CN1311943C - Method for producing metal powder and formed product of raw material for metal - Google Patents

Method for producing metal powder and formed product of raw material for metal Download PDF

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CN1311943C
CN1311943C CNB038133423A CN03813342A CN1311943C CN 1311943 C CN1311943 C CN 1311943C CN B038133423 A CNB038133423 A CN B038133423A CN 03813342 A CN03813342 A CN 03813342A CN 1311943 C CN1311943 C CN 1311943C
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metal
compound
formed body
niobium
tantalum
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CN1658991A (en
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冈部彻
今荤倍正名
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Foundation For The Promotion O.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/001—Starting from powder comprising reducible metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams

Abstract

The present invention provides a metal powder production process capable of efficiently producing a metal at high purity directly from a metal compound, and preferably enables the process to be carried out continuously. The metal powder production process according to the present invention is a process for producing a metal powder by using a metal compound for the raw material and reducing said metal compound, comprising: a molding step in which the metal compound is mixed with a binder, is molded, and is sintered to produce a metal compound feed compact; and, a reducing step in which a metal is formed by reducing the metal compound by contacting the metal compound feed compact with an active metal.

Description

Metal powder production process and metal compound feedstock formed body
Technical field
The metal compound feedstock formed body (feed metal compound formed body) that the present invention relates to a kind of metal powder production process and can be used for this metal powder production process.
Background technology
Not only have high-melting-point such as niobium and the such high-melting-point rare metal of tantalum, and because they at high temperature have chemism, therefore the reguline metal being made powder needs accurate complicated technology.An example as the method that is used to produce this rare metal powder is, atomization process, and this method is with metal molten and carry out the resulting metal fluid of efflorescence, and it is a kind of effective ways that are used to produce powder.Yet because rare metal fusing point height, therefore melting rare metal needs expensive equipment.
In addition, another known method is hydrogenation-dehydrogenation (HDH) method, and rare metal and H-H reaction are to form the resulting hydride of a kind of hydride and mechanical crushing in the method.Yet this method is difficult to the fine powder of production uniform particle size.
At present, with industrial tantalum powder and the material of other high-melting-point rare metal powder as capacitor, and this powder wherein utilizes reactive metal as reducing agent raw material to be reduced mainly by the production of metallothermic reduction method.Using the advantage of metallothermic reduction method is directly to produce pulverous tantalum by reduction reaction.Yet, be difficult to produce effectively a large amount of uniform powders by this reduction reaction, especially when increasing, reaction scale can cause the shortcoming of the uniformity decline of the powder that generates.
Under existing situation,, produce pulverous tantalum thereby can carry out uniform reduction reaction by utilizing a large amount of halide based fused salts that is used for reaction medium (diluting salt or diluent) and adding a small amount of raw material and reducing agent to this reaction medium.This method is suitable for producing highly purified uniform powder.On the other hand, it still exists the demand of reaction medium salt big and be difficult to improve the shortcoming of process scale and speed.
If reduce niobium by the method for a large amount of reaction medium salt of said method utilization, then can obtain uniform powder.Yet,, be difficult to obtain uniform powder if under the situation of the production process of not using reaction medium salt and tantalum, reduce niobium.
Summary of the invention
In view of the problems referred to above of prior art, the object of the present invention is to provide and directly to make highly purified metal dust expeditiously, preferably the producing method for metal powder of performing step serialization simply from metallic compound.Especially provide and directly to make highly purified niobium powder expeditiously, preferably the niobium powder manufacture method of performing step serialization simply from niobium compound.
And, the present invention also aims to utilize above-mentioned manufacture method that suitable metal compound feedstock formed body is provided.
The invention provides and a kind ofly be used for the metallic compound of raw material and reduce the method that this metallic compound produces metal dust by utilization, this method may further comprise the steps: molded step, in this molded step, metallic compound is mixed, carries out moulding and carries out sintering with adhesive, with production metal compound feedstock formed body; Reduction step is in this reduction step, by contacting reducing metal raw materials of compound formed body to make metal with reactive metal as reducing agent the metal compound feedstock formed body; And, also comprise the another one step, in this step, the metal that will form in reduction step by acid treatment separates with accessory substance with reactive metal; Wherein in this molded step, this metal compound feedstock formed body is molded into distance from optional position in this metal compound feedstock formed body to this formed body surface no longer than the shape of 10mm, and this metallic compound is the metallic element compound that is selected from niobium, zirconium, titanium, hafnium, tantalum, rare earth metal and actinide metal.
Can be with niobium compound as metallic compound.Alternatively, can be with tantalum compound as metallic compound.Alternatively, can also be with the compound of the metallic element of selected among zirconium, titanium, hafnium, rare earth metal and actinide metal as metallic compound.
In molded step,, can carry out the metal compound feedstock formed body molded and shaped by mixed-metal compounds, adhesive with as the active metallic compound of reactant.
Preferably, further comprise and to be selected from least a in the reactive metal of calcium, magnesium, sodium, barium and potassium as reducing agent.
Preferably, at least a as reactant in the compound of reactive metal of calcium, magnesium, sodium, barium and potassium will be selected from.
Preferably, niobium oxide or halogenation niobium are used as niobium compound.
Preferably, in reduction step the temperature of formed body at 600-1300 ℃.
