|
IPC classes for russian patent Method of extracting rare-earth elements from wet-process phosphoric acid (RU 2509169):
Another patents in same IPC classes:
Method for opening perovskite concentrate / 2507278
Method involves carbothermal vacuum treatment. Prior to carbothermal treatment, a charge is prepared, which consists of perovskite concentrate and carbon-containing material in the ratio suitable for formation of calcium carbide, and titanium carbides and oxycarbides. Opening is performed in one unit in two stages. At the first stage, carbothermal treatment is performed at the temperature of 1100-1300°C and residual pressure of 10-100 Pa so that solid mixture of calcium carbides and titanium carbides and oxycarbides is obtained. The second stage is performed at the temperature of 1400-1500°C and pressure of 5-10 Pa for dissociation of calcium carbide and its stripping so that elementary calcium and carbon is obtained and with concentration in the residue of precious components of titanium, tantalum, niobium and rare-earth metals, which are contained in perovskite concentrate and are subject to chlorination.
 Phosphosemihydrate processing method / 2507276
Invention refers to processing of freshly obtained phosphosemihydrate and can be used to obtain concentrate of rare-earth elements (REE) and gypsum product for construction materials. Phosphosemihydrate is processed with water solution containing fluorine-ion. Sulphuric acid leaching is performed with displacement and separation of the water solution containing fluorine-ion, as well as with conversion of REE and impurity components to a leaching solution and production of a phosphosemihydrate layer saturated with a sulphuric-acid solution. Then, water displacement of the remaining amount of sulphuric acid solution is performed so that washed phosphosemihydrate and a leaching solution is obtained Phosphosemihydrate is neutralised with a calcium-containing reagent so that a gypsum product is obtained. Rare-earth elements and impurity components are extracted from the leaching solution by sorption using sulphoxy cationite so that a lean sulphuric-acid solution is formed; REE and impurity components are desorbed from saturated cationite by its processing with an ammonium sulphate solution so that a strippant is obtained; REE and impurity components are deposited from the strippant with an ammonium-containing precipitator in two stages and REE deposit is separated.
 Method for opening loparite concentrates / 2506333
Invention refers to metallurgy of rare metals. A method for opening loparite concentrates involves preliminary machining of loparite concentrates and further treatment of activated loparite concentrates with 30% of HNO3 solution at the temperature of 99 °C. To further treatment there subject are activated loparite concentrates with double amount of energy of variation of loparite crystal lattice parameters of at least 73 kJ/mole and with stored total amount of energy, which corresponds to surface of areas of coherent dissipation and microdeformations with at least 9.5 kJ/mole of loparite.
 Method of processing phosphogypsum / 2504593
Method of processing phosphogypsum involves step-by-step agitation sulphuric-acid leaching of rare-earth metals and phosphorus while feeding sulphuric acid to the head step, using the obtained leaching solution of the head step at subsequent leaching steps, separating the undissolved residue from pulp of a tail step and washing with water, treating the leaching solution of the tail step to obtain a mother solution, using the mother solution and the washing solution for leaching. Leaching of the rare-earth metals and phosphorus at the second and subsequent steps is carried out from a mixture of phosphogypsum and the leached pulp from the previous step. Sulphuric acid is fed to the head leaching step in an amount which enables to extract rare-earth metals and phosphorus into the solution at the head step and subsequent steps at pH values at the tail leaching step not higher than pH at the onset of precipitation of rare-earth metal phosphates. The tail step for leaching rare-earth metals and phosphorus is carried out while simultaneously treating the leaching solution by extracting rare-earth metals by sorption with a cationite. The rare-earth metal-saturated cationite is separated from the mother pulp and taken for producing a rare-earth metal concentrate. A portion of the mother solution is pre-purified from phosphorus by precipitation thereof with a basic calcium compound. The obtained phosphorus-containing precipitate is fed for recycling.
 Plasma-carbon production method of rare-earth metals, and device for its implementation / 2499848
Method involves carbon thermal reduction of oxide compound of rare-earth metal in vacuum so that powder of rare-earth metal carbide, which is free from residues of oxygen impurity, is obtained. Then, it is cooled down and mixed with high-melting metal powder in the ratio that is sufficient for performance of exchange reactions between rare-earth metal carbide and high-melting metal, and mixture is heated with hot volumetric plasma discharge to the temperature of ≥1800°C. With that, evaporating rare-earth metal is collected on condensers and hard-alloy carbide of high-melting metal is obtained. The device includes a vacuum system, cathode and anode assemblies arranged concentrically in the chamber, and a steam line and a condenser-cooler, which are coaxial to them. With that, an internal electrode represents an anode of high-current vacuum plasma discharge burning in an annular discharge cavity formed with coaxial cylindrical electrodes. The anode is made from high-melting electrically conducting material in the form of a crucible having a capacity, and a thin-wall cathode enveloping it, outside which there located is a starting resistance heater, is also made from high-melting electrically conducting material, for example tungsten, tantalum or graphite.
