Method of extracting rare-earth metals from aqueous solutions |
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IPC classes for russian patent Method of extracting rare-earth metals from aqueous solutions (RU 2484163):
  
Method of extracting rare-earth metals from technological and productive solutions and pulps / 2484162
Method of extracting rare-earth metals from solutions containing iron (III) and aluminium comprises sorption of rare-earth metals on sorbent. Ampholyte with iminodiacetic functional groups is used as said sorbent. Sorption is carried out after preliminary neutralisation or acidification of solution to pH 4-5 by whatever alkaline or acid agent to add ampholyte in obtained pulp with separation of solid fraction. Sorption is conducted at ampholyte:pulp ratio of 1:50-1:150, phase contact time of 3-6 h and in the presence of reducing agent.
 Method of treating rare-earth phosphate concentrate separated from apatite / 2484018
Invention relates to methods of separating deactivated rare-earth elements during nitric acid treatment of apatite concentrate from nitrate-phosphate solutions. The method of treating a rare-earth phosphate concentrate isolated from apatite involves decomposition of the rare-earth phosphate concentrate with nitric acid, treating the obtained solution with oxalic acid with precipitation of rare-earth oxalates in two steps, at the first step of precipitation of oxalates of thorium and rare-earth elements, 5-10% oxalic acid in stoichiometric amount is added to rare-earth elements present in the solution, and at the second step of precipitation of rare-earth oxalates, 110-115% oxalic acid in stoichiometric amount is added to rare-earth elements present in the initial solution, and the rare-earth oxalates are then calcined to rare-earth oxides.
Method of making scandium oxide from red slag / 2483131
Proposed method comprises multistep leaching of red slag by the mix of sodium carbonate and bicarbonate on forcing annealing furnace flue gases containing carbon dioxide there through to obtained solution. Then, three-step holding of said solution at increased temperatures is performed along with selective separation of precipitates after every said step. At first step, said solution is heated to temperature not exceeding 80°C for, at least, 1 hour. Thereafter, it is settled for, at least, two hours at natural cooling. At second step, said solution is boiled and mixed for, at least, two hours. At third step, said solution is evaporated to 50% of initial volume to add 46%-solution of sodium hydroxide to concentration of Na2Ocaustic of 1.5-2.0 kg/m3. Now, it is boiled for, at least, 2 hours and precipitate containing scandium oxide is settled for 10-16 hours at natural cooling.
 Method for europium (iii) from salt solutions / 2482201
Invention relates to hydrometallurgy, in particular, to the method for extraction of europium (III) from salt solutions by floating extraction. In process of floating extraction of europium (III) cations the organic phase is represented by isooctyl alcohol, and the collector of surfactants of anion type is sodium sodium dodecyl sulfate in the concentration corresponding reaction stoichiometry: Eu+3+3NaDS=Eu(DS)3+Na+, where Eu+3 - cation of europium (III), DS- - dodecyl sulfate-ion. At the same time the floating extraction is carried out at pH=7.5-8.5, and at the ratio of organic and water phases 1/20-1/40.
Processing method of red muds of alumina industry / 2480412
Invention refers to non-ferrous metallurgy, and namely to complex processing of red muds of alumina industry. Processing method of red muds of alumina industry involves obtaining of red mud pulp, extraction and concentration of rich components by combination of classification and magnetic separation methods. After the pulp classification, fine-grain fraction pulp is extracted and subject to vibrocavitation treatment and further magnetic separation with extraction of magnetic and non-magnetic products. At that, magnetic product is subject to additional classification so that iron-bearing and scandium-bearing concentrates are obtained.
 Method of producing scandium oxide / 2478725
Proposed method comprises dissolving scandium-bearing concentrate in sulfuric acid, removing acid-insoluble residue, and precipitating scandium in the presence of ammonium compounds. Then, precipitate is filtered, flushed, dried and calcined to obtain scandium oxide precipitate. With acid-insoluble residue removed, sulfuric acid concentration in filtrate is increased to 540-600 g/dm3, ammonium chloride is added to solution in amount of 26.7-53.5 g/dm3 at 50-70°C and held for one hour at mixing. Produced precipitate is flushed by ethanol at volume ratio of 1-10-11.
