Processing method of scraps of anodes of tantalum oxide-semiconductor capacitors
|
Method of dressing man-made mineral stock of nonferrous metals / 2480290 Invention relates to flotation of man-made stock. Method of flotation of sulfide ores of nonferrous and noble metals comprises conditioning crushed ore with dithiophosphate solution or other sulfhydric collectors in lime medium and flotation. Note here that for reduction in floatability of pyrite and increase in extraction of metal up to 10 wt % of thiourea ((NH2)2CO) or its derivatives are preliminary introduced in the solution of dithiophosphate as a modifying agent. Then, pulp from ore is conditioned, first, with modified dithiophosphate at pH 8.5-9.0 for 3-5 minutes and, then, with, xanthate at pH over 9.0 for 1.0 minute. Then flotation of sulphides of nonferrous metals and mineral forms of noble metals at input of modified of dithiophosphate and xanthate varying from 1:3 to 3:1, respectively. |
 Electrochemical processing method of metal wastes of tungsten-copper alloy wastes / 2479652Invention refers to regeneration of secondary metal-bearing raw material, including to electrochemical processing of metal wastes of tungsten-copper alloys containing 7-50% Cu. The above method involves anodic oxidation of wastes in 10-15% of ammonia solution under action of direct current. At that, the oxidation process is performed with addition to the solution of 0.1-0.5 M NaOH or 0.1-0.5 M KOH at current density of 1000-3000 A/m2. |
|
Red sludge pyrometallurgical processing method / 2479648 Red sludge is melted in a fuel-oxygen skull melting unit, iron is reduced with carbon-bearing reducing agent, and the produced metal and slag are output separately. In addition, sludge is heated and dried in a drying device till humidity is 6-10% with the heat of exhaust gases of the melting unit with the temperature of 1750-1850°C with addition to wet sludge of 3-6% of the weight of lime production wastes. Dried sludge is loaded by means of a sealed loading device from the drying device onto molten slag heated to 1640-1680°C, at the speed of 1.2-1.4 tons per 1 m2 of the heel of molten slag per hour. Reduction of iron from molten charge is performed by means of carbon-bearing materials loaded onto the slag in the quantity providing the content of iron oxides in the final reduced slag within 3-5%. Separate drainage of melting products is performed continuously or periodically, thus maintaining vibrations of the molten metal level in the melting unit of not more than by 200-300 mm by changing the drain speed and the quantity of melting products. |
|
Extraction of rhenium / 2478721 Proposed method comprises extracting essential part of rhenium from catalyst by direct contact between catalyst and one or more polar non-acid, in fact, anhydrous organic solvents. In contact with solvent, solution is formed containing said polar non-acid organic solvent and extracted rhenium. Note here that said polar non-acid organic solvent with molar structure that contains one or more atoms of oxygen, nitrogen and/or halogen. |
 Plasma-chemical method of processing solid domestic and industrial wastes / 2478169Method of processing domestic and industrial wastes involves loading the wastes with preliminary separation by separating glass, concrete, ceramics and metal; drying with partial pyrolysis of organic matter in a shaft furnace; agitation of the processed wastes with further pyrolysis thereof. Temperature of said process is reduced to 500-850°C as a result of the action of reducing plasma-chemical components obtained by steam-oxygen conversion of methane with increase in consumption of steam fed by the counter-current of the moving wastes. Recycled process gas coming from the shaft furnace is cleaned in scrubbers and is divided into fuel gas which is fed into both the methane converter and the exhaust-heat boiler when producing reducing gas with partial addition of natural gas and oxygen. Exhaust gases from the exhaust-heat boiler are cleaned in an adsorber via contact with fine-grained lime. Also, a portion of the formed reducing gases is consumed in the bottom part of the reactor during an instantaneous thermal shock which results from burning soot-dust particles coming from a hot gas cyclone with deposition thereon of dioxins, furans and other harmful components in an atmosphere of oxygen, wherein the formed reducing gases can also be fed as synthesis gas for production of methanol, dimethyl ether, engine fuel and other products. |
 Method for removing arsenic from cobalt production waste / 2477326Method involves solid-phase roasting of wastes mixed with soda to fix arsenic to a water-soluble form of sodium arsenate. Then, water leaching and deposition from arsenic solution is performed. In order to obtained the product from water leaching with low residual arsenic content of 0.7%, solid-phase roasting is performed at 850°C so that a roasted product containing 2.9% of arsenic is obtained. Water leaching of the roasted product is performed with extraction degree of 84%. Deposition from arsenic solution is performed in the form of arsenic sulphide with sodium sulphide at pH=3 with deposition degree of 99.6%, and filtrate with arsenic content of 0.02 g/l for removal of residual amount of arsenic by neutralisation and deposition with iron compounds meets the requirements of sanitary norms. |
 Plant for electrohydraulic dressing of mineral stock including gold bearing stock with high content of clay components / 2477173Invention relates to hydrometallurgy, particularly, to mineral stock dressing devices. Proposed plant comprises reactor, control board, HV transformer, and pulse generator with bank of capacitors. Reactor is composed of rectangular cross-section vertical tube to process dry or wet mineral stock. Shelves are arranged inside said reactor hinged at 45-60 degrees to reactor vertical axis. Said shelves double as grounded electrode. HV electrode is mounted outside the reactor, at hole cut in its wall. Note here that shelf bent edge stays opposite HV electrode head to rest, from inside, onto spring-loaded support to allow vibration of shelves by shock wave effects. |