 Cerium extraction method / 2495147
Cerium extraction is performed after preliminary preparation of a catalyser. Crushing of the used catalyser is performed. Crushed catalyser is subject to annealing at the temperature of 650-800°C during 3-6 hours. After annealing the catalyser is cooled down to room temperature and cerium compound is extracted by dilution of ignited catalyser in concentrated hydrochloric acid. Obtained solution with suspended particles of cerium dioxide is heated to boiling, exposed at boiling temperature of 100-110°C during 30-120 minutes and during 3-12 hours at temperature of 0-20°C so that a deposition is obtained. The obtained deposition is separated from mother solution by means of filtration by draining the solution from the deposition surface to a filter with the size of filtering material pores of not more than 2 mcm. Deposition on the filter is washed from iron compound and dried till constant weight of cerium dioxide.
 Method of extraction of rich components from production solutions for processing of black-shale ores / 2493279
Method includes sorption of rich components from production solutions by ion-exchange material counterflow under controlled pH of environment and oxidation-reduction potential Eh. Sorption is performed by ion-exchange materials in stages from production solutions containing uranium, molybdenum, vanadium and rare earth elements. At the first stage uranium and molybdenum are extracted by anion-exchange material sorption. At the second stage vanadium is extracted by anion-exchange material sorption with hydrogen dioxide available at Eh of 750-800 mV, pH of 1.8-2.0 and temperature of 60°C, at that vanadium sorption is performed till complete destruction of hydrogen dioxide and till Eh is below 400 mV. Then barren solutions are transferred to cationite at pH of 2.0-2.5 and Eh of 300-350 mV for extraction of rare earth elements.
 Processing method of black-shale ores / 2493273
Processing method of black-shale ores includes crushing, counterflow two-stage leaching by sulfuric acid solution upon heating, separation of pulps formed after leaching at both stages by filtration. Then valuable soluble materials are washed from deposit at the second stage with strengthened and washing solutions being produced, marketable filtrate is clarified at the first stage for its further processing. Ore is crushed till the size of 0.2 mm, leaching at the first stage is performed by cycling acid solution with vanadium under atmospheric pressure, temperature of 65-95°C during 2-3 hours, till residual content of free sulphuric acid is equal to 5-15 g/l. Leaching at the second stage is performed at sulphuric acid rate of 9-12% from the quantity of initial hard material under pressure of 10-15 atm and temperature of 140-160°C during 2-3 hours. Cake filtered after the first stage is unpulped by part of strengthened solution which content is specified within 35-45% of total quantity.
 Processing method of black-shale ores with rare metals extracting / 2493272
Processing method of black-shale ores with rare metals extracting includes leaching of ore by sulphuric acid solution with dilution of rare metals. Leaching is performed in autoclave by sulphuric acid solution consisting of free and combined sulphuric acid with ratio of H2SO4(free):H2SO4(comb)=2:1, and containing 25-45 g/l of iron sulphate, 70-90 g/l of aluminium sulphate and 0.5 g/l of nitric acid. At that the process is performed under pressure in autoclave equal to 10-15 atm with mixing at temperature of 140-160°C in concentration range of general H2SO4(gen) equal to 350-450 g/l under pulp density S: L=1:0.7-0.9, preferably 1:0.8, under constant oxidation-reduction potential Eh in the system equal to 350-450 mV during 2-3 hours till residual concentration of free H2SO4(free) is within 45-75 g/l.
 Method of extracting rare-earth metals (rem) from phosphogypsum / 2492255
Proposed method comprises REM and phosphorus leeching by sulfuric acid solution to obtain leaching solution and insoluble residue. Said insoluble solution is processed by calcium compound to pH over 5. PEM concentrate is extracted from said solution by crystallisation and fed to REM and phosphorus leaching stage. Prior to leaching phosphogypsum is subjected to flushing with water to obtain flushing solution containing REM and phosphorus. Said insoluble residue is flushed before processing by calcium compound. Obtained flushing solution is processed by calcium compound to produce pulp with pH not over that of REM phosphate precipitation beginning and combied with said flushing solution. REM is sorbed by cation exchangers and separated to desorb REM therefrom to produce desorbent and recovered cation exchanger. Said recovered cation exchanger is sent to REM sorption while desorbent is sent to REM concentrate production stage. Phosphorus and associated impurities are deposited from sorption mother pulp. Obtained pulp is separated in residue to be recovered and water phase to be used as circulating water.
