Prevention of Scaling and Corrosion of Titanium Alloy Heat Exchanger Tubes at the Risdon Electrolytic Zinc Refinery

Scale build-up in titanium palladium alloy spent electrolyte heat exchangers in the residue treatment plant commissioned at Risdon, Tasmania in 1971 was shown to be a mixture of manganese dioxide and anhydrite (CaSO4). The manganese dioxide was deposited as a result of thermal decomposition of permanganate ions present in the spent electrolyte. It was shown that deposition of manganese dioxide and associated anhydrite scale could be prevented by prior reduction of permanganate ions to the manganous (Mn++) state by the addition of ferrous ions. In the plant this was conveniently accomplished by injecting into the inlet line to the heat exchangers sufficient zinc plant solution containing ferrous sulfate to decolourise the spent electrolyte. This action prevented deposition of such scale for another 21 years, until the heaters were finally decommissioned in March 1992. Measurements indicated that addition of the reducing solution lowered the anodic potential of the titanium alloy by 200 - 300 mV (depending on the solution resistance), but that it was still +300 to 400 mV with respect to a standard calomel electrode. It was shown that, if necessary, a small impressed current could be applied to provide anodic protection. Before scale deposition was overcome by the addition of ferrous sulfate solution, badly scaled heat exchangers were cleaned by recirculating a solution of hydrogen peroxide in spent electrolyte or dilute aqueous sulfuric acid, after laboratory testing of a variety of possible solvents for the scale. Corrosion tests indicated that attack on the titanium alloy by the acidic peroxide cleaning solution was insignificant.