Method of extraction and concentration of thorium out of spent melt of saline sprinkler filter - process waste of chlorinate treatment of loparit concentrate

FIELD: metallurgy.

SUBSTANCE: invention refers to extraction and concentration of thorium out of process waste of loparit concentrates treatment - spent melt of saline sprinkler filter (SSF) of loparit concentrate chlorination process. The method includes preparation of suspension by means of discharge of spent melt of saline sprinkler filter (SSF) into water, incorporation of high molecular flocculant, of holding, filtering, separation of sediment, obtaining of chloride solution, and of treatment with steel scrap and metal magnesium. Prior to obtaining chloride solution the source suspension is heated to 60-90°C and treated with solution of sodium hydroxide to pH 1.5-2.0 and to 0.1-0.3% solution of high molecular flocculant at amount of 3-5% from the source volume of suspension; then suspension is held for 2-4 hrs. Chloride solution is received by means of filtration of spent suspension obtaining sediment of rare metals; chloride solution is then treated with steel scrap and metal magnesium; at that the solution is successively treated first with the steel scrap at amount of 3-5 mass fractions of iron per 1 fraction of iron ions (III) in chloride solution at 80-100°C for 1-3 hrs till achieving the value of pH in a pulp equal to 3.0-3.5. Then the pulp is separated from the non-reacted portion of the steel scrap and is treated with metal magnesium to pH 3.5-4.5, and further with 0.1-0.3% solution of high molecular flocculant taken at amount of 5-20% from the volume of chloride solution. Thus produced pulp is held without mixing for 1-4 hrs and filtered producing thorium containing sediment; the said sediment is washed at filter first with solution containing 1-5 g/dcm3 of sodium sulphite, then with water. Washed out sediment is repulped in solution of sodium hydroxide with concentration of 50-150g/dcm3 at a ratio of "Ж:Т"=3-5 at 60-90°C for 2-3 hrs, after what the pulp is filtered with separation of alkaline filtrate. Thorium containing sediment at the filter is washed with water, pressed at the filter and dried; the alkaline filtrate and process water are merged and mixed, then heated to 80-90°C, and treated with solution of sodium hydroxide to pH 11-13 with production of hydroxide pulp. Hydroxide pulp is filtered and then radioactive sediment is produced at the filter; it is washed out with water and transferred to a special wastes depositary, while filtrate is mixed with 10-20 volumes of shop flush water, heated to 80-90°C and again treated with solution of sodium hydroxide to pH 11-13. Obtained pulp is held and filtered thus producing sediment of rare metals and deactivated chloride solution which is discharged to drainage. Sediment of rare metals is unloaded from the filter, merged with sediment of rare metals extracted from the source suspension, dried, washed out and then transferred for preparation of charge for its further chlorination together with the loparit concentrate.

EFFECT: upgraded efficiency of thorium extraction and simultaneously solving problem of neutralisation and utilisation of process waste.

1 dwg, 1 ex

 

The present invention relates to metallurgy and, in particular, to hydrometallurgical processing technologies of various mineral raw materials, industrial products and waste containing non-ferrous, rare, scattered rare earth (re) metals and is usually associated thorium-232 and child products of its decay. The invention in particular can be used for selective hydrometallurgical extraction and preconcentration of thorium waste, process chlorine processing of loparite concentrates - spent molten salt irrigation filter (SOF) of the chlorination process loparite concentrates while addressing issues related to decontamination and decontamination formed secondary radioactive waste (raw).

Known (As the USSR №1400112 on application No. 4038521/2302 with prior. from 25.07.1986; recorded.: 01.02.1988,, publ. TPMF, 2000, No. 19, s; IPC SW 60/02; 01J 43/10 "the Way of extraction of thorium from hydrochloric acid solutions") method of extraction and preconcentration of thorium from solutions containing thorium and other metals. The known method consists in the selective extraction of thorium by sorption on aminoheterocycles the ampholyte with subsequent desorption of thorium from the material, processing of the eluate and the allocation of a thorium sludge. There is a method allows high izbiratelni the capacity to extract thorium from hydrochloric acid solutions, containing in addition to the thorium ions of other metals. The disadvantage of this method is the complexity of the apparatus-technological design process and therefore large capital and operating costs. Another disadvantage of the known method is the fact that the known method does not provide for the possibility of processing, disposal and decontamination (from radionuclides - daughter decay products of thorium, in particular radium) solutions after extraction of thorium ions.

These shortcomings have other known methods of preconcentration of thorium-based ion-exchange extraction of thorium (Cm. As the USSR №704243; 1420972; Journal of applied chemistry, 1990, vol 63, No. 4, s; Dept. VINITI 10.10.1989, No. 6183-389, page 25; non-ferrous metals, 1993, No. 12, p.30-32; RF Patent №2207393 on application No. 2001129456 with prior from 31.10.2001, are recorded. and publ. 27.06.2003, bull. No. 18).

