Increasing the efficiency of rare earth metal recovery from technological solutions during processing of apatite raw materials

The issues of complex processing of mineral resources are relevant due to the depletion of available raw materials. So, it is necessary to involve technological waste, generated during the processing of raw materials, to obtain valuable components. In the process flow of apatite concentrate treatment using the sulfuric acid method, a large amount of phosphogypsum is produced with an average content of light rare earth metals (REMs) reaching 0.032-0.45 %. When phosphogypsum is treated with sulfuric acid solutions, a part of REMs is transferred to the sulfate solution, from which it can be extracted by means of ion exchange method. The study focuses on sorption recovery of light REMs (praseodymium, neodymium and samarium) in the form of anionic sulfate complexes of the composition [ln(SO4)2]– on polystyrene anion exchanger AN-31. The experiments were performed under static conditions at a liquid-to-solid ratio of 1:1, pH value of 2, temperature of 298 K and initial REM concentration in the solutions ranging from 0.83 to 226.31 mmol/kg. Thermodynamic description of sorption isotherms was carried out by the method based on linearization of the mass action equation, modified for the ion exchange reaction. As a result of performed calculations, the authors obtained the constants of ion exchange equilibrium for Pr, Nd and Sm, as well as the values of the change in the Gibbs energy for the ion exchange of REM sulfate complexes on the AN-31 anion exchanger and the values of total capacity of the anion exchanger. Calculated separation factors indicated low selectivity of AN-31 anionite exchanger for light REMs; however, the anion exchanger is suitable for effective recovery of a sum of light REMs. Based on the average value of ion exchange equilibrium constant for light REMs, parameters of a sorption unit with a fluidized bed of anion exchanger were estimated.

Some thermodynamic and kinetic properties of H2SO4–H3PO4–H2O–Fe(III) system

The values of the electrode potentials of the redox couple Fe(III) / Fe(II) and the half-wave potentials of the reactions Fe3+ + e– = Fe2+ и Fe2+ — e– = Fe3+ on the cyclic voltammogram of a platinum electrode in acid solutions containing Fe(III) salts have been measured to characterize the oxidizing ability of the H2SO4—H3PO4—H2O—Fe(III) system. The values of these experimentally obtained parameters are close. A decrease in the oxidizing ability of H2SO4 and H3PO4 mixtures containing Fe(III) with an increase in the molar fraction of H3PO4 in them occurs due to the formation of Fe(III) complexes with phosphate anions which are inferior to their hydrate and sulfate complexes in the oxidizing ability. The temperature coefficients of the electrode potential (dE / dt) of the redox couple Fe(III) / Fe(II) in the H2SO4—H2O, H2SO4—H3PO4—H2O and H3PO4–H2O systems were determined experimentally. The diffusion coefficients of Fe(III) in the studied solutions were calculated based on the Randles—Shevchik equation. The temperature dependence of the diffusion coefficients of Fe(III) cations is satisfactorily described by the Arrhenius equation. The parameters of this equation are calculated.

Importance of anions in electrodeposition of nickel from gluconate solutions

Electrodeposition of nickel from slightly acidic gluconate solutions containing chloride or/and sulfate ions was investigated. Electrochemical measurements correlated with bath speciations showed nickel chloride complex and nickel sulfate complexes as crucial species affecting cathodic reactions in a potential range up to −1.3V. At more negative potentials, nickel deposition was governed by a release of nickel cation from nickel-gluconate complex. This was further evidenced by differences in nucleation modes, morphology, and structure of the deposits. Wettability of as-plated and chemically modified nickel layers were determined and correlated with their morphology and corrosion resistance.

Adsorption of uranium from its aqueous solutions using activated cellulose and silica grafted cellulose

The present work provides a thorough description of the preparation of two cellulose anion exchange resins. In addition, the application of the prepared resins for treatment the uranium-contaminated wastewater. In the preparation, the first resin was cellulose reacted with 0.3 M HNO3 to produce Activated Cellulose (AC), while the second was AC treated with sodium metasilicate and phosphoric acid to yield Silica Grafted Cellulose (SGC). The efficiency of the two prepared resins for uranium adsorption from aqueous solution was testifying on a batch scale. In solutions of pH ranging from 4 to 7, results showed a high exchange rate and uptaking capacity up to 105 mg/g. However, the addition of NO3−, Fe3+ and Th4+ ions to the target media has an adverse impact on the uranium sorption for AC adsorbent. Otherwise, the addition of uranyl sulfate complexes could ameliorate Fe3+ and Th4+ adsorbed into the SGC.

