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An innovative approach of combining membrane and zero brine technologies for a joint treatment of industrial liquid waste is investigated regarding its environmental impacts compared to the existing liquid waste treatment. The object of investigation is the generation of waste acid solution by a hot dip galvanizing plant in Sicily, Italy. The waste acid solution contains hydrochloric acid, iron and zinc, which makes it a hazardous waste according to EU classifications. Environmental impacts are studied for two scenarios in the Tecnozinco hot-dip galvanizing plant in Sicily, Italy: (i) the current process of pickling with linear disposal of waste acid and (ii) the pickling combined with in-situ treatment of the waste acid using a combination of diffusion dialysis (DD), membrane distillation (MD) and a precipitation reactor. Results are obtained via an attributional life cycle assessment (LCA) approach focusing on the water footprint profile of the process. The linear disposal path creates significant costs, environmental burdens and risks during the 1500 km transport of hazardous liquid waste. The combination of DD and MD, complemented with a zero-brine precipitation reactor, closes internal material loops, could save local water resources and reduces costs as well as environmental impacts. Reduction potentials of 70–80% regarding most LCA impact categories can be expected for the application of the novel technology combination supporting the galvanizing pre-treatment process under study. Therefore, the application of such technology on the way forward to a more circular economy is recommended from an environmental viewpoint, especially in process plants similar to the investigated one. Graphical Abstract

Continuous regeneration of industrial pickling solutions and recovery of valuable materials are implemented in a pilot-scale plant including diffusion dialysis (DD), where HCl is recovered, membrane distillation (MD), where HCl is concentrated, and reactive precipitation (CSTR), where metal ions are recovered in different forms. The integration of the three processes allows to minimize waste streams generation and to accomplish a closed-loop process, thus increasing the environmental sustainability and economic impact of the galvanizing industry. Process reliability was proved through the operation of a demonstrator in the real industrial environment of the Tecnozinco SrL hot-dip galvanizing plant (Carini, Italy), assessing the actual performance in fully reducing spent pickling solution disposal and recovering useful compounds. Tests were conducted firstly with synthetic solutions and then with real waste liquors from the pickling plant. A high acid recovery (80%) can be achieved in the diffusion dialysis unit and quantitative metals separation was accomplished, with iron hydroxide produced at 99% purity. The membrane distillation performance suffers when metal salts are present in large quantities, due to the “salting out” effect, resulting in reduced water vapor pressure, though the use of available low grade waste heat allows energy-sustainable operation of the MD.

Acid recovery from pickling waste solutions is an important step to enhance hot-dip-galvanizing industry process sustainability. Diffusion dialysis (DD) can be used to separate acids and heavy metals (e.g., iron and zinc) from pickling waters, promoting the circular use of such raw materials. In the present study, a laboratory scale unit operating in batch and a continuous large scale unit, both equipped with Fumasep anionic exchange membranes, were tested. Results obtained show that zinc and iron concentration affect the HCl recovery in opposite ways. Iron chlorides enhance acid recovery, while zinc chlorides considerably tend to diffuse through the membrane because of negatively charged chloro-complexes formation and slightly reduce the acid diffusion. A multi-components mathematical model, with a time-dependent and distributed-parameters architecture, was adopted enabling the prediction of operations with hydrochloric acid, zinc, and iron metals both in batch and in continuous dialyzers. As a result, a good comparison between model simulations and experiments was achieved in both configurations.

Diffusion dialysis (DD) is proposed to separate and recover mineral acids and transition metals from electroplating industry process waters promoting a circular approach of resources recovery. In this work, a DD module with two anionic membranes (Fumasep FAD and Neosepta AFN) are used for the separation of H2SO4 from Cu2+ containing solutions. The membrane performances with sole H2SO4 solutions (0.2–2 M) and sole CuSO4 solutions (0.8–1.1 M Cu2+) and with mixtures of H2SO4 (0.6 M) and CuSO4 (0.2–1.1 M Cu2+) as feed are studied. H2SO4 recovery efficiency decreases as the concentration of acid increases. For H2SO4 solutions, the water drag flux from the retentate to the diffusate prevails against the osmotic flux for all concentrations investigated. Conversely, the presence of CuSO4 in solution enhanced the osmotic flux and slightly negatively affected the acid recovery. The osmotic flux is higher for Fumasep FAD. A distributed parameter model consisting of a set of spatial differential equations for the DD channels and a dynamic section including time-dependent differential equations for batch operations is constructed and then validated using experimental results

