WO2018214830A1 - 一种多级深度还原制备高熔点金属粉的方法 - Google Patents

一种多级深度还原制备高熔点金属粉的方法 Download PDF

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WO2018214830A1
WO2018214830A1 PCT/CN2018/087587 CN2018087587W WO2018214830A1 WO 2018214830 A1 WO2018214830 A1 WO 2018214830A1 CN 2018087587 W CN2018087587 W CN 2018087587W WO 2018214830 A1 WO2018214830 A1 WO 2018214830A1
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point metal
oxide
melting point
leaching
powder
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French (fr)
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张廷安
豆志河
刘燕
范世钢
张子木
吕国志
赵秋月
牛丽萍
傅大学
张伟光
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Northeastern University China
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Priority to US16/498,151 priority patent/US11241740B2/en
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid 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
    • C22B34/00—Obtaining refractory metals
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • 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
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • 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
    • 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
    • C22B5/18—Reducing step-by-step
    • 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
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention belongs to the technical field of milling in powder metallurgy process, and particularly relates to a method for preparing high-melting metal powder by multi-stage deep reduction.
  • High melting point metal also known as "refractory metal”. Generally referred to as tungsten, molybdenum, niobium, tantalum, vanadium, zirconium, and may also include niobium and tantalum. These metals are characterized by high melting point, high strength, and strong corrosion resistance. Most of them can form compounds with high melting point, high hardness and good chemical stability with carbon, nitrogen, silicon and boron.
  • Zirconium is a high melting point metal with a small thermal neutron capture cross section and outstanding nuclear properties. It is an indispensable material for the development of the atomic energy industry. It is one of the rare metal resources, its hardness is moderate, it is ductile, its thermal expansion coefficient is very small and it has high corrosion resistance. It is an indispensable strategic raw material for the development of electronics industry and space technology. Tungsten and molybdenum have high melting point and hard mass. Tungsten powder is the main raw material for processing powder metallurgy tungsten products and tungsten alloys. Molybdenum powder is widely used in the fields of paints, coatings and polymer additives. As a sputtering target additive in the semiconductor field, tantalum powder is also increasing in demand.
  • Vanadium powder is used in fast neutron reactor cladding materials, additives for making superconducting materials and special alloys. Tantalum powder can be used as a rocket propeller, and the cathode of an X-ray tube can be manufactured in the electrical industry. Niobium is the most important additive for high melting point alloys, and its alloys can be used as front-end protective layers for rocket nozzles and gliding re-entry vehicles. Niobium is an important high-melting point metal used in the manufacture of electric filaments, satellite and rocket casings, protective plates for atomic reactors, etc., and is used chemically as a catalyst.
  • the method uses sponge zirconium, titanium or zirconium as raw materials, and the raw material cost is high, and the preparation of high-grade zirconium powder is greatly affected by raw materials;
  • the zirconium block and the clam block are used as raw materials, and the metal powder produced by the mechanical method such as ball mill crushing and atomization method has high production cost and uneven particle size, and limits the large-scale application of vanadium powder, zirconium powder and tantalum powder.
  • the industrial production of tantalum powder is mainly based on the sodium heat method, that is, in the halides of Mg, Ca, Sr and Ba, the alkali metal Na and K are used to reduce the cerium oxide to prepare the tantalum powder.
  • the production cost is high and the product is sensitive to temperature. Therefore, after melting in the high temperature region of the direct manufacturing technology of the metal component, the thermal stress generated seriously affects the strength of the component.
  • the preparation process of tungsten powder and molybdenum powder is also prepared by the method of reducing oxide by hydrogen, and the requirements for equipment are high.
  • the production of tantalum powder is mainly carbon or metal reduction method, and the tantalum block must be hydrogenated and crushed first, and the process is complicated and the process is long. Tantalum powder is currently prepared by using KReO 4 and Re 2 O 7 as raw materials, adding KCl as an additive, and reducing by hydrogen. The introduction of hydrogen makes the process highly demanding on equipment and safety.
  • the intermediate product (combustion product) is obtained by one-time reduction by self-propagating rapid reaction, and then the intermediate product is subjected to multi-stage deep reduction to obtain a deep reduction product, and finally the deep reduction product is subjected to acid leaching and impurity removal to obtain tungsten, molybdenum, rhodium, ruthenium.
