CN103600086A - Powder metallurgy tantalum powder and/or niobium powder and preparing method thereof - Google Patents
Powder metallurgy tantalum powder and/or niobium powder and preparing method thereof Download PDFInfo
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- CN103600086A CN103600086A CN201310636343.2A CN201310636343A CN103600086A CN 103600086 A CN103600086 A CN 103600086A CN 201310636343 A CN201310636343 A CN 201310636343A CN 103600086 A CN103600086 A CN 103600086A
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Abstract
The invention provides a preparing method of powder metallurgy tantalum powder and/or niobium powder. The method comprises the steps that (1) heat treatment sintering is conducted, wherein heat treatment sintering is conducted on raw tantalum powder and/or the niobium powder and after sintering is accomplished, cooling is conducted and then passivation is conducted so that a sintered block can be obtained; (2) hydrogenation and powder preparation are conducted, wherein the sintered block obtained through heat treatment is hydrogenated and powder is prepared so that the hydrogenated tantalum powder and/or the hydrogenated niobium powder can be obtained; (3) dehydrogenation and oxygen reduction are conducted, wherein reducibility metal is added to the hydrogenated tantalum powder and/or the niobium powder so that dehydrogenating and deoxygenating heat treatment can be conducted, and therefore a mixture of reducibility metallic oxide, residue reducibility metal, dehydrogenated and deoxidized tantalum powder and/or the niobium powder can be obtained; (4) acid pickling and impurity removal are conducted, wherein acid pickling and drying are conducted on a mixture obtained through dehydrogenation and oxygen reduction so that the tantalum powder and/or the niobium powder suitable for powder metallurgy can be obtained. The method is suitable for recycling and treating the waste tantalum powder and/or the niobium powder generated in the process of production of the high-specific-volume tantalum powder and/or the niobium powder for a capacitor so that the tantalum powder and/or the niobium powder suitable for powder metallurgy can be prepared, investment of needed devices is small, the adaptive capacity to raw materials is strong, the technological process is short, and the safety coefficient of the treatment process is high.
Description
Technical field
The present invention relates to rare metal field of smelting, and be specifically related to tantalum powder and/or niobium powder and preparation method thereof.
Background technology
Tantalum and niobium are rare elements, and their performance is closely similar.Because the oxide-film of tantalum and niobium has very high dielectric constant, so they are widely used in tantalum and/or niobium electrolytic capacitor is made.In addition, because tantalum and/or niobium have high-melting-point and low-vapor pressure, be therefore also applied to heat generating components, boat and the insulation material in Aero-Space, national defence, vacuum high temperature furnace.In addition, tantalum and/or niobium have excellent resistance to corrosion for liquid metal and the strong acid except hydrofluoric acid, and have good thermal conductivity and chemical stability, are also applied to the anti-corrosion material in the fields such as chemical industry and metallurgy.In addition, because tantalum and/or niobium have good biocompatibility, therefore conventionally can be used in medical field as operation suture thread, custom-made prosthesis, Invasive lumbar fusion device, joint prosthesis, bone fracture repair materials etc.Therefore tantalum has strong anti-electronics stress migration ability, also can be used for the barrier layer between copper cash and silicon in manufacturing integration circuit.
When tantalum and/or niobium are used for making electrolytic capacitor, conventionally the anode block of preparing porous with tantalum and/or the niobium raw material of powder type, anode block also needs the silk thread that inserts tantalum and/or niobium as lead-in wire while making, and also usually utilizes tantalum and/or niobium sheet to be processed into capacitor case.In the application of other side, first tantalum and/or niobium powder to be pressed into rod or bar in most cases, then carry out sintering, or even further electronic torch melting or electric arc melting, to reach densified, High Purity; And then be rolled, the processing such as drawing, form rod, plate, sheet, pipe, silk, paper tinsel and other tantalum and/or niobium goods and process material.
Tantalum and/or niobium be as high temperature refractory, and it is smelted and conventionally adopts following technique: first compound is reduced into metal dust, and then purification, sintering, adjustment performance, thereby is made into tantalum and/or the niobium powder of various satisfied different instructions for uses.If tantalum and/or niobium powder are for being processed into rod, plate, sheet, pipe, silk, paper tinsel and other tantalum and/or niobium goods processing material, being commonly called powder used in metallurgy tantalum and/or niobium powder.Compare with tantalum and/or niobium powder with capacitor, the feature of powder used in metallurgy tantalum and/or niobium powder is: (1) apparent density is large; (2) impurity content such as oxygen, nitrogen, hydrogen is low.A powder used in metallurgy tantalum powder for example, its apparent density is greater than 3.7g/cm
3, oxygen content is lower than 1500ppm, and nitrogen content is lower than 100ppm, and hydrogen content is lower than 50ppm.If tantalum and/or niobium powder are for the production of electrolytic capacitor, we are referred to as tantalum and/or niobium powder for capacitor; Compare with powder used in metallurgy tantalum and/or niobium powder, capacitor by tantalum and/or niobium powder feature is: except the impurity contents such as apparent density, oxygen, nitrogen, hydrogen are had requirement, the more important thing is and require to have good electric property.Conventionally capacitor is higher with the specific volume of tantalum and/or niobium powder, and specific area is larger, and apparent density is less, and the impurity contents such as oxygen, nitrogen, hydrogen are higher.For example capacity is the tantalum powder for capacitor of 200,000 μ FV/g, and its apparent density is 1.5-1.9g/cm
3, oxygen content is 9,000-12,500ppm, and hydrogen content reaches 350-500ppm, and because production process must be carried out nitrating processing, nitrogen content will reach 1,500-2,800ppm conventionally.
In producing the process of capacitor with tantalum and/or niobium powder, there are a certain amount of waste product or substandard products in each operation of production line.Recycle these useless tantalums and/or niobium powder, the simplest method is using it as the raw material of producing tantalum and/or niobium compound, is made into the compound that production tantalum and/or niobium powder are used, and as potassium floutaramite, is then reused for the raw material of going back original production tantalum and/or niobium powder.But while recycling by this method the useless tantalum that produces in the production process of capacitor with tantalum and/or niobium powder and/or niobium powder, there is following problem: 1) first above-mentioned recovery method will dissolve useless tantalum and/or niobium powder with acid, this process produces a large amount of hydrogen, thereby hydrogen deflagration accident having very easily occurs, so production risk is high; 2) tantalum resource recycling rate is lower; 3) technological process is long, and production cost is higher, 4) the discharge three wastes are many, and environmental pollution is more serious.
