Method of extraction of rare-earth elements from technological and productive solutions |
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IPC classes for russian patent Method of extraction of rare-earth elements from technological and productive solutions (RU 2462523):
Method of phosphogypsum processing for manufacture of concentrate of rare-earth elements and gypsum / 2458999
Method of phosphogypsum processing involves leaching of phosphogypsum with sulphuric acid solution with change-over of phosphorus and rare-earth elements to the solution, and gypsum residues is obtained, rare-earth elements are extracted from the solution and the gypsum residue is neutralised with the main calcium compound. In addition, leaching is performed with sulphuric acid solution with concentration of 1-5 wt %. After that, rare-earth elements are extracted from the solution by sorption using sulfocationite in hydrogen or ammonia form with further desorption of rare-earth elements with ammonia sulphate solution. After desorption to the obtained strippant there added is ammonia or ammonium carbonate with deposition and separation of hydroxide or carbon-bearing concentrate of rare-earth elements. Extraction of rare-earth elements of medium and yttrium groups to concentrates is 41-67% and 28-51.4% respectively. Specific consumption of neutralising calcium compound per 1 kg of phosphogypsum has been reduced at least by 1.6 times.
Method of processing phosphogypsum with extraction of rare-earth elements and phosphorus / 2457267
Method involves leaching rare-earth elements and phosphorus from phosphogypsum. Leaching is carried out using a bacterial complex consisting of several types of acidophilic thionic bacteria in the active growth phase, adapted for active transfer into the liquid phase of phosphorus and rare-earth elements. Leaching is carried out in tank conditions with bacterial population of 107 cells/ml, solid-to-liquid ratio 1:5-1:9, active or moderate aeration and temperature 15-45°C for 3-30 days.
 Extraction method of amount of rare-earth elements from solutions / 2457266
Extraction method of rare-earth elements from solutions containing multiple excess iron (III) and aluminium, with pH=0.5÷2.5 involves sorption using macroporous sulfocationite as sorbent. At that, as sorbent there used is macroporous sulfocationite containing more than 12 to 20% of divinyl benzene.
 Method of extracting cerium from salt solutions / 2456359
Method of extracting cerium cations from aqueous solutions of its salts involves use of a sodium dodecyl sulphate surfactant collector with concentration corresponding to the reaction stoichiometry: Ce+3+3DS-=Ce[DS-]3, where Ce+3 is a cerium cation, DS- is a dodecyl sulphate ion. Cerium cations are extracted via flotoextraction in an organic phase at pH=7.6-8.3. The organic phase used is isooctyl alcohol.
Method of processing of phospho-gypsum / 2456358
Method of processing of phospho-gypsum involves processing with an aqueous solution containing alkali metal carbonate, heating followed by separation of calcium carbonates and strontium. Before treatment phospho-gypsum is bioleached using bacterial complexes consists of several kinds of acidophilic thion bacteria in an active growth phase and adapted to phospho-gypsum. Bioleaching is carried out in a vat mode when a ratio of S:L = 1:5-1:9, temperature is 15-45°C and aeration is for 3-30 days with transfer of rare earth elements and phosphorus to the liquid phase. The resulting cake is treated with an aqueous solution containing potassium carbonate as an alkali metal carbonate.
Method for extracting scandium from pyroxenite raw material / 2448176
Method involves opening of raw material and leaching of scandium with further separation of solid and liquid phases. As initial raw material there used is scandium-containing pyroxenite refuse ore with fineness of less than 1 mm. Opening of raw material and leaching of scandium is performed using biocomplex of iron oxidating acidophilic thionic bacteria Acidithiobacillus thiooxidahs, Acidithiobacillus ferrooxidans, Leptospirillum ferrooxidans extracted and grown from natural strains of microorganisms incidental to the used initial raw material and adapted with cultures from museum collection, with bacteria population of 107 cells/ml at S:L=1:5-1:7, temperature of 15-45°C, initial Eh 650 mV, pH 1.5-2.15, Fe3+ concentration of 13-17 g/l, Fe2+ - 1.5-3 g/l and at atmospheric pressure. After separation of solid and liquid phases the latter is supplied for obtaining scandium fluoride.