In molded step, preferably, the metal compound feedstock formed body is molded into distance from arbitrfary point the metal compound feedstock formed body to this formed body surface no longer than the shape of 10mm.
Preferably, metal powder production process also comprises a step, in this step, by acid treatment the metal that forms in the reduction step and reactive metal and accessory substance is separated.
In addition, the invention provides a kind of metal compound feedstock formed body, it forms by metallic compound and adhesive being mixed, carry out moulding and carrying out sintering; Wherein from the optional position of this formed body to the distance on this formed body surface no longer than 10mm.
Preferably, metallic compound comprises the raw materials of compound of the metallic element that is selected from niobium, zirconium, titanium, hafnium, tantalum, rare earth metal and actinide metal.
The metal compound feedstock formed body further comprises at least a compound that is selected from the metal of calcium, magnesium, sodium, barium and potassium as reactant.Preferably, this reactant is a kind of in oxide, halide and the carbonate that is selected from the metal of at least a calcium, magnesium, sodium, barium and potassium.
Description of drawings
Fig. 1 shows the cross section block diagram according to Metal Production device of the present invention;
Fig. 2 shows the electron micrograph of the niobium powder of producing in embodiment 1;
Fig. 3 shows the electron micrograph of the tantalum powder that the example A to E of embodiment 2 produces;
Fig. 4 shows the electron micrograph of the tantalum powder of producing among the example F to K among the embodiment 2; And
Fig. 5 A and 5B show the particle size distribution figure of the tantalum powder of producing among the embodiment 2.
The specific embodiment
Production method according to metal dust of the present invention is a kind of technology that is used to produce metal, utilize metallic compound as raw material and reduce this metallic compound, this method may further comprise the steps: molded step, in this molded step, with metallic compound mix with adhesive, moulding and carry out sintering, with production metal compound feedstock formed body (preform blank); And reduction step is in this reduction step, by contacting reducing metal raw materials of compound formed body to make metal with reactive metal as reducing agent the metal compound feedstock formed body.Can be with niobium compound, tantalum compound, zirconium compounds, titanium compound, hafnium compound, rare earth compound, actinide metal compound as metallic compound.
An embodiment as according to metal powder production process of the present invention below will describe the method for utilizing niobium compound to produce niobium powder in detail.
According to the production method of niobium powder of the present invention is a kind ofly to be used for the niobium compound of raw material and to reduce the technology that this niobium compound produces niobium by utilization, this method may further comprise the steps: molded step, in this molded step, niobium compound is mixed with adhesive producing slurry and this slurry is molded as such as sheet material shape, wire rod shape or the such reservation shape of graininess, and carry out sintering to generate niobium compound material forming body (preform blank); And reduction step in this reduction step, generates niobium by niobium compound material forming body is contacted the reduction niobium compound with reactive metal as reducing agent.Niobium oxide or halogenation niobium can be used as aforesaid niobium compound.
Preferably, be selected from calcium, magnesium, sodium, barium, and potassium at least a metal as aforesaid reactive metal.By utilizing this reactive metal reduction niobium compound material forming body can carry out reduction reaction effectively.In addition, owing to can carry out reduction reaction most effectively, therefore the particularly preferred magnesium that is to use is as reactive metal.
Preferably, in above-mentioned reduction step the temperature of formed body between 600-1300 ℃.If the temperature of formed body is lower than 600 ℃, then the steam pressure step-down of reducing agent and reaction trend towards and can not fully react, and if the temperature of formed body is higher than 1300 ℃, the trend that made niobium powder sintering takes place is then arranged.
In aforesaid reduction step, preferably, reactive metal is contacted with niobium compound material forming body (preform blank) under vapor state.In this case, preferably, keeping in the reduction apparatus ventilates carries out reduction reaction by niobium compound material forming body is placed into.For example, utilize supporting material that niobium compound material forming body is arranged on vertical position in the reduction apparatus that has heater, and supporting material is used for a plurality of niobium compound material forming bodies are bearing in vertical position, reactive metal is placed into the bottom of reduction apparatus, on the supporting material or between adjacent niobium compound material forming body, and utilize heater heating reduction apparatus, contact with the reactive metal vaporization and with niobium compound material forming body, thereby reduction reaction takes place.By this way, by niobium compound material forming body is arranged in the reduction apparatus, can keep the evolving path by gas phase, because the reactive metal of vaporization is spread equably, therefore niobium compound material forming body can be contacted more equably with reactive metal, thereby reduction reaction is carried out on time and space more equably, can also improve reduction efficiency simultaneously.In addition, because niobium compound material forming body does not directly contact with reduction apparatus, therefore can avoid polluting reduction apparatus, thereby improve the purity of resulting niobium powder.
In addition, in the above-mentioned molded step that is used for producing niobium compound material forming body, except niobium compound and adhesive, can produce niobium compound material forming body as the reactive metal of reactant by additional mixing in reactant.Although the reactive metal as the previous reaction agent also can be used as adhesive, also can be as the sedimentary structural form and the raising acid treatment efficient of control niobium powder.In this way, except niobium compound and adhesive, can produce niobium compound material forming body by sneaking into, thereby the reaction in reduction step is carried out more evenly, and can enhance productivity as the active metallic compound of reactant.In addition, the granularity of resulting niobium powder also can be controlled by type and the mixing ratio of adjusting the previous reaction agent.In addition, also can prevent from the pollution of autoreactor effectively.
