Search Results (66)

The chemical industry’s transition towards sustainability necessitates the development of eco-friendly processes that can replace petrochemical derivatives. Lignin, the second most abundant plant polymer, has potential as a renewable alternative to phenolic compounds. This study investigates lignin precipitation from softwood black liquor using five organic acids (acetic, citric, lactic, malic, and oxalic) as a sustainable alternative to sulfuric acid. The precipitated lignins were subjected to comprehensive chemical and thermal characterization, revealing higher total phenolic content and enhanced reactivity when organic acids were employed. Notably, organic acid-precipitated lignins demonstrated comparable or superior purity, with ash contents below 0.50%, compared to 3.28% observed for sulfuric acid-precipitated lignin. These findings suggest that organic acids are a viable and greener alternative for lignin precipitation, promoting higher purity and yield, thus supporting lignin valorization efforts. Full article

To maintain the carbon dioxide concentration below the no-return threshold for climate change, we must consider the reduction in anthropic emissions coupled to carbon capture methods applied in synergy. In our recent papers, we proposed a green and reliable method for carbon mineralization using ascorbic acid aqueous solution as the reducing agent for carbon (IV) to carbon (III), thus obtaining oxalic acid exploiting green reagents. Oxalic acid is made to mineralize as calcium (as the model cation) oxalate. Oxalates are solid-state reservoirs suitable for long-term carbon storage or carbon feedstock for manufacturing applications. The carbon mineralization reaction is a double-step process (carbon reduction and oxalate precipitation), and the carbon capture efficiency is invariably represented by a double-slope curve we formerly explained as a decrease in the reducing effectiveness of ascorbic acid during reaction. In the present paper, we demonstrated that the reaction proceeds via a “pure CO₂-capture” stage in which ascorbic acid oxidizes into dehydroascorbic acid and carbon (IV) reduces to carbon (III) and a “mixed” stage in which the redox reaction competes with the degradation of ascorbic acid in producing oxalic acid. Despite the irreversibility of the reduction reaction, that was demonstrated in abiotic conditions, the analysis of costs according to the market price of the reagents endorses the application of the method. Full article

Ferrous oxalate dihydrate is a versatile organic mineral with applications across fields. However, little is known about the feasibility of its synthesis directly from iron-bearing minerals using binary subcritical water (sCW) systems and its associated kinetics. In this study, the sCW+oxalic acid system at either 115 °C or 135 °C was investigated as a reaction medium for ferrous oxalate dihydrate (α-FeC₂O₄∙2H₂O) synthesis, starting from ferrotitaniferous sands. The kinetics of the synthesis reaction were studied, and the physicochemical characterization of the as-synthetized ferrous oxalates was performed. Overall, the sCW synthesis was temperature-dependent, following second-order reaction kinetics according to the proposed precipitation pathway. A high reaction rate constant, significantly high yields (up to 89%), and reduced reaction times (2–8 h) were evident at 135 °C. The as-synthetized product corresponded to the monoclinic α-FeC₂O₄∙2H₂O, showed relatively high specific surface areas (from 31.9 to 33.7 m²∙g⁻¹), and exhibited band gap energies within the visible light range (~2.77 eV). These results suggest that α-FeC₂O₄∙2H₂O can be synthesized using an organic dicarboxylic acid and iron-rich, widely available, low-cost mineral precursors. In addition, the as-prepared α-FeC₂O₄∙2H₂O could be further optimized and tested for catalytic and visible light photocatalytic applications. Full article

Toxicological analyses often necessitate the identification of compounds belonging to diverse functional groups. For GC–MS analyses, derivatization of compounds belonging to different functional groups can pose a challenge and requires the development of comprehensive methods of analysis. One example could be ethylene glycol, whose widespread use is related to possible unintentional or suicidal intoxications. This fact clearly indicates the need to develop sensitive methods for the determination of ethylene glycol and its metabolites in biological material, as only such complex analysis allows for proper toxicological expertise. A simultaneous GC–QqQ–MS/MS method for the determination of ethylene glycol together with its metabolites, glyoxal and glycolic acid, as well as the detection of glyoxylic acid and oxalic acid, was developed and fully validated. A novel approach for simultaneous derivatization of substances from different groups (alcohols, aldehydes, and carboxylic acids) was established. Sample preparation included the addition of three internal standards (BHB-d₄, ethylene glycol-d₄ and methylglyoxal), precipitation with acetonitrile and subsequent derivatization with N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA), as well as pentafluorophenylhydrazine (PFPH). Detection was carried out with the use of triple quadrupole mass spectrometer. The ionization method was electron impact, and quantitative analysis was carried out in multiple reaction monitoring mode. The lower limit of quantification was 1 μg/mL, 0.1 μg/mL, and 500 μg/mL for ethylene glycol, glyoxal, and glycolic acid, respectively. The presented method was applied in three authentic postmortem cases of ethylene glycol intoxication. Full article