If the useless tantalum producing in the production process by capacitor with tantalum and/or niobium powder and/or niobium powder are for the preparation of powder used in metallurgy tantalum and/or niobium powder, can reduce production risk and also greatly improve the utilization rate of tantalum and/or niobium, thereby save day by day poor tantalum and/or niobium resource and reduce costs, the pressure of environmental pollution is relatively light.Yet useless tantalum and/or the common apparent density of niobium powder that this class reclaims are little, and specific area is large, and oxygen, nitrogen, hydrogen content are higher.Porosity can be too large when being pressed into base bar for such tantalum and/or niobium powder, and during sintering, a large amount of volatilizations of impurity can cause disconnected bar; Or impurity inner before the closing of pores does not fully volatilize, thereby be difficult to reach the object of purification, be unfavorable for next step processing.Especially at capacitor, use in high specific capacitance tantalum and/or niobium powder production process, in order to obtain higher specific volume, need to increase tantalum and/or niobium powder specific area; Therefore capacitor produces by high specific capacitance tantalum and/or niobium powder production process useless tantalum and/or niobium powder cause the more outstanding of the problems referred to above performance.For example, when tantalum powder specific area is greater than 1.5m
2after/g, reclaiming the useless tantalum powder obtaining may apparent density only have 0.9g/cm
3, and oxygen content may surpass 6,000ppm, and nitrogen content surpasses 300ppm, and hydrogen content also reaches 1500ppm; And work as specific area, be greater than 3.5m
2after/g, reclaiming the useless tantalum powder obtaining may apparent density only have 0.6g/cm
3, and oxygen content may surpass 14,000ppm, and nitrogen content surpasses 400ppm, and hydrogen content reaches 2500ppm or even higher.And niobium powder is along with specific area increases, apparent density down ratio is larger, and the impurity content increasing degrees such as oxygen, nitrogen, hydrogen are higher.So reclaim the useless tantalum that produces in the production process of capacitor with tantalum and/or niobium powder and/or niobium powder and and then using it as powder used in metallurgy tantalum and/or during niobium powder, must carry out further processing processing.
Chinese patent application CN200610146912.5 discloses a kind of method that improves tantalum and/or niobium powder apparent density, reduction tantalum and/or niobium powder specific area, also reduces the impurity such as tantalum and/or niobium powder oxygen, nitrogen, hydrogen simultaneously.The method comprises the following steps: 1) raw material tantalum and/or niobium powder raw material are pressed into base bar, 2) the base bar of vacuum-sintering compacting; 3) by sintered blank bar hydrogenation powder process; 4) add reducing agent to carry out deoxidation, dehydrogenation heat treatment the tantalum of hydrogenation and/or niobium powder; With 5) tantalum after deoxidation, dehydrogenation heat treatment and/or niobium powder are carried out to pickling, washing and oven dry.The method is suitable for processing specific area and is less than 1.0m
2/ g raw material tantalum and/or niobium powder.But work as raw material tantalum and/or niobium powder specific area and be greater than 1.0m
2during/g, will be very little (may be less than 1.0g/cm to the apparent density of described powder
3) and oxygen content is higher (may be higher than 6,000ppm).When being pressed into base bar, such tantalum and/or niobium powder easily there is following problem: thus tantalum and/or niobium powder and mould inner wall adhesion cause demoulding difficulty, so operating efficiency reduction and even cannot carry out the compacting of base bar; And the method press device used is complicated, so equipment investment is larger.
For specific area is greater than 1.0m
2/ g raw material tantalum and/or niobium powder can adapt to the open method of Chinese patent application CN200610146912.5 to be processed, and in prior art, the common processing method that reclaims useless tantalum and/or niobium powder is first to carry out the heat treatment of high temperature high vacuum powder process; After the tantalum obtaining and/or niobium powder are participated in to reducing agent, oxygen falls; Then carry out pickling, oven dry, screening, obtain specific area and be less than 1.0m
2/ g, oxygen content is lower than the tantalum powder of 4,000ppm.But along with capacitor is more and more higher with tantalum and/or niobium powder specific volume, there are useless tantalum to be recycled and/or niobium powder specific area more and more higher and active also more and more higher, such as useless tantalum and/or niobium powder specific area reclaiming are greater than 1.8m
2when/g is above, the agglomerate intensity after the heat treatment of high temperature high vacuum is too high, causes the broken difficulty of agglomerate, easily when fragmentation, rubs and catches fire, and causes fire.On the other hand, if reduce heat treatment temperature, agglomerate strength decreased, but tantalum powder activity is not effectively reduced; Therefore the passivation time after heat treatment is long especially, production efficiency of equipment is significantly reduced, and in subsequent treatment, involuntary ignition accident easily occurs tantalum powder; Even if missing of ignition, the tantalum powder after processing still has very little apparent density.In addition, when using low heat treatment temperature, tantalum powder specific area is still larger and active more intense, tantalum powder in processing, transportation, storage, use procedure, contact with air dielectric and with airborne oxygen, nitrogen, reaction of moisture, so in tantalum powder, the impurity such as oxygen, nitrogen, hydrogen is still very high, can not reach the requirement of powder used in metallurgy tantalum and/or niobium powder.
In sum, reclaim and process capacitor and have following shortcoming with the useless tantalum producing in high specific capacitance tantalum and/or niobium powder production process and/or the prior art of niobium powder: (1) equipment complex structure, equipment investment are larger; (2) inefficiency; (3) process route is long, the tantalum powder rate of recovery is low, causes processing cost higher; (4) along with capacitor is more and more higher with tantalum and/or niobium powder specific volume, useless tantalum to be recycled and/or niobium powder specific area and activity are more and more higher, and prior art cannot effectively be processed it.The useless tantalum producing in the production process of partition capacitance device with high specific capacitance tantalum and/or niobium powder and/or niobium powder, by existing PROCESS FOR TREATMENT, not only can not obtain qualified powder used in metallurgy tantalum and/or niobium powder, may, due to tantalum and/or the spontaneous combustion of niobium powder, deflagration accident having occur.
