Energy harvesting by waste acid/base neutralization via bipolar membrane reverse electrodialysis

Bipolar Membrane Reverse Electrodialysis (BMRED) can be used to produce electricity exploiting acid-base neutralization, thus representing a valuable route in reusing waste streams. The present work investigates the performance of a lab-scale BMRED module under several operating conditions. By feeding the stack with 1 M HCl and NaOH streams, a maximum power density of ~17 W m−2 was obtained at 100 A m−2 with a 10-triplet stack with a flow velocity of 1 cm s−1, while an energy density of ~10 kWh m−3 acid could be extracted by a complete neutralization. Parasitic currents along feed and drain manifolds significantly affected the performance of the stack when equipped with a higher number of t…

Towards sustainable production of minerals and chemicals through seawater brine treatment using Eutectic freeze crystallization and Electrodialysis with bipolar membranes

European policy encourages the adoption of sustainable systems that promote the efficient use and recovery of minerals and chemicals. In this respect, desalination brines do contain a dramatic amount of valuable minerals and can be valorized through appropriate treatments rather than releasing them into the environment. This paper proposes an innovative brine recovery system for obtaining high purity chemicals through the integration of Eutectic Freeze Crystallization (EFC) and Electrodialysis with Bipolar Membrane (EDBM) technologies. Two separate laboratory-scale experimental campaigns were carried out to validate the potential integration of the two processes. Mirabilite (Na2SO4∙10H2O) h…

Effect of Design Features and Operating Conditions on the Performance of a Bipolar Membrane-Based Acid/Base Flow Battery

In the context of renewable energy sources, storage systems have been proposed as a solution to the issues related to fluctuations in the production and consumption of electric power. The EU funded BAoBaB project is aimed at developing the Acid/Base Flow battery (AB-FB), an environment-friendly, cost-competitive, grid-scale battery storage system based on the cyclic coupling of Bipolar Membrane ElectroDialysis (BMED) and its reverse, the Bipolar Membrane Reverse ElectroDialysis (BMRED) (Pärnamäe et al., 2020). Bipolar membranes promote catalytically water dissociation, thus allowing the storage of electric power in the form of acidic and alkaline solutions (pH gradient), obtained from their…

On the modelling of an Acid/Base Flow Battery: An innovative electrical energy storage device based on pH and salinity gradients

Abstract Electrical energy storage can enhance the efficiency in the use of fluctuating renewable sources, e.g. solar and wind energy. The Acid/Base Flow Battery is an innovative and sustainable process to store electrical energy in the form of pH and salinity gradients via electrodialytic reversible techniques. Two electromembrane processes are involved: Bipolar Membrane Electrodialysis during the charge phase and its opposite, Bipolar Membrane Reverse Electrodialysis, during the discharge phase. For the first time, the present work aims at predicting the performance of this energy storage device via the development of a dynamic mathematical model based on a multi-scale approach with distr…

Modellazione matematica di una Acid/Base Flow Battery: un dispositivo innovativo di accumulo di energia elettrica basato su gradienti di salinità e di pH

La Acid/Base Flow Battery (AB-FB) è una batteria innovativa che rappresenta un metodo sostenibile di immagazzinare energia elettrica. Questa batteria può, in linea teorica, garantire una densità di energia pari a 11 kWh/m3 che è un valore maggiore rispetto a quello fornito dalle tecnologie attualmente più utilizzate nel mondo quali quelle che sfruttano l’energia idroelettrica, l’energia osmotica o ancora l’aria compressa. La batteria AB-FB accumula energia sottoforma di gradienti di salinità e di pH. In particolare, essa funziona grazie ad una unità chiamata “stack” al cui interno ospita una serie di canali che permettono il passaggio di soluzioni elettrolitiche a diversi pH e concentrazion…

Valorization of seawater desalination brines through the integration of Eutectic Freeze Crystallization and Electrodialysis with Bipolar Membranes innovative technologies

