by the absorption of the sulfur trioxide in concentrated sulfuric acid, as in contact processes based on dry gases.
The concentration of the product acid depends on the H2O:SO3 ratio in the catalytically converted gases and on the condensation temperature. [4] [5]
The combustion gases are cooled to the converter inlet temperature of about 420–440 °C. Processing these wet gases in a conventional cold-gas contact process (DCDA) plant would necessitate cooling and drying of the gas to remove all moisture. Therefore, the WSA process is, in most cases, a more cost-efficient way of producing sulfuric acid.
About 80% to 85% of the world’s sulfur production is used to manufacture sulfuric acid. 50% of the world’s sulfuric acid production is used in fertilizer production, mainly to convert phosphates to water-soluble forms. according to the Fertilizer Manual published jointly by the United Nations Industrial Development Organization (UNIDO) and the International Fertilizer Development Center [6]
Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula S8. Elemental sulfur is a bright yellow, crystalline solid at room temperature.
Sulfuric acid or sulphuric acid, known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formula H2SO4. It is a colorless, odorless and viscous liquid that is miscible with water.
Sulfur dioxide or sulphur dioxide is the chemical compound with the formula SO
2. It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic activity and is produced as a by-product of copper extraction and the burning of sulfur-bearing fossil fuels.
Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO4 and related hydrates. In the form of γ-anhydrite (the anhydrous form), it is used as a desiccant. One particular hydrate is better known as plaster of Paris, and another occurs naturally as the mineral gypsum. It has many uses in industry. All forms are white solids that are poorly soluble in water. Calcium sulfate causes permanent hardness in water.
The contact process is the current method of producing sulfuric acid in the high concentrations needed for industrial processes. Platinum was originally used as the catalyst for this reaction; however, as it is susceptible to reacting with arsenic impurities in the sulfur feedstock, vanadium(V) oxide (V2O5) is now preferred.
Flue-gas desulfurization (FGD) is a set of technologies used to remove sulfur dioxide from exhaust flue gases of fossil-fuel power plants, and from the emissions of other sulfur oxide emitting processes such as waste incineration, petroleum refineries, cement and lime kilns.
The Claus process is the most significant gas desulfurizing process, recovering elemental sulfur from gaseous hydrogen sulfide. First patented in 1883 by the chemist Carl Friedrich Claus, the Claus process has become the industry standard.
Amine gas treating, also known as amine scrubbing, gas sweetening and acid gas removal, refers to a group of processes that use aqueous solutions of various alkylamines (commonly referred to simply as amines) to remove hydrogen sulfide (H2S) and carbon dioxide (CO2) from gases. It is a common unit process used in refineries, and is also used in petrochemical plants, natural gas processing plants and other industries.
Flue gas is the gas exiting to the atmosphere via a flue, which is a pipe or channel for conveying exhaust gases from a fireplace, oven, furnace, boiler or steam generator. Quite often, the flue gas refers to the combustion exhaust gas produced at power plants. Its composition depends on what is being burned, but it will usually consist of mostly nitrogen derived from the combustion of air, carbon dioxide, and water vapor as well as excess oxygen. It further contains a small percentage of a number of pollutants, such as particulate matter, carbon monoxide, nitrogen oxides, and sulfur oxides.
Scrubber systems are a diverse group of air pollution control devices that can be used to remove some particulates and/or gases from industrial exhaust streams. An early application of a carbon dioxide scrubber was in the submarine the Ictíneo I, in 1859; a role for which they continue to be used today. Traditionally, the term "scrubber" has referred to pollution control devices that use liquid to wash unwanted pollutants from a gas stream. Recently, the term has also been used to describe systems that inject a dry reagent or slurry into a dirty exhaust stream to "wash out" acid gases. Scrubbers are one of the primary devices that control gaseous emissions, especially acid gases. Scrubbers can also be used for heat recovery from hot gases by flue-gas condensation. They are also used for the high flows in solar, PV, or LED processes.
Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur, and creating products such as ultra-low-sulfur diesel, is to reduce the sulfur dioxide emissions that result from using those fuels in automotive vehicles, aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion.
An integrated gasification combined cycle (IGCC) is a technology using a high pressure gasifier to turn coal and other carbon based fuels into pressurized gas—synthesis gas (syngas). It can then remove impurities from the syngas prior to the electricity generation cycle. Some of these pollutants, such as sulfur, can be turned into re-usable byproducts through the Claus process. This results in lower emissions of sulfur dioxide, particulates, mercury, and in some cases carbon dioxide. With additional process equipment, a water-gas shift reaction can increase gasification efficiency and reduce carbon monoxide emissions by converting it to carbon dioxide. The resulting carbon dioxide from the shift reaction can be separated, compressed, and stored through sequestration. Excess heat from the primary combustion and syngas fired generation is then passed to a steam cycle, similar to a combined cycle gas turbine. This process results in improved thermodynamic efficiency compared to conventional pulverized coal combustion.
Topsoe is a Danish company founded in 1940 by Haldor Topsøe. The company has approximately 2,300 employees, of which 1,700 work in Denmark.
Desulfurization or desulphurisation is a chemical process for the removal of sulfur from a material. This involves either the removal of sulfur from a molecule or the removal of sulfur compounds from a mixture such as oil refinery streams.
Natural-gas processing is a range of industrial processes designed to purify raw natural gas by removing impurities, contaminants and higher molecular mass hydrocarbons to produce what is known as pipeline quality dry natural gas. Natural gas has to be processed in order to prepare it for final use and ensure that elimination of contaminants.
Kalundborg Eco-Industrial Park is an industrial symbiosis network located in Kalundborg, Denmark, in which companies in the region collaborate to use each other's by-products and otherwise share resources.
The SNOX process is a process which removes sulfur dioxide, nitrogen oxides and particulates from flue gases. The sulfur is recovered as concentrated sulfuric acid and the nitrogen oxides are reduced to free nitrogen. The process is based on the well-known wet sulfuric acid process (WSA), a process for recovering sulfur from various process gasses in the form of commercial quality sulfuric acid (H2SO4).
Joint-stock company "Lifosa" is Lithuanian phosphate industry company, situated in Kėdainiai, the geographical center of Lithuania. AB "Lifosa" is one of the biggest producers of fertilizers in the Eastern Europe, exporting more than 98% of its production. The products are exported to 40-45 countries annually on all continents except Australia. The company also produces heat and power. Most of the produced energy is consumed by the company, the rest of the energy is sold. During the utilization of the heat generated by the production of sulfuric acid, a total of about 100 thousand MWh of the heat energy can be supplied to the city of Kėdainiai or about 250 mln. kWh of electricity can be produced.
An alkylation unit (alky) is one of the conversion processes used in petroleum refineries. It is used to convert isobutane and low-molecular-weight alkenes (primarily a mixture of propene and butene) into alkylate, a high octane gasoline component. The process occurs in the presence of an acid such as sulfuric acid (H2SO4) or hydrofluoric acid (HF) as catalyst. Depending on the acid used, the unit is called a sulfuric acid alkylation unit (SAAU) or hydrofluoric acid alkylation unit (HFAU). In short, the alky produces a high-quality gasoline blending stock by combining two shorter hydrocarbon molecules into one longer chain gasoline-range molecule by mixing isobutane with a light olefin such as propylene or butylene from the refinery's fluid catalytic cracking unit (FCCU) in the presence of an acid catalyst.
The Liquid Nitrogen Wash is mainly used for the production of ammonia synthesis gas within fertilizer production plants. It is usually the last purification step in the ammonia production process sequence upstream of the actual ammonia production.