Therefore, the needs of this area existence to the efficient and safe method of the useless tantalum producing in recovery high specific capacitance tantalum and/or niobium powder production process and/or niobium powder.
Summary of the invention
The object of the invention is to overcome the problems referred to above of the prior art, provide a kind of by reclaiming and process useless tantalum and/or the niobium powder producing in the production process of capacitor with high specific capacitance tantalum and/or niobium powder, thereby prepare the method for the tantalum and/or the niobium powder that are applicable to powder used in metallurgy.The present invention also aims to provide a kind of powder used in metallurgy tantalum and/or the niobium powder that can process high-quality tantalum material.
A first aspect of the present invention provides a kind of method of utilizing the useless tantalum that produces in the production process of capacitor with high specific capacitance tantalum and/or niobium powder and/or niobium powder to prepare powder used in metallurgy tantalum and/or niobium powder, and the method comprising the steps of:
(1) heat treatment sintering: by raw material tantalum and/or niobium powder heat treatment sintering, sintering finishes rear cooling and carry out passivation, obtains agglomerate;
(2) hydrogenation powder process: powder process after the agglomerate hydrogenation that heat treatment is obtained, obtains tantalum and/or the niobium powder of hydrogenation;
(3) oxygen falls in dehydrogenation: add reducing metal to carry out dehydrogenation and deoxidation heat treatment the tantalum of hydrogenation and/or niobium powder, obtain the tantalum of reducing metal oxide, residual reducing metal, dehydrogenation and deoxidation and/or the mixture of niobium powder; With
(4) pickling impurity removal: the mixture obtaining after oxygen is fallen in dehydrogenation and carry out pickling, oven dry, obtain being applicable to tantalum and/or the niobium powder of powder metallurgy.
According to the method described in first aspect present invention, wherein said raw material tantalum and/or niobium powder can be the useless tantalum and/or the niobium powder that reclaim in tantalum and/or niobium powder production process for capacitor, can be also tantalum and/or niobium powder that employing industry technology personnel know the special high-specific surface area of producing of the technique of knowing, low-apparent-density, elevated oxygen level; Preferably, in described raw material tantalum and/or niobium powder, can also contain one or more elements that are selected from tungsten, molybdenum, titanium, hafnium, zirconium, carbon, silicon, vanadium, aluminium and tin.
According to the method described in first aspect present invention any one, wherein said raw material tantalum and/or niobium powder have the 1.0m of being greater than
2the specific area of/g and/or higher than the oxygen content of 4000ppm, preferably has the 1.8m of being greater than
2the specific area of/g, more preferably has the 2.0m of being greater than
2/ g, be greater than 3.0m
2/ g, be greater than 4.0m
2/ g, be greater than 5.0m
2/ g, be greater than 6.0m
2/ g, be greater than 7.0m
2/ g or be greater than 8.0m
2the specific area of/g.Further preferred raw material tantalum and/or niobium powder have the 1m of being greater than
2the specific area of/g, the while is higher than the oxygen content of 4,000ppm.
According to the method described in first aspect present invention any one, wherein the heat treatment sintering described in step (1) is in 3.0 * 10 at low vacuum
-1at the temperature of Pa, 1500-2100 ℃, carry out; The time of preferred heat treatment sintering is 1-25 hour, and preferred sintering time is 3-20 hour, 3-18 hour, 3-15 hour, 2-10 hour or 3-10 hour.
According to the method described in first aspect present invention any one, wherein the passivation described in step (1) be temperature be cooled to 50 ℃ or lower than the condition of 50 ℃ under carry out, preferably, described passivation is in agglomerating plant, to pass into air to carry out passivation.
According to the method described in first aspect present invention any one, wherein the step of step (2) hydrogenation powder process comprises:
A) oxide layer is destroyed: by Bas Discharged in equipment, to pass in container hydrogen as protective gas after, then agglomerate is heated to 800-950 ℃ of high temperature, insulation 1-10 hour, makes agglomerate surface oxidation damage layer;
B) inhale hydrogen: oxide layer starts cooling after destroying, while and lower the temperature and pass into hydrogen, last till that temperature drops to normal temperature (25 ℃), makes agglomerate fully inhale hydrogen;
C) fragmentation: adopt this area to know the disintegrating apparatus of knowing and carry out broken powder process, for example, adopt airslide disintegrating mill, Milling and screening machine, jaw crusher powder process.Preferably, 250 mesh standard sieve sieve powder for the powder obtaining after fragmentation, obtain passing through tantalum and/or the niobium powder of 250 mesh sieves completely.
According to the method described in first aspect present invention any one, the hydrogen purity of wherein using in step (2) hydrogenation powder process is higher than 99.95%, and preferably hydrogen purity is higher than 99.995%;
Preferably, described Hydrogen Vapor Pressure is 0.1-3Mpa, and preferred Hydrogen Vapor Pressure is 0.5-1.0Mpa.
According to the method described in first aspect present invention any one, wherein, step is 0.1～3.0Mpa as the pressure of hydrogen of protection gas in a), is preferably 0.5-1.0Mpa;
Preferably, the Hydrogen Vapor Pressure step b) remains on 0.1～3.0Mpa; More preferably, Hydrogen Vapor Pressure remains on 0.5～1.0Mpa.
According to the method described in first aspect present invention any one, wherein, step b) hydrogen content that fully absorbs the agglomerate of hydrogen in is 3,000-6, and 000ppm, is preferably 3,000-5, and 000ppm(is 4000ppm, 4300ppm or 4800ppm for example).
According to the method described in first aspect present invention any one, wherein said reducing metal is selected from magnesium, calcium, rare earth metal or their alloy or combination, is preferably magnesium; Preferably, the tantalum that the consumption of reducing metal is hydrogenation and/or the oxygen in niobium powder are converted into the stoichiometric 1.2-5 of the required reducing metal of reducing metal oxide doubly (for example 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.25 times) completely.
