Extraction method of rare-earth metals from phosphogypsum |
|
IPC classes for russian patent Extraction method of rare-earth metals from phosphogypsum (RU 2471011):
      
Processing method of micro production wastes of constant magnets / 2469116
Method involves oxidation of micro production wastes at temperature of 550-650°C in air atmosphere for destruction of crystal latitude Nd2Fe14B so that Fe2O3, Nd2O3, Fe2B is formed and moisture and oil is removed. Then, anhydrous fluorides of rare-earth metals are obtained and their metallothermic reduction is performed for production of constant magnets. After oxidation from oxidated microwastes is completed, rare-earth metals are leached with nitric acid with concentration of 1-2 mol/l at temperature of 20-80°C. Obtained nitrate solutions containing rare-earth metals and impurity elements are processed with solution of formic acid with extraction of formiates of rare-earth metals in the form of the deposit cleaned from impurity elements, which includes iron, aluminium, nickel, cobalt, copper and other transition metals.
Method of extracting rare-earth elements from wet-process phosphoric acid / 2465207
Invention relates to methods of extracting a concentrate of rare-earth elements from wet-process phosphoric acid, which is obtained in a dihydrate process of processing an apatite concentrate, and can be used in chemical and related industries. The method involves sorption of rare-earth elements and thorium contained in wet-process phosphoric acid at temperature 20-85°C, wherein the sorbent used is a sulphoxide cationite, washing the saturated sorbent with water, desorption of rare-earth elements and thorium with concentrated ammonium sulphate solution to form a desorbate, and treating the desorbate with an ammonia-containing precipitant in form of ammonium carbonate or ammonia gas, which is fed in two steps, wherein at the first step the precipitant is fed until achieving pH 4.5-5.0 with precipitation and separation of a thorium-containing precipitate, and at the second step - until achieving pH of not less than 7 with precipitation and separation of a concentrate of rare-earth elements.
 Method to extract holmium (iii) cations from nitrate solutions / 2463370
Method to extract holmium (III) cations from nitrate solutions includes ion floatation using an anion-type surfactant as a collector. Besides, the collector is dodecyl sodium sulfate in a concentration corresponding to stoichiometry of the following reaction: Ho+3+3C12H25OSO3Na=Ho[C12H25OSO3]3+3Na+, where Ho+3 - holmium cation, C12H25OSO3Na - sodium dodecyl sulfate. Moreover, ion floatation is carried out at pH=6.6-7.4, which makes it possible to achieve 90% extraction of holmium from aqueous solutions of its salts.
 Method to extract lanthanum la+3 cations from aqueous solutions / 2463369
Invention relates to the method for production of pure lanthanum or its oxides from lean or industrial raw materials by method of ion floatation. The method to extract lanthanum La+3 cations from aqueous solutions of salts includes ion floatation using an anion-type surfactant as a collector. Besides, the collector is dodecyl sodium sulfate in a concentration corresponding to the stoichiometric reaction: La+3+3NaDS=La[DS]3+3Na+, where La+3 - lanthanum cation, NaDS - dodecyl sodium sulfate. Moreover, ion floatation is carried out at pH=7.8-8.1, which makes it possible to achieve 98% extraction of lanthanum from aqueous solutions of its salts.
 Method of extraction of rare-earth elements from technological and productive solutions / 2462523
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.
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 extraction of copper and/or nickel from cobalt-bearing solutions / 2465355
Method involves supply of solution with high content of cobalt, which contains cobalt, nickel and copper; sorption by means of contact of the above solution with N-(2-hydroxypropyl)picoline amino resin. Selective elution of cobalt, nickel and copper is performed after sorption by means of continuous gradient acidic elution. At that, pH of the above solution is less than or equal to 2.
 Method of producing high strength and capacity carbon sorbent / 2464226
Invention relates to a method of producing a carbon sorbent used for extracting rare metals, particularly gold cyanide from aqueous alkaline solutions. The method involves treatment of activated carbon with a polymer with amino groups. Activated charcoal is treated using polyhexamethylene guanidine hydrochloride in form of an aqueous solution. After treatment, alkali is added while stirring and the solution is separated from the carbon. The carbon is saturated with ammonia solution, phenol and formalin. The mixture is held while boiling for 1-5 hours and the carbon separated from the solution is dried at 150-160°C.
Method of extraction of rare-earth elements from technological and productive solutions / 2462523
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.