  • High melting point metal powder such as zirconium, vanadium, niobium and tantalum.
  • high-melting-point metal powders such as tungsten, molybdenum, niobium, tantalum, zirconium, vanadium, niobium and tantalum are prepared by multi-stage deep reduction method.
  • the metal oxide is used as raw material, the raw materials are easily obtained, and the cost is low.
  • it has the advantages of short process flow, no intermediate process, low cost and good product performance, so it is easier to achieve continuous.
  • the present invention provides a method for preparing high-melting metal powder by multi-stage deep reduction, and obtaining low-oxygen and high-melting metal powder products by self-propagating high-temperature synthesis, deep reduction and dilute acid leaching. .
  • the method is a method for preparing a high purity, fine, low oxygen, high melting point metal powder.
  • the method has the advantages of low raw material cost, simple operation, low requirements on process conditions and equipment, and lays a foundation for industrial production.
  • the obtained low-oxygen and high-melting metal powder has the advantages of high purity, controllable particle size distribution and high powder activity.
  • the method for preparing a high melting point metal powder by multistage deep reduction of the present invention is carried out according to the following steps:
  • the high-melting-point metal oxide powder is dried to obtain a dried high-melting-point metal oxide powder, and the dried high-melting-point metal oxide powder and the magnesium powder are mixed to obtain a mixture, and the mixture is added to the self-propagating reaction. furnace, self-propagating reaction, after cooling, the resulting refractory metal suboxide Me x O dispersed in the MgO matrix intermediate; wherein the refractory metal suboxide Me x O dispersed in the MgO matrix
  • the intermediate product is a mixture of non-stoichiometric low-valent high melting point metal oxides, with a value between 0.2 and 1;
  • the high melting point metal Me specifically one or more of W, Mo, Ta, Nb, V, Zr, Hf or Re;
  • the high melting point metal oxide is one or a mixture of WO 3 , MoO 3 , Ta 2 O 5 , Nb 2 O 5 , V 2 O 5 , ZrO 2 , HfO 2 , Re 2 O 7 ;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate to obtain a leachate and a leach product, the leach solution is removed, and the leach product is washed. And vacuum drying to obtain a low-cost high-melting-point metal low-oxide oxide Me x O precursor; wherein, the molar concentration of hydrochloric acid is 1 to 6 mol / L;
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate to obtain a filtrate and a filter residue, the filtrate is removed, the filter residue is washed, and vacuum dried to obtain a low-oxygen high-melting metal powder;
  • the molar concentration of hydrochloric acid is 1 to 6 mol / L;
  • the low-oxygen and high-melting-point metal powder contains a component and a mass percentage thereof: O ⁇ 0.8%, a high melting point metal Me ⁇ 99%, and the balance is an unavoidable impurity, and the particle size is between 5 and 60 ⁇ m.
  • the drying step is as follows: the high melting point metal oxide powder is placed in an oven and dried at 100 to 150 ° C for more than 24 hours.
  • the material mixing ratio is calculated separately from the above-mentioned ratio of Mg according to the kind of the high-melting-point metal oxide added.
  • the mixture is processed before being added to the self-propagating reactor, and is processed in one of two ways:
  • the first type the mixture is pressed at 10 to 60 MPa to obtain a bulk material, and the bulk material is added to the self-propagating reactor to perform a self-propagating reaction;
  • the second type without treatment, directly into the self-propagating reactor to carry out a self-propagating reaction.
  • the primary reduction product mainly composed of refractory metal monooxide is obtained by a single reduction reaction process in a self-propagating form, thereby saving energy consumption and suppressing the composite metal oxide impurities during the reduction reaction process. Generation.
  • the self-propagating reaction is initiated by a local ignition method and an integral heating method respectively.
  • the partial ignition method refers to heating the mixture with a heating wire in a self-propagating reactor to induce a self-propagating reaction;
  • the heating method refers to heating the mixture as a whole in a self-propagating reactor until the self-propagation reaction occurs, and the temperature is controlled at 500 to 750 °C.