According to the method described in first aspect present invention any one, wherein the described dehydrogenation in step (3) and deoxidation heat treatment are heat treated under the condition of for example, protecting or vacuumizing in inert gas (argon gas, helium) circulation.Preferably; described heat treatment is heat treated under the first protection of the circulation at inert gas; for example, for example, in 800-950 ℃ (800 ℃, 830 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃ or 950 ℃) lower 1-3 hour (2 hours) of insulation that continue; then vacuumize (preferably in 20-80 minute, progressively reduce pressure to atmospheric pressure lower than 0.06MPa); lower than atmospheric pressure 0.06MPa; in other words-0.06MPa; or at same temperature, be incubated again 1-6 hour (being preferably 2-6 hour, for example 3 hours) under lower pressure.
According to the method described in first aspect present invention any one, the acid that wherein step (4) pickling impurity removal is used is nitre aqueous acid, and preferred concentration is 5-30 (wt) %(for example 15%, 8%, 10%, 18%, 20%, 25% or 28%).Preferably, the consumption of acid is that the solid-to-liquid ratio of mixture and aqueous solution of nitric acid is for example 1 ﹕ 2 of 1 ﹕ 1～3().Preferably, mixture stirs 10-90 minute (for example 60 minutes, 20 minutes, 30 minutes, 50 minutes, 80 minutes) after mixing with aqueous solution of nitric acid.
In a preferred embodiment, the tantalum obtaining after pickling and/or niobium powder can also be washed with pure water, then dry and obtain tantalum and/or niobium powder; More preferably, the tantalum after oven dry and/or niobium powder are crossed 200 mesh sieves, must be powder used in metallurgy tantalum and/or the niobium powder of 200 mesh sieves.
A second aspect of the present invention provides a kind of powder used in metallurgy tantalum and/or niobium powder, and it prepares by the method described in first aspect present invention any one.
Preferably, described powder used in metallurgy tantalum and/or niobium powder had the particle diameter of 200 mesh sieves.
Preferably, described powder used in metallurgy tantalum and/or niobium powder has the 5.0m of being less than
2the specific area of/g, for example, be less than 0.4m
2/ g, be less than 0.3m
2/ g.
Preferably, described powder used in metallurgy tantalum and/or the oxygen content of niobium powder are 300-1500ppm, are preferably 800-1500ppm(for example 890ppm, 1060ppm, 1430ppm, 760ppm or 1230ppm).
Preferably, described powder used in metallurgy tantalum and/or the hydrogen content of niobium powder are below 180ppm, be preferably 150ppm following (for example 90ppm is following, 100ppm is following or 120ppm following), more preferably 80ppm following (for example 20ppm is following, 30ppm is following, 50ppm is following, 40ppm is following, 60ppm is following or 70ppm following).
Preferably, the apparent density of described powder used in metallurgy tantalum powder is 3.5-7g/cm
3, be preferably 3.9-6.5g/cm
3.
Preferably, the apparent density of described powder used in metallurgy niobium powder is 2-6g/cm
3, be preferably 2-5g/cm
3(2.6g/cm for example
3or 3.1g/cm
3).
Detailed Description Of The Invention
In this manual, mentioned each percentage, PPM and ratio all refer to percentage by weight, unless otherwise expressly noted.
In the present invention, term " tantalum and/or niobium powder " refers to the various powder that mainly formed by tantalum and/or niobium; Include but not limited to mixture or the tantalum-niobium alloy powder of tantalum metal powder, niobium metal powder, tantalum powder and niobium powder.
Method of the present invention can be used high-specific surface area, low-apparent-density, elevated oxygen level tantalum and/or niobium powder as raw material, produces powder used in metallurgy tantalum and/or niobium powder.
In the method for the invention, described raw material tantalum and/or niobium powder can be useless tantalum and/or the niobium powder reclaiming by tantalum and/or niobium powder production process from capacitor, can be also tantalum and/or the niobium powder of the high-specific surface area specially produced, low-apparent-density, elevated oxygen level.Yet preferably, use by capacitor with the useless tantalum reclaiming in tantalum and/or each operation of niobium powder production line and/or niobium powder as described raw material tantalum and/or niobium powder.One or more that in addition, also can add by desired content the elements such as tungsten, molybdenum, titanium, hafnium, zirconium, carbon, silicon, vanadium, aluminium, tin are as adulterant.
In method step of the present invention (1), divide dish to pack high temperature high vacuum heat-treatment furnace sintering into raw material tantalum and/or niobium powder, for fear of infiltrate objectionable impurities in target powder, the crucible material that the shove charge of described minute dish is used is the material that is difficult for infiltrating objectionable impurities in target powder, generally selects tantalum crucible, molybdenum crucible or graphite crucible; Sintering vacuum requires lower than 3.0 * 10
-1pa, sintering temperature is 1500-2100 ℃, and sintering time is preferably 1-25 hour, preferably 2-10 hour.Sintering is lowered the temperature after finishing, and when temperature slowly passes into air lower than 50 ℃ in backward sintering furnace heating clamber, carries out passivation, finally obtains agglomerate.
In method step of the present invention (1), described sintering is lower than 3.0 * 10
-1under the high vacuum of Pa pressure, at the temperature of 1500-2100 ℃, carry out 1-25 hour, preferably 2-10 hour.Step (1) sintering condition is the final metallurgical key that improves apparent density, reduction oxygen content with tantalum and/or niobium powder; in the temperature range of 1500-2100 ℃; temperature is higher, the time is longer; the amplitude that raw material tantalum and/or niobium powder granule merge, grow up is larger; seed activity is lower, and final metallurgy is with tantalum and/or niobium powder apparent density is higher, oxygen content is lower.Sintering temperature surpasses 2100 ℃, and sintering time surpasses 10 hours, final metallurgically will tend towards stability by tantalum and/or niobium powder apparent density, oxygen content.If sintering temperature is too low, time is too short, the useless tantalum that specific area is large and/or niobium powder activity decreased are not thorough, when its in further processing with the substance reaction such as the oxygen contacting, water, it will be higher causing the powder used in metallurgy tantalum that finally obtains and/or niobium powder oxygen, hydrogen content, and involuntary ignition even occurs.After sintering finishes, lower the temperature and passivation, so-called passivation, is exactly by controlling tantalum surface oxidation rate, form the form compact and stable oxide-film of one deck, make tantalum enter no longer vigorous oxidation of atmosphere rear surface from vacuum state, to avoid spontaneous combustion, after step (1) processing finishes, obtain agglomerate.