Adsorptive–photocatalytic composites based on activated carbon (AC) and α-ferrous oxalate dihydrate (α-FOD) were synthesized by an original two-step method and subsequently used for the removal of phenol from aqueous solutions. To obtain the composites, ferrotitaniferous black mineral sands (0.6FeTiO₃·0.4Fe₂O₃) were first dissolved in an oxalic acid solution at ambient pressure, and further treated under hydrothermal conditions to precipitate α-FOD on the AC surface. The ratio of oxalic acid to the mineral sand precursor was tuned to obtain composites with 8.3 and 42.7 wt.% of α-FOD on the AC surface. These materials were characterized by X-ray powder diffraction, scanning electron microscopy, and the nitrogen adsorption–desorption method. The phenol removal efficiency of the composites was determined during 24 h of adsorption under dark conditions, followed by 24 h of adsorption–photocatalysis under visible light irradiation. AC/α-FOD composites with 8.3 and 42.7 wt.% of α-FOD adsorbed 60% and 51% of phenol in 24 h and reached a 90% and 96% removal efficiency after 12 h of irradiation, respectively. Given its higher photocatalytic response, the 42.7 wt.% α-FOD composite was also tested during successive cycles of adsorption and adsorption–photocatalysis. This composite exhibited a reasonable level of cyclability (~99% removal after four alternated dark/irradiated cycles of 24 h and ~68% removal after three simultaneous adsorption–photocatalysis cycles of 24 h). The promising performance of the as-prepared composites opens several opportunities for their application in the effective removal of organic micropollutants from water. Full article

The study aimed to investigate the potential antiurolithic effects of extracts, fractions, and betulinic acid (BA) from Citharexylum mirianthum. In vitro analysis involved precipitating calcium oxalate (CaOx) crystals in urine. For in vivo studies, rats were divided into four groups: naive; vehicle; potassium citrate (KC); and BA. Urolithiasis was induced using ethylene glycol and ammonium chloride. After seven days, urine, blood, and kidney tissues were evaluated. The results showed that methanolic extract, hexane, dichloromethane, and ethyl acetate fractions, as well as BA, reduced CaOx crystal formation. In vivo, the vehicle-treated group exhibited reduced urinary volume and Na⁺ excretion, while the BA-treated group showed restored urinary volume and Na⁺ excretion similar to the naive group. BA also significantly reduced urinary monohydrate and dihydrate crystal formation, comparable to the KC group. Other urinary parameters remained unchanged, but plasma analysis revealed decreased Na⁺, K⁺, and Ca²⁺ in the KC group. Renal tissue analysis indicated reduced lipid hydroperoxides and increased reduced glutathione in all urolithiasis groups, with unchanged nitrite levels. BA treatment also improved renal corpuscle morphology. Overall, our findings demonstrate that treatment with BA effectively prevented kidney damage induced by EG+AC ingestion, thereby improving renal function in the urolithiasis model. Full article

