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.

Environmental sustainability of alternative marine propulsion technologies powered by hydrogen - a life cycle assessment approach.

Shipping is a very important source of pollution worldwide. In recent years, numerous actions and measures have been developed trying to reduce the levels of greenhouse gases (GHG) from the marine exhaust emissions in the fight against climate change, boosting the Sustainable Development Goal 13. Following this target, the action of hydrogen as energy vector makes it a suitable alternative to be used as fuel, constituting a very promising energy carrier for energy transition and decarbonization in maritime transport. The objective of this study is to develop an ex-ante environmental evaluation of two promising technologies for vessels propulsion, a H2 Polymeric Electrolytic Membrane Fuel Cell (PEMFC), and a H2 Internal Combustion Engine (ICE), in order to determine their viability and eligibility compared to the traditional one, a diesel ICE. The applied methodology follows the Life Cycle Assessment (LCA) guidelines, considering a functional unit of 1 kWh of energy produced. LCA results reveal that both alternatives have great potential to promote the energy transition, particularly the H2 ICE. However, as technologies readiness level is quite low, it was concluded that the assessment has been conducted at a very early stage, so their sustainability and environmental performance may change as they become more widely developed and deployed, which can be only achieved with political and stakeholder's involvement and collaboration.

Advanced hybrid electro-oxidation & O3 technology for water reuse in the fruit and vegetable process industry.

Alternative sanitising agents are required in the fruit and vegetable processing industry, capable of effectively disinfecting both the product and the washing water to increase its reuse, while not producing harmful by-products like chlorine-based agents. In the present work, electro-oxidation (EO) and ozone are proposed for vegetable process water reuse, being optimised for their individual and combined application. The application of hybrid electro-oxidation and ozone achieved 7 log reduction after 15 min of treatment in batch using boron-doped diamond (BDD) as anode material, showing important synergistic effects when compared with the individual treatments. When the process was applied in continuous mode, up to 6 log reduction of total bacteria was achieved using EO alone with Ru as the anode and stainless steel as the cathode, under 11 mA/cm2 of current density, a cell retention time of 12 s and no addition of chemical reagents (electrolyte). Under these conditions, the absence of microorganisms in water was maintained for more than 24 h, no harmful by-products (chlorate, bromate) were detected and no damage to lettuce seeds were observed when evaluating water reuse potential.

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.