|
Extraction of metals from wastes containing copper and other metals of value / 2476611 Extraction of non-ferrous metals is performed in plasma electric arc furnace of alternating current, which has a group of electrodes and contains a molten liquid copper bath coated with liquid slag. The method involves a melting-reducing stage consisting of the following operations: loading of metallurgical wastes onto the surface of liquid molten copper bath, melting of metallurgical wastes in liquid slag at the slag/bath copper boundary, reduction at least of non-ferrous metals to the oxidation degree, which is more than or is equal to zero, and intensive mixing of the liquid molten copper bath by blowing of inert gas, preferably nitrogen and (or) argon. Mixing is performed so that it can be possible to avoid the formation of a crust, expedite the reduction reaction and cause the transition of copper-soluble non-ferrous metals to the molten copper. |
 Compacted metallurgical product, manufacturing method of compacted metallurgical product and use of compacted metallurgical product / 2476609Product includes solid and/or liquid organic substances, crushed solid metals and/or alloys and their compounds are used as inorganic substances, and substances containing water and/or lubricating-cooling liquid are used as wet substance. Mixture contains metals and/or alloys and their compounds in the form of crushed and fibrous fractions; besides, size of crushed fraction is not more than 0.5 of the fibre length of fibrous fraction. The product is pressed at the share of the crushed fraction, which does not exceed the value providing the interweaving of fibrous fraction so that a frame is formed, and is subject to further deformation with the pressing force exceeding the limit of plastic deformation of fibrous fraction. The product is used as a regulator of processes of solid-phase refining reactions with pyrolysis products of hydrocarbon substances at heating of the product without any air access. |
 Luminescent lamp processing plant / 2475546Plant includes two units, the first one of which is a lamp sorting unit, and the second one is a unit of multistage exit gas cleaning system. The first unit includes a lamp sorting device consisting of a loading assembly, a pneumatic vibrating separator with a crusher and a cyclone, a crushed lamp glass collecting hopper, a lamp base receiving container and a fluorescent dye container. The second unit is made in the form of multistage exit gas cleaning system consisting of a sleeve filter, adsorbers, a gas blower with a compressor, which creates negative pressure in the plant of 5-8 kPa in the lamp loading zone and up to 19-23 kPa before gas blower. The plant is equipped with a series pulverised-coal and gas emission cleaning system consisting of a cyclone, sleeve filters, a working adsorber operating on activated coal, which allows reducing mercury content in exit gases to the level of less than 0.0001 mg/m3. |
|
Procedure for extraction of niobium and tantalum from titanium containing rare earth metal concentrate / 2434958 Procedure for extraction of niobium and tantalum from titanium containing rare earth concentrate consists in treatment of fine crumbled concentrate with reagent containing octanol-1 saturated with fluoro-hydrogen acid with production of pulp by mixing; in transition of main part of niobium and tantalum and part of titanium in form of fluoro-metallate acids into extract and in concentrating residual part of niobium fluorides and tantalum in solid phase and another part of titanium in form of its fluoride compound. Further, pulp is settled and extract is separated from solid phase. Loparite concentrate is used as titanium containing rare earth metal concentrate. Titanium is concentrated in solid phase in form of non-hydrated fluoro-titanate of sodium. Octanol-1 saturated with fluoro-hydrogen acid to concentration 110-140 g/l is used as reagent, while treatment of concentrate is carried out at initial temperature 10-20°C. |
 Method of reduction / 2431546Invention relates to metallurgy, namely, to producing barrier metal powders. Mix containing precursor of barrier metal and nonreacting liquid diluter is fused in first reactor. Said mix is placed in at least second reactor to add reducing agent therein. Reduction of barrier metal precursor to barrier metal is conducted at temperature and in interval that allow initiating reduction reaction. Produced powder features particle shape factor f defined from REM-images in the range of 0.65≤f≤1.00. |
 Extraction method of niobium (v) from fluorine-containing water solution / 2430173Invention refers to extraction of niobium (V) from water fluorine-containing solution with the use of sorbents and can be used in non-ferrous and ferrous metallurgy, as well as for cleaning of industrial and domestic sewage systems. Method involves sorption by contact of solution and anionite. At that, sorption is performed at pH=1-4 with AM-2b anionite pre-treated with acid or water, and containing the following exchange groups: -CH2-N(CH3)2, -CH2-N(CH3)3. |
 Procedure for extraction of niobium from water solution containing fluorine / 2421531Procedure for extraction of niobium from water solution containing fluorine consists in sorption by contacting solution and anionite. Anionite is subjected to acidic or water treatment before sorption. Sorption is carried out with anionite of grade ANP containing exchange groups |
