Regeneration of Hydrochloric Acid Pickle Liquors by Crystallization

Regeneration of hydrochloric acid steel pickle liquors has traditionally been accomplished by pyrohydrolysis. However, a number of factors have recently conspired to reduce the attractiveness of this approach. Moreover, the process is not amenable to small-scale operations. On the other hand, the standard technique for regeneration of sulfuric acid pickle liquors, which is the low-temperature crystallization of ferrous sulfate is applicable to any size operation. A similar technique has recently been developed to regenerate hydrochloric acid. Sulfuric acid is added to the ferrous chloride-bearing spent HCl pickle liquor. The temperature is then reduced to below 0°C, resulting in the crystallization of ferrous sulfate heptahydrate and liberation of free hydrochloric acid. Depending upon the crystallization temperature, variable concentrations of sulfate are left in the regenerated acid. Although this residual sulfate has an impact on the pickling characteristics of the regenerated acid, tests have shown that by adjusting the conditions, pickling rates will be at least equal to those using pure HCI, and an acceptable surface finish will be produced.