• Energy Research

Salinity gradient energy is currently attracting growing attention among the scientific community as a renewable energy source. In particular, Reverse Electrodialysis (RED) is emerging as one of the most promising membrane-based technologies for renewable energy generation by mixing two solutions of different salinity. This work presents a critical review of the most significant achievements in RED, focusing on membrane development, stack design, fluid dynamics, process optimization, fouling and potential applications. Although RED technology is mainly investigated for energy generation from river water/seawater, the opportunities for the use of concentrated brine are considered as well, driven by benefits in terms of higher power density and mitigation of adverse environmental effects related to brine disposal. Interesting extensions of the applicability of RED for sustainable production of water and hydrogen when complemented by reverse osmosis, membrane distillation, bio-electrochemical systems and water electrolysis technologies are also discussed, along with the possibility to use it as an energy storage device. The main hurdles to market implementation, predominantly related to unavailability of high performance, stable and low-cost membrane materials, are outlined. A techno-economic analysis based on the available literature data is also performed and critical research directions to facilitate commercialization of RED are identified.

The mechanism of anionic pollutant removal in an ion exchange membrane bioreactor (IEMB) was studied for drinking water denitrification. This hybrid process combines continuous ion exchange transport (Donnan dialysis) of nitrate and its simultaneous bioreduction to gaseous nitrogen. A nonporous mono-anion permselective membrane precludes direct contact between the polluted water and the denitrifying culture and prevents secondary pollution of the treated water with dissolved nutrients and metabolic products. Complete denitrification may be achieved without accumulation of NO3(-) and NO2(-) ions in the biocompartment. Focus was given to the effect of the concentration of co-ions, counterions, and ethanol on the IEMB performance. The nitrate overall mass transfer coefficient in this hybrid process was found to be 2.8 times higher compared to that in a pure Donnan dialysis process without denitrification. Furthermore, by adjusting the ratio of co-ions between the biocompartment and the polluted water compartment, the magnitude and direction of each individual anion flux can be easily regulated, allowing for flexible process operation and control. Synthetic groundwater containing 135-350 mg NO3(-) L(-1) was treated in the IEMB system. A surface denitrification rate of 33 g NO3(-) per square meter of membrane per day was obtained at a nitrate loading rate of 360 g NO3(-) m(-3)d(-1), resulting in a nitrate removal efficiency of 85%.

Bromate is a disinfection byproduct with carcinogenic properties that has to be removed from drinking water to concentrations below 10 or 25 microg/L. This work evaluates the applicability of the ion exchange membrane bioreactor (IEMB) concept for the removal of bromate from drinking water, in situations where nitrate is also present in concentrations up to 3 orders of magnitude higher than bromate. The batch results obtained show that the biological reduction of bromate was slow and only occurring after the complete reduction of nitrate. The specific bromate reduction rates varied from 0.027 +/- 0.01 mg BrO3(-)/g(cell dry weight) x h to 0.090 mg BrO3(-)/ g(cell dry weight) x h for the studied concentrations. On the other hand, transport studies, using anion exchange membranes showed that Donnan dialysis could efficiently remove bromate from polluted waters. Therefore, the use of a dense, nonporous membrane in the IEMB system, isolates the water stream from the biological compartment, allowing for the uncoupling of the water production rate from the biological reduction rate. The IEMB system was used for the treatment of a polluted water stream containing 200 microg/L of BrO3(-) and 60 mg/L of NO3(-). The concentrations of both ions in the treated water were reduced below the recommended levels. No bromate accumulation was observed in the biocompartment of the IEMB, suggesting its complete reduction in the biofilm formed on the membrane surface contacting the biocompartment. Therefore, the IEMB has proven to be a technology able to solve specific problems associated with the removal of bromate from water streams, since it efficiently removes bromate from drinking water even in the presence of nitrate, a known competitor of bromate biological reduction, without secondary contamination of the treated water by cells or excess of carbon source.

The history of the potential and electrical current evolution of an industrial chlor-alkali membrane electrolyser is a powerful tool to track its operational efficiency progress over time and for deciding the required maintenance instants. For this reason, the performance of a dedicated industrial NaCl electrolyser was systematically analysed as a function of its service time for about 8 years, recording the cell potential versus current density. The documented potential values were normalized taking into account the initial current density, which allowed to reduce data scattering due to small fluctuations of the current density values. The ohmic overpotential contribution, associated to the ion-exchange membranes, showed an average relative error smaller than 3% and the activation overpotential, related to the electrodes’ performance, displayed an average relative error of 6%. Thus, the proposed approach enables rigorous assessing of the performance of industrial chlor-alkali membrane electrolysers for adequate scheduling of their maintenance, which leads to significant operational and economic improvements of the chlor-alkali process.

