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The valorization of ultra-concentrated seawater brines, named bitterns, requires preliminary purification processes, such as membrane filtration, before they can be fully exploited. This study investigates the performance of an ultrafiltration pilot plant aimed at separating organic matter and large particles from real bitterns. An empirical model for the bittern viscosity was developed to better characterize the membrane. Distinct variations in permeability, fouling resistance and rejection coefficient were observed under operational pressures ranging from 2 to 4 bar. Working at low pressure (2 bar), the pilot plant achieves permeability and rejection coefficient values of 17 L/m2hbar and 95%, respectively. Foulant behavior was characterized by determining a “fouling resistance”, obtaining an average value of 1013 m−1. Tests with three distinct bittern samples were conducted to assess the influence of chemical composition and organic matter content on membrane permeability and fouling characteristics. The collected data enabled a comprehensive characterization of the ultrafiltration pilot unit working with this particular saline feed solution, which has very high technical–economic potential.

In agreement with the Water Framework Directive, Circular Economy and European Union (EU) Green Deal packages, the EU-funded WATER-MINING project aims to validate next-generation water resource solutions at the pre-commercial demonstration scale in order to provide water management and recovery of valuable materials from alternative sources. In the framework of the WATER-MINING project, desalination brines from the Lampedusa (Italy) seawater reverse osmosis (SWRO) plant will be used to produce freshwater and recover valuable salts by integrating different technologies. In particular, electrodialysis with bipolar membranes (EDBM) will be used to produce chemicals (NaOH and HCl). A novel EDBM pilot plant (6.4 m2, FuMa-Tech) has been installed and operated. The performance of EDBM for single pass under different flowrates (2–8 L·min−1) for acid, base and saline channels, and two current densities (200 and 400 A·m−2), has been analyzed in terms of specific energy consumption (SEC) and current efficiency (CE). Results showed that by increasing the flowrates, generation of HCl and NaOH slightly increased. For example, ΔOH− shifted from 0.76 to 0.79 mol·min−1 when the flowrate increased from 2 to 7.5 L·min−1 at 200 A·m−2. Moreover, SEC decreased (1.18–1.05 kWh·kg−1) while CE increased (87.0–93.4%), achieving minimum (1.02 kWh·kg−1) and maximum (99.4%) values, respectively, at 6 L·min−1.

Concentrated bitterns discharged from saltworks have extremely high salinity, often up to 300 g/L, thus their direct disposal not only has a harmful effect on the environment, but also generates a depletion of a potential resource of renewable energy. Here, reverse electrodialysis (RED), an emerging electrochemical membrane process, is proposed to capture and convert the salinity gradient power (SGP) intrinsically conveyed by these bitterns also aiming at the reduction of concentrated salty water disposal. A laboratory-scale RED unit has been adopted to study the SGP potential of such brines, testing ion exchange membranes from different suppliers and under different operating conditions. Membranes supplied by Fujifilm, Fumatech, and Suez were tested, and the results were compared. The unit was fed with synthetic hypersaline solution mimicking the concentration of natural bitterns (5 mol/L of NaCl) on one side, and with variable concentration of NaCl dilute solutions (0.01–0.1 mol/L) on the other. The influence of several operating parameters has also been assessed, including solutions flowrate and temperature. Increasing feed solutions’ temperature and velocity has been found to lower the stack resistance, which enhances the output performance of the RED stack. The maximum obtained power density (corrected to account for the effect of electrodic compartments, which can be very relevant in five cell pairs laboratory stacks) reached around 10.5 W/m2cellpair, with FUJIFILM Type 10 membranes, temperature of 40 °C, and a fluid velocity of 3 cm s−1 (as empty channel, considering 270 μm thickness). Notably, the present study results confirm the large potential for SGP generation from hypersaline brines, thus providing useful guidance for the harvesting of SGP in seawater saltworks all around the world.

The SEArcularMINE project aims to recover critical raw materials (CRMs) from brines from saltworks, thus facing a CRM shortage within Europe. To promote a fully circular scheme, the project valorises concentrated brines using electrodialysis with bipolar membranes (EDBM) to generate the required amounts of reactants (i.e., acids and bases). Regarding the performances of new non-woven cloth ion-exchange membranes (Suez): (i) an ultra-thin non-woven polyester cloth and (ii) a thin polypropylene cloth acting as the support structures were assessed. Additionally, the anion layer includes a catalyst to promote the water dissociation reaction. The effect of current density (100, 200, and 300 A m−2) on the performance of two combinations of membranes in an inter-laboratory exercise using 2 M NaCl was evaluated. According to statistical analysis ANOVA, there was an agreement on the results obtained in both laboratories. NaOH/HCl solutions up to 0.8 M were generated working at 300 A m−2 using both combinations of membranes. Regarding the performance parameters, stack set-ups incorporating thin polypropylene membranes showed lower specific energy consumption (SEC) and higher specific productivity (SP) than ultra-thin polypropylene ones. Hence, for ultra-thin polypropylene membranes, SEC was reported to be between 2.18 and 1.69 kWh kg−1NaOH and SP between 974 and 314 kg m−2 y−1.