 Method of extracting rare-earth metals yttrium (iii), cerium (iii) and erbium (iii) from water solutions / 2441087
Proposed method comprises contact of extragent containing rapic acid and inert latent solvent with water solution, mixing obtained mix, settling and phase separation. Kerosene is used as said inert latent solvent. Extraction is performed for 10-15 min in two steps at pH=4.5-5.5 and extragent-to-water solution ratio of 1:10. In first step, extraction is carried out at content of rapic acid in extragent of 5-7 vol. % with separation of cerium (III) and mix of yttrium (III) and erbium (III). In second step, extraction is carried out at content of rapic acid in extragent of 15-17 vol. % with separation of yttrium (III) and erbium (III).
 Method of extracting ions of erbium from water solutions using sodium dodecyl sulphate / 2440853
Invention relates to production of pure rare-earth metals or their oxides from low-grade or technogenic stock by ion flotation. Said ion flotation comprises using sodium dodecyl sulphate as a collector in concentration corresponding to stoichiometric reaction: Me+3+3DS-=Me[DS-]3, where Me+3 is metal cation, DS- is dodecyl sulphate-ion. Erbium salts are used as extracted ions. Note here that maximum yield of erbium is reached at pH=6.4.
 Procedure for processing grinding wastes from manufacture of permanent magnets / 2431691
Invention refers to procedure of extraction of rare earth elements (REE) from grinding wastes of manufacture of permanent magnets. The procedure consists in dissolving grinding wastes in sulphuric acid, in extraction of double salts and sodium REE-Na by sedimentation and in washing double salts. Further, double salts are conversed in hydroxide of REE and hydroxides of REE are washed. Upon washing hydroxides of REE are oxalate conversed, dried and burned producing sum of REE oxides. After sedimentation of double salts of rare earth elements and sodium REE-Na mother solutions are processed producing ferriferous and cobalt cakes.
 Method of cleaning fluorine-containing rare-earth concentrate / 2429199
Concentrate obtained when processing apatite is treated with concentrated sulphuric acid in the presence of hydrated silica at 95-130°C with transition of fluorine to gaseous phase and obtaining a sulphate-phosphate rare-earth concentrate which is leached with water to obtain a sulphate rare-earth concentrate free from fluorine and phosphorus and a sulphate-phosphate solution.
Method for gold extraction from cyanide solutions with dissolved mercury contained in them / 2460814
Method for gold extraction from cyanide solutions with dissolved mercury contained in them, gold-bearing ores formed during leaching, involves sorption of gold and mercury on activated carbon with enrichment of activated carbon with gold and mercury. Then, gold desorption is performed with alkali-cyanide solution under autoclave conditions, gold electrolysis from strippants so that cathode deposit is obtained and its remelting is performed so that finished products are obtained in the form of raw base gold alloy. Prior to gold desorption the selective desorption of mercury is performed by treatment of saturated carbon with alkali-cyanide solution containing 15-20 g/l of sodium cyanide and 3-5 g/l of sodium hydroxide, at temperature of 18-20°C and atmospheric pressure during 10 hours.
Method of extracting gold using macroporous resins / 2459880
Proposed method comprises preparing leaching solution bearing gold, and gold sorption by macroporous resin containing alkyl amine functional groups in amount of 0.01-1.0 mmol/g and 3-12% of cross-links with water retaining capacity making, at least, 30%, and specific surface area varying from 400 to 1200 m2/g. After sorption, gold is eluted.