Known (Concentration of chloride waste processing of loparite concentrates of // non-ferrous metals, 1985, No. 12, p.53-56; waste of chlorination process loparite // non-ferrous metallurgy, 1987, No.1, p.32-33). The method of extraction and preconcentration of thorium waste - waste molten salt irrigation filter (SOF) of the chlorination process loparite concentrates titanium niobate REE, in addition to containing valuable components: Nb, TA, Ti and REE impurity metals Fe, Al and up to 0.6% of thorium in secular radioactive equilibrium with its daughter products of its decay - Ac, Ra, etc.

According to the method of the original radioactive waste is the spent melt SOF dissolved in water (at a ratio of 1:(2-4)), the resulting suspension (chloride solution - suspended particles of the fine dust fraction loparite concentrate, partially - products of the hydrolysis of Nb, TA and Ti) are sequentially injected barium chloride, sulfuric acid or sodium sulfate. Then, the suspension is injected steel scrap (iron shavings), the slurry is heated to 60 to 90° - to transfer Fe (III) Fe (II) and treated with an alkaline reagent lime milk (80-100 g/DM3CaO) or 0.5-3 M solution of sodium hydroxide to achieve a pH of the pulp 4-5, after which the slurry is injected 0.5% solution of polyacrylamide, then the slurry is filtered, the radioactive residue ("cake" - secondary RAO) is separated from the mother liquor, washed, dried, and transported for disposal in store special waste (HSO).

The known method, being very simple in hardware design, provides 99.9% degree of extraction of thorium from the original solution (suspension) in the sediment. The disadvantage of this method is unsatisfactory degree of decontamination solutions from daughter products of the decay of thorium-232, in particular radium, which is associated with incomplete Coosada the receiving radium from sediment BaSO 4.

Known analogues of the closest to the technical essence and achieved the result to the proposed technical solution is the well-known method (A.S. USSR №1185867 on application No. 3498167/2202 with prior. from 06.10.1982, are recorded.: 15.06.1985; Publ. 27.04.1999. Bull. No. 12, s. "The way of extraction of thorium from chloride solutions processing of loparite concentrates", IPC SW 60/02) is adopted for the prototype.

The way the prototype is as follows.

Source of thorium waste, in particular exhaust melt SOF, is dissolved in the water by jet, i.e. the draining of the melt in water at a ratio of melt:water=1:(2-4). The resulting suspension simultaneously process steel scrap and magnesium shavings at 60-80°when the mass ratio of Mg:Th=(1-4):1 and Fe:Mg=(5-15):1, the resulting slurry is then injected 0,2-0,4% solution of high-molecular flocculant, for example hydrolyzed polyacrylamide in an amount of 0.1 to 0.2 DM31 DM3the pulp. The pulp after such processing is allowed to stand for 1 hour and filtered with the Department of thorium sludge (oxyhydrate thorium mixed with other metals, of rare-earth elements, Al, Fe, Nb, TA, Ti, K, Mg, Na, and others).

Known prototype method allows you to selectively extract thorium from complex multicomponent solutions obtained, in particular, when dissolved radioactive waste produced in the production radioactive waste molten salt irrigation filter chlorination process loparite concentrates. The degree of extraction of thorium from solution to the solid phase reaches of 99.96%, and the degree of purification of thorium from iron, calculated as the quotient of the ratio of the concentrations of thorium and iron in the resulting product to the specified value in the initial solution, is 400-410.

The disadvantage of the prototype method is unsatisfactory purification of thorium from some of the metals Al, Fe, Nb, TA, Ti, K, Mg, Na, etc. Another disadvantage of the known method is the fact that known method does not allow for neutralization and decontamination solutions from radionuclides - daughter decay products of thorium, in particular radium

The task of the invention is to increase the efficiency of extraction of thorium from solutions while solving the problem of disposal and recycling of waste and industrial products production, including secondary raw. The technical result that can be achieved with the implementation of the developed method, is to improve the content of thorium in the target product and the provision of processing, disposal and decontamination solutions with simultaneous extraction of rare, scattered and rare earth metals.

Set for the ache is solved by achieving the above technical result of the proposed Method for the extraction and preconcentration of thorium from the spent molten salt irrigation filter waste from production of chlorine technology processing of loparite concentrate, comprising preparing a slurry by draining the spent molten salt irrigation filter (SOF) in the water, the introduction vysokomolekulyarnogo flocculant, exposure, filtration, sludge separation, getting chloride solution, obabko steel scrap and metal magnesium.