Textile industry effluents contain several hazardous substances, such as dye-containing effluents, which pose environmental and aesthetic challenges. Presently, the microbial-based remediation process is in use. This study investigated the application of ferrous–ferric oxide (Fe₃O₄) nanoparticles, a readily formulated nanoadsorbent, to remove scattered dye molecules from industrial effluents. The ferrous–ferric oxide nanoparticles were prepared using a chemical co-precipitation method. The nanoparticles had 26.93 emu g⁻¹ magnetization, with sizes smaller than 20 nm, and possessed a highly purified cubic spinel crystallite structure. The catalytic activity of the iron oxide depended on the dose, photocatalytic enhancer, i.e., H₂O₂ level, pH of the reaction medium, and dye concentration. We optimized the Fenton-like reaction to work best using 1.0 g/L of ferrous–ferric oxide nanoparticles, 60 mM oxalic acid at pH 7.0, and 60 ppm of dye. Iron oxides act as photocatalysts, and oxalic acid generates electron–hole pairs. Consequently, higher amounts of super-radicals cause the rapid degradation of dye and pseudo-first-order reactions. Liquid chromatography–mass spectrometry (LC-MS) analysis revealed the ferrous–ferric oxide nanoparticles decolorized and destroyed Disperse Red 277 in 180 min under visible light. Hence, complete demineralization is observed using a photo-Fenton-like reaction within 3 h under visible light. These high-capacity, easy-to-separate next-generation adsorption systems are suggested to be suitable for industrial-scale use. Ferrous–ferric oxide nanoparticles with increased adsorption and magnetic properties could be utilized to clean environmental pollution. Full article

The mechanisms and conditions under which urinary stones, pathological biominerals in the kidneys and bladder, are formed have not yet been fully clarified. This study aims to understand the role of the system complexity and seven different amino acids (alanine, phenylalanine, glycine, serine, cysteine, histidine, and aspartic acid) in the spontaneous precipitation of calcium oxalate. To elucidate these effects, the conditions simulating hyperoxaluria (c_i(Ca²⁺) = 7.5 mmol dm⁻³ and c_i(C₂O₄²⁻) = 6.0 mmol dm⁻³) were used for the first time. In this work, systematic research on calcium oxalate precipitation was performed in three systems of different chemical complexities: (a) only calcium and oxalate ions, (b) increased ionic strength, and (c) artificial urine at two initial pHs (pH_i = 5.0 and 9.0). In all the investigated systems, the dominant precipitation of calcium oxalate monohydrate (COM) was observed, except in the artificial urine system at pH_i = 9.0, in which a mixture of COM and calcium oxalate dihydrate (COD) was obtained. In all the investigated systems, a significant influence of the selected amino acids on the morphology and crystal growth of COM was observed, with more pronounced changes at pH_i = 9.0. Overall, polar amino acids and nonpolar phenylalanine inhibit the growth of COM, which is a more pathogenic hydrate form. The artificial urine system proved to be more relevant for the observation of effects relevant to kidney stone formation in the human body. Full article

Before steel can be utilized, pickling is necessary to remove surface oxidation products. However, as the ferrous ion concentration in the pickling solution increases, the pickling rate significantly diminishes, necessitating the treatment of spent pickling solution (SPS) to mitigate its hazardous effects prior to disposal. Current industrial methods predominantly rely on neutralization and precipitation techniques, which are cost-prohibitive and generate substantial by-products, thus failing to meet environmental protection standards. In this study, a new method, which is based on the formation of FeC₂O₄·2H₂O precipitate in a strong acid solution, is proposed to treat the SPS. Initially, the SPS undergoes a two-step impurity removal process, followed by the controlled addition of oxalic acid dihydrate (H₂C₂O₄·2H₂O) to precipitate iron. The resulting precipitate is filtered, washed, and vacuum-dried, and the regenerated acid is recycled back into the pickling tank. When 1 g/10 mL of H₂C₂O₄·2H₂O is used, the iron removal rate achieves 60%, and the acidity of the regenerated acid increases by 11.3%. X-ray diffraction pattern (XRD) and thermogravimetric–differential scanning calorimetry (TG-DSC) characterization showed that the precipitate was α-FeC₂O₄·2H₂O, with an average particle size of about 3.19 μm and a purity of 95.24%. This process innovatively achieves efficient recycling of acid and iron resources, offering a potential solution to the industrial challenge of difficult SPS treatment in the steel industry and meeting the urgent need for sustainable development. Full article