Method of phosphogypsum processing for manufacture of concentrate of rare-earth elements and gypsum / 2458999
Method of phosphogypsum processing involves leaching of phosphogypsum with sulphuric acid solution with change-over of phosphorus and rare-earth elements to the solution, and gypsum residues is obtained, rare-earth elements are extracted from the solution and the gypsum residue is neutralised with the main calcium compound. In addition, leaching is performed with sulphuric acid solution with concentration of 1-5 wt %. After that, rare-earth elements are extracted from the solution by sorption using sulfocationite in hydrogen or ammonia form with further desorption of rare-earth elements with ammonia sulphate solution. After desorption to the obtained strippant there added is ammonia or ammonium carbonate with deposition and separation of hydroxide or carbon-bearing concentrate of rare-earth elements. Extraction of rare-earth elements of medium and yttrium groups to concentrates is 41-67% and 28-51.4% respectively. Specific consumption of neutralising calcium compound per 1 kg of phosphogypsum has been reduced at least by 1.6 times.
 Multicolumn sequential extraction of ionic metal derivative / 2458725
Invention may be used in hydrometallurgy. Proposed invention allows separating such metals as uranium, nickel, copper and cobalt present in liquid wastes of ore leaching. Solution containing metal ions is forced through stationary layer of resin, Particularly, through, at least, three zones. Note here that solution drive appliances are arranged between adjacent zones and between last and first zones. Proposed method comprises several sequences, each comprising, at least, one step selected from steps of adsorption, washing and desorption. Every next sequence is performed by shifting fronts into zones downstream of circuit with identical increment unless cyclic shift of inlet and discharge points.
 Method of ion-exchange uranium extraction from sulfuric solutions and pulps / 2458164
Method includes uranium sorption by anion exchange resin, uranium de-sorption from saturated anion exchange resin by sulphuric acid and obtaining finished product from strippant. Note that uranium de-sorption from saturated anion exchange resin is done by sulphuric acid solution with concentration 70-100 g/l with the presence of 1-2 mole/l of ammonia sulphate.
Method of gold extraction from mercury-containing cyanic solutions / 2458160
Method of gold extraction from mercury-containing cyanic solutions consists in sorption by ion-exchange resin of AM-2B mark. Then mercury de-sorption is carried out from saturated ion-exchange resin at a temperature 40-50°C and for 6 hours and aurum de-sorption. Note that mercury de-sorption is done by solution containing sulfuric acid 30-50 g/l with the presence of hydrogen peroxide 5-10 g/l.
Extraction method of amount of rare-earth elements from solutions / 2457266
Extraction method of rare-earth elements from solutions containing multiple excess iron (III) and aluminium, with pH=0.5÷2.5 involves sorption using macroporous sulfocationite as sorbent. At that, as sorbent there used is macroporous sulfocationite containing more than 12 to 20% of divinyl benzene.
 Method for extracting metals from depulped ores / 2454470
Method for extracting metals from depulped ores involves crushing, ore depulping in leached solution and sorption of metal. Leaching is performed in ultrasound pulp cavitation mode. Metal sorption on ion-exchange resin is performed from pulp filtration solution in intensity field of alternating current in sorption activation mode of extracted metal and suppression of sorption of impurities. At that, polarity of electrodes is constantly changed to avoid deposition of metal on cathode. Leaching and sorption of metal is performed in a unit providing solution circulation till the specified completeness of leaching from ore and its complete sorption on ion-exchange resin is achieved.
Method for sorption extraction of iron from nitrate salt solutions / 2453368
Invention relates to ion exchange and can be used for sorption extraction of iron from salt solutions formed when processing aluminium-containing material using acid techniques. Extraction of iron to residual content of Fe2O3 in the purified solution of not more than 0.001% is carried out through sorption of iron with a cationite in H-form, containing aminodiacetic functional groups. The iron sorption and desorption steps are alternated without intermediate washing of the cationite. Iron is desorbed in counterflow conditions with nitric acid solution.
 Method for extraction of palladium (ii) from wasted catalysts / 2442833
The invention relates to hydrometallurgy of precious metals and can be used to extract palladium from wasted catalysts, including catalysts of low-temperature oxidation of carbon oxide (II) based on γ-Al2O3, containing palladium chloride (II) and cupric bromide (II). The method includes acid leaching of palladium from wasted catalysts from the chloride solution. Furthermore, the acid leaching is carried out by 1 M solution of hydrochloric acid. The resulting solution is diluted with water to pH 1. The sorption of palladium is carried out from the diluted solution using chemically modified silica containing grafted groups of γ-aminopropyltriethoxysilane.