New in the proposed method is that before obtaining chloride solution of the original suspension is heated to 60 to 90°C and treated with sodium hydroxide solution to a pH of 1.5-2.0 and 0.1-0.3%solution of high-molecular flocculant in the amount of 3-5% of the original volume of the suspension, the suspension is incubated 2-4 hours, chloride solution obtained by filtering the treated suspension to obtain a precipitate of rare metals processing steel scrap and metal magnesium is subjected to chloride solution, successively process the first steel scrap in the amount of 3-5 wt. parts iron to 1 part ion iron (III) chloride solution at 80-100°C for 1-3 hours to achieve a pH in the pulp of 3.0-3.5, after which the pulp is separated from the unreacted part of the steel scrap and treated with metallic magnesium to a pH of 3.5 to 4.5 and then 0.1-0.3% of high-molecular flocculant, taken in an amount of 5-20% of the total chloride solution, the resulting slurry can withstand without premesis the deposits within 1-4 hours and filtered to obtain thorium sludge, which on the filter is washed first with a solution containing 1-5 g/DM3sodium sulfite, then water-washed precipitate repulping in sodium hydroxide solution concentration of 50-150 g/DM3repulpable lead at W:T=3-5 at 60-90°C for 2-3 hours, after which the pulp is filtered with the Department of alkaline filtrate, thorium precipitate on the filter is washed with water, wring out the filter and dried, alkaline filtrate and prambody unite under stirring with the mother solution, the resulting solution or slurry is heated to 80-90°C, treated with sodium hydroxide solution to a pH of 11-13 obtaining oxyhydrate pulp, it is filtered and receive radioactive precipitate on a filter, washed with water and taken in store special waste, and the filtrate is mixed with 10-20 volumes Guild obivochnyh water, heated to 80-90°and again treated with sodium hydroxide solution to pH 11-13, the resulting slurry can withstand and filtered to obtain the precipitate of rare metals and decontaminated chloride solution, which is discharged into the sewage, sludge rare metals discharged from the filter, together with a precipitate of rare metals, selected from the original suspension, dried, washed and then sent for batch preparation for its subsequent chlorination together with loparite concentrate.

Visupersize the Naya sequence of operations, the methods of their implementation, the availability of new activities and additional operations, a new sequence, new modes and process parameters (pH value of the slurry, temperature, time, concentration, volume ratio of the volumes of solutions and reagents) is selected on the basis of the analysis of the results of research works devoted to the problem of processing, disposal and decontamination of multicomponent complex waste - industrial products production, containing in its composition non-ferrous, rare, scattered and radioactive metals, such as thorium, uranium and daughter products of their decay), REM, and also as background electrolyte chlorides of alkali and alkaline-earth metals. On the basis of these studies were selected optimal conditions for the process, which collectively provide a solution to the task and the achievement of the technical result in the implementation of the developed method:

- the increase in the concentration of thorium in the target product by improving the selectivity of thorium separation from the solution in the sediment and reduce the extent of coprecipitation with oxyhydrates thorium other foreign metals;

- provision of decontamination solutions after separation of thorium them to established norms (to a residual specific activity of less than 6 Bq/kg);

additional extraction of radioactive waste - amrabat is the R melts SOF and workshop obivochnyh water - valuable components (Nb, TA, Ti and REE) and they are disposed on the redistribution of chlorination loparite concentrates.

The order and sequence of operations according to the claimed method is illustrated by the schematic diagram of the developed technical solutions. It is important to note and emphasize that the above technical result of the proposed method is achieved only when all, without exception, operations and in strict compliance with all identified and established optimal conditions and process parameters. Failure to comply with at least one of the modes or the deviation from the optimal values of the parameters: pH, ratio of volumes or concentrations, inevitably leads to the achievement of the technical result is impossible: in this case, sharply reduced the degree of extraction of thorium, the degree of decontamination solution from a number of radionuclides thorium (in particular, radium), increases the content of the target product - oxyhydrate thorium - extraneous metals (Al, Fe, Nb, TA, Ti, K, Mg, Na, and others), reduced output simultaneously obtain concentrates of rare metals that are suitable for recycling.

Thus, it follows that the signs of the claimed method and achieved technical result, there is a causal relationship, arraydata is each of the above features (steps, methods, modes and other) separate necessary and collectively provide a solution to the task of achieving the above technical result.

It should be noted that established a causal relationship is not obvious for specialists and not derived from published data on the chemistry and technology of thorium, rare, scattered and rare earth metals.

Check the patentability of the claimed invention shows that it corresponds to inventive step, as it is not necessary for professionals explicitly. The analysis of the prior art indicates that in book, journal and patent literature contains no information about the possibility of extraction and preconcentration of thorium from waste products, in particular of exhaust melt SOF and processing, disposal and decontamination of the resulting secondary raw.

Information confirming the ability of the proposed method to provide the above technical result is shown in the example.