In method step of the present invention (2), the agglomerate obtaining in (1) step is packed into after hydrogenation vessel, first the air in container is discharged by the row of finding time, then to the purity that passes into 0.5-1.0Mpa in container higher than 99.95% hydrogen as protective gas after, again agglomerate is heated to 800-950 ℃ of high temperature, insulation 1-10 hour, make its surface oxidation damage layer, then cooling has a power failure, not open closely enter purity higher than 99.95% hydrogen, preferably hydrogen purity is higher than 99.995% hydrogen, and make Hydrogen Vapor Pressure maintain 0.1～3.0Mpa, preferably Hydrogen Vapor Pressure is 0.5～1.0Mpa, to make agglomerate, fully inhale hydrogen, make its hydrogen content reach 3, 000-6, 000ppm, obtain having tantalum and/or niobium and the alloy block thereof of good hydrogen fragility.If hydrogen purity is too low or Hydrogen Vapor Pressure is too low, agglomerate is inhaled hydrogen deleterious, and its hydrogen brittleness is bad, will make crushing efficiency reduce, even cannot be broken, if Hydrogen Vapor Pressure is too high, be unfavorable for production safety risk control.Then adopt and know the disintegrating apparatus known as airslide disintegrating mill, Milling and screening machine, jaw crusher powder process, with 250 mesh standard sieves, sieve powder, obtain passing through tantalum and/or the niobium powder of 250 mesh sieves completely.
In the step (3) of the inventive method, described reducing metal is selected from magnesium metal, calcium, rare earth metal, or their alloy or combination, preferable alloy magnesium, its principle can be described as: the metal tantalum after hydrogenation and/or niobium have at high temperature low hydrogen and divide under the condition of depressing and can discharge the wherein characteristic of hydrogen, step (2) is obtained to tantalum and/or niobium powder is heated to high temperature, the inert gas circulation of simultaneously using argon gas etc. not react with material and equipment material, or reaction vessel is vacuumized, make wherein hydrogen release out, while is due to selected reducing metal and oxygen affinity closes energy force rate tantalum and/or niobium is stronger, so reducing metal by capture tantalum and/or niobium in oxygen, generate easily by hydrochloric acid, nitric acid, the reducing metal oxide that sulfuric acid etc. dissolve, the object of oxygen falls in performing step (2) when obtaining tantalum and/or the dehydrogenation of niobium powder.In addition, the tantalum that the consumption of described reducing metal is hydrogenation and/or the oxygen in niobium powder are converted to the stoichiometric 1.2-5 of the required reducing metal of reducing metal oxide doubly completely.In addition, the heat treated that oxygen falls in described dehydrogenation preferably continues insulation 1-3 hour in the situation that argon gas circulates at 800-900 ℃, then under lower than atmospheric pressure 0.06MPa or lower pressure, at same temperature, be incubated again 1-6 hour, fully dehydrogenation, obtains the tantalum of reducing metal oxide, residual reducing metal, dehydrogenation and deoxidation and/or the mixture of niobium powder.
More specifically, in method step of the present invention (3), the tantalum obtaining in step (2) and/or niobium powder are mixed by a certain percentage with magnesium metal; The consumption of described magnesium metal is that tantalum and/or the oxygen in niobium powder of hydrogenation is converted to magnesian 1.2-5.0 doubly completely, if while using magnesium metal, magnesium metal is not enough, in tantalum and/or niobium powder, generation is insoluble in to sour tantalic acid magnesium, causes magnesium in final tantalum and/or niobium powder, oxygen content too high.The mixture that the tantalum obtaining in step (2) and/or niobium powder are mixed with magnesium metal, be divided into equalization and be distributed into boat, reinstall dehydrogenation and fall oxygen stove, first under protecting as the circulation of argon gas or helium, inert gas carries out heat treated, described dehydrogenation is fallen oxygen and preferably at 800-950 ℃, is continued insulation 1-3 hour, if excess Temperature, the undue sintering of tantalum powder, part Mg will wrap up wherein, cause Mg content in final product to increase, if temperature is too low, deoxidation in tantalum and/or niobium powder, dehydrogenation poor effect, cause product oxygen, hydrogen content is higher, then oxygen reaction vessel being fallen in dehydrogenation vacuumizes, in 20-80 minute, the pressure that progressively reduces reaction vessel is to lower than being incubated 1-6 hour under atmospheric pressure 0.06MPa or lower pressure at same temperature again, fully dehydrogenation, with powder used in metallurgy tantalum and/or the niobium powder hydrogen content that guarantees finally to obtain, be reduced to below 80ppm, in evacuation process, if it is too fast that reaction vessel internal pressure declines, superfluous magnesium metal volatilizees fierceness, tantalum and/or niobium powder are taken out of from take up the boat of material, cause loss of material.Then cooling passivation, obtain the tantalum of magnesia, kish magnesium, deoxidation and dehydrogenation and/or the mixture of niobium powder.
In the final step (4) of the inventive method, the mixture that step (3) is obtained carries out pickling, to remove magnesium metal, magnesia in the tantalum of deoxidation and dehydrogenation and/or niobium powder; The mixture that step 4 is obtained with contain 5-30(wt) aqueous solution of the nitric acid of %, concentration of nitric acid is too high, to make tantalum powder oxygen content increase, the solid-to-liquid ratio of tantalum powder and aqueous solution of nitric acid is 1:1-3.0, stirs 10-90min, dissolves magnesium metal, magnesia wherein, then remove by filter acid pickle, divide again dish vacuum drying, with 200 mesh standard sieves, sieve powder, thereby obtain being applicable to tantalum and/or the niobium powder of powder used in metallurgy.
By said method provided by the invention, obtain powder used in metallurgy tantalum and/or niobium powder, it had the particle diameter of 200 mesh sieves, the oxygen content of 300-1500ppm.The apparent density of the powder used in metallurgy tantalum powder being obtained by said method especially, is typically 3.5-7.0g/cm
3; And the apparent density of the powder used in metallurgy niobium powder being obtained by said method is typically 3.0-6.0g/cm
3.