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 gPROMS modelling platform. It is able to simulate steady state operations and run optimization analysis of the process performance. The impact of key operating and design parameters, such as the set-point bath concentration and the DD and MD membrane areas, respectively, was investigated and the optimal arrangement was identified. Finally, operating variables and design parameters were optimized simultaneously in a nonlinear framework as a tradeoff between profitability and environmental impact. We show how the integration of new technologies into the traditional pickling industry could provide a significant benefit for the issues of process sustainability, which are currently pressing.

Commercial hemodialyzers are hollow-fiber cylindrical modules with dimensions and inlet–outlet configurations dictated mostly by practice. However, alternative configurations are possible, and one may ask how they would behave in terms of performance. In principle, it would be possible to depart from the standard counter-flow design, while still keeping high clearance values, thanks to the increase in the shell-side Sherwood number (Sh) due to the cross-flow. To elucidate these aspects, a previously developed computational model was used in which blood and dialysate are treated as flowing through two interpenetrating porous media. Measured Darcy permeabilities and mass transfer coefficients derived from theoretical arguments and CFD simulations conducted at unit-cell scale were used. Blood and dialysate were alternately simulated via an iterative strategy, while appropriate source terms accounted for water and solute exchanges. Several module configurations sharing the same membrane area, but differing in overall geometry and inlet–outlet arrangement, were simulated, including a commercial unit. Although the shell-side Sherwood number increased in almost all the alternative configurations (from 14 to 25 in the best case), none of them outperformed in terms of clearance the commercial one, approaching the latter (257 vs. 255 mL/min) only in the best case. These findings confirmed the effectiveness of the established commercial module design for the currently available membrane properties.

This Special Issue of Membranes journal focuses on electromembrane processes and is motivated by the increasing interest of the scientific community towards their characterization by experiments and modelling for several applications [...]

A novel technology, the ion exchange membrane crystallizer (CrIEM), that combines reactive and membrane crystallization, was investigated in order to recover high purity magnesium hydroxide from multi-component artificial and natural solutions. In particular, in a CrIEM reactor, the presence of an anion exchange membrane (AEM), which separates two-compartment containing a saline solution and an alkaline solution, allows the passage of hydroxyl ions from the alkaline to the saline solution compartment, where crystallization of magnesium hydroxide occurs, yet avoiding a direct mixing between the solutions feeding the reactor. This enables the use of low-cost reactants (e.g., Ca(OH)2) without the risk of co-precipitation of by-products and contamination of the final crystals. An experimental campaign was carried out treating two types of feed solution, namely: (1) a waste industrial brine from the Bolesław Śmiały coal mine in Łaziska Górne (Poland) and (2) Mediterranean seawater, collected from the North Sicilian coast (Italy). The CrIEM was tested in a feed and bleed modality in order to operate in a continuous mode. The Mg2+ concentration in the feed solutions ranges from 0.7 to 3.2 g/L. Magnesium recovery efficiencies from 89 up to 100% were reached, while magnesium hydroxide purity between 94% and 98.8% was obtained.

This paper presents a comprehensive review of studies on electrodialysis (ED) applications in wastewater treatment, outlining the current status and the future prospect. ED is a membrane process of separation under the action of an electric field, where ions are selectively transported across ion-exchange membranes. ED of both conventional or unconventional fashion has been tested to treat several waste or spent aqueous solutions, including effluents from various industrial processes, municipal wastewater or salt water treatment plants, and animal farms. Properties such as selectivity, high separation efficiency, and chemical-free treatment make ED methods adequate for desalination and other treatments with significant environmental benefits. ED technologies can be used in operations of concentration, dilution, desalination, regeneration, and valorisation to reclaim wastewater and recover water and/or other products, e.g., heavy metal ions, salts, acids/bases, nutrients, and organics, or electrical energy. Intense research activity has been directed towards developing enhanced or novel systems, showing that zero or minimal liquid discharge approaches can be techno-economically affordable and competitive. Despite few real plants having been installed, recent developments are opening new routes for the large-scale use of ED techniques in a plethora of treatment processes for wastewater.

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.

The membrane distillation (MD) process for water desalination is affected by temperature polarization, which reduces the driving force and the efficiency of the process. To counteract this phenomenon, spacer-filled channels are used, which enhance mixing and heat transfer but also cause higher pressure drops. Therefore, in the design of MD modules, the choice of the spacer is crucial for process efficiency. In the present work, different overlapped spacers are investigated by computational fluid dynamics (CFD) and results are compared with experiments carried out with thermochromic liquid crystals (TLC). Results are reported for different flow attack angles and for Reynolds numbers (Re) ranging from ~200 to ~800. A good qualitative agreement between simulations and experiments can be observed for the areal distribution of the normalized heat transfer coefficient. Trends of the average heat transfer coefficient are reported as functions of Re for the geometries investigated, thus providing the basis for CFD-based correlations to be used in higher-scale process models.