Preferably, be selected from calcium, magnesium, sodium, barium, and the metal of potassium at least a compound as the previous reaction agent, and more preferably, use oxide, halide, carbonate, hydroxide, chloride and/or the fluoride of these metals.The formed body that the reaction efficiency of reduction step and uniformity can be further comprise as this class active metallic compound of reactant by use improves.
In addition, in aforesaid molded step, the shape of the niobium compound material forming body that makes be preferably can make from formed body arbitrfary point to the distance on this formed body surface no longer than 10mm.Aforesaid " optional position is to the distance on this formed body surface from formed body " expression arrives the shortest distance on surface from the optional position in the formed body.In the reduction step of this production method and since reducing agent from the surface of niobium compound material forming body to the formed body diffusion inside, thereby will be included in niobium compound reduction in the niobium compound material forming body.Therefore, if the shape of formed body as mentioned above, then when finishing reduction reaction apart from the maximum diffusion length of the reducing agent on formed body surface no longer than 10mm, the DIFFUSION TREATMENT of the reducing agent from the formed body diffusion into the surface to formed body inside is not marked change with the variation of position, and runs through this formed body niobium raw material and can evenly and apace be reduced.
In addition, aforesaid niobium powder production method can also comprise the another one step, in this step, by acid treatment niobium, reducing agent, reactant and the accessory substance that forms in the aforementioned reduction step is separated.By providing by acid treatment these materials are carried out separation steps, reducing agent, reactant and the accessory substance that forms after reduction reaction can easily be separated from the target niobium, thereby can the highly purified niobium of large-scale production.In addition, in accordance with the present production process because niobium compound material forming body is used for reaction, though therefore after reducing above-mentioned formed body shape also almost be held.Therefore, by on formed body, carrying out acid treatment after the reduction, thereby has the advantage that to remove reducing agent and accessory substance effectively.
In traditional rare metal production method, it is believed that the maximum reason that can not obtain uniform powder is, because reducing agent becomes inhomogeneous to the diffusion of raw material when also commercial weight increases, therefore because the difference at raw material position, reduction reaction carry out on time and space, cause inhomogeneities under the condition.On the contrary, in production method according to niobium powder of the present invention, owing to produce niobium compound material forming body by mixing niobium raw material, adhesive and/or reactant, and, this mixture carries out reduction reaction by being contacted with reactive metal, even therefore also commercial weight increases, reduction reaction also can all be carried out on time and space equably.In addition,, therefore can carry out continued operation, and can increase the scale of reduction process with a simple device owing to can carry out reduction reaction in the reduction apparatus by niobium compound material forming body is placed into, and the efficient that improves batch processing.That is to say, although the acceleration of adopting traditional metallothermic reduction reaction to carry out continued operation and process is difficult, but be easy to realize continuous operating process owing to for production, heat treatment, reduction, cleaning or the like, be used in the niobium compound material forming body of above-mentioned niobium powder production method, therefore this process can realize continued operation easily, and can increase scale.In addition, although there are many situations, in these cases, if in the process of conventional method material quantity is increased, the granularity of so resulting powder etc. are inhomogeneous, and productivity ratio is reduced, but according to aforementioned production method of the present invention, in the even-grained while that keeps resulting powder, can realize easily that also the scale of reduction process and speed increase, thereby can boost productivity.
Below, with reference to the accompanying drawing of first embodiment of the invention the present invention is described in more detail.Fig. 1 shows the sectional view according to a specific embodiment of Metal Production device of the present invention.
Process units shown in Fig. 1 comprises: reactor 10, this reactor be one by the airtight container of forming such as the such heat proof material of stainless steel; A plurality of plate-shape metal raw materials of compound formed bodys 12 are installed in the reactor 10; And supporting material 13 and 14, be arranged on the top of formed body 12 and below be used for supporting these formed bodys 12 at vertical position.To place the bottom of reactor 10 as the reactive metal 15 of the reducing agent of reduction formed body 12 raw metals.In addition, although in the accompanying drawing in reactor 10 not shown heater, heater can be set, be used for the inside of reactor 10 is heated to predetermined temperature and vaporizes reactive metal 15.
The gas reduction of metallic compound by reactive metals 15 in the diffusion reaction device 10 that is included in the formed body 12 become metal, it utilizes heating of aforementioned heater and vaporization reactive metal 15, then with reducing agent reactive metal 15 from the diffusion into the surface of formed body 12 to inside.
In niobium powder production method according to the present invention, niobium powder can be produced by the metallothermic reduction method of utilizing aforementioned process units.In order to produce aforementioned niobium powder, at first in molded step, produce the niobium compound material forming body that comprises the raw material niobium compound.By this niobium raw material and adhesive and reactant being mixed, be molded into predetermined shape, then firing being preferably under 300-1000 ℃ the temperature, more preferably 800-1000 ℃,, so just obtain this formed body to remove adhesive.If aforementioned firing temperature is lower than 300 ℃, then, will reduce reaction efficiency in the reduction step below, and the purity of the powder that is obtained can reduce also because adhesive and reactant can not be removed fully.If firing temperature surpasses 1000 ℃, then sintering process is too fast, is tending towards causing marked change in niobium compound material forming body.In addition,, preferably, fire step and carried out 1 to 12 hour although depend on the size and the heating-up temperature of formed body, more preferably 1 to 6 hour, even more preferably 3 to 6 hours.In addition, when firing, preferably under air or oxygen atmosphere, carry out.