 Method of extracting yttrium (iii) from salt solutions / 2478724
Method of extracting yttrium (III) from salt solutions involves floatation extraction using an organic phase and a collector. The organic phase used is isooctyl alcohol. The collector used is an anionic surfactant - sodiium dodecyl suphate in a concentration which corresponds to the stoichiometry: Y+3+SDS-=Y[DS]3, where Y+3 is a yttrium cation, DS- is a dodecyl sulphate ion. Floatation extraction is carried out at pH=7.0-7.8 and ratio of the organic phase to the aqueous phase of 1/20-1/40.
 Complex processing method of carbon-silicic black-shale ores / 2477327
Invention refers to complex processing method of carbon-silicic black-shale ores, which contain vanadium, uranium, molybdenum and rare-earth elements. The above method involves ore crushing to the particle size of not more than 0.2 mm and two leaching stages. Oxidation sulphuric-acid leaching is performed at atmospheric pressure. Autoclave oxidation sulphuric-acid leaching is performed at the temperature of 130-150°C in presence of oxygen-containing gas and addition of a substance forming nitrogen oxide, as a catalyst of oxygen oxidation. Ion-exchange sorption of uranium, molybdenum, vanadium and rare-earth elements is performed from the obtained product solution.
Method of extracting rare-earth elements from phosphogypsum / 2473708
Invention relates to the technology of producing compounds of rare-earth elements during complex processing of apatites, particularly extraction of rare-earth elements from phosphogypsum. The method involves preparation of pulp from phosphogypsum and sorption of rare-earth elements on a sorbent. The pulp is prepared from ground phosphogypsum and sulphuric acid solution with pH=0.5-2.5 until achieving liquid:solid ratio of 4-7. Sorption is carried out directly from the phosphogypsum pulp on a sorbent with sulphuric acid functional groups for 5-7 hours with solid:sorbent ratio of 4-7.
 Universal method of selective extraction of salts of transition, rare-earth and actinoid elements from combination solutions by means of nanoporous materials / 2472863
Method involves selective extraction of salts in volumes of nanopores of nanoporous conducting materials due to effect of electrostatic interaction of dipole moments of solvated ionic complexes of transition, rare-earth and actinoid elements with electric field of double electric layer of "nanopore wall - solution" boundary line. The method is implemented by subsequent filling of nanopore of nanoporous conducting material with the solution containing ionic complexes of transition, and/or rare-earth and/or actinoid elements, displacement from nanopore of ionic complexes of transition, rare-earth and actinoid elements weakly localised in nanopores by means of pressure of gases or liquids, by filling of nanopore with solution of inorganic acid of high concentration, and by extracting from nanopores of residual ionic complexes of transition, rare-earth and actinoid elements by means of pressure of gases or liquids. The above method can be implemented in an electrochemical cell.
Method for enrichment of solutions with low gold content / 2482200
Invention relates to hydrometallurgy of noble metals. The method for enrichment of solutions with low gold content includes development of an organic catching film on the surface of a solution in floatation chambers and passage of air bubbles for sublate floatation. At the same time extractants used for gold extraction are added preliminarily to a substance of the organic catching film, being a matrix for processes of gold ions and molecules catching and retaining. The solution with low gold content is filtered, acidified to pH of 1.5-2.0, and a collector is added to it, then the floatation chamber is filled to the half with the specified solution, and with the organic matrix with extractants, the volume of which does not exceed 0.5% of the volume of the entire solution, and intensive mixing is started. After mixing the floatation chamber of the operating machine is filled with the solution to the full, additional floatation is carried out for complete collection of the matrix into a single drop, and then it is separated from the solution.
