Synthesis and Properties of Hydrophilic and Hydrophobic Deep Eutectic Solvents via Heating-Stirring and Ultrasound.

Deep eutectic solvents (DESs) have emerged as a greener alternative to other more polluting traditional solvents and have attracted a lot of interest in the last two decades. The DESs are less toxic dissolvents and have a lower environmental footprint. This paper presents an alternative synthesis method to the classical heating-stirring method. The ultrasound method is one of the most promising synthesis methods for DESs in terms of yield and energy efficiency. Therefore, the ultrasound synthesis method was studied to obtain hydrophobic (Aliquat 336:L-Menthol (3:7); Lidocaine:Decanoic acid (1:2)) and hydrophilic DESs based on choline chloride, urea, ethylene glycol and oxalic acid. The physical characterization of DESs via comparison of Fourier transform infrared (FTIR) spectra showed no difference between the DESs obtained by heating-stirring and ultrasound synthesis methods. The study and comparison of all the prepared DESs were carried out via nuclear magnetic resonance spectroscopy (NMR). The density and viscosity properties of DESs were evaluated. The density values were similar for both synthesis methods. However, differences in viscosity values were detected due to the presence of some water in hygroscopic DESs.

Photocatalytic Activity of Zn x Mn3-x O4 Oxides and ZnO Prepared From Spent Alkaline Batteries.

Oxides with Zn x Mn3-xO4 stoichiometries and ZnO were synthesized from the "black mass" material recovered from spent alkaline batteries. The oxides were characterized by XRF, XRD with Rietveld refinement, SEM, and TEM methods. Optical characterization included diffuse reflectance (DRS) and photoluminescence (PL) measurements. ZnO presented a clear band edge in the UV region, and PL signals were detected. The Zn/Mn oxides showed strong absorption in the UV region and a continuous absorption band in the Vis-IR regions. There is a non-detected PL signal due to excited charges being trapped on sub-band energy states and/or transfer by non-radiative paths. Photocatalytic activity under both irradiation conditions was evaluated using the resazurin dye test, terephthalic acid fluorescence probe method, and NOx air purification evaluation. In the three photoactivity tests, ZnO performed well under both UV and Vis irradiation, whereas no evidence of any appreciable photocatalytic activity was observed for the Zn/Mn oxides. The results are discussed in terms of the findings of previously reported optical measurements.

Recovery of niobium and tantalum by solvent extraction from Sn-Ta-Nb mining tailings.

The slag from the extraction processes of metals from their ores may contain valuable components that, if adequately recovered, can be reintroduced in the technological life cycle. This is the case for the material obtained in Penouta mines in the North of Spain. These mineral sites are a main source of tin obtained from cassiterite. The mineral is submitted to a pyrometallurgical process to separate tin, however cassiterite is not the only mineral present in the veins, and large amounts of other minerals are normally discarded, constituting the slag. In the present case, besides cassiterite, one of the most abundant minerals in the ore is columbo tantalite, the source of the strategic coltan. In this work the raw material (slag) has been treated by acid leaching, using HF/H2SO4 as the leaching agent. Then liquid-liquid extraction of Nb and Ta was performed, with Cyanex®923 extractant, so that both metals were obtained separately. Then they were precipitated from the corresponding aqeuous solution, and calcined in order to yield Nb2O5 of 98.5% purity and tantalum salt, after calcination and purification, of 97.3% purity. The process described in this work opens a possibility to produce high quality materials that are considered critical by the EU from alternative sources exempt of criticality factors.

Tin and silver recovery from wave soldering dross.

This work proposes a method for the recovery of tin and silver from wave soldering dross produced during the manufacture of printed circuit boards. Samples of wave soldering dross were first subjected to carbothermic reduction to obtain an ingot containing the above metals plus other elements. This ingot was then subjected to electrorefining at different densities of electrical current, electrolyte flow rate, and cathode-anode separation distance, to determine the optimum conditions for recovering pure tin. Under such conditions, 82 wt% of the tin in the ingot was recovered at a purity of 99.94%. After subjecting ingots to continuous electrorefining under optimum conditions for 845 h, the slime collected at the anode was removed for the recovery of silver. This slime was subjected to thin-layer leaching with concentrated nitric acid. The leachate produced was subjected to copper-cementation; the silver adhering to the copper rod was collected by washing. This process recovered 92% of the silver in the wave soldering dross ingot at a purity of >99.6%. Some 99% of the copper entering the leachate from the copper rod during cementation was recovered by liquid-liquid extraction with 40% LIX84 (dissolved in EXXOL D100). This method could provide a rapid, inexpensive means of recovering pure tin and silver from wave soldering dross.