The example that can be used for the niobium compound of niobium raw material comprises Nb 2O 5, NbO x(low oxide of preferred niobium, wherein X is 0.5 to 2.5), NbCl 5And K 2NbF 7, the mixing ratio of the niobium raw material in aforesaid niobium compound material forming body preferably is at least 10% percentage by weight, preferably is at least 50% percentage by weight.If the mixing ratio of niobium raw material is at least 50% percentage by weight then reduction reaction can fully be carried out when although if the mixing ratio of niobium raw material is at least 10% percentage by weight, but the amount by the used acid of acid treatment between with the niobium powder separation period increases, and it is tending towards causing leaching efficiency to reduce.
Undoubtedly can use any adhesive, regardless of reduction reaction, as long as this adhesive can easily be removed by heat treatment, operable example comprises collodion and cellulose.In addition, reactant also can be used as adhesive, and can form formed body by mixing niobium raw material and reactant.Preferably 5-80% percentage by weight, more preferably 30-70% percentage by weight, more preferably 30-50% percentage by weight of the mixing ratio of adhesive in aforesaid niobium compound material forming body.If the mixing ratio of adhesive is less than 5% percentage by weight or greater than 80% percentage by weight, the intensity of formed body just is tending towards descending and will being difficult to form formed body so.
When needs, reactant is added in niobium raw material and the adhesive to form formed body by them.By reactant is dispersed in the formed body, can improve the reaction efficiency in the reduction step, and the reduction of niobium raw material can be carried out more equably.Preferably, to be selected from the compound of at least a metal in the group of forming by calcium, magnesium, sodium, barium and potassium as this reactant, more preferably, use oxide, halide, carbonate, hydroxide, chloride and/or the fluoride of these metals.More especially, calcium chloride, calcium carbonate, sodium carbonate or sodium chloride etc. can be used separately or use as mixture.The mixing ratio of previous reaction agent is preferably and can makes for 1 mole of niobium in being included in formed body preferably with the 0-2 mole and more preferably with the 0.5-1 mole cation in the reactant is concocted.When the cation in the reactant for 1 mole of niobium in being included in formed body surpasses 2 moles, if separate that formed niobium is used for then that acid amount that acid cleans is tending towards increasing and leaching efficiency is tending towards reducing by handling.
In addition, aforementioned molded in obtained formed body be shaped as make from formed body optional position to the beeline on this formed body surface preferably no longer than 10mm, and be more preferably 2-5mm.As a result of have this shape, owing to can make the diffusion length of reducing agent in the reduction step that will describe subsequently be no more than 10mm from the formed body diffusion into the surface to formed body inside, therefore can be rapidly and carry out reduction reaction equably.The example of given shape comprises sheet material shape, wire rod shape or graininess.Under situation with sheet material shape, this sheet metal thickness preferably is no more than 20mm to satisfy aforementioned condition, and under the situation with wire rod shape, on the cross section perpendicular to center line, alongst the distance between excircle and the center is preferably no longer than 10mm.Have under the situation of grain shape, diameter preferably is no more than 20mm.
Then, be that formed body 12 is put into reactor 10 according to the formed body that obtains in the aforesaid molded step, as shown in Figure 1.In Fig. 1, article shaped 12 is sheet material shape or wire rod shape, although and as can be seen from the figure they are bearing in vertical position, but the arrangement mode of formed body 12 in reactor is not limited to arrangement mode as shown in FIG., and their arrangement mode can suitably change according to the shape of formed body.
In addition, also will add the bottom of reactor 10 as the shape metal alive of reducing agent 15.Preferably, will be selected from one or both or more kinds of metal in the group of forming by calcium, magnesium, sodium, barium and potassium as reactive metal 15.In process units as shown in FIG., although reactive metal 15 is arranged on the bottom of reactor, reactive metal 15 also can be arranged on as on the supporting material 14 or be arranged between each formed body 12 that is supported in vertical position.For the aforementioned formed body 12 in the reactor 10 of 100 parts of weight, preferably with 50-400 part weight and more preferably add aforementioned reactive metal 15 with 100-300 part weight.When using aforementioned reactive metal 15 less than 50 parts of weight, reduction reaction is tending towards and can not carries out fully, if even when using greater than 400 parts of weight, reduction efficiency can not improve yet.
Then, finish the preparation of reduction step by sealed reactor 10.
Formed body 12 and reactive metal 15 added in the reactors 10, be arranged on this reactor 10 in the heating furnace then and heat., and it is contacted with formed body 12 with reactive metal 15 vaporization and be full of the inside of reactor 10 by heating.Reduction reaction begins to carry out from the surface of formed body 12, reduces and generates metal niobium being included in niobium raw material in the formed body 12.