 Procedure for production of primary refractory metal (versions) / 2415957Procedure consists in heating chemically active gas containing gaseous hydrogen. Further, the procedure consists in bringing oxide of refractory metal to contact with said heated gas in form of particles of pentaoxide of tantalum for reduction of tantalum pentaoxide in form of particles. Also, weight ratio of gaseous atomic hydrogen and tantalum pentaoxide in form of particles is over 1.5:1 at temperature from 1900 °K to 2900 °K with formation of primary metal of tantalum. Another version of the procedure consists in heating chemically active gas containing gaseous hydrogen. Oxide of refractory metal is brought into contact with said heated gas in form of particles of niobium oxide chosen from a group containing of niobium dioxide, niobium pentaoxide and their combination for reduction of said niobium oxide in form of particles. Weight ratio of gaseous hydrogen and niobium oxide in from of particles is at least 9:1 at temperature from 2100°K to 2700°K with formation of primary metal of niobium. |
|
Producing barrier metal powders with improved physical and electrical properties / 2408450 Invention relates to production of barrier metal powder to be used as anode material for electrolytic capacitors. Proposed method comprises feeding first barrier metal powder and reducing component into reactor with hot zone, making said powder and said reducing component interact in nonstatic conditions sufficient for simultaneous agglomeration of first barrier metal powder and reduction in oxygen content in said powder. Said interaction produces component consisting of second barrier metal powder containing barrier metal particles with reduced oxygen content. Note here that nonstatic conditions include agitating, dropping, rotating and combination thereof. Note also that reducing component is selected from the group comprising magnesium, calcium, aluminium, lithium, barium and strontium reducing components and combination thereof. |
|
Removal of magnesium from powders recovered by magnesium / 2406593 Invention relates to production of high-quality powders of heat-resistant metals. In compliance with proposed method, powder containing magnesium tantalate and/or niobate is produced. Said powder is heated in inert atmosphere in the presence of magnesium, calcium and/or aluminium to temperature sufficient for removal of magnesium tantalate and/or magnesium niobate from the powder, and/or it is heated in vacuum to temperature sufficient for removal of magnesium tantalate and/or magnesium niobate from the powder. Note that heating is carried out in whatever sequence. |
 Method of producing valve metal powder / 2405659Present invention relates to a method of reducing primary powder of valve metals and tantalum powder, suitable for use as anode material for electrolytic capacitors. The powder of valve metals is reduced by reducing metals such as aluminium, magnesium, calcium, barium and/or lanthanum and/or their hydrides, in an atmosphere of an inert carrier gas. Reduction is carried out without contact between the reduced powder of valve metals and the liquid reducing metal/metal hydride. The powdered metal and reducing metal/metal hydride are put into a reactor in different places so that the reducing metal/metal hydride can reach the powdered metal only in vapour form. Tantalum with specific surface area of 4-8 m2/g is pressed to density of 5 g/cm3 and sintered at 1210°C for 10 minutes. The obtained anode is formed at formation anode of up to 10 V has specific capacitance of 220000-350000 mcFV/g. Tantalum powder with specific surface area of 3.5-6 m2/g is pressed to density of 5 g/cm3 and sintered at 1210°C for 10 minutes. The obtained anode which is formed at formation voltage of up to 10 V has specific capacitance of 180000-250000 mcFV/g. |
|
Reclamation of barrier metal powders / 2404881 Invention relates to reclamation of barrier metal powders, namely those of niobium, tantalum or alloys thereof. For this, metal is heated to temperature that exceeds melting point of reclaiming material. The latter is most frequently represented by lanthanum, yttrium or cerium. In using lanthanum, reclamation is performed at 940-1150°C. Besides reclamation is carried out in two stage. Note that barrier metal powder is reclaimed that has been produced in reclaiming barrier metal oxide by gaseous lanthanum, yttrium or cerium. |
 Metallothermic reduction of refractory metal oxides / 2404880Invention relates to powder metallurgy. Component of oxide particles is mixed with reducing agent to form homogeneous mix. Obtained mix is fed into furnace for it to be ignited to initiate the exothermal reaction and produce high-temperature flashout. Note here that said mix is fed by disperser other than rotor/stator disperser to distribute it uniformly over the furnace cross section area, while mix furnace reaction zone location time TR varies from 0.1 s to 30 s. Oxide particles are selected from the group including refractory metal oxides, particles of refractory metal oxide alloys, powders of refractory metal sub oxides, powders of refractory metal sub oxides alloys and mixes thereof. Reducing agent is selected from the group including magnesium, aluminium, potassium and mixes thereof. In compliance with one of the versions, exothermal reaction is initiated at constant rate, while reaction zone temperature equal to flashout temperature is set to be constant. Besides exothermal reaction is initiated by heating the mix to ignition temperature or adding another reagent or catalyst. |
 Method of producing scandium oxide / 2478725Proposed method comprises dissolving scandium-bearing concentrate in sulfuric acid, removing acid-insoluble residue, and precipitating scandium in the presence of ammonium compounds. Then, precipitate is filtered, flushed, dried and calcined to obtain scandium oxide precipitate. With acid-insoluble residue removed, sulfuric acid concentration in filtrate is increased to 540-600 g/dm3, ammonium chloride is added to solution in amount of 26.7-53.5 g/dm3 at 50-70°C and held for one hour at mixing. Produced precipitate is flushed by ethanol at volume ratio of 1-10-11. |
FIELD: metallurgy.