The biological degradation of nitrate and perchlorate was investigated in an ion exchange membrane bioreactor (IEMB) using a mixed anoxic microbial culture and ethanol as the carbon source. In this process, a membrane-supported biofilm reduces nitrate and perchlorate delivered through an anion exchange membrane from a polluted water stream, containing 60 mg/L of NO₃⁻ and 100 μg/L of ClO₄⁻. Under ammonia limiting conditions, the perchlorate reduction rate decreased by 10%, whereas the nitrate reduction rate was unaffected. Though nitrate and perchlorate accumulated in the bioreactor, their concentrations in the treated water (2.8 ± 0.5 mg/L of NO₃⁻ and 7.0 ± 0.8 μg/L of ClO₄⁻, respectively) were always below the drinking water regulatory levels, due to Donnan dialysis control of the ionic transport in the system. Kinetic parameters determined for the mixed microbial culture in suspension showed that the nitrate reduction rate was 35 times higher than the maximum perchlorate reduction rate. It was found that perchlorate reduction was inhibited by nitrate, since after nitrate depletion perchlorate reduction rate increased by 77%. The biofilm developed in the IEMB was cryosectioned and the microbial population was analyzed by fluorescence in situ hybridization (FISH). The results obtained seem to indicate that the kinetic advantage of nitrate reduction favored accumulation of denitrifiers near the membrane, whereas per(chlorate) reducing bacteria were mainly positioned at the biofilm outer surface, contacting the biomedium. As a consequence of the biofilm stratification, the reduction of perchlorate and nitrate occur sequentially in space allowing for the removal of both ions in the IEMB.

The hydrodynamics of electrodialysis and reverse electrodialysis is commonly studied by neglecting membrane deformation caused by transmembrane pressure (TMP). However, large frictional pressure drops and differences in fluid velocity or physical properties in adjacent channels may lead to significant TMP values. In previous works, we conducted one-way coupled structural-CFD simulations at the scale of one periodic unit of a profiled membrane/channel assembly and computed its deformation and frictional characteristics as functions of TMP. In this work, a novel fluid–structure interaction model is presented, which predicts, at the channel pair scale, the changes in flow distribution associated with membrane deformations. The continuity and Darcy equations are solved in two adjacent channels by treating them as porous media and using the previous CFD results to express their hydraulic permeability as a function of the local TMP. Results are presented for square stacks of 0.6-m sides in cross and counter flow at superficial velocities of 1 to 10 cm/s. At low velocities, the corresponding low TMP does not significantly affect the flow distribution. As the velocity increases, the larger membrane deformation causes significant fluid redistribution. In the cross flow, the departure of the local superficial velocity from a mean value of 10 cm/s ranges between −27% and +39%.

International audience ; Aqueous organic redox-flow batteries (AORFBs) are an emerging technological solution in the field of grid-scale energy storage, owing to their long lifetime, safety, chemical flexibility, potentially low costs and environmental friendliness. Membranes are a crucial component of the battery as they affect the ohmic resistance and the power density of the cells, as well as the depth-of-discharge and the lifetime and thus, crucially affect the levelised cost of storage of the battery. Herein, we provide a critical discussion of the state-of-the-art literature on membranes for AORFBs, including a summary on the theories used to model the transport of ions and active species through the membrane, as well as a compilation of experimental correlations between various membrane properties and cell performance. Adequate strategies to further improve the performance and lower the cost of AORFBs by employing and designing appropriate membranes are highlighted. Finally, the remaining challenges are summarised and perspectives on future research directions for developing appropriate and low-cost membranes for AORFBs are outlined.

In this review, the state of the art of modified membranes developed and applied for the improved performance of redox flow batteries (RFBs) is presented and critically discussed. The review begins with an introduction to the energy-storing chemical principles and the potential of using RFBs in the energy transition in industrial and transport-related sectors. Commonly used membrane modification techniques are briefly presented and compared next. The recent progress in applying modified membranes in different RFB chemistries is then critically discussed. The relationship between a given membrane modification strategy, corresponding ex situ properties and their impact on battery performance are outlined. It has been demonstrated that further dedicated studies are necessary in order to develop an optimal modification technique, since a modification generally reduces the crossover of redox-active species but, at the same time, leads to an increase in membrane electrical resistance. The feasibility of using alternative advanced modification methods, similar to those employed in water purification applications, needs yet to be evaluated. Additionally, the long-term stability and durability of the modified membranes during cycling in RFBs still must be investigated. The remaining challenges and potential solutions, as well as promising future perspectives, are finally highlighted.