In this reduction step, formed body 12 preferably is heated to 600-1300 ℃, more preferably 800-1000 ℃.When aforementioned temperature is lower than 600 ℃, be tending towards descending and reduction reaction is tending towards and can not carries out fully as the steam pressure of the reactive metal 15 of reducing agent.When aforementioned temperature was higher than 1300 ℃, the niobium powder that is generated was tending towards carrying out sintering.Although depend on size, heating-up temperature of formed body 12 or the like, but the reaction time is approximately 1 to 6 hour, and more specifically, has several millimeters thickness and under situation about heating under 800 ℃ or the higher temperature at tabular formed body 12, if the reaction time is 1 hour or longer, then reduction reaction is finished fully.
Then, after making reactor 10 coolings, the formed body of fully finishing reduction reaction is taken out from reactor 10.The shape of formed body 12 almost remains unchanged in the shape of reaction aftershaping body before the reaction, and the active metallic compound (accessory substance) that this formed body almost produces by the niobium that is generated, by reduction, excessive reducing agent and reactant are formed.Then, by the formed body that takes out in the reactor is carried out acid treatment, the niobium of being produced is separated from active metallic compound, reducing agent, reactant and the product owing to the reduction generation, thereby can be obtained niobium powder.After carrying out acid leach, for example handle and carry out this acid treatment by the replacement that utilizes water or organic solvent.Can the various acid that all example hydrochloric acids, acetate, nitric acid, hydrofluoric acid or sulfuric acid is such be used for aforesaid acid leach.
In in accordance with the present production process, because the formed body that comprises the niobium that is generated that obtains is after having finished reduction reaction, have the shape identical with the formed body 12 of initial handling, therefore in the later separation step, be gratifying, thereby make that niobium powder can be rapid and separated equably at acid-treated sour permeability.
In this way, can be according to raw materials of compound formed body of the present invention easily at realizing the continuous operation flow process in the heat treatment in its production process (molded) step, reduction step, acid treatment step and other steps, the raising of formed body size and quality can easily be provided in large-scale processing, even and the increase of the quantity of the formed body of being processed, also can prevent reaction rate and the inhomogeneity reduction of reaction.Therefore, in accordance with the present production process and according to raw materials of compound formed body of the present invention, this method can easily realize continued operation and production-scale increase.
In addition, according to niobium powder production method of the present invention, owing to by being that medium carries out reduction reaction, can make raw material carry out reduction reaction rapidly and evenly, so it is being effective aspect niobium powder that obtains high-purity and uniform particle size with the formed body that comprises niobium raw material.
Although at length explained the production method of niobium powder in the foregoing embodiments, can be applied to equally in accordance with the present production process in other the production of metal dust.That is to say, when the compound that uses metal target during as raw material, in molded step, mix this compound and adhesive and be molded into predetermined shape, then heat with production metal compound feedstock formed body, the metal compound feedstock formed body that is obtained reduces by reactive metal in reduction step, then preferably by acid treatment reactive metal is separated with accessory substance to generate the metal target powder.Preferably, the compound that will comprise such as the such metallic element of zirconium, titanium, hafnium, tantalum, rare earth metal and actinide metal is used as aforesaid metallic compound.
Then, explain in further detail according to tantalum powder production method of the present invention.Aforesaid tantalum powder production method is a kind of by using tantalum compound to produce the process of tantalum and reduction tantalum compound as raw material, may further comprise the steps: molded step, in this molded step, tantalum compound is mixed with adhesive to produce slurry, this slurry is molded into such as sheet material shape, wire rod shape or the such reservation shape of graininess, and carries out sintering to generate tantalum compound material forming body (preform blank); And reduction step in this reduction step, generates metal tantalum by will contact the aforesaid metal compound feedstock formed body of reduction as the reactive metal of reducing agent with tantalum compound material forming body.The example of operable tantalum compound comprises tantalum oxide and halogenation tantalum.
Firing temperature in above-mentioned molded step is preferably between 300-1000 ℃, more preferably between 800-1000 ℃, although depend on size, heating-up temperature of formed body or the like, preferably about 0.5 to 12 hour of sintering temperature, more preferably about 1 to 6 hour, even more preferably about 1 to 3 hour.If above-mentioned firing temperature is lower than 300 ℃, then adhesive can not be removed from formed body fully, will reduce reaction efficiency in follow-up reduction reaction, and the purity of the powder that is obtained can reduce also, if but temperature surpasses 1000 ℃, then tantalum compound material forming cognition deforms.In addition, preferably in air or oxygen atmosphere, fire.
Preferably, will be selected from least a metal in the group that calcium, magnesium, sodium, barium and potassium forms as aforementioned reactive metal.By utilizing this reactive metal reduction tantalum compound material forming body, thereby reduction reaction is carried out effectively.In addition, it is particularly preferred using reactive metal magnesium, and this is because can carry out reduction reaction most effectively.
The temperature of the formed body in above-mentioned reduction step is preferably between 600-1300 ℃, more preferably between 800-1000 ℃.If the temperature of formed body is lower than 600 ℃, the steam pressure step-down of reducing agent then, reaction trends towards and can not fully react, and if temperature is higher than 1300 ℃, the trend that the tantalum powder sintering takes place is arranged.Although depend on the size of tantalum compound material forming body and heating-up temperature or the like, preferably about 1 to 24 hour of the reaction time in aforementioned reduction step, more preferably about 1 to 6 hour, even more preferably about 3 to 6 hours.