SUBSTANCE: method involves cleaning of scraps by acid treatment with removal of manganese dioxide. Then, deoxidation of cleaned scraps, its hydration, grinding, dehydration at increased temperature is performed so that tantalum hydride powder is agglomerated and tantalum capacitor powder is obtained. At that, acid treatment is performed at room temperature using the solution containing 100-300 g/l of sulphuric acid and 110-300 g/l of hydrogen dioxide, or the solution containing 30-150 g/l of hydrochloric acid and 75-225 g/l of hydrogen dioxide. Scrap hydration is performed by treatment using the solution of hydrofluoric acid with concentration of 1-5%. The obtained capacitor tantalum powder provides specific charge of up to 7300 mcC/g, breakdown voltage of more than 200 V and leakage current of 0.0001-0.0003 mcA/mcC when being used in anodes of tantalum oxide-semiconductor capacitors.
EFFECT: reduction of energy intensity and improvement of environmental friendliness of the process at its simultaneous simplification.
3 cl, 6 ex
The invention relates to the field of processing of scrap anodes of tantalum oxide-semiconductor capacitors formed during the production of capacitors, or when disposing of used capacitors, with the production of standard capacitor tantalum powder.
Scrap tantalum oxide-semiconductor capacitors is a valuable source of raw materials for the production of tantalum capacitor powders. The anode tantalum capacitor is a volume-porous body of sintered tantalum capacitor powder and containing conductive tantalum wire. The pores of the anode is filled with manganese dioxide (MnO2on top of which is coated with carbon-containing layer to create an electrical contact with the copper layer. The content of MnO2in this anode is up to 20%. Technology of processing of scrap, providing for its dissolution with subsequent formation of compounds of tantalum and recovery, accompanied by a significant loss of tantalum at numerous stages of processing. The dissolution of high-purity metal anodes with all related impurities and subsequent processing similar to the processing of ore materials is inefficient. More advanced methods of processing of obtaining condenser powder without full Rast is orenia scrap.
A method of refining scrap anodes of tantalum capacitors (see U.S. Pat. 7981191 USA, IPC B22F 9/04 (2006.01), including the selection of scrap in the form of gray or molded anodes with low levels of contamination, rinsing to remove residual carbon, acid treatment 50% nitric or hydrochloric acid to remove contaminating metal impurities, hydrogenation at 482°C for 3 hours and grind for 30 minutes with the removal of tantalum wire. Then within 6 hours continue grinding until you get a powder with a particle size of 1.1 μm, carry out dehydration, sintering, deoxidation, acid treatment 50% concentrated nitric and hydrochloric acid to remove residual magnesium and sieving the obtained tantalum powder. As starting material can be used tantalum sheet, do not contain significant amounts of impurities. From the resulting powder by pressing and sintering is made the anode, which at 60 had the leakage current 0,0015 µa/µc.
The disadvantage of this method is that it is used for recycling scrap with a low level of contamination and may not be used for processing scrap anodes oxide-semiconductor capacitors. In this way the operation of the dehydrogenation and agglomeration of the powder is carried out separately, which increases the intensity is of the manual, the use of concentrated acids is undesirable factor from the point of view of ecology. In addition, the high leakage current ready anodes testifies to the low purity of the obtained powder.
Known also adopted as a prototype method for processing scrap anodes of tantalum oxide-semiconductor capacitors (see Orlov V.M., Sukhorukov CENTURIES, Matychenko AS Recycling scrap tantalum capacitors // non-ferrous metallurgy. 2005. No. 6. P.10-14), which involves removal of the manganese dioxide from the anode by acid treatment of scrap hot (80°C) hydrochloric acid with respect to W:T=2-3, deoxidation cleared scrap by heat treatment in the presence of magnesium powder at a temperature of 800-900°C, the removal of the formed magnesium oxide 10% solution of hydrochloric acid followed by washing with distilled water and drying. After deoxidation of the scrap is subjected to additional heat treatment in vacuum at a temperature of 1800°C for 3 hours to remove excess magnesium and iron. Next scrap hydronaut in the atmosphere of high purity hydrogen produced by the decomposition of titanium hydride, and ground in a rod mill to provide a bulk density of 4.2-4.5 g/cm3. The obtained powder of tantalum hydride is treated with 15% hydrochloric acid to remove iron, made while grinding, and everyroom with simultaneous agglomeration in the current high-purity argon at a temperature of 1400-1500°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to a particle size of less than 315 μm. The resulting powder was characterized by low content of impurities, and satisfies the requirements of technical conditions on the capacitor powders. Leakage current anodes made from this powder is is 0.0002-0,0003 µa/µc, the specific charge does not exceed 6460 µc/year
The disadvantages of this method include the leaching of manganese dioxide with concentrated hydrochloric acid at elevated temperature, which is accompanied by the release of toxic chlorine gas, and the need for additional high temperature heat treatment in a vacuum to remove residual magnesium and iron. All this reduces the efficiency of the processing of scrap anodes of tantalum capacitors, complicates the process requires special equipment.