 Method of uranium ore processing / 2481411
Proposed process comprises crushing and grinding the ore, sulfuric acid leaching with addition of nitrogen acid as an oxidiser. Then, uranium is extracted and cleaned of impurities with the help of extractive agents mix to wash saturated extractive agent with the solution of sulfuric acid. After extraction, uranium is re-extracted to obtain uranium concentrate by means of 8-10%-solution of sodium carbonate. Uranium is deposited from re-extracted product by hydrogen peroxide with 50-100%-surplus from stoichiometry at equilibrium pH 3.6-4.2, mixing interval of 1- 1.5 h and sedimentation time of, at least, 1 h.
 Extraction of copper from aqueous solutions using plant oils / 2481409
Method of extracting copper from an aqueous solution involves bringing an extractant in form of plant oil into contact with the solution. The mixture is stirred, settled and subjected to phase separation. Extraction is carried out from an aqueous solution with copper concentration ≤5 g/dm3 with ratio of the aqueous phase to the organic phase A:O≤8, pH 5.5-6.5 and 8.5-10.5, wherein pH is controlled for not more than 30 minutes.
Method of extracting yttrium (iii) from salt solutions / 2478724
Method of extracting yttrium (III) from salt solutions involves floatation extraction using an organic phase and a collector. The organic phase used is isooctyl alcohol. The collector used is an anionic surfactant - sodiium dodecyl suphate in a concentration which corresponds to the stoichiometry: Y+3+SDS-=Y[DS]3, where Y+3 is a yttrium cation, DS- is a dodecyl sulphate ion. Floatation extraction is carried out at pH=7.0-7.8 and ratio of the organic phase to the aqueous phase of 1/20-1/40.
 Method for quantitative determination of tin (ii) and (iv) ions in aqueous solutions / 2475548
Method involves extraction using as a complexing agent and an extractant a mixture of antipyrine and sulphosalicylic acid, taken in molar ratio of 3:2. Extraction is carried out in the presence of urotropin in the solution in amount of 0.05-0.15 g. After extraction, concentration of tin (II) and (IV) ions determined using a complexometric technique.
 Method of extracting copper (ii), nickel (ii) and/or cobalt (ii) ions from weakly acidic and aqueous ammonia solutions / 2472864
Invention relates to a method of extracting copper (II), nickel (II) and/or cobalt (II) ions from weakly acidic and aqueous ammonia solutions with an organic reagent, followed by re-extraction with aqueous solution of a mineral acid. The organic reagent used is N',N'-dimethylhydrazides of α-branched tertiary carboxylic acids of general formula (I)
 Para-tertbutylbenzoic acid "n', n'-dialkylhydrazides / 2448174
Invention relates to novel compounds of the N',N'-dialkylhydrazide class and can be used in copper hydrometallurgy. Para-tertbutylbenzoic acid N',N'-dialkylhydrazides of general formula tertC4H9C6H4CONHN(R)2 are obtained, where R is an aliphatic radical CnH2n+1 n=1-10. The compounds, preferably with number of carbon atoms per radical (n) from 6 to 10, are used as an extraction agent for copper (II) from ammonia solutions. Degree of extraction of copper (II) from solutions with ammonia content of up to 8 mol/l is equal to 96.5-99.4%.
 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).
 Procedure for processing uranium ore / 2434961
Silicate uranium ore is crushed and crumbled; further, it is leached with sulphuric acid with addition of nitric acid as oxidant. Uranium is extracted and refined from impurities using mixture of extragents. Also as mixture of extragents there is used synergetic mixture containing di(2-ethyl-hexyl)phosphoric acid - 0.05-0.075 mole/l, tri-alkyl-amine - 0.05-0.075 mole/l in hydrocarbon dissolver at ratio of volumes of organic and water phases VO-VW= 1-3÷6. Upon extraction organic phase saturated with uranium is washed with solution of sulphuric acid. Further, uranium is re-extracted with solution of coal-ammonia salts producing crystals of ammonia-uranyl-tri-carbonate and is filtered. Produced crystals are tempered to production of protoxide-oxide of uranium.
