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Hydrochloric acid regeneration or HCl regeneration is a chemical process for the reclamation of bound and unbound HCl from metal chloride solutions such as hydrochloric acid. [1]
The commercially most relevant field of application for HCl regeneration processes is the recovery of HCl from waste pickle liquors from carbon-steel pickling lines. Other applications include the production of metal oxides such as, but not limited, to Al2O3 and MgO, as well as rare-earth oxides, by pyrohydrolysis of aqueous metal chloride or rare-earth chloride solutions.
A number of different process routes are available. The most widely used is based on pyrohydrolysis and adiabatic absorption of hydrogen chloride in water, a process invented in the 1960s. However tightening environmental standards and stringent air permit policies render it increasingly difficult to establish new pyrohydrolysis-based acid regeneration plants.
The following processes for the regeneration of HCl from spent pickle liquors have been adopted by the ferrous metals processing industry:
Hydrothermal hydrolysis of hydrochloric SPL from carbon-steel pickling lines is a hydrometallurgical reaction, which takes place according to the following chemical formula:
12 FeCl2 + 3 O2 → 8 FeCl3 + 2 Fe2O3
2 FeCl3 + 3 H2O → 6 HCl + Fe2O3
Today hydrothermal hydrolysis, which operates at very low temperatures, consumes only a fraction of the energy other processes demand and produces virtually no emissions, is considered the most effective way to regenerate any given quantity of spent pickle liquor.
Known implementations of the hydrothermal HCl regeneration processes include the PORI process (1974 for J&L Steel, dismantled) and the optimized SMS Demag wet process (2008 for ThyssenKrupp Steel, under construction).
Pyrohydrolysis of hydrochloric spent pickle liquor from carbon steel pickling lines is a hydrometallurgical reaction which takes place according to the following chemical formulae:
4 FeCl2 + 4 H2O + O2 = 8 HCl + 2 Fe2O3
2 FeCl3 + 3 H2O = 6 HCl + Fe2O3
The process is an inversion of the chemical descaling (pickling) process.
The metal chloride solution (in the most common case waste pickle liquor from a carbon steel pickling line) is fed to the venturi evaporator (III), where direct mass and heat exchange with the hot roast gas from the roaster (reactor/cyclone) takes place. The separator (IV) separates the gas and liquid phase of the venturi evaporator product. The liquid phase is re-circulated back to the venturi evaporator to increase mass and heat exchange performance.
Preconcentrated waste acid from the preconcentrator (III / IV) is injected into the reactor (I) by means of one or more spray booms (VIII) bearing one or more injection nozzles each. Injection takes place at reactor top at a pressure between 4 and 10 bar. The reactor is directly fired by tangentially mounted burners that create a hot swirl. Temperatures inside the reactor vary between 700 °C (burner level) and 370 °C (roast gas exit duct). In the reactor the conversion of droplets of preconcentrated waste acid into iron oxide powder and hydrogen chloride gas takes place. Hydrogen Chloride leaves the reactor through the top, while iron oxide powder is removed from the reactor bottom by means of mechanical extraction devices. A cyclone (II) in the roast gas duct ensures separation and feed back of larger oxide particles carried by the roast gas.
In the absorption column (V) the hydrogen chloride compound of the saturated roast gas leaving the preconcentrator is adiabatically absorbed in water (which in many cases is acid rinse water from a carbon steel pickling line). Regenerated acid (typical strength: 18% wt/wt) is collected at absorption column bottom.
The roast gas is conveyed through the system by means of an exhaust gas fan (VI). Fans in plants provide pressure increases of approx. 200 mbar and are feedback-controlled to maintain a relative pressure of -3 mbar between reactor and atmosphere to avoid any overpressure-related leakage of acid gas. To rinse the impeller and cool the gas as well as to remove remaining traces of HCl from the roast gas, the exhaust gas fan is commonly supplied with quenching water, which is separated from the exhaust gas stream by means of a mist eliminator (VII) at the pressure side of the fan. In a final scrubber, commonly consisting of a combination of wet scrubbers such as venturi scrubbers (IX) and scrubber columns (X), remaining traces of HCl and dust are removed. In some plant, absorption chemicals such as NaOH and Na2S2O3 are used to bind HCl and Cl2 (which is created under certain circumstances in several, but not all spray roasting reactors).
Pyrohydrolysis based acid regeneration processes produce a considerable amount of stack emissions containing HCl, particles and chlorine, which has led to numerous violations of the U.S. clean air act in the past. [2]
Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine. On several scales other than the revised Pauling scale, nitrogen's electronegativity is also listed as greater than chlorine's, such as on the Allen, Allred-Rochow, Martynov-Batsanov, Mulliken-Jaffe, Nagle, and Noorizadeh-Shakerzadeh electronegativity scales.
Aqua regia is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but it turns yellow, orange or red within seconds due to the formation of nitrosyl chloride and nitrogen dioxide. It was named by alchemists because it can dissolve the noble metals gold and platinum, though not all metals.