The present invention is directed to the achievement of the technical result consists in increasing the efficiency of the method of recycling scrap anodes of tantalum oxide-semiconductor capacitors by reducing energy consumption and improve environmental performance of the method with obtaining capacitor tantalum powder of high quality. The technical result is also to simplify the method.
The technical result is achieved in that in the method for processing scrap anodes of tantalum on the sydnaya-semiconductor capacitors, including acid processing scrap with the removal of manganese dioxide, deoxidation cleared scrap, its hydrogenation, refining, dehydrogenation at elevated temperatures with the agglomeration of the powder of tantalum hydride and obtaining tantalum capacitor powder according to the invention, the acid treatment of the scrap is carried out at room temperature with a solution containing 100-300 g/l of sulfuric acid and 110-300 g/l hydrogen peroxide or a solution containing 30-150 g/l of hydrochloric acid and 75-225 g/l hydrogen peroxide, and hydrogenation of scrap carried out by treatment with a solution of hydrofluoric acid with a concentration of 1-5%.
The achievement of the technical result is driven by the fact that before the acid treatment, the scrap is ground to a particle size of not more than 2 mm and retrieve live tantalum wire.
The achievement of the technical result also contributes to the fact that before deoxidation scrap is treated with a solution of hydrofluoric acid with a concentration of 3-6%.
The essential features of the claimed invention, defining the scope of legal protection and sufficient to obtain the above-mentioned technical result function and correlate with the results as follows.
Carrying out the acid treatment of the scrap at room temperature due to the use of solutions of sulfuric or hydrochloric acid what you with the addition of hydrogen peroxide, in specific concentrations and ratio.
Processing scrap a solution containing 100-300 g/l of sulfuric acid and 110-300 g/l hydrogen peroxide or a solution containing 30-150 g/l of hydrochloric acid and 75-225 g/l hydrogen peroxide, allows for efficient leaching of manganese dioxide under mild conditions at room temperature, which contributes to obtaining a powder of high quality, makes the process less energy intensive and more environmentally friendly, and also simplifies its instrumentation.
The use of solutions with a concentration of H2SO4more than 300 g/l HCl or more than 150 g/l is irrational, since at this concentration is an intensive decomposition of hydrogen peroxide, and the leaching of manganese dioxide ceases. When the concentration of H2SO4less than 100 g/l HCl or less than 30 g/l leaching of manganese dioxide slows significantly and the volume of the solution is increased to such an extent that the process becomes ineffective.
The minimum amount of hydrogen peroxide required for leaching manganese dioxide corresponds to the stoichiometry. The hydrogen peroxide concentration of less than 110 g/l solution of sulfuric acid and less than 75 g/l solution of hydrochloric acid will be sufficient to complete the reaction leaching according to the stoichiometry. The concentration of peroxide of odor is Yes more than 300 g/l solution of sulfuric acid and more than 225 g/l solution of hydrochloric acid leads to excessive dilution of the acid, what makes the process inefficient.
Hydrogenation of scrap material by treatment with a solution of hydrofluoric acid with a concentration of 1-5% better cleaned from the remnants of magnesium and iron, to saturate the scrap hydrogen without high-temperature heat treatment that reduces energy consumption of the method and makes it easier while maintaining the high quality of the powder. When the concentration of hydrofluoric acid is less than 1% operation hydrogenation slows down, and at a concentration of more than 5% is excessive and uneven dissolution of the scrap material in relation to the required amount of hydrogen.
The combination of the above features is necessary and sufficient to achieve the technical result of the invention to reduce energy consumption and improve the environmental performance of the method with obtaining tantalum capacitor powder of high quality. All this increases the efficiency of processing scrap anodes of tantalum oxide-semiconductor capacitors with simultaneous simplification of the method.
In some cases, of the preferred embodiment of the invention the following specific operations and operational parameters.
The grinding of scrap before acid treatment to a particle size of not more than 2 mm can significantly reduce the length of the diffusion path of the reactants in the pores of the anodes on the Opera the AI leaching, reducing the duration of leaching and reduce the residual content of impurities of manganese. The grinding of scrap to the larger size makes the leaching process less effective. After grinding scrap, it is advisable to extract conductive tantalum wire, thereby increasing the specific surface area of the obtained capacitor powder.