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 cadmium from secondary raw material / 2469112
Method involves leaching of cadmium from raw material in solution of sodium ethylene diamine tetraacetate with its further extraction from solution and regeneration of ethylene diamine tetraacetate. Cadmium leaching is performed in two stages. The solution obtained at the first stage is supplied for extraction of cadmium, and residue of the first stage is supplied to the second cadmium leaching stage. The solution obtained at the second stage is used for leaching of cadmium from raw material at the first stage. Besides, leaching at the second stage is performed in presence of hydrogen peroxide at maintaining its concentration in the range of 10-15 g/dm3 during 2-2.5 hours.
|
FIELD: metallurgy. SUBSTANCE: invention can be used in the technology of obtaining the compounds of rare-earth metals at complex processing of apatites, and namely for obtaining of concentrate of rare-earth metals (REM) from phosphogypsum. Method involves sorption of rare-earth metals. At that, prior to sorption, phosphogypsum is crushed in water so that pulp is obtained in the ratio Solid : Liquid=1:(5-10). Sorption is performed by introducing to the obtained pulp of sorbent containing sulphate and phosphate functional groups, at the ratio of Solid : Sorbent=1:(5-10) and mixing during 3-6 h. EFFECT: increasing REM extraction degree to finished product. 5 tbl, 5 ex
The invention relates to a process of producing compounds of rare earth elements by integrated processing of Apatite, in particular the production of concentrates of rare earth metals (REM) of phosphogypsum. The method for extracting rare earth elements (RU 2225892, publ. 20.03.2004,) [1]. The method comprises leaching of phosphogypsum by sequential processing of multiple portions of phosphogypsum sulfuric acid solution with a concentration of 20-25% at W:T=2-3, the translation of rare earth elements in the solution, crystallization of REE concentrate from the solution obtained by leaching, which is carried out at a temperature of 20-80°With the introduction of the leaching solution of concentrated sulfuric acid to its content in the solution is not less than 30%. Leaching of lanthanides from postopera solutions of sulfuric acid medium concentrations allows you to select the lanthanides from the leaching solution in the form of sulfate concentrate, which does not require the use of expensive extractants or surface-active substances. There is also known a method for extracting rare earth elements from phosphogypsum (the Influence of the main process parameters on the efficiency of leaching of rare earth elements from phosphogypsum sulfuric acid / Amindian, Nfroce, Lambertino, Wedgeworth, Mccollow // Journal of applied chemistry, 1976. - v.49. No. 3. - S-638.) [2]. Solenopsae [2] the lanthanides are extracted from the phosphogypsum, obtained by sulphuric acid processing of Apatite concentrate on mineral fertilizers. Leaching of the first portion of phosphogypsum exercise 2-6%solution of sulfuric acid at the ratio of liquid to solid 2-3. The leaching solution is separated and used for subsequent leaching portions of phosphogypsum. The concentration of sulfuric acid at each stage increases according to the relation The extraction of rare earth elements from phosphogypsum by known methods [1, 2] requires a high cost of reagents (salts, acids), as well as significant energy and truthstar the t when receiving concentrates, filtering and washing of rainfall. In addition, at this stage there is a loss of REM by cocrystallization with gypsum and deposition of double sulfates of REM. The use of inorganic acids for leaching of REE from phosphogypsum leads to a large share of the consumption of resources and increased negative environmental impact on the environment. Closest to the claimed invention to the technical essence and the achieved result is "a Method of extracting rare earth metals from phosphogypsum", EN 2416654 C1, CL SW 59/00 publ. 20.04.2011) [3]. The method comprises leaching of phosphogypsum sulfuric acid solution with the translation of rare earth metals in solution. Before leaching carry out washing of phosphogypsum from phosphorus water. Leaching of phosphogypsum carried out with a solution of sulfuric acid at a concentration from 3 to 250 g/L. Extract rare earth metals from solution leaching is performed by concentrating them on the cation exchanger, removing from the cation exchange resin to produce commodity regenerate and return to a full cycle of leaching depleted in rare earth metals aqueous solution of sulfuric acid. However, it is known that sulfate environment contributes to the re-deposition of dissolved REE in the form of sparingly soluble double sulphates, reducing the degree of recovery of REE from ostypes sulfuric acid (Komissarova, L.N., Shatsky V.M., Pushkin GY, and other Compounds of rare earth elements. Sulfates, SELENATES, Telerate, chromates. - Leningrad: Nauka, 1986. - 365 S.) [4]. The use of cation exchange resin containing sulfuric acid functional groups leads to a decrease in sobiraemosti REM due to competitive sorption of ions of impurities (CA, Mg, Fe, Al, ...), since it is known that the sorbents with sulfuric acid functional groups are not selective to ions of rare-earth metals (Kokotov Y.A. Ion exchangers and ion exchange. - Leningrad: Khimiya, 1980. - 152 C.) [5]. The present invention is to increase the degree of extraction of rare-earth metals in the final product while reducing