State of the Art in Separation and Analysis of Energies

HKUST-1 is a metal-organic framework (MOF) that is widely studied as an adsorbent for CO₂ capture because of its high adsorption capacity and good CO₂/CH₄ selectivity. However, the numerous synthesis routes for HKUST-1 often result in the obtention of MOF in powder form, which limits its application in industry. Here, we report the shaping of HKUST-1 powder via the extrusion method with the usage of bio-sourced polylactic acid (PLA) as a binder. The characterization of the composite was determined by XRD, FTIR, TGA and SEM analyses. The specific surface area was determined from the N₂ adsorption isotherm, whereas the gas adsorption capacities were investigated via measurements of CO₂ and CH₄ isotherms of up to 10 bar at ambient temperature. The material characterization reveals that the composite preserves HKUST-1’s crystalline structure, morphology and textural properties. Furthermore, CO₂ and CH₄ adsorption isotherms show that there is no degradation of gravimetric gas adsorption capacity after shaping and the composite yields a similar isosteric adsorption heat as pristine HKUST-1 powder. However, some trade-offs could be observed, as the composite exhibits a lower bulk density than pristine HKUST-1 powder and PLA has no impact on pristine HKUST-1’s moisture stability. Overall, this study demonstrates the possibility of shaping commercial HKUST-1 powder, using PLA as a binder, into a larger solid-state-form adsorbent that is suitable for the separation of CO₂ from CH₄ with a well-preserved pristine MOF gas-adsorption performance. Full article

Escalating environmental concerns have dictated the need to develop innovative methods for efficiently desulfurizing marine fuels (heavy fuel oils). In this work, the oxidative desulfurization method using deep eutectic solvents (DESs) was applied to reduce the sulfur content in a commercially available heavy fuel oil (HFO) below 0.5 wt.%, as current regulations demand. Initially, the S-compounds in the fuel were oxidized using an oxidative mixture of H₂O₂ with carboxylic acid (either acetic or formic acid). Subsequently, the oxidized S-compounds were extracted from the fuel using a series of environmentally friendly deep eutectic solvents (DESs), the best of which was proven to be a mixture of choline chloride with ethylene glycol at a 1/2 molar ratio. The process was optimized by investigating the effect of several process parameters on the desulfurization efficiency, namely, the H₂O₂/S molar ratio, the H₂O₂/acid molar ratio, the acid type, the oxidation temperature and oxidation time, the solvent/fuel mass ratio, the extraction time, and the extraction temperature. A desulfurization efficiency of 75.7% was achieved under the optimized conditions, reducing the S content in the fuel to 0.33 wt.%. Furthermore, different methods to recycle the DESs were investigated, and consecutive desulfurization and solvent regeneration cycles were performed. The most efficient recycling method was determined to be the anti-solvent addition of excess water, which resulted in 89.5% DES purification by causing precipitation of the dissolved solids. After three cycles of desulfurization and regeneration using different recycling routes, it was found that the regeneration degree declines gradually; however, it is more than 79.3% in all cases. Full article

Furfural is an intermediary and aldehyde compound degraded from paper insulation, which is used with liquid fluid in power transformers. It can be utilized as an important indicator to evaluate the degradation degree of the paper insulation and the condition of transformers to predict their lifetime. However, the conventional methods are inevitably inconvenient as they require additional derivatization with hazardous agents and time-consuming chromatographic separation and processes. In this work, a facile and green analysis method for the determination of furfural concentration in the insulating fluid of operating power transformers was developed. As furfural was selectively extracted from the insulting fluid by deionized water, the aqueous solution could be directly subjected to a UV spectral analysis without any derivatization using hazardous agents or hindrance of the fluid in the UV spectrum. The results showed that the spectral method could obtain a favorable linear relationship between the concentration of furfural and its characteristic absorbance at 280 nm (λ max). The limit of detection (LOD) was below 0.1 ppm, which is a sufficient detection level to evaluate the condition of the insulating fluid. Furthermore, the method was compared with the conventional HPLC and colorimetric analyses, revealing satisfactory accuracy and verification of the results. It is possible to measure the furfural concentration in situ using a portable UV-spectrometer at a single wavelength, 280 nm, after simple extraction in the field. This approach offers a novel and green analytical method to quantitatively determine the aromatic furan compounds in a power transformer’s insulating fluid in place without the use of an organic extraction solvent or hazardous reagents for derivatization and analysis. Full article

Thallium (Tl) is an extremely toxic rare metal to the eco-environment. Trace thallium impurity in ammonium perrhenate is harmful to the high-temperature mechanical properties of rhenium metal used for aeroengine single crystal blade. The di(2-ethylhexyl) phosphoric acid (P204) extraction to remove thallium in ammonium perrhenate solution without additive was innovatively proposed. The migration behavior of trace thallium with the concentration of P204, saponification degree and organic/aqueous phase (O/A) ratio, distribution law of thallium in the extraction system of P204, and mechanism of thallium removal were revealed. It was found Tl removal was rapidly increased to 98.5%, at conditions of P204 0.75 mol/L saponified 70% by ammonia, Tl 3.27 mg/L, O/A 1:1, T 298.15 ± 2 K, 250 rpm, and 3 min. McCabe-Thiele Tl extraction equilibrium isotherms indicates Tl concentration of raffinate less than 18.7 μg/L, a theoretical extraction of two stages and a theoretical stripping of two stages are required when both O/A work lines were at 1.0. Therefore, the method of the P204 solvent extraction system can effectively extract Tl in the forms of TlA(org), TlA₃(org), TlOHA₂(org), and Tl(OH)₂A(org). Meanwhile, the new approach can be a promising process for ammonium rhenate refining. Full article