Method of extracting americium from wastes / 2508413
Method involves dissolving wastes in concentrated nitric acid, oxalate precipitation from the solution, drying and calcining the americium oxalate to americium dioxide. The solution obtained by dissolving wastes with high concentration of impurity cations, one of which is ferric iron, is mixed with a reducing agent for reducing ferric iron to ferrous iron. After reduction, the solution with acidity by nitric acid of 1-2.5 mol/l is taken for extraction of americium with a solid extractant based on different-radical phosphine oxide, followed by washing and re-extraction of americium. Oxalate precipitation is carried out from the re-extract with americium concentration of not less than 3 g/l and nitric acid concentration of not less than 3 mol/l, said precipitation being carried out in two steps: adding an oxalate ion to the americium-containing solution in weight ratio to americium of (2-7):1 and then adding water to the separated precipitate in volume ratio to the precipitate of (3-8):1 and the oxalate ion in weight ratio to americium of (1-4):1. The obtained reaction mixture is boiled and taken for separation of americium oxalate from the solution.
 Method of extracting molybdenum and cerium from spent iron oxide catalysts for dehydrogenating olefin and alkyl aromatic hydrocarbons / 2504594
Extraction of molybdenum and cerium is carried out in two steps, where molybdenum is extracted at the first step and a cerium compound is extracted at the second step. The first step involves crushing a catalyst, adding a solution of a leaching agent in weight ratio to the spent catalyst of (0.5-10):1, in concentration of not less than 0.1 mol/l, stirring the suspension for 4-10 hours at temperature of 90-95°C, filtering the mixture to separate the residue and washing the residue with water. A mixture is then prepared from the filtrate and water from washing the residue containing molybdenum. The mixture is the evaporated to obtain an end product. The second step of extracting the cerium compound is then carried out, where the residue of the crushed catalyst is completely dissolved in hydrochloric acid, water is added and then evaporated to the initial volume of the solution, the undissolved portion is separated by filtering, the remaining solution is neutralised to pH 3.5-4.5 with control thereof, the solution is heated to 90-100°C while stirring, followed by successively adding a calcium salt solution in ratio of calcium to the catalyst from 1:100 to 5:100 and a saturated oxalic acid solution in ratio to the catalyst from 5:1 to 10:1, stirring at temperature of 70-100°C for 2-6 hours, holding the solution to precipitate the cerium compound for 4-24 hours at room temperature, separating the precipitate from the mother solution by filtering, washing and drying to constant mass. The invention also discloses a method of extracting molybdenum only from said catalyst and a method of extracting cerium only from said catalyst.
 Extraction method of gold from tails of cyanidation of carbonic sorption-active ores and washed products / 2493277
Extraction method of gold from tails of cyanidation of carbonic sorption-active ores and washed products includes filtration of pulp from tails on filter press with filtrate return to cyanidation circuit or to neutralisation. Before filtration pulp is heated and filtered at temperature of 70-130°C and pressure of 0.2-0.6 MPa. After filtration cake on filter is washed with preheated cycling cyanide solutions or water at temperature of 70-130°C and pressure of 0.2-0.6 MPa. Primary and washing filtrates are combined, cooled, and gold is extracted by sorption or carbonisation.
 Method of producing nickel from sulfide ore stock / 2492253
Proposed method comprises leaching by chloride solution at feed of oxygen and chlorine. Then, copper is precipitated from said solution to obtain copper sulfide cake and said solution of cleaned of iron, zinc and cobalt. after cleaning nickel is electrically extracted from the solution while effluent is processed to recover chlorine and alkali. Note here that leaching is performed in two steps with solution backflow. Note here that only oxygen is fed to said first step while only chlorine is fed to said second step.
Method for quantitative determination of cerium in steels and alloys / 2491361
Method includes dissolution of a sample of analysed alloy and separation of cerium from the base of the alloy and macrocomponents. At the same time the base and macrocomponents are separated from cerium by serial deposition and extraction of the alloy base and macrocomponents of the alloy from the solution. Deposition is carried out with sodium diethyldithiocarbamate, extraction - with dithizone in chloroform. After separation of the organic phase, the cerium content is detected in water phase with the spectrometric method.
