Corrosion leaching

A sohd waste is considered hazardous if it is either a Hsted waste or a characteristic waste. Listed wastes include a Hst of specific processes that generate a waste and a Hst of discarded commercial chemical products. There are four hazardous waste characteristics ignitabiHty, corrosivity, reactivity, and toxicity. The last refers to the leachabiHty of a waste and the resultant toxicity in the groundwater using the analytical method referred to as toxicity characteristic leaching procedure (TCLP). A Hst of substances included under TCLP is shown in Table 1. 

Localized corrosion, which occurs when the anodic sites remain stationary, is a more serious industrial problem. Forms of localized corrosion include pitting, selective leaching (eg, dezincification), galvanic corrosion, crevice or underdeposit corrosion, intergranular corrosion, stress corrosion cracking, and microbiologicaHy influenced corrosion. Another form of corrosion, which caimot be accurately categorized as either uniform or localized, is erosion corrosion. 

The processiag costs associated with separation and corrosion are stiU significant ia the low pressure process for the process to be economical, the efficiency of recovery and recycle of the rhodium must be very high. Consequently, researchers have continued to seek new ways to faciUtate the separation and confine the corrosion. Extensive research was done with rhodium phosphine complexes bonded to soHd supports, but the resulting catalysts were not sufficiently stable, as rhodium was leached iato the product solution (27,28). A mote successful solution to the engineering problem resulted from the apphcation of a two-phase Hquid-Hquid process (29). The catalyst is synthesized with polar -SO Na groups on the phenyl rings of the triphenylphosphine. 

Polymer-supported catalysts incorporating organometaUic complexes also behave in much the same way as their soluble analogues (28). Extensive research has been done in attempts to develop supported rhodium complex catalysts for olefin hydroformylation and methanol carbonylation, but the effort has not been commercially successful. The difficulty is that the polymer-supported catalysts are not sufftciendy stable the valuable metal is continuously leached into the product stream (28). Consequendy, the soHd catalysts fail to eliminate the problems of corrosion and catalyst recovery and recycle that are characteristic of solution catalysis. 

Chromium compounds are also used ia fire-retardant formulations where their function is to prevent leaching of the fire retardant from the wood and corrosion of the equipment employed. 

The reaction mixture is filtered. The soHds containing K MnO are leached, filtered, and the filtrate composition adjusted for electrolysis. The soHds are gangue. The Cams Chemical Co. electrolyzes a solution containing 120—150 g/L KOH and 50—60 g/L K MnO. The cells are bipolar (68). The anode side is monel and the cathode mild steel. The cathode consists of small protmsions from the bipolar unit. The base of the cathode is coated with a corrosion-resistant plastic such that the ratio of active cathode area to anode area is about 1 to 140. Cells operate at 1.2—1.4 kA. Anode and cathode current densities are about 85—100 A/m and 13—15 kA/m, respectively. The small cathode areas and large anode areas are used to minimize the reduction of permanganate at the cathode (69). Potassium permanganate is continuously crystallized from cell Hquors. The caustic mother Hquors are evaporated and returned to the cell feed preparation system. 

In contrast, the selective dissolution or leaching-out by corrosion of one component of a single-phase alloy is of considerable practical importance. The most common example of this phenomenon, which is also referred to as parting , is dezincification, i.e. the selective removal of zinc from brass (see Section 1.6). Similar phenomena are observed in other binary copper-base alloys, notably Cu-Al, as well as in other alloy systems. 

The various types of localised corrosion have been enumerated in Table 1.2 in Section 1.1, and many of them are dealt with in some detail in other sections of this volume. For this reason this section will be confined to a consideration of the factors that give rise to crevice corrosion, filiform corrosion, pitting, selective leaching and erosion-corrosion and of the mechanisms of these forms of localised attack. 

Rainfall, besides wetting the metal surface, can be beneficial in leaching otherwise deleterious soluble species and this can result in marked decreases in corrosion rate . A recent survey of rainfall analyses for Europe has shown that, with the exception of the UK, the acidity and sulphate content of rainfall markedly increased in the period 1956 to 1966, pH values having fallen by 0 05 to 0-10 units per ann. The exception of the UK may be due to anti-pollution measures introduced in this period. However, even in the UK a pH of 4 is not uncommon for rainfall in industrial areas. The significance of electrolyte solution pH will be discussed in the context of corrosion mechanisms. The remaining cases of electrolyte formation are those in which it exists in equilibrium with air at a relative humidity below 100%. 

For some non-ferrous metals (copper, lead, nickel) the attack by sulphuric acid is probably direct with the formation of sulphates. Lead sulphate is barely soluble and gives good protection. Nickel and copper sulphates are deliquescent but are gradually converted (if not leached away) into insoluble basic sulphates, e.g. Cu Cu(OH)2)3SO4, and the metals are thus protected after a period of active corrosion. For zinc and cadmium the sulphur acids probably act by dissolution of the protective basic carbonate film. This reforms, consuming metal in the process, redissolves, and so on. Zinc and cadmium sulphates are formed in polluted winter conditions whereas in the purer atmospheres of the summer the corrosion products include considerable amounts of oxide and basic carbonate. ... 

Thus for non-ferrous metals, SO is consumed in the corrosion reactions whereas in the rusting of iron and steel it is believed that ferrous sulphate is hydrolysed to form oxides and that the sulphuric acid is regenerated. Sulphur dioxide thus acts as a catalyst such that one SOj" ion can catalyse the dissolution of more than 100 atoms of iron before it is removed by leaching, spalling of rust or the formation of basic sulphate. These reactions can be summarised as follows ... 

Mechanism and sulphur oxidation Apart from its intrinsic interest the economic importance of acid corrosion and more lately interest in ore leaching, has stimulated considerable work on the oxidation of sulphur, Fe and Mn. It must be stressed that the Thiobacilli are obligate aerobes, i.e. that depend on molecular oxygen as a terminal electron acceptor. Possible reactions for the oxidation of sulphur are... 

The presence of active sulphate-reducing bacteria usually results in graphitic corrosion and this has led to a useful method of diagnosing this cause of corrosion. The leaching out of iron from the graphitic residue which is responsible for the characteristic appearance of this type of corrosion leads to an enriched carbon, silicon and phosphorus content in the residue as compared with the original content of these elements in the cast iron. Sulphur is usually lost to some extent but when active sulphate-reducing bacteria are present, this loss is offset by the accumulation of ferrous sulphide in the residue with a consequent increase in the sulphur content of the residue out... 

Tarpaulins are sometimes treated with copper-containing preservatives and water leached from these has been found to cause corrosion of underlying aluminium sheets. 

Calcium hydroxide leached from incompletely cured concrete causes serious corrosion of lead (see Section 9.3). This is because carbon dioxide reacts with the lime solution to form calcium carbonate, which is practically insoluble. Carbonate ions are therefore not available to form a passive film on the surface of the lead . Typically, thick layers of PbO are formed, which may show seasonal rings of litharge (tetragonal PbO) and massicot (orthorhombic PbO) . 

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