the cost of implementation of the method and reduce the negative ecological impact on the environment in the process of practical implementation of the method. To solve the stated problem, the claimed method, according to which the phosphogypsum is crushed and dissolved in water at a ratio of TV:W=1:(5-10), sorption is carried out by introducing into the resulting slurry of the sorbent, containing sulfuric acid and phosphoric acid functional groups, to TV:sorbent=1:(5-10), the leaching is carried out at a stirring within 3-6 hours In the proposed method the dissolution of phosphogypsum is due to the arrival of ions of hydrogen functional groups of the sorbent, so adding the inorganic acid is not required. No sir okisnoi environment eliminates the re-precipitation of dissolved REE in the form of sparingly soluble double sulphates, increasing the degree of extraction of REE from phosphogypsum. High selectivity to REM sorbent containing sulfuric acid and phosphoric acid functional groups leads to the subsequent improvement of the quality of the eluates and facilitate their further processing (Vfront, Linedev, Twimukye. Study of adsorption of scandium from hydrochloric acid solutions by chelating resin PUROLITE S-957 // Chemistry and chemical technology, 2010, T, 9, S-101) [6]. When the ratio W:T less than 5, there is formed a dense, poorly pomeshivaem pulp phosphogypsum, which complicates the process of sorption of REE. When the ratio W:T more than 10 sharply increased volumes of solutions, which leads to an increase in the number of equipment. At the same time, positive effects on extraction of REE is not observed. The maximum sobiraemosti REM achieved during sorption 3-6 hours. When the contact time is less than 3 hours the degree of REE extraction insignificant, when contact time is more than 6 hours increase the degree of extraction does not occur. With regard to TV:sorbent is less than 5, the degree of extraction of REE practically does not change. With the increase of this indicator over 10 extraction ratio decreases REM. Thus, a new technical result achieved by the declared method is to increase the degree of extraction of REE and simplifying the process of extracting rare-earth metals from phosphogypsum. The experimental is Stalnoy verification of the claimed method was carried out when removing phosphogypsum rare-earth metals, namely, the entire group of lanthanides, yttrium and scandium. Their total content was determined by the method of emission spectral analysis with inductively coupled plasma. As a sorbent containing sulfuric acid and phosphoric acid functional groups, used the cation exchanger S-957 (PUROLITE LTD). Can be used as ion-exchange resin Diphonix production Eichrom Technologies. Example 1. Took a portion of phosphogypsum 20 grams (in terms of absolutely dry), crushed, put into the reactor and filled it with water to the ratio of W:T=5, after which the resulting slurry was added to the sorbent in the amount of 4 grams (in terms of dry weight) and kept under stirring for 5 hours at room temperature. Have experience with the same conditions, but without addition of the sorbent. The research results are summarized in table 1. Example 2. Took a portion of phosphogypsum 20 grams (in terms of absolutely dry), crushed, put into the reactor and poured it in different amounts of water, after which the resulting slurry was added to the sorbent in the amount of 4 grams (in terms of dry weight) and kept under stirring for 5 hours at room temperature. The research results are given in table 2 Example 3. Took a portion of phosphogypsum 20 grams (in terms of absolutely dry), were crushed, placed in the reaction is the PR and filled it with water to the ratio of W:T=5, then the resulting slurry was added to the sorbent in the amount of 4 grams (in terms of dry weight) and kept under stirring for 3, 5, 6, 7, and 9 hours at room temperature. The research results are summarized in table 3. Example 4. Took a portion of phosphogypsum 20 grams (in terms of absolutely dry), crushed, put into the reactor and filled it with water to the ratio of W:T=5, after which the resulting slurry was added to the sorbent in the number 1,42; 2; 3,33; 4,0; 5,0; 6,67 (the ratio of solid : sorbent is respectively 14, 10, 6, 5, 4, 3) grams (in terms of dry weight) and kept under stirring for 5 hours at room temperature. The research results are summarized in table 4. Example 5. Took sample of phosphogypsum 20 grams (in terms of absolutely dry), crushed, put into the reactor and filled them with water to the ratio of W:T=5, after which the resulting slurry was added sorbents in the amount of 4 grams (in terms of dry weight) and kept under stirring for 5 hours at room temperature. The research results are summarized in table 5. From the data of tables 1-5 shows that the degree of extraction of rare-earth metals in the final product is not less than 60%. While non-use of inorganic acids for leaching of REE from phosphogypsum reduces the specific consumption of resources and negative ecologicas the e impact on the environment.
The method of extracting rare earth metals from phosphogypsum, including sorption of rare earth metals, characterized in that before the sorption of phosphogypsum are crushed in water to obtain slurry at a ratio of TV:W=1:(5-10), sorption is carried out by introducing into the resulting slurry of the sorbent, containing sulfuric acid and phosphoric acid functional groups, with a ratio of TV:sorbent=1:(5-10) and stirring for 3-6 hours
|
where