 Procedure for separation of actinoide from lanthanide in water medium by complexation and membrane filtration / 2427658
Procedure consists in stage of introduction of complex forming compound to contact with water medium containing said actinoid and one or more lanthanides. Also, the said complex forming compound in not complexated state is not retained with the said membrane and is capable to form complex with said actinoid containing the said element and at least two molecules of the said complex forming compound, also, complex is capable to be retained with the membrane. Further, there is performed the stage of water medium passing through the membrane for formation of filtrate containing water effluent depleted with said actinoid from one side, and retentate containing the said complex.
Method for extraction separation of tantalum and niobium from acid fluoride-sulfate solution / 2269582
Invention relates to a method for extraction separation of tantalum and niobium. Method involves extraction separation of tantalum from niobium with organic solvent. As an organic solvent method involves using a mixture of methyl isobutyl ketone taken in the amount 40-80 vol.% with aliphatic (C7-C9)-alcohol taken in the amount 20-60 vol.%. At the extraction process tantalum transfers into organic phase and niobium - into aqueous phase. Then organic and aqueous phases are separated. Invention provides enhancing the extraction degree of tantalum into organic phase and to enhance the separation degree of tantalum and niobium in extraction.
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FIELD: metallurgy. SUBSTANCE: proposed method comprises extraction of rare-earth metal cations by organic phase including extragent solution in inert diluter. Naphthenic acid is used as said extragent. Kerosene is used as inert diluter. Extraction is conducted in three stages at relationship between organic and aqueous phases O:A=1·(9-11) at every stage. Note here that, at first stage, europium cations (III) are extracted at content of naphthenic acid in kerosene of 10-13 vol. % and aqueous solution pH 5.0-5.1. At second stage, samarium cations (III) are extracted at content of naphthenic acid in kerosene of 13-16 vol. % and aqueous solution pH 4.6-4.7. At third stage cerium and lanthanum cations (III) are extracted at the same content of extragent and pH 5.0-5.1. EFFECT: higher yield. 4 dwg, 1 ex
The invention relates to metallurgy, in particular to the processing of ores and concentrates containing rare earth metals, and can be used in technologies for rare earth metals from dilute or secondary raw materials at the stage of separation amounts of lanthanides. The well-known "Method of extraction of lanthanides and actinides from nitric acid solutions" (patent RU №2193012, etc. etc. 20.11.2002), including the extraction solution of phosphine oxide raznorabochego in heavy fluorinated or chlorinated inert diluents. The process is carried out in the presence of tributyl phosphate in an amount of 10-60% of the total volume of the organic phase. The disadvantages of the method: the use of expensive and toxic organophosphorus extractants, a multi-stage separation process, the high consumption of extractant. Known "Method of extraction of rare earth metals mixtures thereof (patent RU No. 2049133, etc. etc. 27.11.1995), including countercurrent extraction with an organic solvent from an aqueous solution of rare earth metals and the re-extraction processing of the organic phase with an aqueous solution of mineral acid. The extraction is performed with the output part of the extract, with its subsequent counterflow reextracting in three stages: when the ratio A:B=(1-3):1 in the first stage, a:=(3-5):1 and output parts of an organic solvent with what UPRAVLENIE it in the main loop in the second stage, and the ratio A:B=(5-10):1 in the third stage. The disadvantages of the method are the use of 100% of tributyl phosphate, and high consumption of extractant. Known "Method of extraction of neodymium from concentrate rare earth metals cerium group" (patent RU №2030463, DPR 10.03.1995), including the state electrochemical oxidation of cerium to CeO2and the stage of extraction of rare earth metals with tributyl phosphate in a weight ratio of the amount of rare earth metals in the source solution and the extractant 1:(0.6 to 0.8) to obtain a raffinate. Then hold reextraction neodymium from the organic phase. The disadvantages of this method are the high consumption and the use of concentrated extractant, and not a complete separation of rare earth metals. The method for extracting metals (RU patent No. 2009228, DPR 15.03.1994)adopted for the prototype, including extraction of metals with solutions of nitrogen-containing