Hydrochloric acid pickling is a common practice in steel manufacturing industry. During the process, acid is consumed to dissolve surface oxides and metals ions are accumulated in the solution, which becomes less effective with time. In addition, the costly and risky waste acid disposal is another issue affecting the hot-dip galvanizing industry. In this work, a novel sustainable waste acid recovery process from pickling solutions based on circular approach is proposed to tackle these issues. The innovative system allows (i) the continuous regeneration of pickling solutions to enhance process rate and performance and (ii) minimise the highly expensive and environmentally risky wastewater disposal. In this way, refilling pickling baths with fresh acid, as done in conventional operation, can be avoided and can be carried out continuously under optimal working conditions. Moreover, the recovery of valuable substances (e.g. metal hydroxide or salts solution) can be obtained as an additional benefit. Continuous treatment and regeneration of pickling solution can be accomplished by coupling diffusion dialysis (DD) and membrane distillation (MD) technologies with a reactive precipitation unit where iron ions can be separated from the zinc-rich solution, in order to recover valuable products. To this purpose, a steady state process simulator was developed to predict the operation of the proposed integrated process.

Hydrochloric acid recovery from pickling solutions was studied by employing a batch diffusion dialysis (DD) laboratory test-rig equipped with Fumasep membranes. The effect of main operating parameters such as HCl concentration (0.1–3 M) and the presence of Fe2+ (up to 150 g/l) was investigated to simulate the system operation with real industrial streams. The variation of HCl, Fe2+ and water flux was identified. When only HCl is present, a recovery efficiency of 100% was reached. In the presence of FeCl2, higher acid recovery efficiencies, up to 150%, were observed due to the so-called “salt effect”, which promotes the passage of acid even against its concentration gradient. A 7% leakage of FeCl2 was detected in the most severe conditions. An original analysis on water flux in DD operation has indicated that osmotic flux prevails at low HCl concentrations, while a dominant “drag flux” in the opposite direction is observed for higher HCl concentrations. A comprehensive mathematical model was developed and validated with experimental data. The model has a time and space distributed-parameters structure allowing to effectively simulate steady-state and transient batch operations, thus providing an operative tool for the design and optimisation of DD units.

Pickling is one of the most important steps in steel manufacturing industry. During the process, an acid reacts with the surface oxides causing metal ions accumulation in the pickling solution. Disposal of the waste acid represents a critical issue for the hot-dip galvanizing industry in terms of environmental damage and high costs. Recovering of the main products by using an integrated process, with the perspective of a circular approach, could minimize the wastewater production, leading to reinvigorate this industrial sector economy. In this context, recovery of the metal ions mainly present in the pickling solution, such as Fe and Zn, becomes a critical issue. In this work, the reactive precipitation process reliability was proved through lab-scale experiments, in order to collect information for the design of a pilot-plant to be installed in the Tecnozinco SrL (Carini, Italy) hot-dip galvanizing plant. Experiments were carried out in a continuous stirred tank reactor by feeding the acidic metals-rich stream, an alkaline reactant and an oxidant. The quantity of Fe in the outlet solution and its speciation in the precipitate were detected to evaluate the recovery efficiency and the process quality, whereas Zn concentration in the precipitated was detected for determining the product purity. Some key parameters, such as temperature and pH, were studied by varying inlet streams flow rates. A very effective metals separation was observed by obtaining Fe(III) hydroxide at a high purity of 99 %. Zn ions were successfully separated by keeping them in solution with the aim of generating a zinc/ammonium chloride stream, to be reused in the fluxing baths of the hot-dip galvanizing plant.