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…

Simulation of a regeneration plant for spent pickling solutions via spray roasting

Nowadays, pyrohydrolysis techniques are widely applied for regeneration of spent pickling liquors providing an excellent environmental and economical strategy to the problem of waste disposal/recovery, also thanks to the high acid recovery efficiencies (>99%) achieved. In fact, in these processes, iron chlorides are converted into iron oxides and hydrogen chloride at high temperature in spray roasting or fluidized bed reactors. Though the state-of-the-art technologies have been successfully applied only to large-scale plants, the development of small-scale units, able to perform a delocalized regeneration of spent solutions where these latter are actually produced, would be strongly needed …

Electrochemical incineration of organic pollutants: effect of the nature of the pollutants and of the operative conditions

Recovery of zinc from spent pickling solutions by liquid–liquid extraction using TBP

In this paper, recovery of zinc from real spent pickling solutions by liquid–liquid extraction with tributyl phosphate (TBP) was studied. In particular, the effects of some parameters were investigated, such as the volume ratio between the organic phase and real spent pickling liquor (O/A) (1:2, 1:1, 2:1, 4:1), the stirring time (5–20–30 min) and the TBP concentration (10%–55%–100%), in order to determine the conditions leading to higher zinc extraction efficiency, as well as selectivity in relationships to other metals such as iron. After zinc extraction, TBP was successfully regenerated. Among several tested solutions, water allows zinc recovery higher than 90%, especially at 10% diluted …

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…

Synthesis and characterization of nanostructured materials applied to energy devices

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 …

Synthesis and Characterization of Nanostructured Electrodes for Innovative Lead Acid Batteries

Electrochemical oxidation of organics at metal oxide electrodes: The incineration of oxalic acid at IrO2-Ta2O5 (DSA-O2) anode

Abstract The electrochemical incineration of oxalic acid (OA) at Ti/IrO2–Ta2O5 (DSA-O2) anode was investigated to find the influence of the operative parameters on the performances of the process. Polarization curves and chronoamperometric measurements indicate the probable occurrence of a direct electrochemical oxidation of OA at the surface of the DSA anode. In incineration electrolyses, the performances of the process in terms of OA conversion and current efficiency dramatically depend on the adopted operative conditions. Interestingly, very high OA removal and current efficiency were obtained when the process was performed at relatively high temperatures (50 °C) or in the presence of Na…

Electrochemical incineraton of oxalic acid at boron doped diamond electrodes: influence of operative parameters

TRATAMIENTO ELECTROQUIMICO DE CONTAMINANTES ORGANOCLORADOS ALIFATICOS. ELUCIDACION DE LOS CAMINOS DE REACCION.

Los hidrocarburos alifáticos clorados conjugan toxicidad con una alta estabilidad química, capacidad de bioacumulación y difusión de largo alcance. Los cloroetanos son particularmente ubicuos en la industria y en los productos domésticos, y su introducción en el medio ambiente puede entrañar riesgos para los seres vivos. Actualmente, la USEPA (US Environmental Protection Agency) está llevando a cabo el llamado “Endocrine Disruptor Screening Program (EDSP)”, en el cual tanto el 1,2-dicloroetano (DCA) como el 1,1,2,2-tetracloroetano (TCA) son considerados prioritarios debido a sus efectos potenciales sobre el sistema endocrino. El DCA se encuentra también en la lista de substancias prioritari…

Oxidation of carboxylic acids in water at IrO2-Ta2O5 and Boron Doped Diamond anodes

Abstract A detailed study was dedicated to the anodic oxidation of three carboxylic acids (namely, oxalic, formic and maleic acid) with the objective to evaluate in a systematic way the effect on the oxidation of carboxylic acids of numerous relevant parameters, including the nature and the concentration of the carboxylic acid, the alimentation regime (potentiostatic vs. amperostatic), the current density and the working potential values, the flowdynamic regime, the temperature and the nature of the electrode material. It was observed that the effect of some operative parameters strongly depends on the nature of the electrode and of the carboxylic acid. As an example, the efficacy of abatem…

