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Date submitted2024-03-22
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Date accepted2024-09-24
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Date published2025-02-25
Behaviour of cerium (III) phosphate in a carbonate-alkaline medium
- Authors:
- Tatyana E. Litvinova
- Stepan A. Gerasev
The article investigates the behaviour of rare earth metals in carbonate-alkaline systems. The results of experimental studies on rare earth element extraction from phosphogypsum, a large-tonnage industrial waste forming in production of phosphoric acid are presented. Using the liquid phase leaching method, it was possible to extract more than 53 % of rare earth elements from old phosphogypsum and more than 69 % from fresh phosphogypsum due to solid phase treatment with a 4 mol/l potassium carbonate solution at temperature 90 °C. The behaviour of model cerium (III) phosphate in a carbonate-alkaline medium is characterized: a solubility isotherm is obtained as well as the dependences of the degree of cerium extraction into solution on temperature, carbonate ion concentration, interphase ratio, stirring intensity, and pH. The ability of soluble rare earth element complexes to precipitate over time was established, which was confirmed using cerium and neodymium as an example. Within 240 h after the end of the experiment, approximately 25 % of cerium and 17 % of neodymium were precipitated from the liquid phase. A similar property was recorded in representatives of the light group and was not noted in elements of the heavy group. The ability to self-precipitate in future can serve as a basis for developing an alternative approach to separating rare earth metals into groups after extraction in a carbonate ion medium. Also, based on the analysis of experimental data, the mechanism of cerium (III) phosphate dissolution in a carbonate-alkaline medium was characterized. An assumption was made that rare earth metal phosphates dissolve sequentially passing into an insoluble carbonate and then into a soluble carbonate complex.
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Date submitted2021-06-17
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Date accepted2021-10-18
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Date published2021-12-16
Dissolution kinetics of rare earth metal phosphates in carbonate solutions of alkali metals
- Authors:
- Tatyana E. Litvinova
- Ivan L. Oleynik
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.