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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. [1]
This process was patented in 1831 by British vinegar merchant Peregrine Phillips. [2] [3] [4] In addition to being a far more economical process for producing concentrated sulfuric acid than the previous lead chamber process, the contact process also produces sulfur trioxide and oleum.
In 1901 Eugen de Haën patented the basic process involving combining sulfur dioxide and oxygen in the presence of vanadium oxides, producing sulfur trioxide which was easily absorbed into water, producing sulfuric acid. [5] This process was improved remarkably by shrinking the particle size of the catalyst (e.g. ≤ 5000 microns), a process discovered by two chemists of BASF in 1914. [6] [7] [8]
The process can be divided into four stages:
Purification of the air and sulfur dioxide (SO2) is necessary to avoid catalyst poisoning (i.e. removing catalytic activities). The gas is then washed with water and dried with sulfuric acid.
To conserve energy, the mixture is heated by exhaust gases from the catalytic converter by heat exchangers.
Sulfur dioxide and dioxygen then react as follows:
According to the Le Chatelier's principle, a lower temperature should be used to shift the chemical equilibrium towards the right, hence increasing the percentage yield. However too low of a temperature will lower the formation rate to an uneconomical level. Hence to increase the reaction rate, high temperatures (450 °C), medium pressures (1-2 atm), and vanadium(V) oxide (V2O5) are used to ensure an adequate (>95%) conversion. The catalyst only serves to increase the rate of reaction as it does not change the position of the thermodynamic equilibrium. The mechanism for the action of the catalyst comprises two steps:
Hot sulfur trioxide passes through the heat exchanger and is dissolved in concentrated H2SO4 in the absorption tower to form oleum
Note that directly dissolving SO3 in water is impractical due to the highly exothermic nature of the reaction. Acidic vapor or mists are formed instead of a liquid.
Oleum is reacted with water to form concentrated H2SO4.
This includes the dusting tower, cooling pipes, scrubbers, drying tower, arsenic purifier and testing box. Sulfur dioxide has many impurities such as vapours, dust particles and arsenous oxide. Therefore, it must be purified to avoid catalyst poisoning (i.e.: destroying catalytic activity and loss of efficiency). In this process, the gas is washed with water, and dried by sulfuric acid. In the dusting tower, the sulfur dioxide is exposed to a steam which removes the dust particles. After the gas is cooled, the sulfur dioxide enters the washing tower where it is sprayed by water to remove any soluble impurities. In the drying tower, sulfuric acid is sprayed on the gas to remove the moisture from it. Finally, the arsenic oxide is removed when the gas is exposed to ferric hydroxide.
The next step to the contact process is double contact double absorption (DCDA). In this process the product gases (SO2) and (SO3) are passed through absorption towers twice to achieve further absorption and conversion of SO2 to SO3 and production of higher grade sulfuric acid.
SO2-rich gases enter the catalytic converter, usually a tower with multiple catalyst beds, and are converted to SO3, achieving the first stage of conversion. The exit gases from this stage contain both SO2 and SO3 which are passed through intermediate absorption towers where sulfuric acid is trickled down packed columns and SO3 reacts with water increasing the sulfuric acid concentration. Though SO2 too passes through the tower it is unreactive and comes out of the absorption tower.
This stream of gas containing SO2, after necessary cooling is passed through the catalytic converter bed column again achieving up to 99.8% conversion of SO2 to SO3 and the gases are again passed through the final absorption column thus achieving not only high conversion efficiency for SO2, but also enabling production of a higher concentration of sulfuric acid.
The industrial production of sulfuric acid involves proper control of temperatures and flow rates of the gases as both the conversion efficiency and absorption are dependent on these.
Catalysis is the increase in rate of a chemical reaction due to an added substance known as a catalyst. Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst.
An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.
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.
Oleum, or fuming sulfuric acid, is a term referring to solutions of various compositions of sulfur trioxide in sulfuric acid, or sometimes more specifically to disulfuric acid.
Sulfur trioxide (alternative spelling sulphur trioxide, also known as nisso sulfan) is the chemical compound with the formula SO3. It has been described as "unquestionably the most [economically important]" sulfur oxide. It is prepared on an industrial scale as a precursor to sulfuric acid.
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.
An acidic oxide is an oxide that either produces an acidic solution upon addition to water, or acts as an acceptor of hydroxide ions effectively functioning as a Lewis acid. Acidic oxides will typically have a low pKa and may be inorganic or organic. A commonly encountered acidic oxide, carbon dioxide produces an acidic solution when dissolved.
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 lead chamber process was an industrial method used to produce sulfuric acid in large quantities. It has been largely supplanted by the contact process.
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.
Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V2O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.
Sulfamic acid, also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, sulphamic acid and sulfamidic acid, is a molecular compound with the formula H3NSO3. This colourless, water-soluble compound finds many applications. Sulfamic acid melts at 205 °C before decomposing at higher temperatures to water, sulfur trioxide, sulfur dioxide and nitrogen.
Disulfuric acid (alternative spelling disulphuric acid) or pyrosulfuric acid (alternative spelling pyrosulphuric acid), also named oleum, is a sulfur oxoacid. It is a major constituent of fuming sulfuric acid, oleum, and this is how most chemists encounter it. As confirmed by X-ray crystallography, the molecule consists of a pair of SO2(OH) groups joined by an oxide.
Selective catalytic reduction (SCR) means of converting nitrogen oxides, also referred to as NO
x with the aid of a catalyst into diatomic nitrogen, and water. A reductant, typically anhydrous ammonia, aqueous ammonia, or a urea solution, is added to a stream of flue or exhaust gas and is reacted onto a catalyst. As the reaction drives toward completion, nitrogen, and carbon dioxide, in the case of urea use, are produced.
Sulfur compounds are chemical compounds formed the element sulfur (S). Common oxidation states of sulfur range from −2 to +6. Sulfur forms stable compounds with all elements except the noble gases.
Chlorosulfuric acid (IUPAC name: sulfurochloridic acid) is the inorganic compound with the formula HSO3Cl. It is also known as chlorosulfonic acid, being the sulfonic acid of chlorine. It is a distillable, colorless liquid which is hygroscopic and a powerful lachrymator. Commercial samples usually are pale brown or straw colored.
Selective non-catalytic reduction (SNCR) is a method to lessen nitrogen oxide emissions in conventional power plants that burn biomass, waste and coal. The process involves injecting either ammonia or urea into the firebox of the boiler at a location where the flue gas is between 1,400 and 2,000 °F (760 and 1,090 °C) to react with the nitrogen oxides formed in the combustion process. The resulting product of the chemical redox reaction is molecular nitrogen (N2), carbon dioxide (CO2), and water (H2O).
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.
Catalytic oxidation are processes that rely on catalysts to introduce oxygen into organic and inorganic compounds. Many applications, including the focus of this article, involve oxidation by oxygen. Such processes are conducted on a large scale for the remediation of pollutants, production of valuable chemicals, and the production of energy.
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).