Processing of scrap before it deoxidizing solution of hydrofluoric acid with a concentration of 3-6% allows you to remove the most contaminated, mainly compounds of manganese, the surface layer of the anode scrap and improve the quality of the powder.
The above private features of the invention allow a method to optimally from the point of view of reducing energy consumption and improve environmental performance of the method with obtaining tantalum capacitor powder high quality while simplifying the method.
The essence of the proposed method and achieved results more clearly can be illustrated by the following Examples.
In General, the method for processing scrap anodes of tantalum oxide-semiconductor capacitors according to the invention is as follows. Perform sorting of scrap material by size. Small anodes (the least no larger than 2 mm) n is directly subjected to acid treatment. Large anodes are pre-ground to a particle size of not more than 2 mm, using, for example jaw crusher, followed by the separation of conductive tantalum wire. Acid treatment of the scrap is carried out at room temperature dilute solution of sulfuric (100-300 g/l) or hydrochloric (30-150 g/l) acid, hydrogen peroxide, respectively 110-300 g/l and 75-225 g/l After completion of the leaching scrap is separated from the solution, which is sent for recycling. For a more complete removal of manganese dioxide scrap re-treated with a solution of the same composition, which is then used for the primary processing of the next lot of scrap. If necessary, the scrap is treated with a solution of hydrofluoric acid with a concentration of 3-6% for the dilution and removal of contaminated manganese surface layer, then washed with deionized water until neutral and dried. Then to remove oxygen contained in the anode oxide, scrap is subjected to the standard procedure of solid-phase magnesium deoxidation. The resulting magnesium oxide is removed with diluted mineral acids, for example hydrochloric or nitric. Cleared of magnesium oxide raskalennyi scrap hydronaut by treatment with a solution of hydrofluoric acid with a concentration of 1-5%. Hydrogen produced when the solution is AI tantalum, absorbed by its clean surface, providing the necessary fragility anode scrap. What if this update surface helps reduce the impurity content of magnesium and iron, introduced during the operation of deoxidation. After processing hydrofluoric acid propitiously scrap washed with deionized water until neutral and ground to a particle size less than 40 microns. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration in a known manner by heating the powder in a stream of high purity argon to a temperature of 1350-1500°C with a holding time at maximum temperature for about 1 hour. The sinter is crushed in the cone inertial crusher type KYD-60 to particles less than 315 μm obtaining agglomerated tantalum capacitor powder. From powder to prepare anodes weighing 0.5 g, is sintered at a temperature of 1600-1650°C for about 45 min in vacuum with a residual pressure of not more than 5·10-5mm Hg Anodes formed in solution H3PO4with a concentration of 0.01% at a temperature of 80°C, the voltage molding 82, a current density of 35 mA/g and a standard measure electrical characteristics.
Example 1. Carry out the processing of the lot scrap anodes of tantalum oxide-semiconductor capacitors mass 1 kg is the Smallest anodes of 1.5 m is. Scrap processed in two phases at room temperature, diluted sulfuric acid solution containing 300 g/l H2SO4and 110 g/l H2O2for 6 and 4 hours. After separation of the scrap solution of the first stage are sent to recycling. The solution of the second stage is used for the primary processing of the next lot of scrap. Processed scrap washed with deionized water until neutral and dried. Dried scrap is subjected to the magnesium deoxidation in an argon atmosphere at a temperature of 850°C for 4 hours. After deoxidation scrap treated twice for 2 hours 18% HCl solution to remove magnesium oxide, after which raskalennyi scrap is treated for 1 hour with 5% solution of hydrofluoric acid and washed with deionized water. The hydrogen content in the scrap is of 0.27%.
Propitiously scrap milled in a rod mill for 90 minutes to provide a particle size less than 40 microns and a bulk density of 4.2 g/cm3. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration by heating the powder in a stream of high purity argon to a temperature of 1350°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to particles less than 315 μm with getting 0,71 kg agglomerated tantalum capacitor powder. Containing the s impurities in the powder is ×10-4%: Mn 5 Mg not more than 5, Fe not more than 10, Ni not more than 5, the oxygen - 1300. From powder to prepare anodes. Electrical characteristics of the anodes were: the specific charge - 7300 µc/g, a breakdown voltage of about 200 V, the leakage current is 0,0003 µa/µc.