Nickel (Ni) and cobalt (Co) are strategic metals that have found applications in a wide range of metallurgical and industrial uses. In this study, the dissolution of a mixed nickel–cobalt hydroxide precipitate using organic acids (citric, oxalic, and malic acid) was investigated. Citric acid was found to be the best leaching agent yielding the following dissolution rates: 91.2% Ni, 86.8% Co, and 90.8% Mn. Oxalic acid resulted in low dissolution, which is likely due to the formation of insoluble metal oxalates. The impact of acid concentration, leaching time, and temperature on metal dissolution was systematically examined. The optimal dissolution conditions were identified as 0.5 M citric acid at 30 °C for 30 min, utilizing a 1/20 solid/liquid ratio and a stirring speed of 400 revolutions per minute (rpm). The attempt to use oxidants, such as potassium permanganate (KMnO₄) and hydrogen peroxide (H₂O₂), to achieve selective dissolution in an organic acid environment was not successful, which was different from that in the sulfuric acid case. As for the leaching kinetics in the organic acids, it seems that the leaching of Ni correlates with the Shrinking Core Model, specifically regarding porous-layer diffusion control. Based on the experimental results, the activation energy for the leaching of Ni was estimated to be 3.1 kJ/mol. Full article

Recent studies in hydrometallurgy are focused on developing eco-friendly and selective leach agents such as organic acids. These agents can extract metal ions, which are usually separated through precipitation methods. When traditional methods are used, the separation is complex and time-consuming, and each metal cation is required to be isolated separately. Moreover, extracted metal salts are subsequently recombined in the regeneration of cathode materials. To simplify this, a novel simultaneous precipitation approach has been developed, allowing the separation of metal salts that can directly contribute to regenerating novel cathode materials, bypassing the need for separate isolation. This study aimed to recover cobalt, nickel, and manganese from the organic leach solution of spent lithium-ion batteries (LIBs) through co-precipitation of metal oxalates. The investigation includes the selection of organic acids and the best parameters for the leaching process, as well as testing different molar ratios of the metals M²⁺ (M = Co, Ni, Mn) to oxalic acid (1:3, 1:4.5, 1:6, and 1:7.5) to examine the effects of the precipitating agent on the recovery percentages of the metals. The findings indicate that 2 M citric acid and 4 vol% H₂O₂ is the optimal parameter in the leaching process. Meanwhile, in the co-precipitation process, an increase in the molar ratio leads to a corresponding rise in the resulting metal recoveries. At the ratio of 1:7.5, cobalt, nickel, and manganese were recovered to the extent of 99.26%, 98.93%, and 94.01%, respectively. Nevertheless, at the increased molar ratio, the co-extraction of lithium and aluminum was observed, resulting in reduced selectivity and decreased precipitate purity. Full article

CuO/ZnO/Al₂O₃ catalysts are commonly used for the methanol steam reforming reaction. The oxalate precursor of CuO/ZnO/Al₂O₃ catalysts were prepared via the co-precipitation method using oxalic acid as the precipitator, deionized water and ethanol as the solvent, and microwave radiation and water baths as aging heating methods, respectively. This suggests that ethanol selects the crystalline phase composition of oxalate precursors and limits their growth. Microwave irradiation prompted the isomorphous substitution between Cu²⁺ of CuC₂O₄ and Zn²⁺ of ZnC₂O₄ in the mother liquid; Zn²⁺ in ZnC₂O₄·xH₂O was substituted with Cu²⁺ in CuC₂O₄, forming the master phase (Cu,Zn)C₂O₄ in the precursor. Moreover, the solid solution Cu-O-Zn formed after calcination, which exhibited nano-fibriform morphology. It has the characteristics of small CuO grains, a large surface area, and strong synergistic effects between CuO and ZnO, which is conducive to improving the catalytic performance of methanol steam reforming. The conversion rate of methanol reached 91.2%, the space time yield of H₂ reached 516.7 mL·g⁻¹·h⁻¹, and the selectivity of CO was only 0.29%. Full article