The most common beneficiation method for feldspar is flotation with a cationic (amine) collector under acidic conditions. However, there are several disadvantages to this, such as environmental pollution and equipment corrosion. In order to resolve such problems, it is important to study the flotation of feldspar using anionic collectors under natural pH conditions. The purpose of this paper is to study the effects and mechanism of Fe³⁺ on flotation separation of feldspar and epidote using sodium oleate (NaOL) at a natural pH. Through flotation experiments, adsorption measurements, zeta potential testing, FTIR analysis and X-ray photoelectron spectroscopy (XPS), the mechanism of Fe³⁺ on the surface of feldspar and epidote is revealed, and the reason behind the difference in flotation of the two minerals is discussed. The flotation test results show that Fe³⁺ can significantly improve the flotation behavior of minerals when NaOL is used as a collector under natural pH, and the highest recovery rates of feldspar and epidote are 90% and 43%, respectively. Analysis of the solution and adsorption measurement results show that Fe³⁺ is adsorbed on the minerals′ surface in the form of Fe(OH)₃, which promotes the adsorption of NaOL on the minerals’ surface through Fe(OH)₃, activating the flotation of feldspar and epidote. The difference in adsorption of Fe³⁺ between feldspar and epidote is the reason for this difference in flotation behavior. The results of the zeta potentials show that after being treated with Fe³⁺, the electrostatic adsorption of NaOL displays a significant negative shift on the surface of feldspar, while there is almost no electrostatic adsorption of NaOL on the surface of Fe³⁺-treated epidote. FTIR analysis confirmed that the difference in the adsorption of Fe³⁺ and NaOL on the surface of feldspar and epidote is due to the fact that there are more active particles (metal bonds) on the surface of feldspar than on the surface of epidote, and the properties of these metal bonds can be changed by Fe³⁺, which allows NaOL to be more easily adsorbed on the mineral surface through –COO⁻. The possible adsorption form is “mineral-Fe³⁺–COO⁻“. Compared with the infrared spectrum of epidote, there is a new absorption peak at 1713.68 cm⁻¹, which can be attributed to the C=O characteristic peak of NaOL in the infrared spectrum of Fe³⁺–NaOL-treated feldspar, which is why the floatability of feldspar is better than epidote. XPS confirmed that the Fe on the surface of feldspar is Fe³⁺ in the form of Fe(OH)3, while Fe on the surface of epidote is mainly Fe₂O₃ (Fe–O) contained in mineral crystals. Furthermore, there is less adsorption of Fe³⁺ on the surface of epidote, and this discrepancy leads to the difference in the adsorption of NaOL on the minerals’ surface, which itself leads to the difference in flotation behavior between feldspar and epidote. These findings indicate that the flotation separation of feldspar and epidote can be achieved using Fe³⁺ and NaOL under natural pH. This study may provide a reference for the flotation mechanism of feldspar and epidote under natural pH. Full article

Most commercially available lithium ion battery systems and some of their possible successors, such as lithium (metal)-sulfur batteries, rely on liquid organic electrolytes. Since the electrolyte is in contact with both the negative and the positive electrode, its electrochemical stability window is of high interest. Monitoring the electrolyte decomposition occurring at these electrodes is key to understand the influence of chemical and electrochemical reactions on cell performance and to evaluate aging mechanisms. In the context of lithium-sulfur batteries, information about the analysis of soluble species in the electrolytes—besides the well-known lithium polysulfides—is scarcely available. Here, the irreversible decomposition reactions of typically ether-based electrolytes will be addressed. Gas chromatography in combination with mass spectrometric detection is able to deliver information about volatile organic compounds. Furthermore, it is already used to investigate similar samples, such as electrolytes from other battery types, including lithium ion batteries. The method transfer from these reports and from model experiments with non-target analyses are promising tools to generate knowledge about the system and to build up suitable strategies for lithium-sulfur cell analyses. In the presented work, the aim is to identify aging products emerging in electrolytes regained from cells with sulfur-based cathodes. Higher-molecular polymerization products of ether-based electrolytes used in lithium-sulfur batteries are identified. Furthermore, the reactivity of the lithium polysulfides with carbonate-based solvents is investigated in a worst-case scenario and carbonate sulfur cross-compounds identified for target analyses. None of the target molecules are found in carbonate-based electrolytes regained from operative lithium-titanium sulfide cells, thus hinting at a new aging mechanism in these systems. Full article

This review explores the potential of separating and recycling rare earth elements (REEs) from different energy conversion systems, such as wind turbines, electric vehicles batteries, or lighting devices. The REEs include 17 elements (with global production of 242 kilometric tons in 2020) that can be found abundantly in nature. However, they are expensive and complicated to extract and separate with many environmental challenges. The overall demand for REEs is continuously growing (with a 10% yearly increase) and it is quite clear that recycling has to be developed as a supply strategy in addition to conventional mining. However, the success of both mining and recycling depends on appropriate separation and processing technologies. The overall REE recycling situation today is very weak (only 2% of REEs are recovered by recycling processes compared with 90% for iron and steel). The biggest recycling potentials rely on the sectors of lamp phosphors (17%), permanent magnets (7%), and NiMH batteries (10%) mainly at the end-of-life stage of the products. The profitability of rare earth recycling mostly depends on the prices of the elements to accommodate the processing costs. Therefore, end-of-life REE recycling should focus on the most valuable and critical REEs. Thus, the relevant processes, feed, and economic viability warrant the detailed review as reported here. Full article