Tantalum of the present invention and/or niobium powder Fei Shi particle diameter are measured by assay method Fei Shi method > > (standard No. GB/T3249) prescriptive procedure of standard < < refractory metal and compound powder granularity, apparent density is measured by the funnel method > > of mensuration first (standard No. GB/T1479) prescriptive procedure of standard < < metal dust apparent density, size distribution is measured by mensuration dry screen point-score > > (standard No. GB/T1480) prescriptive procedure of standard < < metal dust granularmetric composition, sampling process samples by sampling method > > (standard No. GB/T5314) prescriptive procedure of standard < < powder used in metallurgy powder, oxygen, nitrogen, hydrogen content and specific surface area analysis method are as shown in table 1.
Table 1 chemical impurity analytical method
The beneficial effect of the invention
Preparation method of the present invention is applicable to reclaim and process useless tantalum and/or the niobium powder producing in the production process of capacitor with high specific capacitance tantalum and/or niobium powder, thereby prepares tantalum and/or the niobium powder that is applicable to powder used in metallurgy.The equipment investment that the inventive method needs is little, adaptable to raw material, and technological process is short, and processing procedure safety coefficient is high.
The specific embodiment
Prepare the useless tantalum powder 1095kg that tantalum powder for capacitor production process reclaims, be numbered Ta powder 1, its physical property, chemical impurity analysis result are in Table 2.Prepare the useless niobium powder 379kg that niobium powder for capacitor production process reclaims, numbered raw material niobium powder 1, its physical property, chemical impurity analysis result are in Table 3.
Embodiment 1
Get Ta powder 1 and amount to 200kg, divide 30 dishes to take up it with tantalum crucible, be then placed on bin, send into heat-treatment furnace, start evacuation system, low vacuum is in 3.0 * 10
-2power transmission heating after Pa, sintering temperature is 1500 ℃, and sintering time is 3 hours.Sintering is lowered the temperature after finishing, and when detected temperatures slowly passes into air lower than 50 ℃ in the chamber of backward sintering furnace material place, carries out passivation, after coming out of the stove, obtains agglomerate.Agglomerate is packed into after hydrogenation vessel; first the air in container is discharged by the row of finding time; then to the hydrogen of purity 99.995% that passes into 0.5Mpa in container as protective gas after; again agglomerate is heated to 800-950 ℃ of high temperature; be incubated 3 hours, the cooling that then has a power failure, not open closely enters the hydrogen that purity is 99.995%; and make Hydrogen Vapor Pressure maintain 0.5～1.0Mpa, obtain having the hydrogenated tantal piece of good hydrogen fragility.Then adopt jaw crusher powder process, with 250 mesh standard sieve sieve powder, obtain passing through the hydrogenated tantal powder of 250 mesh sieves completely, analyze oxygen in hydrogenated tantal powder, hydrogen content, analysis result: oxygen content is 23, 000ppm, hydrogen content is 4, 300ppm, in this hydrogenated tantal powder, evenly mix stoichiometric 1.6 times of required magnesium metal, press the conversion of hydrogenated tantal grain weight amount, 5.5% the magnesium metal for hydrogenated tantal grain weight amount, be divided into equalization and be distributed into metal tantalum boat, reinstall dehydrogenation and fall oxygen stove, first under protecting as the circulation of argon gas, inert gas carries out 830 ℃ of heat treated 2 hours, then oxygen reaction vessel being fallen in dehydrogenation vacuumizes, after vacuum 29 minutes, the pressure of reaction vessel is progressively reduced to lower than atmospheric pressure 0.08MPa, then at 830 ℃, find time to be again incubated 3 hours, then cooling passivation, obtain magnesia, the mixture of the tantalum of the deoxidation of kish magnesium and dehydrogenation and/or niobium powder.Finally, by above-mentioned mixture with contain 15(wt) the nitre aqueous acid of % is that 1:2.0 mixes by tantalum powder and the solid-to-liquid ratio of aqueous solution of nitric acid, stirs 60min, then with pure water, filter, remove acid pickle, then divide dish vacuum drying, with 200 mesh standard sieve sieve powder, obtain final powder used in metallurgy tantalum powder.This powder used in metallurgy tantalum powder is numbered to powder used in metallurgy tantalum powder 1, analyzes its physical property, chemical impurity, analysis result is in Table 2.
Embodiment 2
Get Ta powder 1 and amount to 200kg, divide 30 dishes to take up it with graphite crucible, heat treatment sintering temperature is 1500 ℃, and sintering time is 10 hours, and other conditions are with embodiment 1.The powder used in metallurgy tantalum powder finally obtaining is numbered to powder used in metallurgy tantalum powder 2, analyzes its physical property, chemical impurity, analysis result is in Table 2.
Embodiment 3
Get Ta powder 1 and amount to 200kg, with graphite crucible, divide 30 dishes to take up it, heat treatment sintering temperature is 2100 ℃, and sintering time is 10 hours, other conditions are heat-treated sintering by the condition of embodiment 1, hydrogenation powder process, analyze oxygen in hydrogenated tantal powder, hydrogen content, analysis result: oxygen content is 13, 000ppm, hydrogen content is 5, 600ppm, in this hydrogenated tantal powder, evenly mix stoichiometric 2.0 times of required magnesium metal, press the conversion of hydrogenated tantal grain weight amount, 4.0% the magnesium metal for hydrogenated tantal grain weight amount, other conditions are carried out dehydrogenation by the condition of embodiment 1 and are fallen oxygen, pickling impurity removal.This powder used in metallurgy tantalum powder is numbered to powder used in metallurgy tantalum powder 3, analyzes its physical property, chemical impurity, analysis result is in Table 2.
Table 2 tantalum mealiness energy
From analysis result, can find out, the useless tantalum powder that tantalum powder for capacitor production process reclaims, average grain diameter, apparent density are too little, and specific area is too large, oxygen, hydrogen content are high especially, cannot use as metallurgical Ta powder at all.Such tantalum powder will be processed by prior art, existence is caught fire or the problem of press strip difficulty, but according to PROCESS FOR TREATMENT of the present invention, process is simple, safety, and it is good to obtain powder used in metallurgy tantalum powder physical property: average grain diameter, apparent density increase substantially, specific area, oxygen content, hydrogen content significantly reduce, and adopt higher temperature sintering, and nitrogen content also obviously improves.