In addition, in aforesaid reduction step, reactive metal preferably contacts with tantalum compound material forming body with vapor state.At this moment, preferably, tantalum compound material forming body is placed in the reduction apparatus to keep ventilating carries out reduction reaction.For example, utilize supporting material that tantalum compound material forming body is arranged on vertical position in the reduction apparatus that has heater, supporting material is used for a plurality of tantalum compound material forming bodies are bearing in vertical position, with reactive metal be placed into the bottom of reduction apparatus, on the supporting material or between adjacent tantalum compound material forming body, utilize heater heating reduction apparatus, the reactive metal vaporization contacts with tantalum compound material forming body, and reduction reaction takes place.By this way, by tantalum compound material forming body is arranged in the reduction apparatus, can keep ventilating.Because the reactive metal of vaporization evenly spreads, so tantalum compound material forming body can contact more equably with reactive metal, thereby reduction reaction is carried out more equably, can also improve reduction efficiency simultaneously on time and space.In addition, because tantalum compound material forming body does not directly contact with reduction apparatus, therefore can avoid polluting reduction apparatus, thereby increase the purity of resulting tantalum powder.
In addition, in the above-mentioned molded step that is used for producing the tantalum compound formed body, except tantalum compound and adhesive, can produce tantalum compound material forming body by the active metal that adds as reactant.Although the reactive metal as the previous reaction agent also can be used as adhesive, also can be used to control the sedimentary morphosis of tantalum powder and increase acid treatment efficient.In this way, except tantalum compound and adhesive, can produce tantalum compound material forming body by sneaking into as the active metallic compound of reactant, thereby the reaction in reduction step is more even, production efficiency also can increase.In addition, the granularity of the tantalum powder that is obtained also can be controlled by type and the mixing ratio of adjusting the previous reaction agent.In addition, also can effectively prevent the pollution of reactor.
Preferably, the compound that is selected from least a metal of calcium, magnesium, sodium, barium and potassium is used as the previous reaction agent, and, preferably, use oxide, halide, carbonate, hydroxide, chloride and/or the fluoride of these metals.More specifically, calcium chloride, calcium carbonate, sodium carbonate, sodium chloride etc. can be used separately or as mixture.The mixing ratio of previous reaction agent be preferably can make with respect to 1 mole be included in the formed body tantalum with the cation in the reactant preferably with the 0-2 mole and more preferably the 0.5-1 mole mix.Such active metallic compound that reaction efficiency in the reduction step and uniformity can further comprise as reducing agent by use improves.
In addition, in aforesaid molded step, the body formed shape of tantalum compound material forming is preferably from metal compound feedstock formed body optional position and is no more than 10mm to the distance on this formed body surface.The distance on the arrival surface that aforesaid " optional position is to the distance on this formed body surface from the metal compound feedstock formed body " is represented is the shortest distance apart from the optional position in the formed body.In the reduction step of this production method,, the tantalum compound that is included in the tantalum compound material forming body is reduced because reducing agent spreads to formed body from the surface of tantalum compound material forming body.Therefore, if the shape of formed body as mentioned above, in finishing reduction reaction, reducing agent is no more than 10mm from the maximum diffusion length on formed body surface, not along with the position marked change, the tantalum raw material can evenly and apace reduce in whole formed body to the DIFFUSION TREATMENT of the reducing agent from the diffusion into the surface of formed body to formed body.
In addition, aforesaid tantalum powder production method can also increase a step, and in this step, the tantalum that forms in the aforementioned reduction step is by acid treatment and reducing agent, reactant and separation of by-products.By a step is provided, in this step, with these separating substances, can easily tantalum, reducing agent, the reactant of target and the accessory substance of following reduction reaction to produce be separated, thereby can produce highly purified tantalum on a large scale by acid treatment.In addition, in manufacturing method according to the invention, because tantalum compound material forming body is used for reaction, even after reduction, almost also can keep the shape of aforementioned formed body.Therefore, by after reduction reaction, carrying out acid treatment, thereby has the advantage that to remove reducing agent and accessory substance effectively.
Although the present invention describes in detail by embodiment, following embodiment is not limited to the present invention.
Embodiment 1
In the present embodiment, utilize process units shown in Figure 1, produce niobium by the metallothermic reduction reaction.
With weight percent content is that the reactant of 0-80% (is selected from CaCl 2, CaCO 3, Na 2CO 3, and NaCl in one or both or more) add (Nb in the niobium raw material 2O 5, 100g) in.More specifically, the amount of the reactant of adding makes cationic amount (Ca 2+, Na +) for 1 mole of Nb, be respectively 0,1/10,1/5 or 1/2 mole.
Then, aforesaid niobium raw material and reactant are mixed with adhesive to produce slurry.Collodion solution with 5% (5% nitrocellulose, 40% ether and 55% ethanol) has the volume identical with reducing agent with aforesaid raw material as adhesive.
An amount of acetone is being added in the resulting slurry with after regulating viscosity, pouring slurry into thickness is that several millimeters and width are in the mould of 20cm, to make a plurality of formed bodys.Two thickness of the formed body of making are about 3mm and 6mm.
Then, resulting formed body is a sintering 1 hour in the stove under 1000 ℃ in air themperature, so that adhesive, solvent and moisture are thoroughly removed from the mixture of niobium raw material and reactant.As carrying out the result that this is fired, can preserve this reducing agent and prevent the carbon contamination of formed niobium powder.