Example 2. Carry out the processing of the lot scrap anodes of tantalum oxide-semiconductor capacitors mass 1 kg is the Smallest anodes is 6 mm. Scrap is crushed using a jaw crusher to a particle size of not more than 2 mm sieve with a mesh size of 2 mm sieved tantalum current-carrying wire. Shredded scrap in the number 0,98 kg, treated in two phases at room temperature, diluted sulfuric acid solution containing 182 g/l H2SO4and 185 g/l H2O2for 6 and 4 hours. After separation of the scrap solution of the first stage are sent to recycling. The solution of the second stage is used for the primary processing of the next lot of scrap. Scrap processed within 4 hours of a 4% solution of hydrofluoric acid, then washed with deionized water until neutral and dried. Dried scrap is subjected to the magnesium deoxidation in an argon atmosphere at a temperature of 850°C for 4 hours. After deoxidation scrap treated twice for 2 hours 18% HCl solution to remove magnesium oxide, after which raskalennyi scrap clicks the organisms within 1 hour with a 2% solution of hydrofluoric acid and washed with deionized water. The hydrogen content in the scrap is 0.3%.
Propitiously scrap milled in a rod mill for 90 minutes to a particle size less than 40 microns and a bulk density of 4.3 g/cm3. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration by heating the powder in a stream of high purity argon to a temperature of 1400°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to particles less than 315 μm to obtain 0.64 kg agglomerated tantalum capacitor powder. The content of impurities in the powder is, ×10-4%: Mn 5 Mg not more than 5, Fe not more than 10, Ni not more than 5, the oxygen - 1000. From powder to prepare anodes. Electrical characteristics of the anodes were: the specific charge - 7050 µc/g, a breakdown voltage of about 200 V, the leakage current is is 0.0002 ua/µc.
Example 3. Carry out the processing of the lot scrap anodes of tantalum oxide-semiconductor capacitors mass 1 kg is the Smallest anodes is 4.5 mm. Scrap is crushed using a jaw crusher to a particle size of not more than 2 mm sieve with a mesh size of 2 mm sieved tantalum current-carrying wire. Shredded scrap in the amount of 0.95 kg processed in two phases at room temperature, diluted sulfuric acid solution containing 100 g/l H2SO4and 300 g/l H2O2for 6 and 4 hours is. After separation of the scrap solution of the first stage are sent to recycling. The solution of the second stage is used for the primary processing of the next lot of scrap. Scrap processed within 4 hours of a 6% solution of hydrofluoric acid, then washed with deionized water until neutral and dried. Dried scrap is subjected to the magnesium deoxidation in an argon atmosphere at a temperature of 850°C for 4 hours. After deoxidation scrap treated twice for 2 hours 18% HCl solution to remove magnesium oxide, after which raskalennyi scrap is treated for 1 hour with 1% solution of hydrofluoric acid and washed with deionized water. The hydrogen content in the scrap is 0.25%.
Propitiously scrap milled in a rod mill for 90 minutes to a particle size less than 40 microns and a bulk density of 4.4 g/cm3. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration by heating the powder in a stream of high purity argon to a temperature of 1450°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to particles less than 315 μm with getting 0,61 kg agglomerated tantalum capacitor powder. The content of impurities in the powder is, ×10-4%: Mn 5 Mg not more than 5, Fe not more than 10, Ni not more than 5, the oxygen - 1100. From a powder preparing the anodes. Electrical characteristics of the anodes were: the specific charge - 6500 µc/g, a breakdown voltage of about 200 V, the leakage current is is 0.0002 ua/µc.
Example 4. Carry out the processing of the lot scrap anodes of tantalum oxide-semiconductor capacitors mass 1 kg is the Smallest anodes is 3.5 mm. Scrap is crushed using a jaw crusher to a particle size of not more than 2 mm sieve with a mesh size of 2 mm sieved tantalum current-carrying wire. Shredded scrap in the amount of 0,94 kg, treated in two phases at room temperature, diluted hydrochloric acid solution containing 150 g/l HCl and 75 g/l H2O2for 6 and 4 hours. After separation of the scrap solution of the first stage are sent to recycling. The solution of the second stage is used for the primary processing of the next lot of scrap. Scrap is treated for 4 hours with 3% solution of hydrofluoric acid, then washed with deionized water until neutral and dried. Dried scrap is subjected to the magnesium deoxidation in an argon atmosphere at a temperature of 850°C for 4 hours. After deoxidation scrap treated twice for 2 hours 18% HCl solution to remove magnesium oxide, after which raskalennyi scrap is treated for 1 hour with 3% solution of hydrofluoric acid and washed with deionized water. The content in Dorada in the scrap is reported to be 0.29%.
Propitiously scrap milled in a rod mill for 90 minutes to a particle size less than 40 microns and a bulk density of 4.3 g/cm3. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration by heating the powder in a stream of high purity argon to a temperature of 1400°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to particles less than 315 μm to obtain 0.6 kg agglomerated tantalum capacitor powder. The content of impurities in the powder is, ×10-4%: Mn 5 Mg not more than 5, Fe not more than 10, Ni not more than 5, the oxygen - 1100. From powder to prepare anodes. Electrical characteristics of the anodes were: the specific charge - 7230 µc/g, a breakdown voltage of about 200 V, the leakage current is is 0.0002 ua/µc.