High Efficiency Electrodes Based on Nanostructured Materials for Energy Devices

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…

Mining minerals and critical raw materials from bittern: Understanding metal ions fate in saltwork ponds

Seawater represents a potential resource for raw materials extraction. Although NaCl is the most representative mineral extracted other valuable compounds such as Mg, Li, Sr, Rb and B and elements at trace level (Cs, Co, In, Sc, Ga and Ge) are also contained in this “liquid mine”. Most of them are considered as Critical Raw Materials by the European Union. Solar saltworks, providing concentration factors of up-to 20 to 40, offer a perfect platform for the development of minerals and metal recovery schemes taking benefit of the concentration and purification achieved along the evaporation saltwork ponds. However, the geochemistry of these elements in this environment has not been yet thoroug…

Incenerimento elettrochimico di acido ossalico in presenza di NaCl

Influence of operative parameters on the electrochemical incineration of oxalic acid.

Electrochemical processes for the treatment of chlorinated ethanes in water solutions

In the present work, the electrochemical treatment of water solutions containing chloro ethanes was performed by cathodic reduction, anodic oxidation and coupled processes with the aim of evaluate the effectiveness of these methodologies.

Electrochemical oxidation of organics in water: Role of operative parameters in the absence and in the presence of NaCl

The electrochemical oxidation of organics in water was investigated theoretically and experimentally to determine the role of several operative parameters on the performances of the process in the presence and in the absence of sodium chloride. Theoretical considerations were used to design the experimental investigation and were confirmed by the results of the electrochemical oxidation of oxalic acid (OA) at boron doped diamond (BDD) or IrO(2)-Ta(2)O(5) (DSA-O(2)) anodes in a continuous batch recirculation reaction system equipped with a parallel plate undivided electrochemical cell. Polarization curves and chronoamperometric measurements indicated that, in the presence of chlorides, the a…

A viable path toward a high energy density anode for lithium-ion batteries

INNOVATIVE CHEMICAL PROCESSES FOR THE TREATMENT OF WATERS POLLUTED BY RECALCITRANT ORGANIC SUBSTANCES

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…

Innovative chemical processes for the treatment of water polluted by recalcitrant organic substances

In the last years, many research groups have focused their attention on the innovative chemical processes adopted for the treatment of water effluents polluted by recalcitrant organic substances, i.e., substances resistant to biological treatment. The electrochemical oxidation is one of the most studied technologies because it presents high versatility and low cost, it is realized under mild conditions of pressure and temperature and generally it does not involve the use of toxic substances [1]. In this work, the comparative performance of different electrochemical approaches such as direct oxidation processes, oxidation by means of electrogenerated chlorine and electro-Fenton was investiga…

Loading carbonaceous materials with silver for the treatment of chloro-organic compounds in aqueous phase

Many electrochemical technologies, either based on novel concepts (such as microbial fuel cells), experimental setups (such as photoelectrochemical or solar photoelectro-Fenton reactors) or materials (mainly focused on the use of large O2-overpotential anodes like BDD) have been devised in recent years for water remediation. Special attention has been paid to highly toxic, biorefractory organic pollutants such as the chlorinated hydrocarbons, which conjugate toxicity with chemical stability, bioaccumulation and long-range diffusivity [1]. Electroreduction at silver cathodes becomes an interesting alternative to degrade chloro-organic compounds, but it may lead to the accumulation of reactio…