 Selective recovery of molybdenum(vi) / 2247166
Invention relates to sorption-mediated recovery of molybdenum from solutions containing heavy metal cations. Method of invention comprises providing solution to be treated, sorption of molybdenum(VI) on anionite at pH < 7. Sorption is conducted from solutions with anionites AM-2b and AMP at solution pH below pH of hydrolytic precipitation of heavy metal cations but higher than pH of formation of molybdenum cations (pH ~ 1).
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FIELD: metallurgy. SUBSTANCE: method for extracting rare-earth elements from the technological and productive solutions containing iron (III) and aluminium, with a pH-0.5÷2.5, includes the sorption of rare-earth elements with strong-acid cation resin. As the strong-acid cation resin the microporous strong-acid cation resin is used based on hypercrosslinked polystyrene having a size of micropores 1-2 nm. EFFECT: higher efficiency of the process due to greater sorption capacity of the said strong-acid cation resin, high kinetics of sorption and selectivity, improvement of the subsequent quality of eluates and simplification of the process of their further processing. 5 tbl, 5 ex
The invention relates to hydrometallurgy rare metals, in particular to the extraction of rare earth elements (REE) by integrated processing of technological and productive solutions, and can be used in the technology of production of concentrates REE. In connection with the recovery of rare earth industry in Russia is an actual task associated extraction of rare earth elements (REE) in ferrous, non-ferrous and rare metal industry, as well as involvement in the processing of non-traditional raw materials. The characteristics of the data sources are typically low content of REE and complex chemical composition. In this regard, many waste industry technology concentration and extraction of REE are useless and unproductive. In addition, the choice of method of REE extraction is often associated with the impossibility of changing the chemical composition of process intermediates in closed technologies. Sorption extraction of REE seems to be the most appropriate at the stage of initial concentration. A serious problem with sorption recovery of REE from the technological and productive solutions with pH 0,5÷2,5 is the presence of large amounts of iron(III) and Al, because it is known that such an environment is non-selective for the separation of iron(III) and Al (for the most interfering impurities) from REE, as at the stage of sorption, and at the stage of desorption [Bolshakov K.A. Chemistry and technology of rare and scattered elements. Part 2 - M.: Higher school. 1976. - 360 C.]. In practice, the task of extracting REE of these solutions solved by hydrolytic precipitation of iron(III) and Al alkaline agents [Mursalimova M., Stroeva EV Determination of equilibrium parameters of ion sorption of yttrium and lanthanum of mineralized solutions and iron-containing slurries on carboxylic cation exchanger KB-4 gel type. // Vestnik OSU, No. 5, 2006, pp.86-90]. The disadvantages of this method include large losses REE (20÷25%) due to co-precipitation with hydroxides of iron(III) and Al, the use of strong solutions of precipitators, large consumption, education trudnoobrabatyvaemyh wastewater. Another way is advance recovery solution with a pH of 0.5÷2.5 the most disturbing impurities of iron(III) to iron(II) iron shavings, urea, sodium sulfite, etc., When such an organization process, the selection of sorption systems with significant coefficients of the separation of iron(II) and REE is much wider [A.S. 2070595. The method of extraction of cerium / Shevchuk Ivan Alekseevich, Simon Tamara Nikolaevna, Rockoon Antonina Nikolaevna // Publ. 20.12.1996]. The disadvantage of this method is the change of the chemical composition of process solutions with a high consumption of reagents-restore is she. At the same time, in many industries, the maintenance of high concentrations of dissolved iron(III) is dictated by technological necessity, because its presence promotes leaching (oxidizing) the ability of the solutions [Eaatem. Physico-chemical Geotechnology exploration for uranium and gold in the Kyzylkum region. - M.: Moscow state mining University. 1999. - 331 S.]