Combining Membrane and Zero Brine Technologies in Waste Acid Treatment for a Circular Economy in the Hot-Dip Galvanizing Industry: A Life Cycle Perspective
AbstractAn 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 w…
Diffusion Dialysis for Separation of Hydrochloric Acid, Iron and Zinc Ions from Highly Concentrated Pickling Solutions
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 c…
Metals Recovery from Waste Pickling Solutions by Reactive Precipitation
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 …
Diffusion dialysis for the treatment of H2SO4-CuSO4 solutions from electroplating plants: Ions membrane transport characterization and modelling
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 agai…
DEVELOPMENT AND MODELING OF MEMBRANE PROCESSES FOR THE REGENERATION OF ACID PICKLING SOLUTIONS
The doctoral thesis focuses on a novel integrated process for the recovery and valorisation of acid and metal salts present in the waste solutions of the pickling process. The proposed process is based on the integration of two innovative membrane technologies, the Diffusion Dialysis and the Membrane Distillation, coupled with a reactive precipitation section. This hybrid process allows the recovery and the enhancement of waste solutions, as well as optimal operating conditions for the continuous pickling process, thus improving its efficiency. Hydrochloric acid recovery was assessed through a detailed study on the Diffusion Dialysis process by implementing a wide experimental campaign usin…
Economic Benefits of Waste Pickling Solution Valorization
An integrated hybrid membrane process, composed of a diffusion dialysis (DD), a membrane distillation (MD) and a reactive precipitation unit (CSTR), is proposed as a promising solution for the valorization and onsite recycling of pickling waste streams. An economic analysis was performed aiming to demonstrate the feasibility of the developed process with a NPV of about EUR 40,000 and a DPBP of 4 years. The investment and operating costs, as well as the avoided costs and the benefits for the company operating the plant, were analyzed with an extensive cost tracking exercise and through face-to-face contact with manufacturers and sector leaders. A mathematical model was implemented using the …
Experimental investigation and modeling of diffusion dialysis for HCl recovery from waste pickling solution
Abstract 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% l…
Design of a novel membrane-integrated waste acid recovery process from pickling solution
Abstract 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 wast…
Experimental investigation and modelling of diffusion dialysis for the recovery of waste acid solutions
Pickling is widely used as a chemical pre-treatment method for cleaning metal surfaces before other surface treatments and it consumes large amount of acids and water
An integrated approach for the HCl and metals recovery from waste pickling solutions: pilot plant and design operations
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 g…
AN INTEGRATED APPROACH FOR THE HCl AND METALS RECOVERY FROM WASTE PICKLING SOLUTIONS: PILOT PLANT DESIGN AND OPERATIONS
Pickling is one of the key steps in the hot-dip galvanizing process, where HCl solutions are largely used to remove metal oxides from metallic surfaces, thus generating spent waste liquors containing high concentrations of metals and acid. Disposal of the industrial pickling waste dramatically affects the hot-dip galvanizing industry economics and environmental footprint. Thus, reducing strong acid waste disposal is one of the most beneficial steps to enhance the process sustainability. Moreover, the continuous regeneration of pickling solutions enhances pickling rate and process performance, also minimizing industrial wastewater disposal and chemicals consumption promoting the circular use…