Scale-Up of Membrane-Based Zinc Recovery from Spent Pickling Acids of Hot-Dip Galvanizing

Zinc recovery from spent pickling acids (SPAs) can play an important role in achieving a circular economy in the galvanizing industry. This work evaluates the scale-up of membrane-based solvent extraction technology aimed at the selective separation of zinc from industrial SPAs as a purification step prior to zinc electrowinning (EW). The experiments were carried out at a pilot scale treating SPAs batches of 57 to 91 L in a non-dispersive solvent extraction (NDSX) configuration that simultaneously performed the extraction and backextraction steps. The pilot plant was equipped with four hollow fiber contactors and 80 m² of total membrane area, which was approximately 30 times higher than previous bench-scale studies. Tributylphosphate diluted in Shellsol D70 and tap water were used as organic and stripping agents, respectively. Starting with SPAs with high Zn (71.7 ± 4.3 g·L^-1) and Fe (82.9 ± 5.0 g·L^-1) content, the NDSX process achieved a stripping phase with 55.7 g Zn·L^-1 and only 3.2 g Fe·L^-1. Other minor metals were not transferred, providing the purified zinc stripping with better quality for the next EW step. A series of five consecutive pilot-scale experiments showed the reproducibility of results, which is an indicator of the stability of the organic extractant and its adequate regeneration in the NDSX operation. Zinc mass transfer fluxes were successfully correlated to zinc concentration in the feed SPA phase, together with data extracted from previous laboratory-scale experiments, allowing us to obtain the design parameter that will enable the leap to the industrial scale. Therefore, the results herein presented demonstrate the NDSX technology in an industrially relevant environment equivalent to TRL 6, which is an essential progress to increase zinc metal resources in the galvanizing sector.