  • the leaching temperature of the leaching intermediate product is 20 to 30 ° C, and the leaching time is 60 to 180 min.
  • the low-valent high-melting-point metal low-oxide oxide Me x O precursor contains a component and a mass percentage thereof: O: 5 to 20%, and unavoidable impurities ⁇ 0.5%.
  • the balance is a high melting point metal having a particle size of 0.8 to 15 ⁇ m.
  • the specific steps of the washing and vacuum drying are: washing the leaching product of the leaching solution with water until the washing liquid is neutral, and then drying in a vacuum oven under vacuum conditions, the temperature is 20 ⁇ . 30 ° C, the time is at least 24h;
  • the washing is washed with water, specifically by dynamic washing, that is, the washing liquid in the washing tank maintains a constant water level during the washing process, and how much fresh water is replenished and washed to neutrality.
  • the reaction parameter is that the temperature is raised under the condition of a vacuum degree of ⁇ 10 Pa.
  • the leaching depth reduction product has a leaching temperature of 20 to 30 ° C and a leaching time of 15 to 90 min.
  • the specific steps of the washing and vacuum drying are: washing the leaching product of the leaching solution with water until the washing liquid is neutral, and then drying in a vacuum oven under vacuum condition, the temperature is 20 ⁇ . 30 ° C, the time is at least 24h;
  • the washing is washed with water, specifically by dynamic washing, that is, the washing liquid in the washing tank maintains a constant water level during the washing process, and how much fresh water is replenished and washed to neutrality.
  • the self-propagating high-temperature synthesis process is used as a reduction reaction, and the chemical energy of the chemical reaction is fully utilized.
  • the self-propagating high-temperature synthesis process converts chemical energy into heat energy. Once the reaction is self-propagating, it can be self-sustained without additional energy. At the same time, the temperature gradient of the reaction is high, the activity of the product is high, and the particle size of the product is controllable. Since the self-propagating reaction temperature is high, Mg is vaporized during the reaction, resulting in loss of Mg. By adjusting the amount of magnesium compounded, the composition and phase of the Me x O product can be controlled.
  • Me a O b +yMg a/x Me x O+(ba/x)MgO+(y+a/xb)Mg
  • Me is a high melting point metal
  • a, b take different values according to the high melting point metal Me
  • x, y are the parameters in the stoichiometry of the chemical reaction
  • x is 0.2 to 1
  • y is based on x The number is adjusted.
  • the MgO impurity generated during the self-propagation reaction is loose, the product is easily broken, the MgO impurity has high reactivity, the intermediate Me x O exists in the form of particles or particle skeleton, and the MgO impurity is wrapped on the surface of Me x O or filled in the Me x O skeleton. Conducive to the leaching of dilute hydrochloric acid.
  • the process is efficient, energy-saving, short in process, low in equipment requirements, clean, efficient and safe production process, easy to industrialize.
  • This method can also be used to prepare other high melting point variable metal powders.
  • FIG. 1 is a process flow diagram of a method for preparing a high melting point metal powder by multistage deep reduction according to the present invention.
  • the high melting point metal oxide powder, magnesium powder, calcium powder, and hydrochloric acid used in the following examples are all industrial grade products.
  • the particle size of the high melting point metal oxide powder, magnesium powder and calcium powder is ⁇ 0.5 mm.
  • the self-propagating reactor used in the following examples is a self-propagating reactor disclosed in the patent "ZL200510047308.2", which consists of a reaction vessel, a heater, a sight glass, a transformer, a function recorder, a thermocouple, and a vent valve.
  • the time of the self-propagating reaction in the following examples was 5 to 90 s.
  • the drying time in the following examples was at least 24 h.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the tungsten oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain a dried tungsten oxide powder.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 25 ° C, and the leaching time is 120 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide W x O precursor; wherein the molar concentration of hydrochloric acid is 2 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 10-40% excess according to the reaction theory required;
  • the low-temperature, high-melting-point metal oxide W x O precursor contains components and mass percentages thereof: O: 12%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 25 ° C, the leaching time is 30 min, the filtrate and the filter residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 30 ° C for 24 h under vacuum to obtain a low-oxygen tungsten powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 5 to 30% of hydrochloric acid;
  • the low-oxygen tungsten powder contains components and mass percentages thereof: W is 99.3%, oxygen is 0.34%, and the balance is an unavoidable impurity, and the particle size is 38 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the tungsten oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain a dried tungsten oxide powder.