EXAMPLE

For conducting experiments (see drawing) extraction and preconcentration of thorium and decontamination and recycling of radioactive waste and recycling valuable components have been investigated solutions (more precisely, susp is nsii), get in the shop of chlorine processing of loparite concentrates containing, wt.%: 31,6 REE, 36,8 TiO2, 7,7 Nb2O5, 0,58 TA2About5, 0,62 ThO2, 1,0 Fe2About3, 2,0 SiO2the specific activity of the original loparite concentrates 190-240 kBq/kg

When the chlorination of these concentrates in salt chlorinators salt formed radioactive waste - waste molten salt irrigation filter (SOF)containing, wt.%: 0,10 That 0,43 Nb, 0,14 Ti, 1,74 Th, 4,17 REE, 9,10 Fe, 10,48 Al, 2,32 SiO2, 4,2 H.O., specific activity 90800 kBq/kg

In accordance with the accepted and valid in the shop currently, technology melt SOF periodically poured into water, mainly when the ratio of the melt:water=1:2. The resulting suspension (chloride solution - solid phase ˜40-60 g/DM3dust fraction loparite concentrate, and others) has the following composition by major component, g/DM3: 0,11 Th; 13,3 Al; 10,9 Fe; 38,2 REE and a small amount of chlorides and oxychlorides Nb, TA, Ti.

These suspensions are the source of technological raw materials - the proposed method for obtaining thorium concentrates, as well as associated production of concentrates of rare, scattered and rare earth metals.

According to data developed by the technical solution while conducting experiments one of the first Opera which s is the selection of the suspension concentrates of the amount of Nb, TA, Ti and REE, which is in the initial suspension in the solid phase, and in the form of colloid and polyallelic particles and partially in the form of hydrolyzed ion - complexes of different composition and different stages of polymerization.

For separation from the aqueous phase to precipitate compounds of Nb, TA and Ti, mainly in the form of oxyhydrates, the original suspension was heated to 80±2°C and kept at this temperature under stirring for 30 minutes. Then the suspension was treated with a solution (50 g/DM3) sodium hydroxide - with continuous stirring to achieve a pH in the pulp 2,0±0,2, after which the suspension was imposed 0.2% solution of hydrolyzed polyacrylamide (GPA) in an amount of 30 cm31 DM3suspension. The thus treated suspension was kept for 30 minutes without mixing for flocculation sludge and more complete transfer from solution to the solid phase colloid and polyallelic particles oxyhydrates, Nb, TA and Ti. Then the suspension was filtered, the precipitate of oxides and oxyhydrates, Nb, TA, Ti and REE were separated from the chloride solution. For extraction and preconcentration of thorium this solution was heated to 60 to 90°and sequentially processed first steel scrap (metal shavings - 3 "bindweed"), taken in an amount 5 times as compared with the stoichiometric required for full recovery is Eliza (III) to iron (II):

FeCl3+Fe+HCl=2FeCl2+1/2H2

The treatment was performed for 2 hours to achieve a pH in the pulp 2,0±0,2 (due to the interaction of steel scrap with free hydrochloric acid):

2HCl+Fe→FeCl2+H2

Then the solution was separated from the unreacted part of the steel scrap and processed metal magnesium (magnesium shavings), which was downloaded in solution (slurry) portions. The treatment led to achieve a pH in the pulp 3,5±0,2 due to the interaction of magnesium metal with hydrochloric acid in the solution. In these conditions from the solution into the solid phase is passed over 99.99% of thorium and more than 90% of the aluminum in the form of oxyhydrates, thorium and aluminum. For flocculation of sediment slurry was treated with 0.2% GPA in an amount of 0.1 DM31 DM3the pulp, after which the pulp without stirring was kept for 2 hours to "ripen", flocculation and settling of the precipitate, after which the slurry was filtered, thorium precipitate was separated from the mother liquor, washed with 3 volumes of water (1 volume of sediment), were unloaded from the filter and repulpable when W:T=4 solution (100 g/DM3) sodium hydroxide, the resulting slurry was heated to 90±2°C and kept at this temperature for 2 hours, after which the slurry was filtered, the precipitate of thorium was separated from the alkaline races is the thief of sodium aluminate (Na[Al(OH) 4]), washed on the filter first with hot (90±2° (C) solution (100 g/DM3) sodium hydroxide (2 volume 1 volume of sediment), then heated (90+2° (C) water, the washed precipitate of thorium were unloaded from the filter and dried in a vacuum drying Cabinet at a temperature of 100±5°C for 4 hours. The finished product contained 40±2% Th, and impurities of Fe, Al and other metals.