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 of extracting americium / 2477758
Invention relates to methods of extracting americium in form of americium dioxide from solutions. The invention can be used in the technology of extracting americium from production and radioactive wastes. The method involves concentrating nitric acid solution containing americium and impurities to americium content of not less than 100 mg/l by multi-step deposition of a precipitate containing americium, followed by dissolution thereof each time in a new portion of the starting solution. The precipitate containing americium is obtained from each portion of the solution by adding to 3.8-6.0 M nitric acid solution, which contains americium and impurities, ammonium hydroxide or an alkali metal hydroxide until achieving residual acidity of 0.1-0.2 M, oxalic acid to concentration of 10-50 g/l and adjusting acidity of the obtained reaction mixture to pH 0.6-2.3 if there are hydrolysable impurities in the starting solution and to pH 0.6-3.5 if not. The precipitate obtained by deposition from the americium-concentrated solution is then calcined and the calcined precipitate is then dissolved in nitric acid solution. Americium is then extracted from the obtained solution by a tributyl phosphate-based solid extractant, re-extracted, americium oxalate is deposited from the re-extract and then calcined to americium dioxide.
 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 of extracting gold from mineral stock bearing minor gold fractions / 2467083
Invention relates to mineral stock processing and may be used for extracting gold fractions of grain size smaller than 0.07 mm. Proposed method comprises preparing water suspension with addition of flocculating agent. Damped ground paper bulk is added to said suspension, paper bulk features reduced moisture resistance and mineral component-to-bulk ratio making 1: 0.05. Then, mix is mixed in mixer for 10 s. After mixing, paper bulk is separated on sieve with mesh size not exceeding 0.2 mm. Now, paper bulk is rinsed to produce concentrate to be dried and fused.
 Method of processing natural uranium chemical concentrate / 2451761
Invention relates to processing natural uranium chemical concentrate. Proposed method comprises concentrate leaching by nitric acid solution to obtain suspension, adding coagulant into suspension and suspension separation. Clarified solution is separated from residue and directed to extraction. Note here that polyacrylamide-based anion coagulant is used and suspension with said coagulant is subjected to permanent magnetic field effects. Coagulant concentration and duration of magnetic field effects are selected to ensure concentration of insoluble residue now exceeding 100 mg/l in clarified solution. In extraction from clarified solution, no antifloating emulsions are observed.
Electrolytic method of producing ultrafine gadolinium hexaboride powder / 2507314
Powder is synthesised by electrolysis from a molten medium which includes gadolinium chloride and calcium fluoroborate in a background electrolyte at temperature of 550±10°C in an atmosphere of purified and dried argon. The background electrolyte used is a eutectic mixture of potassium, sodium and caesium chlorides, with the following ratio of components, wt %: gadolinium chloride 3.0-7.0, potassium fluoroborate - 6.0-10.0, eutectic mixture of potassium, sodium and caesium chlorides - the balance.
|
FIELD: chemistry.
SUBSTANCE: 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 treating an apatite concentrate, and can be used in industry. Wet-process phosphoric acid heated to 65-80°C, which contains rare-earth elements and fluorine, aluminium, titanium and iron impurities, is mixed with ammonia in an amount which ensures the molar ratio NH3:P2O5=(0.2-1.0):1. Ammonium fluoride is then added to the acid in amount of 20-30 g/l to obtain a suspension and transfer the main part of rare-earth elements and part of the impurity components into the precipitate. The precipitate of the rare-earth element concentrate is separated from the phosphoric acid solution.
EFFECT: extracting rare-earth elements with low consumption of the fluorine-containing precipitation agent, which simplifies further processing of the phosphoric acid solution into mineral fertiliser.
3 cl, 9 tbl, 4 ex
The invention relates to a method of allocating concentrate rare earth elements from wet-process phosphoric acid obtained in digitatum processing of Apatite concentrate, and can be used in the chemical industry.
During the processing of Apatite concentrate, containing about 1 wt.% oxides of rare earth elements (REE), phosphoric acid (EPA) is widely used sulfuric acid method, which is implemented in industry as palpitates or digitalneho processes. In digitatum process up to 25% of REE phosphate rock goes in wet-process phosphoric acid, while the total content of REE in the acid is about 1.1-1.4 g/l compared to the original Apatite concentrate the amount of REE enriched in yttrium and REE moderate and severe groups. This makes EPA digitalneho process especially attractive for REE extraction. However, the known methods for extracting inherent disadvantages.