  • the mixture was mixed to obtain a mixture, and the mixture was pressed at 10 MPa to obtain a bulk material, which was added to a self-propagating reactor to initiate a self-propagating reaction by local ignition.
  • the temperature was controlled at 750 ° C, and after cooling, a high melting point metal was obtained.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 25 ° C, and the leaching time is 120 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide W x O precursor; wherein, the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of addition with the intermediate product is 10% of the excess of hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide W x O precursor contains components and mass percentages thereof: O: 20%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 25 ° C, and the leaching time was 15 min, and the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 30 ° C for 24 h under vacuum to obtain a low-oxygen tungsten powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 10% hydrochloric acid;
  • the low-oxygen tungsten powder contains components and mass percentages thereof: W is 99.5%, oxygen is 0.13%, and the balance is an unavoidable impurity, and the particle size is 28 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the tungsten oxide powder is placed in an oven and dried at 100 to 150 ° C for 24 hours to obtain a dried tungsten oxide powder.
  • the temperature is controlled at 650 ° C, and after cooling, a high melting point metal is obtained.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 25 ° C, and the leaching time is 60 min, and the leaching solution is obtained.
  • the low-temperature high-melting-point metal oxide W x O precursor contains components and mass percentages thereof: O: 5%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 20 ° C, the leaching time was 30 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen tungsten powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 30% hydrochloric acid;
  • the low-oxygen tungsten powder contains components and mass percentages thereof: W is 99.6%, oxygen is 0.09%, and the balance is an unavoidable impurity, and the particle size is 41 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the molybdenum oxide powder is placed in an oven and dried at 100-150 ° C for 24 h to obtain a dried molybdenum oxide powder.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 25 ° C, and the leaching time is 90 min, and the leaching solution is obtained. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 30 ° C for 24 h to obtain a low-cost high-melting metal oxide Mo x O precursor; wherein the molar concentration of hydrochloric acid is 4 mol / L, dilute hydrochloric acid The amount of addition with the intermediate product is 10% of the excess of hydrochloric acid required according to the reaction theory;
  • the low-temperature and high-melting-point metal oxide Mo x O precursor contains a component and a mass percentage thereof: O: 10%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size thereof is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 20 min, the filtrate and the filter residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen molybdenum powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 5 to 30% of hydrochloric acid;
  • the low-oxygen molybdenum powder contains components and mass percentages thereof: Mo is 99.0%, oxygen is 0.31%, and the balance is an unavoidable impurity, and the particle size is 28 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the molybdenum oxide powder is placed in an oven and dried at 100-150 ° C for 24 h to obtain dried molybdenum oxide powder.
  • the temperature is controlled at 700 ° C, and after cooling, a high melting point metal is obtained.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 25 ° C, and the leaching time is 100 min, and the leaching solution is obtained. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-cost high melting point metal oxide Mo x O precursor; wherein the molar concentration of hydrochloric acid is 2 mol / L, dilute hydrochloric acid The amount of addition with the intermediate product is 10% of the excess of hydrochloric acid required according to the reaction theory;
  • the low-temperature and high-melting-point metal oxide Mo x O precursor contains a component and a mass percentage thereof: O: 10%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size thereof is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 20-30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the leached product is dynamically used. Washing method, vacuum drying at 25 ° C for 24 h, to obtain low-oxygen molybdenum powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and deep reduction products added according to the reaction theory requires an excess of 5 to 30% of hydrochloric acid ;
  • the low-oxygen molybdenum powder contains components and mass percentages thereof: Mo is 99.2%, oxygen is 0.34%, and the balance is an unavoidable impurity, and the particle size is 33 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the molybdenum oxide powder is placed in an oven and dried at 100-150 ° C for 24 h to obtain a dried molybdenum oxide powder.