. Therefore, development of a method for the selective extraction of REE from solutions with pH 0.5÷2.5, containing iron(III) and Al without changing the chemical composition of the solutions, is an extremely important task. The known method [Smirnov DI, Molchanov T.V., Divers LI, Peganov, VA Sorption extraction of rare earth elements, yttrium and aluminium from red mud. // Non-ferrous metals. - 2002. No. 8. - P.64-69], in which the recovery of REE from the technological solution of pH 0.5÷2.5 is carried out by adsorption on the gel sulfonic cation exchanger KU-2. Obtained after deposition of rough concentrate contains, %: REE - 1; iron - 2,0-2,2; aluminum - 15-18; water - 82. This is followed by a stage with resultant deposition rates in order to bring the draft of REM concentrate to commercial products 30-40%. The main disadvantages of this method are the low sorption capacity of the cation by the sum of the REE, and hence the complex subsequent operation of bringing the draft REE concentrate to commodity productivety disadvantages lead to the need for additional equipment reactors for dissolution of hydrates, filters for filtering a large number of intermediates, as well as to additional consumption rather expensive reagent alkali leaching of aluminum. In addition, the degree of REE extraction this method is sufficiently low output is 60%. The closest in technical essence and the achieved result is a method (prototype) of REE extraction in the presence of iron(III) and Al from solutions with pH 0.5÷2.5, which for REE extraction uses sulfonic cation macroporous structure with the content of divinylbenzene from 8 to 12% [Ehitajate, Antoniow. Inch. 1963, 8, №9, 2189]. Such sulfonic cation is obtained by copolymerization of monomers (styrene and divinylbenzene in the presence of inert additives, and then removed from the structure of the polymer. However, a significant drawback sulfonic cation macroporous structures are relatively low magnitude of their sorption capacity due to the fact that the process of copolymerization with divinylbenzene not always ensures a uniform distribution of cross-linking in a polymer mesh. This leads to the formation of cavities in the volume of the macroporous sulfonic cation, is not available for sorbed ions, and hence to a decrease of the sorption capacity. In addition, swollen in water macroporous and largely the spruce the sulfonic cation change in volume upon contact with concentrated solutions of electrolytes. The volume change layer sulfonic cation exchanger reduces the efficiency of the separation process and shortens the life of the sulfonic cation exchanger. Satisfying the above requirements are microporous sulfonic cation-based supersewn polystyrene. The process of forming supersewn polystyrene grid is fundamentally different from the synthesis of traditional copolymers of styrene and divinylbenzene. Supersewn polystyrene receive not the copolymerization of styrene and divinylbenzene, as by stitching dissolved or highly swollen chains of polystyrene large number of hard-bridges-struts. This leads to the fact that all supersewn the polystyrene virtually disappear small cavity characteristic of the gel porous copolymer of styrene with a radius of 0.1÷0.5 nm, and appear larger cavity having a size distribution of 1÷2 nm micropores. The result is a porous structure with a very large inner surface of more than 1000 m2/, the Size of the macropores in the macroporous sulfonic cation varies from 50 to 1000 nm, depending on the content of divinylbenzene. The size of the micropores is commensurate with the size of hydrated ions simple mineral electrolytes, which makes the main effect in the separation process, reducing the ability more hydrated (and thus having greatly the th size) ion iron(III) and Al in solutions with pH 0.5÷2.5, because of the sieve effect, to penetrate into the volume of the microporous sulfonic cation exchanger to its functional groups. A characteristic feature of the microporous sulfonic cation exchanger based on supersewn polystyrene is that it does not change in volume when water is replaced by concentrated solutions of electrolytes due to the fact that the three-dimensional grid supersewn polystyrene has a very rigid frame. The present invention is to create a more efficient sorption method for REE extraction from solutions of pH 0.5÷2.5, containing iron(III) and Al. This object is achieved according to the method which consists in sorption extraction sums REE microporous sulfonic cation exchanger based on supersewn polystyrene. Example 1 Sorption was carried out in static conditions of HCl, H2SO4, HNO3(pH 0.5; 1; 1.5; 2; 2.5), containing 1000 mg/DM3Rare earth elements (lanthanum). Weighed samples sulfonic cation (0.5 g) was contacted with stirring with 50 cm3the above solution for 5 days. The solutions were analyzed by atomic emission method with inductively coupled plasma. Sobiraemosti and the degree of extraction was determined as the difference of the initial and final concentrations of ions in solution.
