Hydrogen sulphide corrosion

To prepare gas for evacuation it is necessary to separate the gas and liquid phases and extract or inhibit any components in the gas which are likely to cause pipeline corrosion or blockage. Components which can cause difficulties are water vapour (corrosion, hydrates), heavy hydrocarbons (2-phase flow or wax deposition in pipelines), and contaminants such as carbon dioxide (corrosion) and hydrogen sulphide (corrosion, toxicity). In the case of associated gas, if there is no gas market, gas may have to be flared or re-injected. If significant volumes of associated gas are available it may be worthwhile to extract natural gas liquids (NGLs) before flaring or reinjection. Gas may also have to be treated for gas lifting or for use as a fuel. 

Melbourne and Metropolitan Board of Works (1989), Hydrogen sulphide control manual — Septicity, corrosion and odour control in sewerage systems, Technological Standing Committee on Hydrogen Sulphide Corrosion in Sewerage Works, vols. 1 and 2. 

Parker CD, Prisk A (1953) The oxidation of inorganic compounds of sulphur by various sulphur bacteria. J Gen Microbiol 8 344-364 Parker CD, Jackson D (1965) The microbial flora of concrete surfaces. Hydrogen Sulphide Corrosion of Concrete Sewers Melbourne and Metropolitan Board of Works, Melbourne, Australia Technical Paper No. A8, Part 6, pp 1-29... 

Corrosion service Carbon dioxide (CO2) or hydrogen sulphide (H2S) in formation tluids will cause rapid corrosion of standard carbon steel and special steel may be required... 

If produced gas contains water vapour it may have to be dried (dehydrated). Water condensation in the process facilities can lead to hydrate formation and may cause corrosion (pipelines are particularly vulnerable) in the presence of carbon dioxide and hydrogen sulphide. Hydrates are formed by physical bonding between water and the lighter components in natural gas. They can plug pipes and process equipment. Charts such as the one below are available to predict when hydrate formation may become a problem. 

The most common contaminants in produced gas are carbon dioxide (COj) and hydrogen sulphide (HjS). Both can combine with free water to cause corrosion and H2S is extremely toxic even in very small amounts (less than 0.01% volume can be fatal if inhaled). Because of the equipment required, extraction is performed onshore whenever possible, and providing gas is dehydrated, most pipeline corrosion problems can be avoided. However, if third party pipelines are used it may be necessary to perform some extraction on site prior to evacuation to meet pipeline owner specifications. Extraction of CO2 and H2S is normally performed by absorption in contact towers like those used for dehydration, though other solvents are used instead of glycol. 

Ultramodern techniques are being applied to the study of corrosion thus a very recent initiative at Sandia Laboratories in America studied the corrosion of copper in air spiked with hydrogen sulphide by a form of combinatorial test, in which a protective coat of copper oxide was varied in thickness, and in parallel, the density of defects in the copper provoked by irradiation was also varied. Defects proved to be more influential than the thickness of the protective layer. This conclusion is valuable in preventing corrosion of copper conductors in advanced microcircuits. This set of experiments is typical of modern materials science, in that quite diverse themes... combinatorial methods, corrosion kinetics and irradiation damage... are simultaneously exploited. 

Hydrogen sulphide and sulphur dioxide are also usually the result of pollution sometimes they are produced by the interaction of two contaminants, but sometimes bacterial action may be contributory. Both gases may initiate or accelerate corrosion of most metals. 

In sea-water systems such attack may occur under dead barnacles or shellfish, the decomposing organic matter assisting corrosion. Pitting is most likely to occur in polluted in-shore waters, particularly when hydrogen sulphide is present. In such contaminated waters non-protective sulphide scales are formed and these tend to stimulate attack. 

Other chemicals Copper and copper alloys are unsuitable for handling hydrogen peroxide " or molten sulphur . Hydrogen sulphide accelerates corrosion of most copper-base materials. In its presence brasses high in zinc are usually found to behave better than other copper alloys. ... 