The method for extracting rare earth elements from wet-process phosphoric acid (see path 2381178, IPC C01F 17/00, SW 25/237 (2006.01), 2010), including the introduction at a temperature of 65-80°C in the circulating phosphoric acid with a concentration 31,0-38.5 wt.% compounds of sodium in an amount to provide its content in the purified phosphoric acid 5-10 g/l in terms of n is Na 2O. as compounds of sodium are using him carbonate, sulfate or chloride. The precipitate of crystals of sodium fluorosilicate preparation of Na2SiF6separated by filtering from the purified phosphoric acid, give it the sulfuric acid to provide a concentration of 10-15 wt.% and incubated the mixture of acids within 1-5 hours with the crystallization of the precipitate of the double sulphates REE and sodium. The precipitate was separated by filtration from the acid solution and washed with sulfuric acid with a concentration of not less than 36%. The method extracts the 72,9-87,7% of rare-earth elements, including yttrium yttrium and REE groups, in the form of a double sulfate with sodium.
This method is characterized by insufficiently high extraction of rare-earth elements, including yttrium and REE, yttrium group, is a multistage and long lasting, due to the need to pre-precipitate of sodium fluorosilicate preparation and conduct of the two crystallization and filtration. This leads to increased energy consumption and increasing the number of units of the equipment used. The method does not allow to extract REE production of phosphoric acid, which is unacceptable to enter sulfuric acid. All this reduces the effectiveness of the method.
Known also adopted as a prototype, the method for extracting rare earth elements from wet-process phosphoric acid, with whom containing a series of REE and impurity components fluorine, aluminum, silicon, titanium and iron (see U.S. Pat. RF 2443630, IPC C01F 17/00 (2006.01), 2012), including introducing heated to 65-80°C EPA reagent-precipitator in the form of fluoride or byflorida of ammonia with the formation of the suspension and transfer the main part of the REE and part of the impurity components in the solid phase. When this reagent is injected into the precipitator acid concentration, which in terms of the fluoride ion is determined from the relation: A=n-(2,a1+1,9a2+1,a3+1,a4+0,348a5-a6), where a is the concentration of fluoride ion, g/l, n is the stoichiometry coefficient, n=1-3, a1and2and3and4, a5, a6- the initial concentration in the acid respectively Al2O3, SiO2, TiO2, Fe2O3, ΣLn2O3and fluorine, g/l Suspension was incubated for up to 1 h, after which the sediment REE concentrate is separated from the phosphoric acid solution by filtration and washed with water. The method provides recovery into concentrate 85,4-97,0% REE at a flow rate of fluoride ion, respectively, 19,3 and 57.9 g/l By a known method retrieves 68,2-96.4% of yttrium and REE, yttrium group.
The disadvantage of this method is that a high recovery of REE is provided with increased flow containing the fluoride ion reagent-precipitator. Because sediment REE concentrate passes a relatively small part of the in troduction the military fluorine, then after separation of the REE concentrate from the phosphate solution before further use of the solution, you must remove the main part of fluorine. All this reduces the effectiveness of the method.
The present invention is directed to the achievement of the technical result consists in increasing the efficiency of the method by providing a high degree of REE extraction under reduced reagent consumption-precipitator.
The technical result is achieved in that in the method for extracting rare earth elements from wet-process phosphoric acid containing REE and impurity fluorine, aluminum, titanium and iron, including the introduction of heated acid reagent-precipitator in the form of ammonium fluoride with the formation of the suspension and transfer the main part of the REE and part of the impurity components in the sludge and the sludge separation of REE phosphate from solution according to the invention, before the introduction of ammonium fluoride in the acid injected ammonia in an amount to provide a molar ratio of NH3:P2O5=(0,2-1,0):1.
The achievement of the technical result is driven by the fact that the ammonium fluoride is injected in the amount of 20-30 g/l
The achievement of the technical result also contributes to the fact that ammonia is introduced into the acid in an amount to provide a molar ratio of NH3:P2O5=(0.4 to 0.5):1.
The essential features for the run of the invention, determine the scope of the requested legal protection and sufficient to obtain the above-mentioned technical result function and correlate with the results as follows.
Introduction to wet-process phosphoric acid with ammonia at a molar ratio of NH3:P2O5=(0,2-1,0):1 before the introduction of ammonium fluoride leads to partial neutralization of the acid, providing a high degree of REE extraction under reduced reagent consumption-precipitator - ammonium fluoride and has no impact on subsequent processing of phosphate solution of mono - ammonium dihydrophosphate. The effect of neutralization of ammonia on the efficiency of extraction of REE concentrate is determined by the fact that, as research has shown, most REE, mainly cerium group, not deposited in the form of fluorides of rare-earth elements, and as containing REE, fluorine and ammonium group of the compounds of complex structure, less soluble in phosphate solutions than the fluorides of rare-earth elements.