anion exchange resins containing at least two organic radicals in organic inert diluent. The extraction of metals are solutions of amines and/or Quaternary ammonium bases, two organic radicals, each of which represent 2,4-diethylacetal. The disadvantage is the use of concentrated solutions of amines and salts of Quaternary ammonium bases, which are toxic compounds and require Visalia is used. The technical result is to increase the degree of extraction of light lanthanides from the General solution of their salts. The technical result is achieved in that in the method of extracting rare earth metals from aqueous solutions, including extraction of metal cations by organic phase containing the extractant solution in an inert diluent, as extractant use of naphthenic acid, in an inert solvent used kerosene, and extraction was carried out in three stages when the volume ratio between organic and aqueous phases O:=1:(9-11) at each stage, the first stage extracts the europium (III) if the content of 10-13% vol. naphthenic acid in kerosene and pH of the water solution of 5.0 to 5.1, second stage remove samarium (III) if the content of 13-16% naphthenic acid in kerosene and pH of an aqueous solution of 4,6-4,7, and in the third stage remove the cerium (III) and lanthanum (III) with the same content of the extractant and pH=5.0 to 5.1. Using as extractant naphthenic acid provides increased recovery of cations of rare earth metals due to the chemical structure of naphthenic acid, namely the presence of five-membered cycle at the end of the carbon chain, which provides high extraction ability of naphthenic acid with respect to cations of rare earth metals and the difference in extragroup the STI cations of rare earth metals naphthenic acid. Use as inert solvent kerosene reduces the viscosity of the extractant and, consequently, rapid separation of the phases. Carrying out the extraction at a ratio of volumes of organic and aqueous phase a:=1:(9-11) at each stage provides the optimum balance of low flow of the extractant and a high degree of concentration of the cations of rare earth metals in the organic phase. Removing the first stage of the cations of europium (III) an organic phase containing a solution of about 10-13.% naphthenic acid in kerosene, with a ratio of organic and aqueous phase a:=1:(9-11) and the pH of an aqueous solution of 5.0 to 5.1 allows to obtain a high degree of extraction of cations of europium (III) due to the high extraction ability of naphthenic acid with respect to cations of europium (III) and due to differences in extraparameter cations europium (III) under these conditions (obtained experimentally). Removing the second stage of cations samarium (III) an organic phase containing a solution of 13-16% naphthenic acid in kerosene, with a ratio of organic and aqueous phase a:=1:(9-11) and the pH of an aqueous solution of 4,6-4,7 allows to obtain a high degree of extraction of cations samarium (III) due to the high extraction ability of naphthenic acid with respect to cations of samarium (III) and due to differences in extraparameter is ational samarium (III) under these conditions (obtained experimentally). Removing the third stage of the cations of cerium (III) with the same content of the extractant, i.e., organic phase containing a solution of 13-16% naphthenic acid in kerosene, with a ratio of organic and aqueous phase a:=1:(9-11) and pH=5.0 to 5.1 allows to obtain a high degree of extraction of cations of cerium (III) due to the high extraction ability of naphthenic acid with respect to cations of cerium (III) and due to differences in extraparameter cations of cerium and lanthanum naphthenic acid under these conditions (obtained experimentally). The method is illustrated by drawings, where figure 1 shows the dependence of the distribution coefficients of lantanoides from the pH of the aqueous phase, figure 2 presents the dependence of the distribution coefficients of LREE concentration of the extractant in an inert diluent kerosene, figure 3 presents the scheme of the installation for carrying out the extraction, figure 4 presents the sequential extraction extraction of europium, samarium, cerium and lanthanum. The method is based on the experimental dependencies of the distribution coefficients of europium, samarium, cerium and lanthanum from the pH of the aqueous phase in the range from 3 to 5.5 at a constant concentration of the solution of the extractant in kerosene 15 vol.%, presented in figure 1, and the dependency of the distribution coefficients of europium, samarium, cerium and lanthanum of aconcentration extractant in an inert diluent kerosene in the range from 3 to 15 vol.