The atmospheric pollution prevailing in special industrial or laboratory locations may induce more severe corrosion, e.g. the vapours from concentrated hydrochloric or acetic acid will etch tin, and moist sulphur dioxide will produce a sulphide tarnish, as will hydrogen sulphide at temperatures above about 100°C. The halogens attack tin readily. The commonly used volatile corrosion inhibitors are without adverse action although the benefit derived from their use is doubtful. 

Abbott studied the corrosion of contacts, and proposed quality tests in dilute mixtures of hydrogen sulphide, nitrogen dioxide and chlorine in air at controlled temperature and humidity . These gave good results in a project seeking improved procedures for British and lEC standards . 

Organic materials Corrosive vapours are sometimes emitted by organic materials used either in packaging or in the manufactured article, and may be troublesome in confined spaces. Some woods, particularly unseasoned oak and sweet chestnut, produce acetic acid (see Section 18.10), and certain polymers used in paints, adhesives and plastics may liberate such corrosive vapours as formic acid and hydrogen sulphide . It may be necessary to carry out exposure trials, particularly where materials capable of liberating formaldehyde or formic acid are involved. Most corrosion problems of this kind can be prevented by using desiccants, and in many cases they are confined to imperfectly cured materials. For an excellent review see Reference 9. 

Adsorbed species may also accelerate the rate of anodic dissolution of metals, as indicated by a decrease in Tafel slope for the reaction. Thus the presence of hydrogen sulphide in acid solutions stimulates the corrosion of iron, and decreases the Tafel slope The reaction path through... 

Fe-HS )jds has been postulated to lead to easier anodic dissolution than that through (Fe-014)3 5. This effect of hydrogen sulphide is thought to be responsible for the acceleration of corrosion of iron observed with some inhibitive sulphur compounds, e.g. thioureas , at low concentrations, since hydrogen sulphide has been identified as a reduction product. However, the effects of hydrogen sulphide are complex, since in the presence of inhibitors such as amines , quaternary ammonium cations , thioureas ", ... 

Oil and Gas Production This sector is a major user of corrosion monitoring equipment, in particular for offshore fields where ramifications of corrosion and consequent maintenance are far more serious and costly compared with onshore production. Carbon steel is used for approximately 70-80 70 of production facilities. The development of a field is assessed on a defined corrosion risk which may not be correct, leading to serious corrosion. In addition, a reservoir may become more corrosive as the field is extracted owing to (a) increased water content, and (b) eventual souring of the field (hydrogen sulphide production). 

Examples include hydrochloric acid, nitric acid, and sulphuric acid. These are strong acids which are almost completely dissociated in water. Weak acids, such as hydrogen sulphide, are poorly dissociated producing low concentrations of hydrogen ions. Acids tend to be corrosive with a sharp, sour taste and turn litmus paper red they give distinctive colour changes with other indicators. Acids dissolve metals such as copper and liberate hydrogen gas. They also react with carbonates to liberate carbon dioxide ... 

Parker, C.D. (1945a), The corrosion of concrete 1. The isolation of a species of bacterium associated with the corrosion of concrete exposed to atmospheres containing hydrogen sulphides, Aust. J. Expt. Biol. Med. Sci, 23, 81-90. 

At high temperatures the metal will react slowly with certain gases. With carbon monoxide it produces a surface film of carbide, with nitrogen it produces a nitride film, and with hydrogen sulphide it reacts to form molybdenum disulphide. All of these films presumably interfere with the flow of gas to the metal surface, and in each case only a thin film of the product arises. Molybdenum is also very resistant to corrosive attack by mineral acids except for those such as nitric acid or chromic... 

The formation of iron sulphide, or any other metal sulphide, and subsequent hydrolysis to release hydrogen sulphide, represents a corrosion process. The various oxidation processes discussed ail involve the production of hydrogen sulphide, sulphur dioxide or sulphuric acid. In the absence of effective protection, any one of these is a potential corrodent, especially in association with any wear which takes place. 

---