Growth and Electrochemical Performance of Lead and Lead Oxide Nanowire Arrays as Electrodes for Lead-Acid Batteries

n this work, we present the growth and electrochemical performance of nanostructured lead and lead oxide electrodes for lead-acid batteries. The electrodes were obtained by template electrodeposition in polycarbonate membranes, acting as template. Electrochemical tests were conducted at constant current in 5M aqueous solution of sulphuric acid, after assembling nanostructured lead and lead oxide electrodes in a zero-gap configuration using a commercially available separator. The main advantages of these electrodes are the high specific energy and power density, and the wide surface area, about 70 times higher than the geometrical one. These features allowed high discharge rates, up to 20C. …

Electrochemical abatement of chloroethanes in water: Reduction, oxidation and combined processes

An electrochemical route, based on the anodic oxidation to carbon dioxide coupled with the cathodic reduction to de-halogenated hydrocarbons, was proposed for the treatment of waters contaminated by chloroethanes. The electrochemical abatement of two model compounds, namely 1,2-dichloroethane and 1,1,2,2-tetrachloroethane, was carried out by cathodic reduction at silver, anodic oxidation at boron doped diamond (BDD) and combined processes. The anodic oxidation gives rise to a high abatement of the concentration of both these compounds and of COD. The reduction of 1,1,2,2-tetrachloroethane proceeds also with high abatement but with the formation of some halogenated intermediates and final pr…

Electrochemical incineration of organic pollutants: effect of the nature of the pollutants and of the temperature

The electrochemical oxidation of some organic pollutants, including three carboxylic acids (oxalic, formic and maleic), at boron doped diamond (BDD) and DSA anodes, using galvanostatic alimentation, was investigated in order to study the effect of the temperature and of the nature of the pollutants on the process. In incineration electrolyses, the performances of the process in terms of carboxylic acid conversion and current efficiency dramatically depend on the adopted operative conditions. The abatement of the organic pollutant depends on the nature of the carboxylic acid. Quite interestingly, the opposite effect of the nature of the substrate on the performances of the process was observ…

Ricerca e Innovazione Responsabili in didattica. Il progetto IRRESISTIBLE

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…

Nanotechnology for Solar Energy Conversion

Nel presente lavoro è descritto un modulo didattico sviluppato, nell’ambito del progetto europeo IRRESISTIBLE, dall’unità di Palermo sul tema dell’applicazione delle nanoscienze allo sfruttamento dell’energia solare. L’attività è stata rivolta ad alunni del biennio dell’Istituto Tecnico, nell’ambito delle discipline Scienze Chimiche Integrate e Scienze e Tecnologie Applicate Chimca e ad alunni dell’ultimo anno del Liceo Scientifico, nell’ambito della disciplina Fisica. Tra le varie attività , anche sperimentali, è stata realizzata una cella DSSC che, insieme ad altro materiale di comunicazione preparato dagli stessi studenti, è stata presentata alla mostra scientifica Esperienza inSegna e a…

High-performance of PbO2 nanowire electrodes for lead-acid battery

Abstract PbO2 nanowires were obtained by template electrodeposition in polycarbonate membranes and tested as positive electrode for lead-acid battery. Nanowires were grown on the same material acting as current collector that was electrodeposited too. The nanostructured electrodes were assembled in a zero-gap configuration using commercial negative plate and separator. Cell performance was tested by galvanostatic charge/discharge cycles in a 5 M H2SO4 aqueous electrolyte. PbO2 nanostructured electrodes were able to deliver at 1C rate an almost constant capacity of about 190 mAh g−1 (85% of active material utilization), close to the theoretical value (224 mAh g−1). The nanowire array provide…

Comparative electrochemical treatments of two chlorinated aliphatic hydrocarbons. Time course of the main reaction by-products.