European policy encourages the adoption of sustainable systems that promote the efficient use and recovery of resources. Accordingly, this study proposes integrating two innovative technologies, including Eutectic Freeze Crystallization (EFC) and Electrodialysis with Bipolar Membranes (EDBM), for treating seawater desalination brines. Two experimental campaigns were conducted to assess the viability of this novel treatment chain. Using two lab-test rig units, the effect of various operating conditions on the outputs and general performance of both EFC and EDBM was evaluated. Firstly, results showed that EFC could manage seawater brines to (i) obtain pure sodium sulphate, and fresh water in …

Electrodialysis with bipolar membranes for the generation of NaOH and HCl solutions from brines: an inter-laboratory evaluation of thin and ultrathin non-woven cloth-based ion-exchange membranes

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&…

The acid–base flow battery : Sustainable energy storage via reversible water dissociation with bipolar membranes

The increasing share of renewables in electric grids nowadays causes a growing daily and seasonal mismatch between electricity generation and demand. In this regard, novel energy storage systems need to be developed, to allow large-scale storage of the excess electricity during low-demand time, and its distribution during peak demand time. Acid–base flow battery (ABFB) is a novel and environmentally friendly technology based on the reversible water dissociation by bipolar membranes, and it stores electricity in the form of chemical energy in acid and base solutions. The technology has already been demonstrated at the laboratory scale, and the experimental testing of the first 1 kW pilot pla…

Scale-up of electrodialysis with bipolar membrane (EDBM) unit for valorisation of waste brine by experimental analysis

A Bi-objective Optimization Study of an Acid-Base Flow Battery for High Efficiency and Improved Power Density

Electrical energy storage is critical for a broader penetration of renewable energies with intermittent nature, such as solar and wind energy. The Acid/Base Flow Battery (AB-FB) is a unique, sustainable, and environmental-friendly storage technology with high electrolyte solution energy density. The method relies on reversible electrodialytic technologies using bipolar membranes to transform electrical energy into chemical energy related to pH gradients and vice versa. The charge phase is accomplished by using bipolar membrane electrodialysis, whereas the discharge phase is performed via bipolar membrane reverse electrodialysis. In a previous work, we developed an advanced multi-scale proce…

An experimental investigation on ionic shortcut currents reduction in Acid-Base Flow Battery systems

ELECTRICAL ENERGY STORAGE DEVICES BASED ON pH AND SALINITY GRADIENTS: MODELLING, EXPERIMENTS AND PILOTING

Electrodialysis with Bipolar Membranes for the Sustainable Production of Chemicals from Seawater Brines at Pilot Plant Scale

Environmental concerns regarding the disposal of seawater reverse osmosis brines require the development of new valorization strategies. Electrodialysis with bipolar membrane (EDBM) technology enables the production of acid and base from a salty waste stream. In this study, an EDBM pilot plant with a membrane area of 19.2 m2 was tested. This total membrane area results much larger (i.e., more than 16 times larger) than those reported in the literature so far for the production of HCl and NaOH aqueous solutions, starting from NaCl brines. The pilot unit was tested both in continuous and discontinuous operation modes, at different current densities (200-500 A m-2). Particularly, three differe…

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…

Bipolar membrane reverse electrodialysis for the sustainable recovery of energy from pH gradients of industrial wastewater: Performance prediction by a validated process model

Abstract The theoretical energy density extractable from acidic and alkaline solutions is higher than 20 kWh m−3 of single solution when mixing 1 M concentrated streams. Therefore, acidic and alkaline industrial wastewater have a huge potential for the recovery of energy. To this purpose, bipolar membrane reverse electrodialysis (BMRED) is an interesting, yet poorly studied technology for the conversion of the mixing entropy of solutions at different pH into electricity. Although it shows promising performance, only few works have been presented in the literature so far, and no comprehensive models have been developed yet. This work presents a mathematical multi-scale model based on a semi-…