The molar ratio of NH3:P2O5less than 0.2 leads to a decrease of REE extraction in rare earth concentrate, and the molar ratio of NH3:P2O5more than 1 does not increase the extraction of REE rare earth concentrate, but increases the viscosity of the solution, making it difficult filtration separation of rare earth concentrate.
The combination of Visayas is the R characteristics are necessary and sufficient to achieve the technical result of the invention, bringing a high degree of REE extraction under reduced reagent consumption-precipitator, which increases the efficiency of the method.
In some cases, of the preferred embodiment of the invention, the following operational parameters.
Introduction to the heated acid reagent-precipitator in the form of ammonium fluoride leads to the formation of the suspension and the translation of the main part of REE and part of the impurity components in the sediment. The introduction of ammonium fluoride in the amount of 20-30 g/l, which corresponds to 10.3 to 15.4 g/l of fluoride ion, provides at a reduced flow precipitator high recovery of REE in the precipitate of rare earth concentrate. To produce a well filterable precipitate is possible to extract suspension for 0.5 to 0.8 hours.
Reducing consumption of ammonium fluoride less than 20 g/l leads to a decrease of REE extraction, especially REE moderate and severe groups. Increased consumption of ammonium fluoride more than 30 g/l does not increase the extraction of REE rare earth concentrate, but leads to unnecessary increase of the flow rate of the reagent-precipitator and complicates the removal of fluoride during subsequent processing phosphate solution on mineral fertilizers.
The introduction of ammonia to the acid in an amount corresponding to the molar ratio of NH3:P2O5=(0.4 to 0.5):1, as shown by research, provides the most complete extraction of all REE in red is Zemelny concentrate.
The above private features of the invention allow a method to optimally from the point of view of providing a high degree of REE extraction under reduced reagent consumption-precipitator.
Example 1. Take 1 l of EPA with a concentration of 38 wt.% and a density of 1.26 g/cm3. Content 100% H3PO4is 1260·0,38=478,8, the Content of REE and major impurity components are shown in Table 1.
| Table 1 |
| Content, mg/l |
| Y2O3 |
La2O3 |
Ce2O3 |
Pr2O3 |
Nd2O3 |
Sm2O3 |
Eu2O3 |
Gd2O3 |
| 150,9 |
221,6 |
440,5 |
52,5 |
200,7 |
20,2 |
6,3 |
35,5 |
| Tb2O3 |
Dy2O3 |
Ho2O3 |
Er2O3 |
Tm2O3 |
Yb2O3 |
Lu2O3 |
ΣTr2O3 |
| 2,62 |
13,42 |
of 2.21 |
5,43 |
0,6 |
3,13 |
0,37 |
1155,9 |
| Content, g/l |
| Na2O |
MgO |
CaO |
Al2O3 |
TiO2 |
Fe2O3 |
F |
| 2,73 |
1,40 |
1,72 |
2,56 |
1,20 |
2,82 |
of 5.75 |
Heated to 65°C EPA injected ammonia in the number 0,011 standards. m3(8,35 g), which corresponds to the molar ratio of NH3:P2O5=0,2. After this acid is administered 20 g/l of reagent-precipitator in the form of ammonium fluoride (10.3 g/l of fluoride ion) with the formation of the suspension and transfer the main part of the REE and part of the impurity components in the sediment. The precipitate was separated from the phosphoric acid solution by filtration. The component content in the phosphate solution are shown in Table 2, and removing the precipitated REE and major impurity components in Table 3.
| Table 2 |
| Content, mg/l |
| Y2O3 |
La2O3 |
Ce2O3 |
Pr2O3 |
Nd2O3 |
Sm2O3 |
Eu2O3 |
8,4 |
1,55 |
equal to 4.97 |
0,83 |
3,97 |
2,31 |
0,86 |
3,00 |
| Tb2O3 |
Dy2O3 |
Ho2O3 |
Er2O3 |
Tm2O3 |
Yb2O3 |
Lu2O3 |
ΣTr2O3 |
| 0,57 |
3,59 |
0,71 |
1,97 |
0,27 |
1,69 |
0,24 |
34,9 |
| Content, g/l |
| Na2O |
MgO |
CaO |
Al2O3 |
TiO2 |
Fe2O3 |
F |
| 2,092 |
0,548 |
0,759 |
0,587 |
1,332 |
2,400 |
of 13.75 |
| Table 3 |
| Removing precipitates % |
| Y |
La |
CE |
Pr |
Nd |
Sm |
Eu |
Gd |
Tb |
Dy |
But |
| 94,0 |
99,2 |
98,7 |
of 98.2 |
97,9 |
92,9 |
91,5 |
to 92.1 |
87,2 |
83,9 |
81,1 |
| Er |
Tm |
Yb |
Lu |
ΣTr |
Na |
Mg |
Ca |
Al |
Ti |
Fe |
| 78,8 |
73,2 |
69,0 |
60,0 |
96,8 |
10,8 |
50,3 |
75,5 |
77,9 |
15,4 |
11,2 |
The degree of REE extraction from EPA in the sediment was 96.8%.
