Comparative Study of the Application of Chelating Resins for Rare Earth Recovery

The adsorption properties of chelating ion exchange resins containing mixed sulfonic/phosphonic (SP), aminophosphonic (AP) or iminodiacetic (IDA) acid functional groups were investigated towards the rare earth elements (REE). The aim of this work was to determine the potential for such resins to assist in the isolation of a mixed rare earth product under conditions relevant to the hydrometallurgical processing of rare earth containing minerals. The selectivity of the resins towards La, Sm and Ho, versus the common impurity metals; Al, Fe and Th, was determined in sulfuric acid media. The chelating resins all displayed a similar selectivity with Fe and Th adsorbed in preference to the REE and Al (i.e.Th≃ Fe>> REE≃ Al). The IDA resin displayed a far superior performance compared to both phosphonic resins (SP and AP) as well as a strong acid cation exchange resin for the adsorption of REE in the presence of very high Na or Ca concentrations. Equilibrium and kinetic adsorption isotherms for La were measured and successfully modelled with all resins, and the elution characteristics of selected resins investigated in both batch and column operation. A number of areas were identified where these resins could be exploited to provide an advantage in the hydrometallurgical processing of RE

Estrogenic hormone removal from wastewater using NF/RO membranes

This paper investigates the separation process of two estrogenic hormones, estrone and estradiol, using eight commercial NF and low pressure RO membranes. The results indicate that the separation mechanism of estrone and estradiol in membrane filtration processes is similar. While estrogenic hormone retention by porous membranes decreases with decreasing adsorption and the subsequent retention is relatively low, tight NF and RO membranes can retain estrogenic hormones effectively. It appears that the presence of organic matter in solution can enhance retention due to the interaction of such substances with estrogenic hormones. The results also suggest that physicochemical interactions within the membrane can play an important role. There is no cross flow effect on retention, whereas an increase in transmembrane pressure may lead to a decrease in steroid hormones retention for some membranes

Application of chelating weak base resin Dowex M4195 to the recovery of uranium from mixed sulfate/chloride media

The use of untreated seawater or bore water in uranium mineral processing circuits may represent a cheaper and more sustainable water resource for Australia’s mining operations. Using present technologies, the increased salinity from these water sources results in decreased uranium extraction and increased extraction of impurities. There is incentive to overcome these challenges, either through new technologies, or repurposing existing technologies. The ion exchange behaviour of U from sulfate media on the weakly basic chelating resin Dowex M4195 (bis-picolylamine functionality) and the effect of competing chloride and impurity metal ions (Th, Fe, Al, Cu, Ni) has been studied. Experiments to determine acid, and sulfate media behaviour, and extraction thermodynamics including the effect of increasing chloride concentration upon extraction behaviour were carried out. Dowex M4195 was found to have pK1 and pK2 values at 4.13 ± 0.04 and 2.1 ± 0.1 determined at 1.0 M NaCl. Dowex M4195 shows affinity for U(VI) over Fe3+ and Al3+ in sulfuric acid media with a U(VI) pH50 a full pH unit below that of Fe3+ at 0.17 and 1.82 respectively. With increasing chloride concentrations U and Th extraction is suppressed but Fe extraction increases. At the highest chloride concentrations explored Fe is preferentially extracted over U, and Th is not extracted at all. As chloride concentration increases the extraction of U passes through a minimum (40%) before increasing to around 60% for 4.0 M chloride at pH 1.80. Al3+ is not extracted by M4195 under any conditions explored. Dowex M4195 does show high selectivity for Cu and Ni over everything else

The sulfuric acid bake and leach route for processing of rare earth ores and concentrates: A review

Rare earths are critical to numerous materials and applications underpinning modern civilisation. The majority of the world's rare earth reserves are hosted in the three minerals bastnasite, monazite and xenotime. A key step in the processing of rare earth mineral concentrates is the chemical decomposition of the mineral structure to release the constituent elements. The sulfuric acid bake has historically been, and is also currently, one of the major processes used for this step. Current sulfuric acid bake processes for the Bayan Obo deposit in China and the Mt. Weld deposit in Australia together account for more than half of the world's rare earth production. In the sulfuric acid bake, the rare earth elements are converted to rare earth sulfates which are dissolved in a subsequent water leach. The conditions required to achieve mineral decomposition vary widely for different rare earth minerals. Adjustment of process conditions may often be used to achieve some degree of impurity rejection which is beneficial to downstream processing. This paper reviews the application of the sulfuric acid bake process to ores/concentrates containing mainly monazite, xenotime and bastnasite, and other less common rare earth minerals including euxenite, samarskite, fergusonite, loparite, allanite, eudialyte and pyrochlore. The reported effects of feed mineralogy and process variables such as reaction temperature, bake duration, acid to concentrate ratio and particle size are presented along with a brief review of current understanding of the bake chemistry and water leach results

Beneficial effect of iron oxide/hydroxide minerals on sulfuric acid baking and leaching of monazite

The sulfuric acid bake/leach process is an established industrial process for the extraction of rare earths from hard-rock monazite ores/concentrates. The chemical reactions in the monazite acid bake can be strongly influenced by the gangue mineralogy of the ore/concentrate. In this work, the beneficial effect of three iron oxide/hydroxide minerals, namely hematite, goethite and magnetite, added to high grade monazite concentrate in the acid bake (temperature range of 200–800°) and leach process was investigated to understand the role of iron gangue. Baked solids and leach residues were characterised by elemental analyses, XRD, SEM-EDS and FT-IR. It was found that the addition of iron minerals to the monazite acid bake had a significant impact on bake chemistry, acting to significantly increase the leaching of both the rare earth elements and thorium, compared to monazite alone, mainly for temperatures above 300 °C. The increased dissolution of rare earth elements and thorium was attributed to the formation of an amorphous and insoluble iron sulfate-polyphosphate type phase in preference to insoluble rare earth and thorium containing polyphosphates identified during acid baking of monazite alone. After baking at 650 °C, the iron sulfate-polyphosphate type phase was altered to a more soluble form, leading to an increase in dissolution of iron, phosphorus and thorium. Acid baking at 800 °C led to the formation of FePO4, Fe2O3, CePO4 (monazite) and in some cases CeO2, causing a decrease in leaching of rare earths and thorium, and either an increase or a decrease in leaching of iron and phosphorus depending on the formation of FePO4 versus Fe2O3