Dissolution kinetics of rare earth metal phosphates in carbonate solutions of alkali metals

Treatment of apatite raw materials is associated with the formation of large-tonnage waste – phosphogypsum. The content of rare earth metals in such waste reaches 1 %, which makes it possible to consider it a technogenic source for obtaining rare earth metals and their compounds. Up to the present moment, there are neither processing plants, nor an efficient process flow to handle phosphogypsum dumps. It is rational to use a way that involves extraction of valuable components and overall reduction of phosphogypsum dumps. Such process flow is available with carbonate conversion of phosphogypsum to alkali metal or ammonium sulfate and calcium carbonate upon the condition of associated extraction of rare earth metal (REM) compounds. Associated extraction of REM compounds becomes possible since they form strong and stable complexes with hard bases according to Pearson, which among other things include carbonate, phosphate and sulfate anions. Formation of lanthanide complexes with inorganic oxygen-containing anions is facilitated by the formation of high-energy Ln-O bonds. The study focuses on the dissolution of lanthanide phosphates in carbonate media. It was established that formation of REM carbonate complexes from their phosphates is a spontaneous endothermic process and that formation of lanthanide carbonates and hydroxides serves as thermodynamic limitation of dissolution. A shift in equilibrium towards the formation of carbonate complexes is achieved by increasing the temperature to 90-100 °C and providing an excess of carbonate. The limiting stage of REM phosphate dissolution in carbonate media is external diffusion. This is indicated by increasing rate of the process with an intensification of stirring, first order of the reaction and the value of activation energy for phosphate dissolution from 27 to 60 kJ/mol. A combination of physical and chemical parameters of the process allowed to develop an engineering solution for associated REM extraction during carbonate conversion of phosphogypsum, which included a 4-5 h conversion of phosphogypsum at temperature of 90-110 °C by an alkali metal or ammonium carbonate solution with a concentration of 2-3 mol/l. As a result, a solution with alkali metal (ammonium) sulfate is obtained, which contains REMs in the form of carbonate complexes and calcium carbonate. The rate of REM extraction into the solution reaches no less than 93 %. Rare earth metals are separated from the mother liquor by precipitation or sorption on anion exchange resins, while the excess of alkali metal or ammonium carbonate is returned to the start of the process.

Hydrogeochemical Characteristics of Uranium and Radon in Groundwater from the Goesan Area of the Ogcheon Metamorphic Belt (OMB), Korea

Uranium and radon concentrations in groundwater from the Goesan area of the Ogcheon Metamorphic Belt (OMB), central Korea, whose bedrock is known to contain the highest uranium levels in Korea, were analyzed from 200 wells. We also measured the uranium concentrations in the bedrock near the investigated wells to infer a relationship between the bedrock geology and the groundwater. The five geologic bedrock units in the Goesan area consist of Cretaceous granite (Kgr), Jurassic granite (Jgr) and three types of metasedimentary rocks (og1, og2, and og3). The percentages of the groundwater samples over 30 μg/L (maximum contaminant level, MCL of US EPA) were 2.0% of the 200 groundwater samples; 12% of Kgr and 1.8% of Jgr exceeded the MCL, respectively. Overall, 16.5% of the 200 groundwater samples exceeded 148 Bq/L (alternative maximum contaminant level, AMCL of US EPA); 60.0% of Kgr and 25.0% of Jgr exceeded the AMCL, but only 0% of og1, 7.9% of og2, and 2.6% of og3 exceeded the value, respectively. No direct correlation was found between uranium concentration and radon concentration in water samples. Radon has a slightly linear correlation with Na (0.31), Mg (−0.30), and F (0.36). However, uranium behavior in groundwater was independent of other components. Based on thermodynamic calculation, uranium chemical speciation was dominated by carbonate complexes, namely the Ca2UO2(CO3)3(aq) and CaUO2(CO3)32− species. Although uraniferous mineral phases designated as saturation indices were greatly undersaturated, uranium hydroxides such as schoepite, UO2(OH)2 and U(OH)3 became possible phases. Uranium-containing bedrock in OMB did not significantly affect radioactive levels in the groundwater, possibly due to adsorption effects related to organic matter and geochemical reduction. Nevertheless, oxidation prevention of uranium-containing bedrock needs to be systematically managed for monitoring the possible migration of uranium into groundwater.

Modelling the Effect of Temperature on the Stability of Bromide and Carbonate Complexes of Europium, Gadolinium, Terbium and Determination of their Thermodynamic Functions

A method has been developed for calculating the stability constants of inorganic complexes of rare-earth metals at various temperatures, based on analysis of the literature data by obtaining a linear regression equation on the form: . Using this method, the stability constants of bromide LnBr2+ and carbonate LnCO3+ complexes of europium, terbium, and gadolinium in aqueous solutions at temperatures of 50, 75, and 100 ° C were obtained. The obtained values of the coefficients А(T1) and В(T1) of the linear regression equation can be used to calculate the stability constants of complexes of europium, terbium, and gadolinium with other inorganic ligands at given temperatures. Based on the temperature dependence of the stability constants of bromide and carbonate complexes, their standard entropies and enthalpies of formation were calculated. Based on the obtained values of the thermodynamic functions, an assumption was made about the outer-sphere or inner-sphere nature of the complex.

Meta-studtite stability in aqueous solutions. Impact of HCO3−, H2O2 and ionizing radiation on dissolution and speciation

Four different uranyl-(peroxide)-carbonate complexes were identified during studtite and meta-studtite dissolution in aqueous solution containing 10 mM HCO3− by 13C NMR.

Hydrocarbon potential in entrails of the earth of Ukraine and main trend of its development

The article deals with the current state of mineral and raw hydrocarbon base of Ukraine. The main promising directions of geological exploration for oil and gas are identified and determined: in reef-carbonate complexes, deep-seated petroliferous complexes, crystalline basement, non-anticlinal traps in sandy bodies, non-traditional HC sources.

Uranium Removal from Groundwater and Wastewater Using Clay-Supported Nanoscale Zero-Valent Iron

The peculiarities of sorption removal of uranium (VI) compounds from the surface and mineralized groundwater using clay-supported nanoscale zero-valent iron (nZVI) composite materials are studied. Representatives of the main structural types of clay minerals are taken as clays: kaolinite (Kt), montmorillonite (MMT) and palygorskite (Pg). It was found that the obtained samples of composite sorbents have much better sorption properties for the removal of uranium from surface and mineralized waters compared to natural clays and nZVI.It is shown that in mineralized waters uranium (VI) is mainly in anionic form, namely in the form of carbonate complexes, which are practically not extracted by pure clays. According to the efficiency of removal of uranium compounds from surface and mineralized waters, composite sorbents form a sequence: montmorillonite-nZVI > palygorskite-nZVI > kaolinite-nZVI, which corresponds to a decrease in the specific surface area of the pristine clay minerals.