Embodiment 4
Get raw material niobium powder 1 and amount to 100kg, used niobium crucible to divide 30 dishes to take up, condition by embodiment 1 is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 28, 000ppm, hydrogen content is 3, 400ppm, in this hydrogenated niobium powder, evenly mix stoichiometric 1.2 times of required magnesium metal, press the conversion of hydrogenated niobium grain weight amount, 5.0% the magnesium metal for hydrogenated niobium grain weight amount, be divided into equalization and be distributed into metal niobium boat, by the condition of embodiment 1, carry out dehydrogenation again and fall oxygen, pickling is numbered powder used in metallurgy niobium powder 1 by this powder used in metallurgy niobium powder, analyze its physical property, chemical impurity, analysis result is as table 3.
Embodiment 5
Get raw material niobium powder 1 and amount to 100kg, condition by it by embodiment 3 is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 16,000ppm, hydrogen content is 3,800ppm, in this hydrogenated niobium powder, evenly mixing stoichiometric 2.1 times of required magnesium metal, by hydrogenated niobium grain weight amount conversion, is 5.0% magnesium metal of hydrogenated niobium grain weight amount, be divided into equalization and be distributed into metal niobium boat, then by the condition of embodiment 3, carry out dehydrogenation and fall oxygen, pickling demagging.This powder used in metallurgy niobium powder is numbered to powder used in metallurgy niobium powder 2, analyzes its physical property, chemical impurity, analysis result is as table 3.
Table 3 niobium mealiness energy
From analysis result, can find out, the useless niobium powder that niobium powder for capacitor production process reclaims, average grain diameter, apparent density are too little, and specific area is too large, oxygen, hydrogen content are high especially, cannot use as metallurgical Ta powder at all.Such tantalum powder will be processed by prior art, existence is caught fire or the problem of press strip difficulty, but according to PROCESS FOR TREATMENT of the present invention, process is simple, safety, and it is good to obtain powder used in metallurgy tantalum powder physical property: average grain diameter, apparent density increase substantially, specific area, oxygen content, hydrogen content significantly reduce, and adopt higher temperature sintering, and nitrogen content also obviously improves.
Embodiment 6
Get Ta powder 1 and amount to 120kg, raw material niobium powder 1 amounts to 80kg, mix, condition by it by embodiment 3 is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 17,800ppm, hydrogen content is 4,000ppm, in this hydrogenated tantal niobium alloy powder, evenly mixing stoichiometric 1.9 times of required magnesium metal, by hydrogenated tantal niobium alloy grain weight amount conversion, is 5.0% magnesium metal of hydrogenated tantal niobium alloy grain weight amount, be divided into equalization and be distributed into metal niobium boat, then by the condition of embodiment 3, carry out dehydrogenation and fall oxygen, pickling demagging.This powder used in metallurgy tantalite niobite power is numbered to powder used in metallurgy tantalum-niobium alloy powder 1, analyzes its physical property, chemical impurity, analysis result is as table 4.
Embodiment 7
Get Ta powder 1 and amount to 195kg, from market purchasing purity higher than 99.9%,-200 object tungsten powder 5.0kg, both are mixed, condition by it by embodiment 3 is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 14, 200ppm, hydrogen content is 4, 600ppm, in this hydrogenated tantal alloyed powder, evenly mix stoichiometric 2.25 times of required magnesium metal, press the conversion of hydrogenated tantal alloyed powder weight, 5.0% the magnesium metal for hydrogenated tantal alloyed powder weight, be divided into equalization and be distributed into metal tantalum boat, by the condition of embodiment 3, carry out dehydrogenation again and fall oxygen, pickling demagging.This powder used in metallurgy tantalum tungsten powder is numbered to powder used in metallurgy tantalum alloy powder 1, analyzes its physical property, chemical impurity, analysis result is as table 4.
Embodiment 8
Get Ta powder 1 and amount to 180kg, from market purchasing purity higher than 99.5%,-200 object hafnium powder 20.0kg, both are mixed, condition by it by embodiment 3 is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 18, 500ppm, hydrogen content is 4, 500ppm, in this hydrogenated tantal alloyed powder, evenly mix stoichiometric 1.8 times of required magnesium metal, press the conversion of hydrogenated tantal alloyed powder weight, 5.0% the magnesium metal for hydrogenated tantal alloyed powder weight, be divided into equalization and be distributed into metal tantalum boat, by the condition of embodiment 3, carry out dehydrogenation again and fall oxygen, pickling demagging.This powder used in metallurgy tantalum hafnium powder is numbered to powder used in metallurgy tantalum alloy powder 2, analyzes its physical property, chemical impurity, analysis result is as table 4
Embodiment 9
Get raw material niobium powder 1 and amount to 99.0kg, from market purchasing purity higher than 99.6%,-200 object zirconium powder 1.0kg, mixed, condition by it by embodiment 3 is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 19, 500ppm, hydrogen content is 5, 300ppm, in this hydrogenated niobium alloyed powder, evenly mix stoichiometric 1.7 times of required magnesium metal, press the conversion of hydrogenated niobium alloyed powder weight, 5.0% the magnesium metal for hydrogenated niobium alloyed powder weight, be divided into equalization and be distributed into metal niobium boat, by the condition of embodiment 3, carry out dehydrogenation again and fall oxygen, pickling demagging.This powder used in metallurgy niobium zirconium powder is numbered to powder used in metallurgy niobium alloy powder 1, analyzes its physical property, chemical impurity, analysis result is as table 4
Table 4 niobium mealiness energy
From analysis result, can find out, useless tantalum and/or niobium powder that capacitor reclaims by tantalum and/or niobium powder production process, because average grain diameter, apparent density are too little, and specific area is too large, oxygen, hydrogen content are high especially, cannot use as metallurgical Ta powder at all, also cannot be by prior art processing smoothly, but according to PROCESS FOR TREATMENT of the present invention, can obtain the alloyed powder of well behaved powder used in metallurgy tantalum and/or niobium.
Claims (13)
1. a method of preparing powder used in metallurgy tantalum and/or niobium powder, the method comprising the steps of:
(1) heat treatment sintering: by raw material tantalum and/or niobium powder heat treatment sintering, sintering finishes rear cooling and carry out passivation, obtains agglomerate;
(2) hydrogenation powder process: powder process after the agglomerate hydrogenation that heat treatment is obtained, obtains tantalum and/or the niobium powder of hydrogenation;
(3) oxygen falls in dehydrogenation: add reducing metal to carry out dehydrogenation and deoxidation heat treatment the tantalum of hydrogenation and/or niobium powder, obtain the tantalum of reducing metal oxide, residual reducing metal, dehydrogenation and deoxidation and/or the mixture of niobium powder; With
(4) pickling impurity removal: the mixture obtaining after oxygen is fallen in dehydrogenation and carry out pickling, oven dry, obtain being applicable to tantalum and/or the niobium powder of powder metallurgy.
