Life cycle assessment of zinc and iron recovery from spent pickling acids by membrane-based solvent extraction and electrowinning.

In this paper we conducted a life cycle assessment to evaluate the environmental performance of the valorization of spent pickling acid (SPA) generated in the hot-dip galvanizing (HDG) process. We analyzed the environmental impacts of treating one m3 of SPA, comparing the reference treatment consisting of neutralization, precipitation, stabilization, and landfilling of the metallic sludge (scenario #1), with the innovative LIFE2ACID technology (scenario #2) that produces secondary zinc and iron chloride in solution through non-dispersive solvent extraction (NDSX) and electrowinning (EW). The results showed that the materials credits achieved by the implementation of LIFE2ACID technology turned most of the impact categories evaluated (toxicity, acidification, eutrophication, ozone depletion, etc.) into environmental benefits. Scenario #2 was adapted to achieve either zinc-only recovery (#2.1) or simultaneous iron and zinc recovery (#2.2). The abiotic depletion potential (ADP) of fossil fuels increased slightly from scenario #1 to scenario #2.1 because of the higher energy demand and NaOH consumption of EW, and because only zinc was recovered. However, the valorization of both zinc and iron chloride in scenario #2.2 reduced the ADP-fossil by 27%, compared to the reference treatment. Furthermore, the global warming impact was reduced by 20% and 97% in scenarios #2.1 and #2.2, respectively. With the focus on promoting the circular economy concept, we conclude that the LIFE2ACID technology significantly improves the environmental performance of SPA management. Next steps should consider the life-cycle costs analysis in specific scenarios to find out the trade-off between environmental and economic objectives.

Circular economy in hot-dip galvanizing with zinc and iron recovery from spent pickling acids.

The management of spent pickling acids (SPA) is an environmental challenge for the hot-dip galvanizing (HDG) industry. Bearing in mind its elevated content of iron and zinc, SPA can be regarded as a source of secondary materials in a circular economy approach. This work reports the pilot scale demonstration of non-dispersive solvent extraction (NDSX) in hollow fiber membrane contactors (HFMCs) to perform the selective zinc separation and SPA purification, so that the characteristics needed for use as a source of iron chloride are achieved. The operation of the NDSX pilot plant, which incorporates four HFMCs with a 80 m2 nominal membrane area, is carried out with SPA supplied by an industrial galvanizer, and consequently technology readiness level (TRL) 7 is reached. The purification of the SPA requires of a novel feed and purge strategy to operate the pilot plant in continuous mode. To facilitate the further implementation of the process, the extraction system is formed by tributyl phosphate as the organic extractant and tap water as the stripping agent, both easily available and cost-effective chemicals. The resulting iron chloride solution is successfully valorized as a hydrogen sulfide suppressor to purify the biogas generated in the anaerobic sludge treatment of a wastewater treatment plant. Additionally, we validate the NDSX mathematical model using pilot scale experimental data, providing a design tool for process scale-up and industrial implementation.

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.