Subcritical Water Extraction of Valuable Metals from Spent Lithium-Ion Batteries.

The leaching of valuable metals (Co, Li, and Mn) from spent lithium-ion batteries (LIBs) was studied using subcritical water extraction (SWE). Two types of leaching agents, hydrochloric acid (HCl) and ascorbic acid, were used, and the effects of acid concentration and temperature were investigated. Leaching efficiency of metals increased with increasing acid concentration and temperature. Ascorbic acid performed better than HCl, which was attributed to ascorbic acid's dual functions as an acidic leaching agent and a reducing agent that facilitates leaching reactions, while HCl mainly provides acidity. The chemical analysis of leaching residue by X-ray photoelectron spectroscopy (XPS) revealed that Co(III) oxide could be totally leached out in ascorbic acid but not in HCl. More than 95% of Co, Li, and Mn were leached out from spent LIBs' cathode powder by SWE using 0.2 M of ascorbic acid within 30 min at 100 °C, initial pressure of 10 bar, and solid-to-liquid ratio of 10 g/L. The application of SWE with a mild concentration of ascorbic acid at 100 °C could be an alternative process for the recovery of valuable metal in spent LIBs. The process has the advantages of rapid reaction rate and energy efficiency that may benefit development of a circular economy.

Aluminum leaching from water treatment sludge using hydrochloric acid and kinetic study.

Water treatment sludge (WTS) is abundantly produced in the world; the waste contributes to the environmental problems. Therefore, for WTS utilization, aluminum leaching was employed using hydrochloric acid in this study. Al leaching efficiency increased from 72% to 80% as hydrochloric acid concentration increased from 1 to 4 M. Decreasing the particle size and increasing the temperature increased Al leaching efficiency. The proposed kinetic model revealed that the rate-controlling step followed a series of two leaching mechanisms: initially controlled by product-layer diffusion and then by a chemically controlled reaction. For instance, at 70 °C, the initial stage is well fitted by product-layer diffusion (R2 = 0.87) compared to R2 = 0.60 for chemical reaction; while for the second stage, R2 = 0.95 was observed via chemical reaction compared to R2 = 0.74 for product-layer diffusion. The activation energies in these two stages were 9.58 kJ/mol and 10.73 kJ/mol, respectively. The proposed model was well validated by using data from literature and thus will be useful for other applications of leaching and extraction processes.

Cryolite (Na3AlF6) crystallization for fluoride recovery using an electrolytic process equipped with a sacrificial aluminum anode.

An electro-crystallization process equipped with a sacrificial aluminum anode was operated under an optimum condition to promote the formation of crystalline cryolite for the recovery of fluoride from synthetic F-containing wastewater. The effects of pH, Al/F molar ratio, initial F concentration, and electrolytes were investigated experimentally, and the results were compared with data obtained from chemical equilibrium modeling. Cryolite was successfully produced under optimum pH values of 5 to 6 and Al/F molar ratios of less than 1/6. The F removal increased with increasing Al/F molar ratio until reaching the molar ratio of 1/6 and decreased thereafter due to the formation of AlFn3-n species. The adsorption of AlFn3-n by Al(OH)3 precipitates contributed part of F removal. The removal efficiency reached 100% when the initial fluoride concentration was high while it was around 90% with the low initial fluoride concentration. XRD and SEM/EDX analysis showed that the obtained solids matched well to the commercial cryolite. Finally, the operating costs of chemical-crystallization (the process with Al ions added chemically) and electro-crystallization were compared, and the cost of the former was less than the latter. Energy consumption was the main contributor to the operating cost of the electro-crystallization process.

Effect of competing amines on the removal of tetramethylammonium hydroxide from solution using ion exchange.

Tetramethylammonium hydroxide (TMAH, TMA(+)) has been widely used as the photoresist developer in semiconductor and thin film transistor liquid crystal display manufacturing. In this study, TMAH-containing wastewater was treated by ion exchange method. Strong acid cation exchange resin was used. A kinetics study revealed that the ion exchange reaction reached equilibrium within 20 min and it could be described by a pseudo-second-order model. To assess the effects of competing ions, wastewater was spiked with three different amines, namely ethylamine (EA(+)), diethylamine (DEA(+)), and triethylamine (TEA(+)). TMAH uptake decreased when in the presence of amines, and it decreased in the order EA(+) < DEA(+) < TEA(+). It could be attributed to different proton affinity (PA) and the strength of affinity between amine molecules and resin matrix, as found from the ab initio calculation values and Langmuir isotherm parameters. However, the interaction energy between sulphonic acid groups and interfering amines in solution using density functional theory (DFT) calculation resulted in a different trend compared with that of PA. The difference might be caused by stabilization of amines by resin matrix and different molecular structures.

Harvesting of Scenedesmus obliquus FSP-3 using dispersed ozone flotation.

The Scenedesmus obliquus FSP-3, a species with excellent potential for CO(2) capture and lipid production, was harvested using dispersed ozone flotation. While air aeration does not, ozone produces effective solid-liquid separation through flotation. Ozone dose applied for sufficient algal flotation is similar to those used in practical drinking waterworks. The algae removal rate, surface charge, and hydrophobicity of algal cells, and fluorescence characteristics and proteins and polysaccharides contents of algogenic organic matter (AOM) were determined during ozonation. Proteins released from tightly bound AOM are essential to modifying the hydrophobicity of bubble surfaces for easy cell attachment and to forming a top froth layer for collecting floating cells. Humic substances in the suspension scavenge dosed ozone that adversely affects ozone flotation efficiency of algal cells.

Dispersed ozone flotation of Chlorella vulgaris.

Flotation separation of Chlorella vulgaris, a species with excellent potential for CO(2) capture and lipid production, was studied using dispersed ozone gas. Pure oxygen aeration did not yield flotation. Conversely, applying ozone effectively separation algae from broth through flotation. The ozone dose applied for sufficient algal flotation is <0.05 mg/g biomass, much lower than those used in practical drinking waterworks (0.1-0.3 mg/g suspended solids). Main products, lipid C16:0, was effectively collected in the flotage phase. The algae removal rate, surface charge, and hydrophobicity of algal cells, and proteins and polysaccharides contents of algogenic organic matter (AOM) were determined. Certain quantities of proteins were present in the cultivated algal suspension, hence, minimal quantity of ozone was required to release intracellular proteins as surfactants to lead to effective flotation.