Royal solutions - filtrate after separation from the pulp oxyhydrate thorium containing chlorides REE, Fe (II), K, Mg, Na, and Promode, alkaline solutions after repulpable the precipitate and wash were combined, the resulting slurry was heated to 80±2°and treated with a solution (150 g/DM3) sodium hydroxide to pH 12±0,2 under continuous stirring, which was carried out by filing under the layer of pulp compressed air, kept at 80±2°C for 2 hours under stirring and filtered. Radioactive sludge metal oxyhydrates occupied by co-precipitation, sorption and ion exchange radionuclides (≈99% of their content in the initial solution) was separated from the chloride radioactive solution, washed with water for removal from the phase precipitate radioactive stock solution (Abeats=500 Bq/kg). Washed radioactive sludge was sent to HSA, and the mother liquor and Promode was combined with 15 volumes of CIS who's radioactive shop obivochnyh water, containing g/DM3: 0,33 Nb, 0,11 Th, 110 Ti, 0,66 REE, 0,22 TA and having a specific activity of 250 Bq/kg

United chloride solution were decontaminated, for which it was heated by direct steam up to 80±2°C for 30 minutes and then treated with stirring and (simultaneous supply of steam to the reactor) solution (150 g/DM3) sodium hydroxide to pH 12±0,2. Upon reaching the pH in the pulp specified value of the slurry in the reactor was kept for another 1 hour, then filtered. Under these conditions, the degree of decontamination is more than 99.9%, and the residual specific activity of the deactivated solutions in all experiments, performed under optimal conditions, less than 6 Bq/kg (3 to 5 Bq/kg). These deactivated chloride solutions were dumped in the shop drains. The precipitate was removed from the filter was dried and progulivali. The results of chemical analysis showed that the obtained residue contains, wt%: 1,26 Nb2O5; 11,12 TA2O5; 28,29 TiO2; and 5,81 Al2O3, 18,78 FeO3, 2,32 SiO2and other

The content of valuable components of the residue, and the precipitate separated from the slurry in the first stage of processing of the initial suspension, similar to that of the loparite concentrates, therefore, these sediments should be considered as man-made rare metal raw material, which is suitable to process together with the original is loparite concentrate.

The results of the experiments showed that the developed method provides:

- first, highly selective extraction and preconcentration of thorium from the complex composition of the radioactive complex multicomponent waste with obtaining thorium concentrates implemented and used to obtain nuclear fuel a new generation of operating on the thorium fuel cycle;

- secondly, decontamination of all liquid radioactive waste (salt solutions and wash water and sewage)generated when chlorine processing technology loparite concentrates to currently installed standards and requirements;

- thirdly, petroleum extraction and disposal of radioactive waste rare, scattered and rare earth metals.

The method of extraction and preconcentration of thorium from the spent molten salt irrigation filter - waste production loparite concentrate, comprising preparing a slurry by draining the spent molten salt irrigation filter (SOF) in the water, the introduction of high-molecular flocculant, exposure, filtration, sludge separation, getting chloride solution, processing steel scrap and metal magnesium, wherein before receiving chloride solution source suspensionrebate to 60-90° C and treated with sodium hydroxide solution to a pH of 1.5-2.0 and 0.1-0.3%solution of high-molecular flocculant in the amount of 3-5% of the original volume of the suspension, the suspension is incubated for 2-4 h, chloride solution obtained by filtering the treated suspension to obtain a precipitate of rare metals processing steel scrap and metal magnesium is subjected to chloride solution, successively process the first steel scrap in the amount of 3-5 parts by weight of iron to 1 part ion iron (III) chloride solution at 80-100°C for 1-3 h to achieve a pH in the pulp of 3.0-3.5, after which the pulp is separated from the unreacted part of the steel scrap and treated with metallic magnesium to a pH of 3.5 to 4.5 and then 0.1 to 0.3%solution of high-molecular flocculant, taken in an amount of 5-20% of the total chloride solution, the resulting slurry incubated without stirring for 1-4 h and filtered to obtain uterine fluids and thorium precipitate, which on the filter is washed first with a solution containing 1-5 g/DM3sodium sulfite, then water-washed precipitate repulping in sodium hydroxide solution concentration of 50-150 g/DM3if F:T=3-5 at 60-90°C for 2-3 h, and then the slurry is filtered with the Department of alkaline filtrate, thorium precipitate on the filter is washed with water, press on filetree dried, the alkaline filtrate and prambody unite under stirring with the mother solution, heated to 80-90°C, treated with sodium hydroxide solution to a pH of 11-13 obtaining oxyhydrate pulp, it is filtered and receive radioactive precipitate on a filter, washed with water and taken in store special waste, and the filtrate is mixed with 10-20 volumes Guild obivochnyh water, heated to 80-90°and again treated with sodium hydroxide solution to pH 11-13, the resulting slurry can withstand and filtered to obtain the precipitate of rare metals and decontaminated chloride solution, which is discharged into the sewage, sludge rare metals discharged from the filter, together with a precipitate of rare metals, selected from the original suspension, dried, washed and then sent for batch preparation for its subsequent chlorination together with loparite concentrate.