A plurality of formed bodys that obtain and magnesium reducing agent (reactive metal 15) are placed in the reactor 10, guarantee the ventilation and the sealed reactor 10 of reactor 10 simultaneously.Then, the reactor 10 that comprises formed body 12 and reducing agent 15 is placed under 1000 ℃ and reaches 6 hours in the electric furnace, after abundant reduction reaction, whole reactor is taken out from stove and it is cooled off.
After the reduction reaction at the formed body (mixture of metal niobium powder, auxiliary agent, MgO and Mg) that utilizes aqueous acetic acid solution (1+1) to clean roughly to be obtained afterwards, moisture HCl solution with 1N cleans formed body twice, then water, alcohol and acetone replace, and carry out drying then.
The niobium that is obtained is estimated: Fig. 2 shows the electron scanning micrograph of the niobium powder that is obtained, this niobium powder preparation process is, the raw materials of compound formed body and the magnesium steam of the square thing of 50 * 20 * 3mm were reacted 6 hours down at 1000 ℃, make its cooling, utilize water acetic acid solution (1+1) to clean roughly, moisture HCl solution with 1N cleans twice with formed body, and water, alcohol and acetone replace, and carry out drying.In addition, according to the type (horizontal axis) and the cationic proportion (vertical axis) of auxiliary agent the photo among Fig. 2 is arranged with matrix form.
As shown in the drawing, the granularity of niobium powder can be controlled by the type and the amount that change auxiliary agent in the raw materials of compound formed body.Wherein the horizontal width of a photos is about 15 μ m, although powder size depends on the type and the amount of auxiliary agent, can obtain the niobium powder of initial granularity between 0.5-3 μ m.
Embodiment 2
In the present embodiment, utilize process units shown in Figure 1 equally, react by metallothermic reduction and make tantalum.
By with composition mixing tantalum raw material (Ta as shown in table 1 2O 5), reactant (is selected from CaCl 2, CaCO 3, Na 2CO 3, at least a among the NaCl) and adhesive prepare slurry.Collodion solution with 5% (5% nitrocellulose, 40% ether and 55% ethanol) has the volume identical with reactant with aforesaid tantalum raw material as adhesive.The viscosity that amount that can be by changing reactant and the adhesive that is added are regulated aforementioned slurry.
Then, the gained slurry being joined tabular to make in the mould, thickness is the formed body of 5-10mm.
Then, be sintering 3 hours in 1000 ℃ the stove with resulting formed body in air themperature, thereby adhesive, solvent and moisture are thoroughly removed from tantalum raw material and reactant.As the result who carries out sintering, can preserve this reducing agent and the carbon contamination of the tantalum powder that prevents to form.
Formed body and 20 magnesium reducing agents (reactive metal 15) that restrain that the 4-10 sheet is obtained are placed in the reactor 10, guarantee the ventilation of reactor simultaneously, and by Wolfram Inert Gas welded seal reactor 10.Then, the reactor 10 that comprises formed body 12 and reducing agent 15 is placed under 700-1000 ℃ and reaches 6-24 hour in the electric furnace, after carrying out abundant reduction reaction, its cooling is taken out and made to whole reactor from stove.
After the reduction reaction at the formed body (mixture of metal tantalum powder, auxiliary agent, MgO and Mg) that utilizes water acetic acid solution (1+1) to clean roughly to be obtained afterwards, moisture HCl solution with 1N cleans formed body twice, then water, alcohol and acetone replace, and carry out drying then.
Table 1
Example The reactant type X Mixed proportion Reduction step
Ta 2O 5 (g) Reducing agent (g) Time (hour) Temperature (℃)
A CaCl 2 1 5.18 2.61 6 1000
B CaCO 3 1 4.96 2.25 6 1000
C CaO 1 5.16 1.29 6 1000
D Na 2CO 3 1 5.00 1.15 6 1000
E NaCl 1 5.03 1.40 6 1000
F -- 0 5.07 -- 6 1000
G CaCl 2 0.1 5.02 0.27 6 1000
H CaCl 2 0.2 5.03 0.50 6 1000
I CaCl 2 0.5 5.12 1.26 6 1000
J CaCl 2 1 5.10 2.52 6 1000
K CaCl 2 2 5.02 4.98 6 1000
L CaCl 2 1 5.01 2.54 6 700
M CaCl 2 1 5.01 2.54 6 800
N CaCl 2 1 5.01 2.54 6 900
O CaCl 2 1 5.01 2.54 6 1000
P CaCl 2 1 3.05 1.52 3 1000
Q CaCl 2 1 3.04 1.52 6 1000
R CaCl 2 1 3.03 1.56 12 1000
S CaCl 2 1 3.04 1.55 24 1000
In addition, in table 1, X represents to be included in the cationic molal quantity in the reactant for 1 mole of tantalum.
Utilize the state of the tantalum powder that sem observation obtains, and show size distribution by the optical diffraction analysis.