From table 1 it follows, is the microporous sulfonation extracts lanthanum effectively, both gel and macroporous sulfonic cation, selected from solutions of pH range. Example 2 Sorption was carried out in static conditions of the sulfuric acid solution (pH 1.5)containing 1000 mg/DM3Rare earth elements (lanthanum). Weighed samples sulfonic cation (0.5 g) was contacted with stirring with 50 cm3the above solution for 0.2; 1; 2; 4; 8 hours. The solutions were analyzed by atomic emission method with inductively coupled plasma. Sobiraemosti and the degree of extraction was determined as the difference of the initial and final concentrations of ions in solution.
From table 2 it follows that the kinetics of extraction of lanthanum microporous sulfonic cation exchanger is much higher than the sorption kinetics of lanthanum on the gel and macroporous sulfonic cation selected from solutions of pH range. Example 3 Sorption was carried out in static conditions of the sulfuric acid solution (pH 1.5)containing 1000 mg/DM3Rare earth elements (lanthanum). Weighed samples sulfonic cation (0.5 g) was contacted with stirring with 50 cm3the above solution at a temperature of 20; 40; 60; 80°C for 3 hours. The solutions were analyzed by atomic emission method with inductively coupled plasma. Sobiraemosti and the degree of extraction was determined as the difference of the initial and final concentrations of ions in solution.
From table 3 it follows that the temperature of the sorption of lanthanum sulfonic cation has no significant impact on the degree of extraction from acidic solutions. Example 4 Sorption was carried out in static conditions of the sulfuric acid solution (pH 0.5; 1; 1.5; 2; 2.5)containing 50 mg/DM3lanthanum, 1000 mg/DM3iron(III) and 1000 mg/DM3aluminum. Weighed samples sulfonic cation (0.5 g) was contacted with stirring with 50 cm3the above solution at a temperature of 20°C for 5 days. The solutions were analyzed by atomic emission method with inductively coupled plasma. Sobiraemosti and the degree of extraction was determined as the difference of the initial and final concentrations of ions in solution.
From table 4 it follows that microprecipitation has a significantly greater capacity for rare earth elements (lanthanum) in the presence of 20-fold excess of iron(III) and Al and a lower capacity for these elements in comparison with gel and macroporous sulfonic cation during sorption from solutions of the selected pH range. Example 5 Sorption was carried out in static conditions from sulfuric acid solutions (pH 1.5)containing 50 mg/DM3lanthanum, or containing 50 mg/DM3cerium, or containing 50 mg/DM3dysprosium, or containing 50 mg/DM3lutetium, or containing 50 mg/DM3the sum of the REE. Weighed samples sulfonic cation (0.5 g) was contacted with stirring with 50 cm3the above solution at a temperature of 20°C for 5 days. The solutions were analyzed by atomic emission method with inductively coupled plasma. Sobiraemosti and the degree of extraction was determined as the difference of the initial and final concentrations of ions in solution.
Thus, the technical result of the proposed method is zlecenia REE from solutions with pH 0.5÷2.5 is determined by the high efficiency of this method due to the greater sorption capacity of microporous sulfonic cation exchanger by REE in the presence of iron(III) and aluminium, high sorption kinetics and selectivity, which leads to the subsequent improvement of the quality of the eluates and facilitate their further processing. The method for extracting rare earth elements from the technological and productive solutions containing iron (III) and aluminium, with a pH 0,5÷2,5, including sorption of rare earth elements sulfonic cation exchanger, characterized in that as a sulfonic cation exchanger using microporous sulfonation based supersewn polystyrene, having a size of micropores of 1-2 nm.
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