 

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FIELD: chemical technology; deactivation and decontamination of radioactive industrial products and/or wastes.

SUBSTANCE: proposed method designed for deactivation and decontamination of radioactive industrial products and/or production wastes incorporating Th-232 and its daughter decay products (Ra-228, Ra-224), as well as rare-earth elements, Fe, Cr, Mn, Al, Ti, Zr, Nb, Ta, Ca, Mg, Na, K, and the like and that ensures high degree of coprecipitation of natural radionuclides of filtrates, confining of radioactive metals, and their conversion to environmentally safe form (non-dusting water-insoluble solid state) includes dissolution of wastes, their treatment with barium chloride, sulfuric acid, and lime milk, and separation of sediment from solution. Lime milk treatment is conducted to pH = 9-10 in the amount of 120-150% of that stoichiometrically required for precipitation of total content of metal oxyhydrate; then pulp is filtered and barium chloride is injected in filtrate in the amount of 0.4 - 1.8 kg of BaCl2 per 1 kg of CaCl2 contained in source solution or in pulp and pre-dissolved in sulfuric acid of chlorine compressors spent 5-20 times in the amount of 0.5 - 2.5 kg of H2SO4 per 1 kg of BaCl2. Then lime milk is added up to pH = 11 - 12 and acid chloride wash effluents of equipment and production floors are alternately introduced in sulfate pulp formed in the process at pulp-to-effluents ratio of 1 : (2-3) to pH = 6.5 - 8.5. Filtrate pulp produced in this way is filtered, decontaminated solution is discharged to sewerage system, sediment of barium and calcium sulfates and iron oxysulfate are mixed up with oxyhydrate sediment formed in source pulp neutralization, inert filler and 0.5 - 2 parts by weight of calcium sulfate are introduced in pasty mixture while continuously stirring them. Compound obtained in the process is placed in molds, held therein at temperature of 20 - 50 oC for 12 - 36 h, and compacted in blocks whose surfaces are treated with water-repelling material.

EFFECT: reduced radioactivity of filtrates upon separation of radioactive cakes.

8 cl, 1 dwg, 1 ex

FIELD: chemical technology; recovery of deactivated and decontaminated radioactive industrial wastes.

SUBSTANCE: proposed method that can be used for deactivating and decontaminating industrial radioactive wastes incorporating Tb-232 and their daughter decay products (Ra-228, Ra-224), as well as rare-earth elements, Fe, Cr, Mn, Sl, Ti, Zr, Nb, Ta, Ca, Mg, Na, K, and the like includes dissolution of wastes, treatment of solutions or pulps with barium chloride, sulfuric acid, and lime milk, and separation of sediment from solution. Lime milk treatment is conducted to pH = 9 - 10 in the amount of 120-150% of total content of metal oxyhydrates stoichiometrically required for precipitation, pulp is filtered, and barium chloride in the amount of 0.4 - 1.8 kg of BaCl2 per 1 kg of CaCl2 contained in source solution or in pulp, as well as pre-diluted sulfuric acid spent 5 - 20 times in chlorine compressors in the amount of 0.5 - 2.5 kg of H2SO4 per 1 kg of BaCl2 are introduced in filtrate. Alternately introduced in sulfate pulp formed in the process are lime milk to pH = 11 - 12, then acid chloride wash effluents from equipment and industrial flats at pulp-to-effluents ratio of 1 : (2 - 3) to pH = 6.5 - 8.5, and pulp obtained is filtered. Decontaminated solution is discharged to sewerage system and sediment of barium and calcium sulfates and iron oxysulfate are mixed up with oxyhydrate sediment formed in source pulp neutralization process; then 35 - 45 mass percent of inert filler, 10 - 20 mass percent of magnesium oxide, and 15 -m 25 mass percent of magnesium chloride are introduced in pasty mixture formed in the process while continuously stirring ingredients. Compound obtained is subjected to heat treatment at temperature of 80 - 120 oC and compressed by applying pressure of 60 to 80 at.

EFFECT: reduced radioactivity of filtrates upon separation of radioactive cakes due to enhanced coprecipitation of natural radionuclides.

7 c, 1 ex

FIELD: chemistry.