Forming sulfate- and REE-rich fluids in the presence of quartz

The presence of sulfate-rich fluids in natural magmatic hydrothermal systems and some carbonatite-related rare earth element (REE) deposits is paradoxical, because sulfate salts are known for their retrograde solubility, implying that they should be insoluble in high-temperature geofluids. Here, we show that the presence of quartz can significantly change the dissolution behavior of Na2SO4, leading to the formation of extremely sulfate-rich fluids (at least 42.8 wt% Na2SO4) at temperatures >∼330 °C. The elevated Na2SO4 solubility results from prograde dissolution of immiscible sulfate melt, the water-saturated solidus of which decreases from ≥∼450 °C in the binary Na2SO4-H2O system to ∼270 °C in the presence of silica. This implies that sulfate-rich fluids should be common in quartz-saturated crustal environments. Furthermore, we found that the sulfate-rich fluid is a highly effective medium for Nd mobilization. Thermodynamic modeling predicts that sulfate ions are more effective in complexing REE(III) than chloride ions. This reinforces the idea that REEs can be transported as sulfate complexes in sulfate-rich fluids, providing an alternative to the current REE transport paradigm, wherein chloride complexing accounts for REE solubility in ore fluids.

More crystal field theory in action: the metal–4-picoline (pic)–sulfate [M(pic) x ]SO4 complexes (M = Fe, Co, Ni, Cu, Zn, and Cd)

Seven crystal structures of five first-row (Fe, Co, Ni, Cu, and Zn) and one second-row (Cd) transition metal–4-picoline (pic)–sulfate complexes of the form [M(pic) x ]SO4 are reported. These complexes are catena-poly[[tetrakis(4-methylpyridine-κN)metal(II)]-μ-sulfato-κ2 O:O′], [M(SO4)(C6H7N)4] n , where the metal/M is iron, cobalt, nickel, and cadmium, di-μ-sulfato-κ4 O:O-bis[tris(4-methylpyridine-κN)copper(II)], [Cu2(SO4)2(C6H7N)6], catena-poly[[bis(4-methylpyridine-κN)zinc(II)]-μ-sulfato-κ2 O:O′], [Zn(SO4)(C6H7N)2] n , and catena-poly[[tris(4-methylpyridine-κN)zinc(II)]-μ-sulfato-κ2 O:O′], [Zn(SO4)(C6H7N)3] n . The Fe, Co, Ni, and Cd compounds are isomorphous, displaying polymeric crystal structures with infinite chains of M II ions adopting an octahedral N4O2 coordination environment that involves four picoline ligands and two bridging sulfate anions. The Cu compound features a dimeric crystal structure, with the CuII ions possessing square-pyramidal N3O2 coordination environments that contain three picoline ligands and two bridging sulfate anions. Zinc crystallizes in two forms, one exhibiting a polymeric crystal structure with infinite chains of ZnII ions adopting a tetrahedral N2O2 coordination containing two picoline ligands and two bridging sulfate anions, and the other exhibiting a polymeric crystal structure with infinite chains of ZnII ions adopting a trigonal bipyramidal N3O2 coordination containing three picoline ligands and two bridging sulfate anions. The structures are compared with the analogous pyridine complexes, and the observed coordination environments are examined in relation to crystal field theory.

First-row transition metal–pyridine (py)–sulfate [(py)xM](SO4) complexes (M= Ni, Cu and Zn): crystal field theory in action

The crystal structures of three first-row transition metal–pyridine–sulfate complexes, namelycatena-poly[[tetrakis(pyridine-κN)nickel(II)]-μ-sulfato-κ2O:O′], [Ni(SO4)(C5H5N)4]n, (1), di-μ-sulfato-κ4O:O-bis[tris(pyridine-κN)copper(II)], [Cu2(SO4)2(C5H5N)6], (2), andcatena-poly[[tetrakis(pyridine-κN)zinc(II)]-μ-sulfato-κ2O:O′-[bis(pyridine-κN)zinc(II)]-μ-sulfato-κ2O:O′], [Zn2(SO4)2(C5H5N)6]n, (3), are reported. Ni compound (1) displays a polymeric crystal structure, with infinite chains of NiIIatoms adopting an octahedral N4O2coordination environment that involves four pyridine ligands and two bridging sulfate ligands. Cu compound (2) features a dimeric molecular structure, with the CuIIatoms possessing square-pyramidal N3O2coordination environments that contain three pyridine ligands and two bridging sulfate ligands. Zn compound (3) exhibits a polymeric crystal structure of infinite chains, with two alternating zinc coordination environments,i.e.octahedral N4O2coordination involving four pyridine ligands and two bridging sulfate ligands, and tetrahedral N2O2coordination containing two pyridine ligands and two bridging sulfate ligands. The observed coordination environments are consistent with those predicted by crystal field theory.