Corrosion sulfidation

Compared to the corrosion aggressivity of chloride ions, sulfate ions are generally considered to be less aggressive. However, they can be converted to highly corrosive sulfide ions by 2maerobic sulfate reducing bacteria (SRB). 

Transformations refer, for example, to microbial actions that can change relatively innocuous chemicals such as sulfates into very corrosive sulfide species that may accelerate hydrogen entry and increase corrosion rates. 

Sulfate ions are generally considered to be more benign in their direct corrosive action toward metallic materials than chlorides. However, concrete may be attacked as a result of high sulfate levels. The presence of sulfates also poses a major risk for metallic materials since these ions are nutrients to SRBs that convert these benign ions into highly corrosive sulfides. 

During oxidation of reduced sulfur compounds, more corrosive sulfides are produced under anoxic conditions, causing cathodic reactions. The corrosion rate increases as the reduced and oxidized FeS concentrations increase (Lee et al. 1993a, b). Cathodic depolarization processes also can yield free O2 which reacts with polarized hydrogen on metal surfaces. 

HjS in presence of water is known to cause sour corrosion. This name covers different mechanisms uniform corrosion, sulfide stress cracking (SSC) and hydrogen induced cracking (HIC). 

Finally, there are some limits regarding LPG fuels butadiene content (0.5 wt. % maximum, ISO 7941), the absence of hydrogen sulfide (ISO 8819) and copper strip corrosion (class 1, ISO 6251) which are not usually problems for the refiner. 

Corrosion protection is indispensable, especially concerning certain vulnerable parts of the aircraft such as the combustion chamber and turbine. The potential hazards are linked to the presence of sulfur in various forms mercaptans, hydrogen sulfide, free sulfur, and sulfides. 

In the 1950 s, crude oils were either corrosive (sour), or non-corrosive (sweet). Crudes containing more than 6 ppm of dissolved H2S were classed as sour because, beyond this limit, corrosion was observed on the walls of storage tanks by formation of scales of pyrophoric iron sulfides. 

Hydrogen chloride released dissolves in water during condensation in the crude oil distillation column overhead or in the condenser, which cause corrosion of materials at these locations. The action of hydrochloric acid is favored and accelerated by the presence of hydrogen sulfide which results in the decomposition of sulfur-containing hydrocarbons this forces the refiner to inject a basic material like ammonia at the point where water condenses in the atmospheric distillation column. 

Zinc is also used extensively to galvanize other metals such as iron to prevent corrosion. Zinc oxide is a unique and very useful material for modern civilization. It is widely used in the manufacture of paints, rubber products, cosmetics, pharmaceuticals, floor coverings, plastics, printing inks, soap, storage batteries, textiles, electrical equipment, and other products. Lithopone, a mixture of zinc sulfide and barium sulfate, is an important pigment. 

Sweetening. Another significant purification appHcation area for adsorption is sweetening. Hydrogen sulfide, mercaptans, organic sulfides and disulfides, and COS need to be removed to prevent corrosion and catalyst poisoning. They ate to be found in H2, natural gas, deethanizer overhead, and biogas. Often adsorption is attractive because it dries the stream as it sweetens. 

Recovery of Ammonia. The filter Hquor contains unreacted sodium chloride and substantially all the ammonia with which the brine was originally saturated. The ammonia may be fixed or free. Fixed ammonia (ammonium chloride [12125-02-97]) corresponds stoichiometrically to the precipitated sodium bicarbonate. Free ammonia includes salts such as ammonium hydroxide, bicarbonate, and carbonate, and the several possible carbon—ammonia compounds that decompose at moderate temperatures. A sulfide solution may be added to the filter Hquor for corrosion protection. The sulfide is distilled for eventual absorption by the brine in the absorber. As the filter Hquor enters the distiller, it is preheated by indirect contact with departing gases. The warmed Hquor enters the main coke, tile, or bubble cap-fiUed sections of the distiller where heat decomposes the free ammonium compounds and steam strips the ammonia and carbon dioxide from the solution. 

Another ak pollutant that can have very serious effects is hydrogen sulfide, which is largely responsible for the tarnishing of silver, but also has played a destmctive role in the discoloration of the natural patinas on ancient bronzes through the formation of copper sulfide. Moreover, a special vulnerabihty is created when two metals are in contact. The electromotive force can result in an accelerated corrosion, eg, in bronzes having kon mounting pins. 

Lead shows excellent resistance to phosphoric and sulfuric acid in almost all concentrations and at elevated temperatures, as well as to sulfide, sulfite, and sulfate solutions. The corrosion film is insoluble lead sulfate which rapidly reforms if it is damaged. Lead is also resistant to chlorides, fluorides, and bromates at low concentrations and low temperatures. However, because lead is soluble in nitric and acetic acids, it is not resistant to these acids. 

Organic compounds normally cause Htde or no corrosion of magnesium. Tanks or other containers of magnesium alloys are used for phenol [108-95-2] methyl bromide [74-96 ] and phenylethyl alcohol [60-12-8]. Most alcohols cause no more than mild attack, but anhydrous methanol attacks magnesium vigorously with the formation of magnesium methoxide [109-88-6]. This attack is inhibited by the addition of 1% ammonium sulfide [12135-76-1] or the presence ofwater. 

Nickel sulfide, NiS, can be prepared by the fusion of nickel powder with molten sulfur or by precipitation usiag hydrogen sulfide treatment of a buffered solution of a nickel(II) salt. The behavior of nickel sulfides ia the pure state and ia mixtures with other sulfides is of iaterest ia the recovery of nickel from ores, ia the high temperature sulfide corrosion of nickel alloys, and ia the behavior of nickel-containing catalysts. 

Other Specialty Chemicals. In fuel-ceU technology, nickel oxide cathodes have been demonstrated for the conversion of synthesis gas and the generation of electricity (199) (see Fuel cells). Nickel salts have been proposed as additions to water-flood tertiary cmde-oil recovery systems (see Petroleum, ENHANCED oil recovery). The salt forms nickel sulfide, which is an oxidation catalyst for H2S, and provides corrosion protection for downweU equipment. Sulfur-containing nickel complexes have been used to limit the oxidative deterioration of solvent-refined mineral oils (200). 

Alkali Treatment. Caustic washing is the treatment of materials, usually products from petroleum refining, with solutions of caustic soda. The process consists of mixing a water solution of lye (sodium hydroxide or caustic soda) with a petroleum fraction. The treatment is carried out as soon as possible after the petroleum fraction is distilled, since contact with air forms free sulfur, which is corrosive and difficult to remove. The lye reacts either with any hydrogen sulfide present to form sodium sulfide, which is soluble in water, or with mercaptans, foUowed by oxidation, to form the less nocuous disulfides. 

Various patents (22—24) have been issued claiming the use of tetrakis(hydroxymethyl)phosphonium sulfate in, for example, water treating, pharmaceuticals (qv), and in the oil industry where this compound shows exceptional activity toward the sulfate-reducing bacteria that are a primary cause of hydrogen sulfide formation and consequent problems associated with souring and corrosion (25). 

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