SUBSTANCE: group of inventions pertains to the metallurgy of rare metals, in particular to the method of chloric decomposition of polymetallic niobium-tantalum containing raw material with obtaining of chlorides of niobium and/or tantalum and a device (chlorinator) for carrying out the chlorination process. The method involves chlorinating polymetallic niobium and/or tantalum containing materials in molten chlorides using chlorine, condensation and separation of the obtained pentachlorides of niobium and/or tantalum and chlorides of admixtures and tapping of the melt. Chlorination is done in the layer of melt with height of 500-1000 mm, containing iron chloride (up to 25% iron) and/or copper (up to 40% copper), as well as sodium chloride in quantity of not less than 1.2 kg for 1 kg of iron and not less than 2.2 kg for 1 kg of aluminium in the initial materials. The process is carried out at 550-850°C with consumption of chlorine of 1.7-2.2 kg for 1 kg of the initial materials. Tapping of the melt is done from the upper level through a tapping line. The chlorinator is water cooled, lined with graphite and equipped with a separation chamber, located in the upper part of the chlorinator. The ratio of the diameter of the chlorinator to the diameter of the separation chamber is equal to (2÷2.5):3, and the ratio of their heights is (1÷2):1. There is a removable graphite pipe for supplying chlorine, which runs through a water cooled connection pipe, tightly joined to the cover of the chlorinator, to the bottom of the chlorinator. Tapping of the melt is done from the upper level through a heated tapping line, lined with graphite.

EFFECT: design of a efficient method of chloric decomposition of polymetallic niobium-tantalum containing raw materials with obtaining of chlorides of niobium and/or tantalum.

2 cl, 1 dwg, 3 ex

FIELD: non-ferrous metallurgy, possibly production of highly purified powders of tantalum and niobium with large specific surface by metal thermal reduction.

SUBSTANCE: method is realized at using as corrosion protection means layer of halide of alkali metal formed on inner surface of vessel before creating in reaction vessel atmosphere of inert gas. Charge contains valve metal compound and halide of alkali metal. It is loaded into reaction vessel and restricted by protection layer of halide of alkali metal having melting temperature higher than that of charge by 50 - 400°C. Before loading charge, valve metal compound and alkali metal halide may be mixed one with other. Mass of protection layer of alkali metal halide Ml and charge mass Mc are selected in such a way that that to satisfy relation Ml = k Mc where k - empiric coefficient equal to 0.05 - 0.5. Gas atmosphere of reaction vessel contains argon, helium or their mixture. Fluorotantalate and(or) oxyfluorotantalate or fluoroniobate and(or) oxyfluoroniobate of potassium is used as valve metal compound. Sodium, potassium or their mixture is used as alkali metal. Chloride and(or) fluoride is used as alkali metal halide. Valve metal compound and alkali metal halide may contain alloying additives of phosphorus, sulfur, nitrogen at content of each additive in range 0.005 - 0.1% and 0.005 - 0.2% of mass valve metal compound respectively. Invention lowers by 1.3 - 2 times contamination of powder with metallic impurities penetrating from vessel material. Value of specific surface of powder is increased by 1.2 - 1.8 times, its charge is increased by 10 - 30 %, leakage current are reduced by 1.2 - 1.5 times.

EFFECT: improved quality of valve metal powder, enhanced efficiency of process due to using heat separated at process of reducing valve metal for melting protection layer.

9 cl, 1 tbl, 4 ex

FIELD: hydrometallurgy; ore concentrates processing.

SUBSTANCE: the invention is pertaining to the field of hydrometallurgy, in particular, to processing of the loparite concentrate. The method includes a decomposing of the loparite concentrate at the temperatures of 103-105°C and the concentration of hydrofluoric acid of 38-42 mass % with production of the pulp containing fluorides of titanium, rare earth elements (REE), niobium, tantalum and sodium. The pulp is filtered at the temperature of 90-95°C with extraction into the fluorotitanium solution of fluorides of niobium and tantalum and no less than 58 % of sodium in terms ofNa2O and separation of the sediment containing fluorides of rare earth elements (REE) and a residual sodium. The produced solution is cooled down to 18-24°C with separation of the second sediment of sodium fluorotitanate. After that they extract niobium and a tantalum from the solution by octanol-1 extraction at a ratio of the organic and water phases as 1.1 : 1. The sediment of REE fluorides is washed from fluorotitanate by sodium water in a single phase at the temperature of 90-95°C and at the solid :liquid ratio = 1:2-2.5. The cleansing solution is separated and evaporated with extraction of the additional sediment of sodium fluorotitanate. After extraction of niobium and tantalum the fluorotitanium solution is evaporated and filtered with separation of the first sediment of sodium fluorotitanate from the concentrated solution of fluorotitanium acid, which is directed to extraction of titanium. The gained first, second and additional sediments of sodium fluorotitanate are combined and subjected to conversion with production of sodium fluorosilicate and the conversional fluorotitanium acid added to fluorotitanium solution before its evaporation. The technical result of the invention is a decrease in 2.0-2.5 times of the volume of the cleansing solutions at provision of a high degree of extraction of compounds of titanium and other target products. The produced sodium fluorotitanate contains the decreased amount of the impurity ingredients of calcium and strontium.

