Precipitation of Iron Fluoride Trihydrate from Mixed Acid Pickle Liquors

We are developing a cost-saving and environmentally friendly process with low energy consumption to recover the metal content and recycle the acid from spent pickle baths. The metals are precipitated as metal fluorides, which can be turned into metal oxides and hydrofluoric acid by thermal hydrolysis. In the proposed process the solution is concentrated by nanofiltration and the metals are precipitated in a subsequent crystallization step. Different nanofiltration membranes have been evaluated in experimental batch tests. The membrane MPF-34 from Koch Membrane Systems offered both good flux and acceptable metal retention even after long periods of acid storage. The solubility of B-FeF3.3H20 has been measured at varying acid concentrations and at different temperatures. The solubility decreases with increasing hydrofluoric acid and nitric acid concentrations. This suggests that the crystallization process should be operated at high acid concentrations. The crystal growth rate of B-FeF3.3H2O is found to be quite low but increases significantly with temperature. This suggests that the crystallization process should be operated at higher temperatures (40 - 60°C). Within the project a pilot plant has been constructed where the spent pickle bath solution is concentrated by nanofiltration to the desired metal fluoride supersaturation, and B-FeF3.3H2O is crystallized in a 10 L continuous crystallizer.