% at constant pH=5, presented in figure 2. The method is as follows. As extractant use technical naphthenic acid. Naphthenic acid is diluted with inert organic diluent is kerosene. Extraction was carried out in three stages when the volume ratio between organic and aqueous phase a:=1:(9-11) at each stage. In the first stage, add in the specified ratio of the organic phase, containing a solution of about 10-13.% naphthenic acid in kerosene, and remove cations europium (III) at pH of an aqueous solution of 5.0 to 5.1. The organic extract containing the cations of europium (III), is separated in a known manner, and the raffinate, containing cations of samarium, cerium and lanthanum are used in the second stage of extraction. In the second stage to the specified raffinate added in the same ratio of the organic phase containing solution 13-16% naphthenic acid in kerosene, and extractant in the organic phase is extracted cations samarium (III) at pH of an aqueous solution of 4.6 to 4.7. The organic extract containing the cations samarium (III), is separated in a known manner, and a raffinate containing cations of cerium and lanthanum, used in the third stage of extraction. In the third stage to the specified raffinate added in the same ratio of the organic phase containing solution 13-16% naphthenic acid in kerosene, and extractant in the organic phase is extracted cations of cerium (III)at pH of an aqueous solution of 5.0 to 5.1. The organic extract containing the cations of cerium (III), is separated in a known manner, and of the raffinate extract cations of lanthanum (III). Necessary to balance the duration of contact of the aqueous and organic phases is established experimentally, and is no more than 10 minutes Duration separation is not more than 15 minutes Monitoring of pH is performed using the pH-meter pH-150 MA combined electrode brand esque 10601/4. Control over the content of metal cations in the aqueous phase carried out using x-ray spectral fluorescence analyzer SPECTROSCAN U. An example of the method. Use of nitrate, chloride and sulfate aqueous solutions of lanthanide. Prepare a solution of 10 vol.% and 13 vol.%. naphthenic acid in kerosene. In thermostated glass vessel with a stirrer placed organic and aqueous phase in a volume ratio of 1:10 respectively. The acidic solution containing europium (III), samarium (III), cerium (III) and lanthanum (III), neutralize, adjusted to pH=5. The first stage extraction is carried out with the concentration of naphthenic acid in kerosene 10 vol.%. In the organic extractant phase is extracted 81% of the cations of europium (III), with partition coefficients βEu/Sm=1,7, βEu/Ce=2,6, βEu/La=29. Next, the raffinate, containing cations of samarium (III), cerium (III) and lanthanum (III), are sent to second the stage of extraction. In the second stage when carrying out the extraction solution 13% vol. naphthenic acid in kerosene at a pH of the aqueous phase of 4.7 is removing cations samarium (III) with partition coefficients βSm/Ce=2, βSm/La=11. Removing cations samarium (III) extraction is 80%. Next, the raffinate containing cations of cerium (III) and lanthanum (III), are sent to the third stage of extraction, which when using 13% vol. solution of naphthenic acid in kerosene when the pH of the aqueous phase of 5.0 extracts in organic phase cations of cerium (III) in aqueous solution cations of lanthanum (III) separation factor βCe/La=11. Removing cations of cerium (III) extraction is 90%. In all cases, extraction of the studied metals was observed a clear stratification of the organic and aqueous phases, the absence of a third phase or precipitation, satisfactory viscosity of the obtained organic solutions. Reextraction saturated organic phase carried out by the known methods. Thus, the method allows to obtain a high degree of extraction of lanthanides from aqueous solutions of their salts. The method of extracting rare earth metals from aqueous solutions, including extraction of cations of rare earth metals with an organic phase containing the extractant solution in an inert diluent, characterized in that as the former is regenta use of naphthenic acid, as the inert solvent used kerosene, and extraction was carried out in three stages when the volume ratio between organic and aqueous phases O:=1:(9-11) at each stage, the first stage is extracted cations europium (III) if the content of 10-13% vol. naphthenic acid in kerosene and pH of the water solution of 5.0 to 5.1, second stage remove cations samarium (III) if the content of 13-16% naphthenic acid in kerosene and pH of an aqueous solution of 4,6-4,7, and in the third stage, remove cations of cerium (III) and lanthanum (III) with the same content of the extractant and pH 5.0 to 5.1.
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