Recovery of valuable metals from end-of-life cylindrical lithium-ion batteries (LiBs) by leaching using acetic acid in the presence of an organic reductant is a promising combination to overcome environmental concerns that arise from employing inorganic reagents. This study investigated the effect of using molasses as a reductant in acetic acid leaching of a mixture of cathode and anode materials (black mass) prepared using mechanical treatments from spent LiBs. The effects of temperature, solid/liquid ratio, stirring speed, and acid concentration on the leaching of target metals (Co, Ni, Mn, and Li), current collector metal foil elements (Al and Cu), and Fe from the battery casing, with and without reductant, were investigated to obtain the optimum leaching conditions. The effect of adding the molasses at the start of leaching and after 1 h of leaching was tested. Acid leaching without molasses extracted the target metals Li, Ni, Co, and Mn with an efficiency <35% for all leaching parameters. However, the Al and Fe extractions increased as the acid molarity increased. Molasses addition at the start of leaching increased the extraction of the target metals to >96% at temperatures >50 °C. This is likely due to oxidation of the reducing sugars in the molasses that reduced the insoluble Co(III), Ni(III), and Mn(IV) components to soluble Co(II), Ni(II), and Mn(II) species, respectively. The kinetics of Co extraction in the presence of molasses were analysed, which has indicated that the rate-determining step in the Co leaching process is the reduction of Co(III) on the surface of particles in the black mass. Excess molasses can precipitate out target metals, especially Co, due to the presence of oxalic acid in the molasses. The reducing effect precipitated Cu(II) to Cu₂O, and could further reduce Co to metal, which suggests that leaching with the optimum dosage of acetic acid and molasses may selectively precipitate copper. Full article

Naturally occurring organic materials containing humic acids show a strong affinity towards rare earth elements (REE) and other critical elements. Leaching experiments on lignite coal waste produced from construction sand production revealed that the contained REEs were associated with the organic matter. Furthermore, adsorption studies revealed that the lignite waste was capable of extracting REEs from a model solution and increased the REE content of the lignite waste by more than 100%. As such, this study aimed to utilize the lignite waste to adsorb REEs from pregnant leach solutions and acid mine drainage sources having low REE concentrations and subsequently leach the lignite material to produce pregnant leach solutions containing relatively high amounts of REEs, which benefits the performance and economic viability of downstream separation and purification processes. An integrated flowsheet was developed based on this concept and tested at a pilot scale. The pregnant leachate solution (PLS) was generated from a heap leach pad containing 2000 tons of Baker seam coarse refuse. The pilot scale circuit was comprised of aluminum precipitation, adsorption using the waste lignite, and rare earth-critical metal (RE-CM) precipitation stages in succession. The results indicated that the aluminum precipitation stage removed over 88% and 99% of the Al and Fe, respectively. The adsorption stage increased the REE content associated with the waste lignite from 457 ppm to 1065 ppm on a whole mass basis. Furthermore, the heavy REE (HREE) content in the feedstock increased by approximately 250%, which raised the percentage of HREE in the REE distribution by 19 absolute percentage points. In addition to the REEs, concentrations of other critical elements such as Mn, Ni, and Zn also improved by 75%, 37%, and 250%, respectively. Bench-scale tests revealed that increasing the solids concentration in the waste lignite and PLS mix from 1% to 20% by weight enhanced the adsorption efficiency from 32.0% to 99.5%, respectively. As such, a new flowsheet was proposed which provides significantly higher REE concentrations in the PLS that can be fed directly to solvent extraction and/or oxalic acid precipitation and, thereby, enhancing process efficiency and economics. Full article

Hydrometallurgical methods for NdFeB recycling typically consist of several unit operations and require the extensive use of energy, water and chemicals which may negatively affect the applicability of these methods on an industrial scale. Based on the data from our previous studies, a simplified process of rare earth elements (REE) recovery from spent NdFeB magnets was developed further. The possibility of regenerating the leaching agent, as well as water recovery, in the process was investigated. This study also investigates a possibility of scaling up the recycling process developed on a laboratory scale. The leaching and precipitation stages were tested on a larger scale, where about 1 kg of end-of-life magnets was used as feed to the leaching step. In this study, end-of-life magnets were obtained from the manual disassembly of computer hard disc drives. After disassembly, the magnets were demagnetized, broken into pieces and fed to the leaching process. In the following step, rare earths were precipitated in the form of oxalates. The rare earths’ precipitation efficiency reached a maximum of 95.6%. The results showed that the co-precipitation of Fe highly depends on the amount of oxalic acid used as the precipitant. Smaller losses of Fe were achieved while using a stoichiometric amount of oxalic acid in relation to the REE present in the solution. At the end of the investigated process, rare earth oxalates were calcinated to oxides and their purity was investigated. The recirculation of a solution after oxalate precipitation and acid regeneration was tested with hydrochloric and sulfuric acids used as leaching agents. Solution recirculation was found to be possible only in the case of hydrochloric acid. Full article