Fig. 3 and Fig. 4 are the state photos that resulting tantalum powder among the example A to K that SEM shows is shown.As shown in Figure 3, the tantalum powder that is obtained is coralliform, and it has the granularity of 0.1-0.5 μ m.In addition, when using the calcium compound reactant, the granularity of the tantalum powder that is obtained is uniform.On the contrary, when using NaCl or NaCO 3During as reactant, the tantalum powder that comprises two types of particles that is obtained, this particle of two types comprise that those have the particle of 0.1-0.2 μ m small grain size and the particle with about 0.5 μ m coarsegrain.In addition, as shown in Figure 4, be granularity by the tantalum powder that mixing ratio obtained of reducing agent in the raising formed body.
Fig. 5 A is the particle size distribution figure that the tantalum powder that obtains among example B, D and the O is shown.Shown in curve, when using sodium compound, has the more powder of small grain size when being tending towards obtaining than the use calcium compound as reactant.In addition, it also shows when using calcium compound, and the granularity of the tantalum powder that is obtained is more uniform.
Fig. 5 B is the particle size distribution figure that the tantalum powder that obtains among example H, I and the O is shown.Shown in this curve, the granularity of the tantalum powder that is obtained increases with the increase of the mixed proportion of the reactant in the formed body as can be known.
Based on these results, as can be seen, the granularity of tantalum powder can be controlled by type and the quantity that changes the reactant in the raw materials of compound formed body.
Industrial applicability
As mentioned above, according to niobium powder production method of the present invention, because reduction reaction is carried out equably, and niobium compound material forming body can be placed into and carry out reduction reaction in the reduction apparatus continuously, therefore can improve process scale, and can utilize simple device to carry out batch machining effectively, thereby can be directly by producing highly purified niobium powder in the niobium compound effectively.
In addition, according to tantalum powder production method of the present invention, because can make reduction reaction carries out equably and tantalum compound material forming body can be placed in the reduction apparatus, carry out reduction reaction continuously, therefore can improve process scale, and can utilize simple device to carry out batch machining effectively, thereby can be directly by producing highly purified tantalum powder in the tantalum compound effectively.
In addition, according to metal powder production process of the present invention, not only can produce niobium and tantalum powder, and can produce highly purified powder effectively from metallic compound as zirconium, titanium, hafnium, rare earth metal and actinide metal, and preferably, can produce continuously.
In addition, the formed body that raw materials of compound formed body according to the present invention is a kind of metallic compound, by mixed-metal compounds and adhesive, then be shaped to reservation shape, fire and form, because the optional position that has from formed body is no more than the structure of 10mm to the distance on formed body surface, so reducing agent can be no longer than 10mm from the distance of the diffusion into the surface of formed body, thereby can make metallic compound more evenly and reduction promptly.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (13)

1. metal powder production process, it utilizes metallic compound to produce as the raw material and the described raw material that reduces, and said method comprising the steps of:
Molded step in described molded step, is mixed described metallic compound, is carried out moulding and carry out sintering with production metal compound feedstock formed body with adhesive;
Reduction step in described reduction step, is made metal by described metal compound feedstock formed body being contacted with reactive metal as reducing agent to reduce described metal compound feedstock formed body; And
Also comprise the another one step, in described step, the described metal that will form in described reduction step by acid treatment separates with accessory substance with described reactive metal;
Wherein in described molded step, described metal compound feedstock formed body is molded into distance from optional position in described metal compound feedstock formed body to described formed body surface no longer than the shape of 10mm,
Described metallic compound is the metallic element compound that is selected from niobium, zirconium, titanium, hafnium, tantalum, rare earth metal and actinide metals.
2. metal powder production process according to claim 1 wherein is used as described metallic compound with niobium compound.
3. metal powder production process according to claim 1 wherein is used as described metallic compound with tantalum compound.
4. metal powder production process according to claim 1, wherein with the compound of the metallic element of selected among zirconium, titanium, hafnium, rare earth metal and actinide metal as described metallic compound.
5. metal powder production process according to claim 1, wherein in described molded step, described metal compound feedstock formed body is by mixed-metal compounds, adhesive and carry out molded and shaped as the active metallic compound of reactant.
6. metal powder production process according to claim 1, at least a reactive metal that wherein will be selected from calcium, magnesium, sodium, barium and the potassium is used as described reducing agent.
7. metal powder production process according to claim 5, the compound that wherein will be selected from least a reactive metal in calcium, magnesium, sodium, barium and the potassium is as described reactant.
8. metal powder production process according to claim 2 wherein will be selected from a kind of as described niobium compound in niobium oxide and the halogenation niobium.
9. metal powder production process according to claim 1, wherein in described reduction step, the temperature of described metal compound feedstock formed body is 600-1300 ℃.
10. metal compound feedstock formed body, it is by mixed-metal compounds and adhesive, molded and shaped and fire and form; Wherein
The distance on the surface from the optional position in described formed body to described formed body is no longer than 10mm.
11. metal compound feedstock formed body according to claim 10, wherein said metallic compound comprises the raw materials of compound of the metallic element that is selected from niobium, zirconium, titanium, hafnium, tantalum, rare earth metal and actinide metal.
12. metal compound feedstock formed body according to claim 10, wherein said metal compound feedstock formed body further comprise at least a compound that is selected from the metal of calcium, magnesium, sodium, barium and potassium as reactant.
13. metal compound feedstock formed body according to claim 12, wherein said reactant are to be selected from a kind of at least a oxide, halide and the carbonate that is selected from the metal of calcium, magnesium, sodium, barium and potassium.
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