From spent alkaline batteries to Zn x Mn3-x O4 by a hydrometallurgical route: synthesis and characterization.

A series of Zn/Mn binary oxides with different molar ratios (1.4-11) were synthesized via co-precipitation from a solution obtained through the acidic (HCl) leaching of a black mass originating from the mechanical recycling of spent alkaline and Zn-C batteries. The oxides obtained were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Magnetic properties of the samples were also investigated. The Raman spectroscopy results showed all the binary metallic oxides belong to the Zn x Mn3-x O4 (0.25 ≤ x ≥ 1.75) type. All showed a spinel crystalline structure. The saturation magnetization decreases with the Zn/Mn molar ratio; a maximum of 13.19 emu g-1 was found for the molar ratio of 11 at the Curie temperature (25.5 K). XPS showed that all the synthesized compounds contained Mn2+, Mn3+ and Mn4+. Mn2+ was the most prominent at a molar ratio of 11, Mn3+ was most common at a molar ratio of 2, and Mn4+ at 1.4.

Oxidation and waste-to-energy output of aluminium waste packaging during incineration: A laboratory study.

This work reports the oxidation behaviour and waste-to-energy output of different semi-rigid and flexible aluminium packagings when incinerated at 850°C in an air atmosphere enriched with 6% oxygen, in the laboratory setting. The physical properties of the different packagings were determined, including their metallic aluminium contents. The ash contents of their combustion products were determined according to standard BS ISO 1171:2010. The net calorific value, the required energy, and the calorific gain associated with each packaging type were determined following standard BS EN 13431:2004. Packagings with an aluminium lamina thickness of >50µm did not fully oxidise. During incineration, the weight-for-weight waste-to-energy output of the packagings with thick aluminium lamina was lower than that of packagings with thin lamina. The calorific gain depended on the degree of oxidation of the metallic aluminium, but was greater than zero for all the packagings studied. Waste aluminium may therefore be said to act as an energy source in municipal solid waste incineration systems.

Valorisation of waste ilmenite mud in the manufacture of sulphur polymer cement.

This paper reports the preparation of sulphur polymer cements (SPCs) incorporating waste ilmenite mud for use in concrete construction works. The ilmenite mud raw material and the mud-containing SPCs (IMC-SPCs) were characterised physico-chemically and radiologically. The optimal IMC-SPC mixture had a sulphur/mud ratio (w/w) of 1.05 (mud dose 20 wt%); this cement showed the greatest compressive strength (64 MPa) and the lowest water absorption coefficient (0.4 g cm(-2) at 28 days). Since ilmenite mud is enriched in natural radionuclides, such as radium isotopes (2.0·10(3) Bq kg(-1)(228)Ra and 5.0·10(2) Bq kg(-1)(226)Ra), the IMC-SPCs were subjected to leaching experiments, which showed their environmental impact to be negligible. The activity concentration indices for the different radionuclides in the IMC-SPCs containing 10% and 20% ilmenite mud met the demands of international standards for materials used in the construction of non-residential buildings.

Microencapsulation of phosphogypsum into a sulfur polymer matrix: physico-chemical and radiological characterization.

The aim of this work is to prepare a new type of phosphogypsum-sulfur polymer cements (PG-SPC) to be utilised in the manufacture of building materials. Physico-chemical and radiological characterization was performed in phosphogypsum and phosphogypsum-sulfur polymer concretes and modeling of exhalation rates has been also carried out. An optimized mixture of the materials was obtained, the solidified material with optimal mixture (sulfur/phosphogypsum=1:0.9, phosphogypsum dosage=10-40 wt.%) results in highest strength (54-62 MPa) and low total porosity (2.8-6.8%). The activity concentration index (I) in the PG-SPC is lower than the reference value in the most international regulations and; therefore, these cements can be used without radiological restrictions in the manufacture of building materials. Under normal conditions of ventilation, the contribution to the expected radon indoor concentration in a standard room is below the international recommendations, so the building materials studied in this work can be applied to houses built up under normal ventilation conditions. Additionally, and taking into account that the PG is enriched in several natural radionuclides as (226)Ra, the leaching experiments have demonstrated that environmental impact of the using of SPCs cements with PG is negligible.