Silane is an inorganic compound with chemical formula, SiH4. It is a colourless, pyrophoric, toxic gas with a sharp, repulsive smell, somewhat similar to that of acetic acid. Silane is of practical interest as a precursor to elemental silicon. Silane with alkyl groups are effective water repellents for mineral surfaces such as concrete and masonry. Silanes with both organic and inorganic attachments are used as coupling agents.
The compound hydrogen chloride has the chemical formula HCl and as such is a hydrogen halide. At room temperature, it is a colourless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hydrogen chloride gas and hydrochloric acid are important in technology and industry. Hydrochloric acid, the aqueous solution of hydrogen chloride, is also commonly given the formula HCl.
Iron(III) chloride is the inorganic compound with the formula FeCl3. Also called ferric chloride, it is a common compound of iron in the +3 oxidation state. The anhydrous compound is a crystalline solid with a melting point of 307.6 °C. The color depends on the viewing angle: by reflected light the crystals appear dark green, but by transmitted light they appear purple-red.
The Weldon process is a process developed in 1866 by Walter Weldon for recovering manganese dioxide for re-use in chlorine manufacture. Commercial operations started at the Gamble works in St. Helens in 1869. The process is described in considerable detail in the book, The Alkali Industry, by J.R. Partington,D.Sc.
The Deacon process, invented by Henry Deacon, is a process used during the manufacture of alkalis by the Leblanc process. Hydrogen chloride gas was converted to chlorine gas, which was then used to manufacture a commercially valuable bleaching powder, and at the same time the emission of waste hydrochloric acid was curtailed. To some extent this technically sophisticated process superseded the earlier manganese dioxide process.
Praseodymium(III) chloride is the inorganic compound with the formula PrCl3. Like other lanthanide trichlorides, it exists both in the anhydrous and hydrated forms. It is a blue-green solid that rapidly absorbs water on exposure to moist air to form a light green heptahydrate.
Sodium chlorate is an inorganic compound with the chemical formula NaClO3. It is a white crystalline powder that is readily soluble in water. It is hygroscopic. It decomposes above 300 °C to release oxygen and leaves sodium chloride. Several hundred million tons are produced annually, mainly for applications in bleaching pulp to produce high brightness paper.
Copper(II) chloride is the chemical compound with the chemical formula CuCl2. The anhydrous form is yellowish brown but slowly absorbs moisture to form a blue-green dihydrate.
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.
Iron(II) chloride, also known as ferrous chloride, is the chemical compound of formula FeCl2. It is a paramagnetic solid with a high melting point. The compound is white, but typical samples are often off-white. FeCl2 crystallizes from water as the greenish tetrahydrate, which is the form that is most commonly encountered in commerce and the laboratory. There is also a dihydrate. The compound is highly soluble in water, giving pale green solutions.
Tin(II) chloride, also known as stannous chloride, is a white crystalline solid with the formula SnCl2. It forms a stable dihydrate, but aqueous solutions tend to undergo hydrolysis, particularly if hot. SnCl2 is widely used as a reducing agent (in acid solution), and in electrolytic baths for tin-plating. Tin(II) chloride should not be confused with the other chloride of tin; tin(IV) chloride or stannic chloride (SnCl4).
Pickling is a metal surface treatment used to remove impurities, such as stains, inorganic contaminants, and rust or scale from ferrous metals, copper, precious metals and aluminum alloys. A solution called pickle liquor, which usually contains acid, is used to remove the surface impurities. It is commonly used to descale or clean steel in various steelmaking processes.
Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.
Roasting is a process of heating a sulfide ore to a high temperature in the presence of air. It is a step in the processing of certain ores. More specifically, roasting is often a metallurgical process involving gas–solid reactions at elevated temperatures with the goal of purifying the metal component(s). Often before roasting, the ore has already been partially purified, e.g. by froth flotation. The concentrate is mixed with other materials to facilitate the process. The technology is useful in making certain ores usable but it can also be a serious source of air pollution.
Chlorine gas can be produced by extracting from natural materials, including the electrolysis of a sodium chloride solution (brine) and other ways.
Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the digestive systems of most animal species, including humans. Hydrochloric acid is an important laboratory reagent and industrial chemical.
Eco pickled surface (EPS) is a process applied to hot rolled sheet steel to remove all surface oxides and clean the steel surface. Steel which has undergone the EPS process acquires a high degree of resistance to subsequent development of surface oxide (rust), so long as it does not come into direct contact with moisture. EPS was developed by The Material Works, Ltd., which has filed several patent applications covering the process. It is primarily intended to be a replacement of the familiar acid pickling process wherein steel strip is immersed in solutions of hydrochloric and sulfuric acids to chemically remove oxides.
Iron(III) sulfide, also known as ferric sulfide or sesquisulfide (Fe
2S
3), is one of the three iron sulfides besides FeS and FeS2. It is a solid, black powder but decays at ambient temperature into a yellow-green powder.