A comprehensive multi-scale model for bipolar membrane electrodialysis (BMED)

Bipolar membrane electrodialysis (BMED) is a technology combining solute and solvent dissociation to produce chemicals. In the recent decades, it has been typically studied for the production of valuable acid and base solutions from salt streams. Although many works have been devoted to the experimental investigation of BMED, only a few efforts have focused on its mathematical modelling. In the present work, a comprehensive process model based on a multi-scale approach with distributed parameters is presented for the first time. Five models related to four different dimensional scales were fully integrated to form a comprehensive tool. The integrated model was developed by using the process…

Ionic shortcut currents via manifolds in reverse electrodialysis stacks

Abstract Reverse electrodialysis (RED) is a blue energy technology for clean and sustainable electricity harvesting from the mixing entropy of salinity gradients. Recently, many efforts have been devoted to improving the performance of RED units by developing new ion-exchange membranes and by reducing the detrimental phenomena affecting the process. Among these sources of “irreversibility”, the shortcut currents (or parasitic currents) flowing through alternative pathways may affect the process efficiency. Although such phenomena occur in several electrochemical processes (e.g. fuel cells, bipolar plate cells and vanadium redox flow batteries), they have received a poor attention in RED uni…

On the modelling of an Acid/Base Flow battery: an innovative electrical energy storage device based on pH and salinity gradients

The Acid/Base Flow Battery (AB-FB) is an innovative and sustainable way to store electric energy. It can theoretically guarantee an energy density of about 11 kWh/m3, which is higher than that provided by pumped hydropower, osmotic energy storage and compressed air. The AB-FB stores energy as pH and salinity gradients by employing a stack provided with (i) channels, hosting the solutions at difference pH and concentrations, separated by (ii) monopolar and bipolar ion exchange membranes. Two different membrane processes are involved: the Bipolar Membrane Electrodialysis (ED-BM) as charging step and its opposite, Bipolar Membrane Reverse Electrodialysis (RED-BM) as discharging step. The prese…

Simulation-based design of a bipolar membranes electrodialysis unit for chemicals production from brines

Nowadays environmental concerns are modifying the production and consumption patterns used so far. An important objective to improve our society is the use of sustainable processes that can reduce industrial waste streams. Bipolar membranes electrodialysis (EDBM) is an emerging environmentally friendly process that could be easily integrated into a circular economy approach to valorize waste brines. It is an electro-membrane process that allows the production of chemicals using only water, electrical energy and a salty solution. When electric current is applied to the electrodes of the EDBM stack, water dissociation takes place in the bipolar membranes. Therefore, the ions from water are co…

Acid and alkaline production from multi-ionic brines via Electrodialysis with Bipolar Membranes

In recent years, a great attention has grown towards the brine valorization through chemicals production and mineral recovery as an alternative to conventional disposal. Electrodialysis with Bipolar Membranes (EDBM) is an emerging process that can be used for the production of alkaline and acidic solutions from salt solutions. Within the SEArcularMINE project framework, the exploitation of saltworks bitterns (highly concentrated solutions generated during the sea-salt production process) is proposed for minerals recovery and NaOH and HCl solutions production. In this work, an EDBM unit, equipped with commercial ion exchange membranes, was tested for the first time in closed-loop mode with: …

Production of acidic and alkaline solutions via Electrodialysis with bipolar membranes from synthetic and real brines from saltworks

1. Introduction In recent decades, there has been a great deal of interest at both the industrial and academic levels in identifying unconventional sources for chemical production and raw material recovery. In this context, brine disposal, which was previously addressed as a priority to reduce environmental problems, is now seen as an opportunity to apply new or existing technologies in circular processes that allow for the valorization of previously considered waste solutions [1]. In this regard, Electrodialysis with bipolar membranes (EDBM) can be used to produce acidic and alkaline solutions from salty solutions. EDBM is an electro-membrane process distinguished by the alternated positio…