Example 2. Take 1 l of EPA with a concentration of 38 wt.% and a density of 1.26 g/cm3. The content of REE and major impurity components are shown in Table 1. Heated to 80°C EPA injected ammonia in the number of 0.022 standards. M3(16.7 g), which corresponds to the molar ratio of NH3:P2O5=0,4. After this, the acid is injected 30 g/l of reagent-precipitator in the form of ammonium fluoride (15,4 g/l of fluoride ion) with the formation of the suspension and transfer the main part of the REE and part of the impurity components in the sediment. The precipitate was separated from the phosphoric acid solution by filtration. The content component is in the phosphate solution are shown in Table 4, and removing the precipitated REE and major impurity components in Table 5.
| Table 4 |
| Content, mg/l |
| Y2O3 |
La2O3 |
CE2About3 |
Pr2O3 |
Nd2O3 |
Sm2O3 |
Eu2O3 |
Gd2O3 |
| 0,32 |
0,255 |
0,55 |
0,061 |
0,27 |
0,13 |
0,017 |
0,054 |
| Tb2O3 |
Dy2O3 |
But2About3 |
Er2O3 |
Tm2O3 |
Yb2O3 |
Lu2O3 |
ΣTr2O3 |
| 0,007 |
being 0.036 |
0,006 |
0,016 |
0,002 |
0,018 |
0,003 |
1,75 |
| Content, g/l |
| Na2O |
MgO |
CaO |
Al2O3 |
TiO2 |
Fe2O3 |
F |
| 2,522 |
1,200 |
0,462 |
0,523 |
1,190 |
2,703 |
16,0 |
| Table 5 |
| Removing precipitates % |
| Y |
La |
CE |
Pr |
Nd |
Sm |
Eu |
Gd |
Tb |
Dy |
But |
| 99,7 |
99,7 |
99,7 |
99,7 |
99,7 |
99,4 |
99,2 |
99,8 |
99,7 |
99,7 |
99,7 |
| Er |
Tm |
Yb |
Lu |
ΣTr |
Na |
Mg |
Ca |
Al |
Ti |
Fe |
| 99,7 |
99,7 |
99,4 |
99,2 |
99,8 |
7,7 |
14,3 |
73,2 |
79,5 |
0,8 |
4,1 |
The degree of REE extraction from EPA in sediment was 99.8%.
Example 3. Take 1 l of EPA with a concentration of 38 wt.% and a density of 1.26 g/cm3. The content of REE and major impurity components are shown in Table 1. Heated to 75°C EPA injected ammonia in the number 0,0275 standards. M3(20,9 g), which corresponds to the molar ratio of NH3:P2O5=0,5. After this, the acid is injected 25 g/l of reagent-precipitator in the form of ammonium fluoride (12.8 g/l of fluoride ion) with formation of a suspension, which was incubated for 0.7 hour. The precipitate, containing the main part of the REE and part of the impurity components, separate the phosphate from the solution by filtration. The component content in the phosphate solution are shown in Table 6, and extracted the e in the sediment REE and major impurity components in Table 7.
| Table 6 |
| Content, mg/l |
| Y2O3 |
La2O3 |
CE2About3 |
Pr2O3 |
Nd2O3 |
Sm2O3 |
Eu2O3 |
Gd2O3 |
| 1,26 |
1,55 |
5,12 |
0,60 |
2,45 |
0.63 |
0,19 |
0,61 |
| Tb2O3 |
Dy2O3 |
Ho2O3 |
Er2O3 |
Tm2O3 |
Yb2O3 |
Lu2O3 |
ΣTr2O3 |
| 0,083 |
0,46 |
0,079 |
0,22 |
to 0.032 |
0,26 |
0,042 |
13,59 |
| Content, g/l |
| Na2O |
MgO |
CaO |
Al2O3 |
TiO2 |
Fe2O3 |
F |
| 2,541 |
1,271 |
0,667 |
0,673 |
1,198 |
2,745 |
12,4 |
| Table 7 |
| Removing precipitates % |
| Y |
La |
CE |
Pr |
Nd |
Sm |
Eu |
Gd |
Tb |
Dy |
But |
| 99,2 |
99,3 |
98,8 |
the 98.9 |
98,8 |
96,9 |
97,0 |
98,3 |
96,8 |
96,6 |
96,4 |
| Er |
Tm |
Yb |
Lu |
ΣTr |
Na |
Mg |
Ca |
Al |
Ti |
Fe |
| 95,9 |
94,7 |
91,7 |
88,6 |
98,8 |
7,0 |
9,2 |
61,3 |
73,7 |
0,2 |
2,6 |
The degree of REE extraction of Afcv precipitate was 98,8%.
