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 bicarbonatewater 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 unit. The impact of using current commercial membranes and future enhanced membranes on the efficiency of the system was evaluated, along with the effect of operating and design parameters through sensitivity analyses. Results 2 indicated that exergy efficiency up to 8.5% may be obtained by considering enhanced future membranes and multi-column regeneration units.
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 brine, developed within the EU-funded ZERO BRINE project. The pilot crystallizer was tested with the retentate of the nanofiltration unit processing the spent brine from the industrial water production plant of Evides Industriewater B.V. (Rotterdam, The Netherlands).Magnesium and calcium hydroxide were selectively precipitated by adding alkaline solution in two consecutive steps and controlling reaction pH. Performance was assessed in terms of recovery efficiency and purity of produced crystals, observing in most investigated cases a recovery of about 100% and 97% and a purity above 90% and 96%, for magnesium and calcium hydroxide, respectively.
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.
The continuous depletion of minerals caused by land mining
and
the increase in their demand
have pushed the development of novel sustainable technological processes
for mineral recovery from unconventional sources. In this context,
magnesium (Mg) has gained considerable attention for its peculiar
properties and high relevance of its compounds, such as magnesium
hydroxide, Mg(OH)2. In the present work, the influence
of several operating conditions on the Mg(OH)2 precipitation
process was thoroughly investigated by adopting a novel multiple feed-plug
flow reactor. The influence of (i) initial Mg2+ concentrations
in the feed stream; (ii) brine and alkaline flow rates; and (iii)
the product recycling strategy (seeded crystallization) was considered.
The results marked the possibility of improving sedimentation and
filterability properties of Mg(OH)2 suspensions by adopting
the recycling strategy to overcome industrial issues associated with
the production of Mg(OH)2 suspensions using NaOH solutions.
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