Example 5. Carry out the processing of the lot scrap anodes of tantalum oxide-semiconductor capacitors mass 1 kg is the Smallest anodes is 4.5 mm. Scrap is crushed using a jaw crusher to a particle size of not more than 2 mm sieve with a mesh size of 2 mm sieved tantalum current-carrying wire. Shredded scrap in the amount of 0.97 kg processed in two phases at room temperature, diluted hydrochloric acid solution containing 90 g/l HCl and 130 g/l H2O2for 6 and 4 hours. After separation of the scrap solution of the first stage guide n the recycling. The solution of the second stage is used for the primary processing of the next lot of scrap. Processed scrap washed with deionized water until neutral and dried. Dried scrap is subjected to the magnesium deoxidation in an argon atmosphere at a temperature of 850°C for 4 hours. After deoxidation scrap treated twice for 2 hours 18% HCl solution to remove magnesium oxide, after which raskalennyi scrap is treated for 1 hour with a 2% solution of hydrofluoric acid and washed with deionized water. The hydrogen content in the scrap is 0.23%.
Propitiously scrap milled in a rod mill for 90 minutes to a particle size less than 40 microns and a bulk density of 4.5 g/cm3. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration by heating the powder in a stream of high purity argon to a temperature of 1500°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to particles less than 315 μm to obtain 0.65 kg agglomerated tantalum capacitor powder. The content of impurities in the powder is, ×10-4%: Mn 5 Mg not more than 5, Fe not more than 10, Ni not more than 5, the oxygen - 1100. From powder to prepare anodes. Electrical characteristics of the anodes were: the specific charge - 6100 µc/g, a breakdown voltage of about 200 V, the leakage current is 0.0001 ua/IWC is.
Example 6. Carry out the processing of the lot scrap anodes of tantalum oxide-semiconductor capacitors mass 1 kg is the Smallest anodes is 1.1 mm. Scrap processed in two phases at room temperature, diluted hydrochloric acid solution containing 30 g/l HCl and 225 g/l H2O2for 6 and 4 hours. After separation of the scrap solution of the first stage are sent to recycling. The solution of the second stage is used for the primary processing of the next lot of scrap. Scrap processed within 4 hours of a 6% solution of hydrofluoric acid, then washed with deionized water until neutral and dried. Dried scrap is subjected to the magnesium deoxidation in an argon atmosphere at a temperature of 850°C for 4 hours. After deoxidation scrap treated twice for 2 hours 18% HCl solution to remove magnesium oxide, after which raskalennyi scrap is treated for 1 hour with 5% solution of hydrofluoric acid and washed with deionized water. The hydrogen content in the scrap is of 0.27%.
Propitiously scrap milled in a rod mill for 90 minutes to provide a particle size less than 40 microns and a bulk density of 4.2 g/cm3. The obtained powder of tantalum hydride digitalout with simultaneous agglomeration by heating the powder in a stream vysokochistogo the argon to a temperature of 1350°C with a holding time at the maximum temperature for 1 hour. The sinter is crushed to particles less than 315 μm to obtain 0.7 kg agglomerated tantalum capacitor powder. The content of impurities in the powder is, ×10-4%: Mn 5 Mg not more than 5, Fe not more than 10, Ni not more than 5, the oxygen - 1300. From powder to prepare anodes. Electrical characteristics of the anodes were: the specific charge - 7260 µc/g, a breakdown voltage of about 200 V, the leakage current is 0,0003 µa/µc.
From the above Examples it is seen that in the inventive method, the acid treatment of scrap, compared with the prototype, is conducted at room temperature and no additional heat treatment of the scrap material in a vacuum at a temperature of 1800°C, which allows to reduce the energy intensity of the method and to improve its environmental friendliness while simplifying the way. The resulting processing scrap capacitor tantalum powder provides when used in the anodes of tantalum oxide-semiconductor capacitors: the specific charge to 7300 µc/g, the breakdown voltage of more than 200 V and the leakage current of 0.0001-0,0003 µa/µc, which testifies to the effectiveness of the claimed method. The method according to the invention is relatively simple and can be implemented in an industrial environment.
1. Method for processing scrap anodes of tantalum oxide-semiconductor capacitors, including cleaning acid treatment of refuse removal dioc the IDA manganese, the deoxidation of cleared scrap, its hydrogenation, refining, dehydrogenation at elevated temperatures with the agglomeration of the powder of tantalum hydride and obtaining tantalum capacitor powder, characterized in that the acid treatment of the scrap is carried out at room temperature with a solution containing 100-300 g/l of sulfuric acid and 110-300 g/l hydrogen peroxide or a solution containing 30-150 g/l of hydrochloric acid and 75-225 g/l hydrogen peroxide, and hydrogenation of scrap carried out by treatment with a solution of hydrofluoric acid with a concentration of 1-5%.
2. The method according to claim 1, characterized in that before the acid treatment, the scrap is ground to a particle size of not more than 2 mm and retrieve live tantalum wire.
3. The method according to claim 1, characterized in that before deoxidation scrap is treated with a solution of hydrofluoric acid with a concentration of 3-6%.