Example 4. Take 1 l of EPA with a concentration of 38 wt.% the density of 1.26 g/cm3. The content of REE and major impurity components are shown in Table 1. Heated to 70°C EPA injected ammonia in the number 0,055 standards. M3(41.8 g), which corresponds to the molar ratio of NH3:P2O5=1,0. After this acid is administered 20 g/l of reagent-precipitator in the form of ammonium fluoride (10.3 g/l of fluoride ion) with the formation of the suspension and transfer the main part of the REE and part of the impurity components in the sediment. The precipitate was separated from the phosphoric acid solution by filtration. The component content in the phosphate solution are shown in Table 8, and removing the precipitated REE and major impurity components in Table 9.
| Table 8 |
| Content, mg/l |
| Y2O3 |
La2O3 |
Ce2O3 |
Pr2O3 |
Nd2O3 |
Sm2O3 |
Eu2O3 |
Gd2O3 |
| 1,87 |
2,24 |
5,71 |
0,73 |
2,94 |
0,67 |
0,53 |
0,73 |
| Tb2O3 |
Dy2O3 |
Ho2O3 |
Er2O3 |
Tm2O3 |
Yb2O3 |
Lu2O3 |
ΣTr2O3 |
| 0,092 |
0,51 |
0,094 |
0,33 |
0,006 |
0,63 |
0,097 |
17.36 |
| Content, g/l |
| Na2O |
MgO |
CaO |
Alsub> 2O3 |
TiO2 |
Fe2O3 |
F |
| 2,087 |
0,641 |
0,379 |
0,294 |
at 1,138 |
2,063 |
11,4 |
| Table 9 |
| Removing precipitates % |
| Y |
La |
CE |
Pr |
Nd |
Sm |
Eu |
Gd |
Tb |
Dy |
But |
| 98,8 |
99,0 |
98,7 |
98,6 |
98,5 |
96,7 |
to 91.6 |
97,9 |
96,5 |
96,2 |
95,7 |
| Er |
Tm |
Yb |
Lu |
ΣTr |
Na |
Mg |
Ca |
Al |
Ti |
Fe |
| 93,9 |
99,0 |
79,9 |
73,8 |
98,5 |
23,6 |
54,2 |
78,0 |
88,5 |
10,4 |
26,8 |
The degree of REE extraction from EPA in the precipitate amounted to 98.5%. As seen from the above Examples, the method according to the invention provides extraction of REE concentrate to 96.8-99.8 per cent compared with 85.4-97,0% in the prototype. The proposed method reduces the consumption of fluorine-containing reagent precipitator from 19.3-to 57.9 g/l to 10.3 to 15.4 g/l in terms of the fluoride ion. Reducing consumption of fluorine-containing reagent precipitator provides a reduction in the content of fluorine in the phosphate solution, which simplifies the further processing. The inventive method is relatively simple and can be implemented based on standard equipment using ammonium fluoride, which can be obtained in digitatum process per the processing of Apatite concentrate. All this increases the efficiency of the method.
1. The method of extraction of rare earth elements (REE) from wet-process phosphoric acid containing REE and impurity fluorine, aluminum, titanium and iron, including the introduction of heated acid reagent-precipitator in the form of ammonium fluoride with the formation of the suspension and transfer the main part of the REE and part of the impurity components in the sludge and the sludge separation of REE phosphate from solution, characterized in that before the introduction of ammonium fluoride in the acid injected ammonia in an amount to provide a molar ratio of NH3:P2O5=(0,2-1,0):1.
2. The method according to claim 1, characterized in that the ammonium fluoride is injected in the amount of 20-30 g/l
3. The method according to claim 1, characterized in that the ammonia is introduced into the acid in an amount to provide a molar ratio of NH3:P2O5=(0.4 to 0.5):1.
|