EFFECT: the invention ensures a decrease in two-two and a half times of the volume of the used cleansing solutions at provision of a high degree of extraction of compounds of titanium and other target products and a decreased amount of impurities of calcium and strontium in the sodium fluorotitanate.

7 cl, 1 dwg, 1 tbl, 3 ex

FIELD: metallurgy of rare and dispersed metals, chemical technology.

SUBSTANCE: 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.

EFFECT: improved separating method.

5 tbl, 5 ex

FIELD: metallurgy; methods of preparation of charges for production of niobium-bearing material.

SUBSTANCE: the invention is dealt with production of niobium-bearing materials used for production of special steels. The technical result is an increased degree of transition of niobium into an alloy, decreased share of impurities in the alloy, decreased production costs. For this purpose the charge for production of a niobium-bearing material contains the raw material containing niobium pentaoxide, a nickel-bearing material, aluminum, calcium oxide, calcium fluoride and an exothermic oxidative additive. At that in the capacity of the exothermic oxidative additive it contains potassium chlorate with moisture of 2-12% at the following ratio in shares in respect to the total weight of the charge: niobium pentaoxide - 0.470-0.520, nickel - 0.190-0.270, aluminum - 0.180-0.200, calcium oxide - 0.030-0.040, calcium fluoride - 0.003-0.004, potassium chlorate with moisture of 2-12% - 0.043-0.049. At preparation of the charge after mixing of components it is exposed to compaction in the crucible up to the value of the plastic strength of 0.4-10.0 MPa.

EFFECT: the invention ensures an increased degree of niobium transition into an alloy, decreased share of impurities in the alloy, decreased production costs.

2 cl, 1 tbl, 3ex

FIELD: electrometallurgy, namely processes for producing high-purity niobium ingots used in power generation plants operating with use of low-temperature superconductivity effect.

SUBSTANCE: method comprises steps of electron-beam refining of consumable niobium blank; using blank of niobium of given kind containing niobium uniformly distributed along its length and produced by iodide refining as consumable blank in order to produce niobium ingots with predetermined (in range 200 - 500) relation of specific resistances at temperature values 193K and 9.2K; determining mass relation of niobium of given kind and niobium produced by iodide refining according to relation of specific resistances at temperature values 193 K and 9.2 K with use of expression mn/mu = (500 - ρ2939.2)/(800 + 2 x ρ2939.2) where mn - mass of niobium of given kind, g; mu - mass of niobium produced by iodide refining, g; ρ293 - specific resistance of niobium at temperature 193K, ohm x m2/m ; ρ9.2 - specific resistance of niobium at temperature 9.2K, ohm x m2/m.

EFFECT: enhanced efficiency of process, lowered cost price of high-purity niobium ingots.

2 tbl, 2 ex

FIELD: production of pure niobium.

SUBSTANCE: method includes reducing fusion of niobium pentoxide with aluminum and calcium to provide crude ingots followed by heat treatment and multiple electron beam refining. As an additional raw material in step of reducing fusion sublimates (preferably in non-oxidized form) from second and subsequent electron beam refining are used. Such sublimates are obtained by subsequent cooling of furnace smelting chamber under residual pressure of 10-2-10-4 mmHg for 1.0-3.0 h, letting-to-helium under 1-3 mmHg for 1.0-3.0 h, and letting-to-air for 20-40 min. Sublimates are added in amount of 4.5 % based to feeding niobium pentoxide. Claimed method affords the ability to increase niobium pentoxide consumption by 73 kg in respect to 1000 kg of pure niobium in crude ingots.

EFFECT: production of pure niobium with increased effectiveness without deterioration of refined niobium quality.

2 cl, 1 tbl

The invention relates to pyrometallurgy, in particular the production of niobium from its oxide, and can be used for the production of ferroniobium

The invention relates to the field of hydrometallurgical processing of tantalum raw materials and are aimed at achieving its complex use

The invention relates to ferrous metallurgy and can be used to obtain alloy powders of tantalum or niobium

FIELD: metallurgy.

SUBSTANCE: invention refers to non-ferrous metallurgy and can be used for extraction of vanadium out of ashes which is waste produced by burning of sulphuric vanadium containing black oil in heat engines of heat and hydropower stations. The method consists in the following: source ashes are mixed with sodium carbonate and water at a weight ratio of 100:(10-60):(30-50), then produced mixture is held at temperature of 100-150°C, preferably 115-120°C, during 2 hours. Vanadium is leached out of produced self-diffusing cake with water at temperature of 95-100° and a ratio of liquid: solid = (1.5-3):1.

EFFECT: avoiding of generating harmful gas exhausts at extraction of vanadium and implementation of available equipment.

1 tbl, 2 ex

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