2. method claimed in claim 1, described raw material tantalum and/or niobium powder are the useless tantalum and/or the niobium powder that reclaim in tantalum and/or niobium powder production process for capacitor, or employing industry technology personnel know tantalum and/or the niobium powder of the special high-specific surface area of producing of the technique of knowing, low-apparent-density, elevated oxygen level;
Preferably, in described raw material tantalum and/or niobium powder, contain one or more elements that are selected from tungsten, molybdenum, titanium, hafnium, zirconium, carbon, silicon, vanadium, aluminium and tin.
3. the method described in claim 1 or 2, described raw material tantalum and/or niobium powder have the 1.0m of being greater than
2the specific area of/g and/or higher than the oxygen content of 4000ppm.
4. method claimed in claim 1, wherein the heat treatment sintering described in step (1) is in 3.0 * 10 at low vacuum
-1at the temperature of Pa, 1500-2100 ℃, carry out; The time of preferred heat treatment sintering is 1-25 hour, and preferred sintering time is 3-20 hour, 3-18 hour, 3-15 hour, 2-10 hour or 3-10 hour.
5. method claimed in claim 1, wherein the passivation described in step (1) be temperature be cooled to 50 ℃ or lower than the condition of 50 ℃ under carry out, preferably, described passivation is in agglomerating plant, to pass into air to carry out passivation.
6. method claimed in claim 1, wherein the step of step (2) hydrogenation powder process comprises:
A) oxide layer is destroyed: by Bas Discharged in equipment, to pass in container hydrogen as protective gas after, then agglomerate is heated to 800-950 ℃ of high temperature, insulation 1-10 hour, makes agglomerate surface oxidation damage layer;
B) inhale hydrogen: oxide layer starts cooling after destroying, while and lower the temperature and pass into hydrogen, last till that temperature drops to normal temperature (25 ℃), makes agglomerate fully inhale hydrogen;
C) fragmentation: adopt this area to know the disintegrating apparatus of knowing and carry out broken powder process, for example, adopt airslide disintegrating mill, Milling and screening machine, jaw crusher powder process,
Preferably, 250 mesh standard sieve sieve powder for the powder obtaining after fragmentation, obtain passing through tantalum and/or the niobium powder of 250 mesh sieves completely.
7. the method described in claim 1 to 6 any one, the hydrogen purity of wherein using in step (2) hydrogenation powder process is higher than 99.95%, and preferably hydrogen purity is higher than 99.995%;
Preferably, described Hydrogen Vapor Pressure is 0.1-3Mpa, and preferred Hydrogen Vapor Pressure is 0.5-1.0Mpa.
8. method claimed in claim 6, wherein, step is 0.1～3.0Mpa as the pressure of the hydrogen of protection gas in a), is preferably 0.5-1.0Mpa;
Preferably, the Hydrogen Vapor Pressure step b) remains on 0.1～3.0Mpa; More preferably, Hydrogen Vapor Pressure remains on 0.5～1.0Mpa.
9. the hydrogen content that fully absorbs the agglomerate of hydrogen method claimed in claim 6, wherein, step b) is 3,000-6, and 000ppm, is preferably 3,000-5, and 000ppm(is 4000ppm, 4300ppm or 4800ppm for example).
10. method claimed in claim 1, wherein said reducing metal is selected from magnesium, calcium, rare earth metal or their alloy or combination, is preferably magnesium;
Preferably, the tantalum that the consumption of reducing metal is hydrogenation and/or the oxygen in niobium powder are converted into the stoichiometric 1.2-5 of the required reducing metal of reducing metal oxide doubly completely.
11. methods claimed in claim 1, wherein the described dehydrogenation in step (3) and deoxidation heat treatment are heat treated under the condition of for example, protecting or vacuumizing in inert gas (argon gas, helium) circulation;
Preferably; described heat treatment is heat treated under the first protection of the circulation at inert gas; for example, for example, in 800-950 ℃ (800 ℃, 830 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃ or 950 ℃) lower 1-3 hour (2 hours) of insulation that continue; then vacuumize (preferably in 20-80 minute, progressively reduce pressure to atmospheric pressure lower than 0.06MPa); under lower than atmospheric pressure 0.06MPa or lower pressure, at same temperature, be incubated again 1-6 hour (being preferably 2-6 hour, for example 3 hours).
12. methods claimed in claim 1, the acid that wherein step (4) pickling impurity removal is used is nitre aqueous acid, preferred concentration is 5-30 (wt) %(for example 15%, 8%, 10%, 18%, 20%, 25% or 28%);
Preferably, the consumption of acid is that the solid-to-liquid ratio of mixture and aqueous solution of nitric acid is for example 1 ﹕ 2 of 1 ﹕ 1～3();
Preferably, mixture stirs 10-90 minute (for example 60 minutes, 20 minutes, 30 minutes, 50 minutes, 80 minutes) after mixing with aqueous solution of nitric acid;
Preferably, the tantalum obtaining after pickling and/or niobium powder are washed with pure water again;
Preferably, the tantalum after oven dry and/or niobium powder are crossed 200 mesh sieves.
13. powder used in metallurgy tantalum and/or niobium powders, its method by any one in claim 1-12 prepares;
Preferably, described powder used in metallurgy tantalum and/or niobium powder had the particle diameter of 200 mesh sieves;
Preferably, described powder used in metallurgy tantalum and/or the oxygen content of niobium powder are 300-1500ppm, are preferably 800-1500ppm(for example 890ppm, 1060ppm, 1430ppm, 760ppm or 1230ppm);
Preferably, the apparent density of described powder used in metallurgy tantalum powder is 3.5-7g/cm
3, be preferably 3.9-6.5g/cm
3;
Preferably, the apparent density of described powder used in metallurgy niobium powder is 2-6g/cm
3, be preferably 2-5g/cm
3(2.6g/cm for example
3or 3.1g/cm
3).
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