Experimental assessment of reverse electrodialysis in closed loop configuration fed by NH4HCO3-water solutions

Closed loop reverse electrodialysis is a novel technology for converting low-temperature waste heat into electric energy. This innovative heat engine consists of two units: (i) a reverse electrodialysis unit where power is produced exploiting the concentration difference between a diluted and a concentrated salt solution and (ii) a thermally driven regeneration unit where low-grade waste heat is used to re-establish the original salinity gradient between the two salt solutions. Among all the possible salt solutions suitable as working fluid in such application, Thermolytic salts solutions, in particular Ammonium bicarbonate solutions, may be promising thanks to their characteristic thermall…

Effective magnesium recovery via seawater brines mining

In the last couple of decades, a rising interest has been focused on the research of novel and unconventional sources for mining minerals, such as industrial waste brines. As an example, brines are produced by desalination plants and discharged directly, or after being treated, into receiving water bodies possibly causing environmental concerns and renouncing the possibility to recover minerals [1,2]. Within this framework, the Water Mining WU-H2020 project aims at implementing an advanced Zero Liquid Discharge (ZLD) demo systems for the extraction of minerals and valuables products from industrial waste brines through a circular approach. The ZLD demo plant consists of: (i) Nano Filtration…

Development of a pilot plant for the recovery of magnesium hydroxide from waste brines

Waste brines from various industrial processes, mainly from saltworks, are an important source of minerals, such as magnesium, table salt and potable water.

Thermolytic reverse electrodialysis heat engine: model development, integration and performance analysis

Abstract Salinity gradient heat engines represent an innovative and promising way to convert low-grade heat into electricity by employing salinity gradient technology in a closed-loop configuration. Among the aqueous solutions which can be used as working fluid, ammonium bicarbonate-water solutions appear very promising due to their capability to decompose at low temperature. In this work, an experimentally validated model for a reverse electrodialysis heat engine fed with ammonium bicarbonate-water solutions was developed. The model consists of two validated sub-models purposely integrated, one for the reverse electrodialysis unit and the other for the stripping/absorption regeneration uni…

Regeneration units for thermolytic salts applications in water & power production: State of the art, experimental and modelling assessment

Abstract Thermolytic solutions are often proposed as high salinity or “draw” stream to generate a chemical potential driving force in Salinity Gradient Power (SGP) and Forward Osmosis (FO) technologies. Depleted “draw” solutions exiting the process can be regenerated by a thermal process powered at very-low grade heat, which is able to decompose the salt into gaseous ammonia and carbon dioxide, which can be stripped and then reabsorbed in the draw solution, restoring its initial concentration. In this work, two different experimental prototypes for the regeneration of ammonium bicarbonate aqueous solution were designed, built and tested. The effect of several operating parameters on the reg…

SELECTIVE CRYSTALLISATION OF MAGNESIUM AND CALCIUM HYDROXIDES FROM INDUSTRIAL WASTE BRINES: A PILOT STUDY

In the last years, a rising interest has been focused on the valorization of waste brines from industrial processes, such as desalination plants. In most current scenarios, waste brines are disposed directly, or after being treated, into a receiving water bodies, often causing environmental concerns and, more importantly, renouncing to the possibility of using such a waste as source of valuable raw materials. In fact, these brines are typically rich in useful salts and minerals, whose recovery can increase the environmental and economical sustainability of the industrial process [1-2]. The ZERO BRINE EU-H2020 project aims at the development of technologies for the recovery of salts, mineral…

The first operating thermolytic reverse electrodialysis heat engine

Abstract Thermolytic reverse electrodialysis heat engine (t-RED HE) has been recently proposed as a technology for converting low-temperature waste heat into electricity. The construction and operation of the first world lab-scale prototype unit are reported. The system consists of: (i) a reverse electrodialysis unit where, the concentration gradient between two solutions of thermolytic salts is converted into electricity and (ii) a thermally-driven regeneration unit where low-temperature heat is used to restore the initial conditions of the two feed streams. Regeneration is based on a degradation process of salts into gaseous ammonia and carbon dioxide, which can be removed almost entirely…

Modelling and experimental investigation of a novel ion exchange membrane crystallizer for magnesium recovery

A pilot-plant for the selective recovery of magnesium and calcium from waste brines

Abstract The problem of brines disposal has raised great interest towards new strategies for their valorisation through the recovery of minerals or energy. As an example, the spent brine from ion exchange resins regeneration is often discharged into rivers or lakes, thus impacting on the process sustainability. However, such brines can be effectively reconcentrated, after removal of bivalent cations, and reused for the resins regeneration. This work focuses on developing and testing a pilot plant for selective recovery of magnesium and calcium from spent brines exploiting a novel proprietary crystallization unit. This is part of a larger treatment chain for the complete regeneration of the …

Techno-economic analysis of a novel hybrid system for the valorisation of SWRO brines in a minor Sicilian island

In small remote islands, freshwater scarcity is an issue to which several viable solutions have already been found employing constantly evolving desalination technologies. The several RO plants in the Canary and minor Sicilian Islands are just an example . However, the beneficial application of seawater desalination is accompanied by a problematic matter: the production of high salinity brines. Not only do they compromise the aquatic ecosystem but their treatment in order to respect environmental regulations is costly too. Worth noting how these so-called “wastewater streams” present a high concentration of valuable raw materials, such as magnesium and calcium or sodium chloride, that are e…

ION EXCHANGE MEMBRANE CRYSTALLIZER FOR MAGNESIUM RECOVERY FROM SEAWATER AND INDUSTRIAL BRINE

The treatment and valorisation of waste brines deriving from industrial processes raised in the last years a strong interest in order to promote the whole process sustainability both in terms of minimisation of environmental impacts and raw materials recovery within a circular economy approach. With this respect, magnesium recovery from brines can be an interesting and practical example. In this work, a novel ion exchange membrane crystallizer (CrIEM1) is presented. In a CrIEM reactor, the presence of an Anion Exchange Membrane, separating a brine and an alkaline solutions, allows the passage of hydroxyl ions from the alkaline to the brine compartment, where crystallization of magnesium hyd…

A simulation tool for ion exchange membrane crystallization of magnesium hydroxide from waste brine

Abstract Increasing attention is nowadays paid to the management and valorisation of industrial waste brines aiming also at the recovery of raw materials. Magnesium has been listed as a Critical Raw Material by EU, prompting researchers to investigate novel routes for its recovery. Within this framework, a novel Crystallizer with Ion Exchange Membrane (CrIEM), is proposed as an innovative way to recover magnesium from industrial waste brines exploiting low-cost alkaline reactants. In the present work, a novel mathematical model of the CrIEM process is proposed to provide a useful tool for its design in different working conditions. Batch and feed & bleed continuous configurations have been …

Modelling of an innovative membrane crystallizer for the production of magnesium hydroxide from waste brine

Background The discharge of industrial waste brines into natural water bodies has gained large interest in recent years, both for its possible environmental impact, but also for the high potential of raw materials recovery contained in brines, pushing towards a circular economy approach. Among such raw materials, magnesium is often abundant and has been defined as aCritical Raw Material by EU [1]. Within this framework, a Crystallizer with Ion Exchange Membrane (CrIEM) has been proposed as an innovative process to recover magnesium from waste brines exploiting low-cost alkaline reactants. In the present work, a novel mathematical model of the CrIEM process is proposed providing a useful too…

A Novel Ionic Exchange Membrane Crystallizer to Recover Magnesium Hydroxide from Seawater and Industrial Brines

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 …