The chlorinated aliphatic hydrocarbons conjugate toxicity with high chemical stability, bioaccumulation and long-range diffusivity. Chloroethanes are particularly ubiquitous in the industry and in household products, and their entry to the environment may entail potential risks for the living beings. At present, the US Environmental Protection Agency is carrying out the Endocrine Disruptor Screening Program (EDSP), where 1,2-dichloroethane (DCA) and 1,1,2,2-tetrachloroethane (TCA) are considered as priorities for their potential effects on the endocrine system. DCA is also found in the list of priority substances drawn up by the European Commission. To avoid the release of chloroethanes int…

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

effect of the temperature on the electrochemical incineration of organic pollutants

Diossido di titanio e alcune sue applicazioni. Spunti didattici

Il diossido di titanio, TiO2, ampiamente utilizzato come pigmento di colore bianco, è uno dei materiali più studiati nell’ambito della ricerca per le sue proprietà fotocatalitiche. Esso, infatti, contribuisce alla fotodegradazione di sostanze inquinanti, motivo per cui è utilizzato nel settore della purificazione dell’aria e dell’acqua e per la realizzazione di vetri autopulenti, disponibili commercialmente. Nel presente lavoro viene suggerito un percorso didattico con l’obiettivo di mettere in evidenza le proprietà fotocatalitiche del diossido di titanio oltre che può essere utilizzato per affrontare concetti fondamentali quali la struttura a bande dei solidi e la fotocatalisi. Il percorso…

Electrochemical incineration of oxalic acid at boron doped diamond anodes: Role of operative parameters

The electrochemical incineration of oxalic acid (OA) at boron doped diamond (BDD) anodes was investigated both theoretically and experimentally in order to find the influence of the operative parameters on the performances of the process. Polarization curves and chronoamperometric measurements indicate the probable occurrence of a direct electrochemical oxidation of OA at the surface of the BDD anode at low pH and of a hydroxyl radical-mediated reaction at high pH. When incineration electrolyses are performed at low pH with potentiostatic alimentation, a dramatic influence of the potential is observed. In amperostatic incineration, high CE are obtained when most part of the process was unde…

Desalination of oilfield produced waters via reverse electrodialysis: A techno-economical assessment

Produced waters (PWs) are oilfield waste streams rich in minerals and hydrocarbons whose production rate is largely increased in last decades following the corresponding increase of energy demand. The high salinity level of PWs inhibits the adoption of cheap biological treatments. Also, desalination techniques based on osmotic membranes would require severe pre-treatments. As an alternative, Reverse ElectroDialysis (RED) and Assisted Reverse ElectroDialysis (ARED) are here proposed for the first time to reduce the salinity level of PWs. RED may also guarantee an operation cost reduction thanks to its energy generation. An ad-hoc model for RED and ARED is here developed in order to deal suit…

Power Production from Produced Waters via Reverse Electrodialysis: A Preliminary Assessment

Wastewaters generated by crude oil extraction processes, called “produced waters” (PWs), are complex solutions that contain organic compounds, mainly hydrocarbons, and often exhibit high salinity. The large amounts of PWs represent a global issue because of their environmental impact. An approach widely used in the oil industry is the reinjection of this wastewater into the extraction wells after a suitable treatment. The high salt concentration of such solutions may be used in salinity gradient technologies to produce green electricity. Among these technologies, reverse electrodialysis (RED) is one of the most promising. In this work, the application of RED for energy generatio…

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…

Electrochemical treatment of aqueous solutions containing one or many organic pollutants at boron doped diamond anodes. Theoretical modeling and experimental data

The electrochemical oxidation of organics in water at boron doped diamonds (BDD) was experimentally investigated with the aim to discuss the correlations among the conversion of the pollutants and the instantaneous current efficiency ICE with the operative conditions. A simple theoretical model previously developed for the oxidation of oxalic acid accounting for the cases of mass transfer control, oxidation reaction control and mixed kinetic regimes was adopted and extended to challenge its predictive capability in the case of organics of different nature and in systems with more pollutants. A quite good agreement, between theoretical predictions and experimental data pertaining to the elec…

ULTRAFAST LEAD ACID BATTERIES USING NANOSTRUCTURED ELECTRODES

Electrochemical oxidation of carboxylic acids at boron doped diamonds