  • the temperature is controlled at 520 ° C, and after cooling, a high melting point metal is obtained.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, and the leaching time is 120 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide Mo x O precursor; wherein, the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 35% of the excess of hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Mo x O precursor contains components and mass percentages thereof: O: 12%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 20-30 ° C, the leaching time is 15 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed.
  • Method vacuum drying at 25 ° C for 24 h, to obtain low-oxygen molybdenum powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 5 to 30% hydrochloric acid;
  • the low-oxygen molybdenum powder contains components and mass percentages thereof: Mo is 99.4%, oxygen is 0.37%, and the balance is an unavoidable impurity, and the particle size is 44 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100 to 150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 720 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 20 ° C, and the leaching time is 60 min, and the leaching solution is obtained. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide Ta x O precursor; wherein, the molar concentration of hydrochloric acid is 6 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 15% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Ta x O precursor contains a component and a mass percentage thereof: O: 10%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 30 ° C, the leaching time was 15 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 25% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Ta is 99.1%, oxygen is 0.45%, and the balance is an unavoidable impurity, and the particle size is 22 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100 to 150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 600 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 24 ° C, and the leaching time is 90 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide Ta x O precursor; wherein the molar concentration of hydrochloric acid is 3 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 15% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Ta x O precursor contains a component and a mass percentage thereof: O: 10%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 20 ° C, the leaching time was 30 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 20 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 20% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Ta is 99.3%, oxygen is 0.25%, and the balance is an unavoidable impurity, and the particle size is 34 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100 to 150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 650 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 24 ° C, and the leaching time is 120 min to obtain a leaching solution. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide Ta x O precursor; wherein, the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 30% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Ta x O precursor contains a component and a mass percentage thereof: O: 20%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 20 ° C, the leaching time was 30 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 20 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 6 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 5% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Ta is 99.5%, oxygen is 0.25%, and the balance is an unavoidable impurity, and the particle size is 44 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 580 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 24 ° C, and the leaching time is 120 min to obtain a leaching solution. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-cost high-melting metal oxide Nb x O precursor; wherein, the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 30% by weight of the hydrochloric acid required according to the reaction theory;
  • the low melting point metal oxide is Nb x O precursor, and composition containing as mass percentages: O: 5%, inevitable impurities ⁇ 0.5%, the balance being a refractory metal, having a particle size in the Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 20 ° C, the leaching time was 30 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 30 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 20% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Nb is 99.5%, oxygen is 0.16%, and the balance is an unavoidable impurity, and the particle size is 42 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 700 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 24 ° C, and the leaching time is 90 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-cost high-melting metal oxide Nb x O precursor; wherein the molar concentration of hydrochloric acid is 3 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 30% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Nb x O precursor contains components and mass percentages thereof: O: 7%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 20 ° C, the leaching time is 90 min, the filtrate and the filter residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 20% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Nb is 99.2%, oxygen is 0.41%, and the balance is an unavoidable impurity, and the particle size is 46 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 700 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-melting-point metal Me x O of the high-melting-point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 24 ° C, and the leaching time is 80 min to obtain a leachate And leaching the product, removing the leachate, and drying the leached product in a dynamic washing manner at 20 ° C for 24 h to obtain an oxide Nb x O precursor of a low-cost high-melting metal; wherein the molar concentration of hydrochloric acid is 4 mol/L, dilute hydrochloric acid The amount of the intermediate product added is 30% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-melting and high-melting-point metal oxide Nb x O precursor contains a component and a mass percentage thereof: O: 18%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 30 ° C, the leaching time was 15 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 20 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 20% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Nb is 99.3%, oxygen is 0.22%, and the balance is an unavoidable impurity, and the particle size is 51 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the vanadium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain vanadium oxide powder after drying.
  • the temperature was controlled at 500 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric valence state high melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 24 ° C, and the leaching time is 120 min to obtain a leaching solution. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 25 ° C for 24 h to obtain a low-cost high-melting metal oxide V x O precursor; wherein, the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 40% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature and high-melting-point metal oxide V x O precursor contains a component and a mass percentage thereof: O: 6%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 20 ° C for 24 h under vacuum to obtain a low-oxygen vanadium powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 30% hydrochloric acid;
  • the low-oxygen vanadium powder contains components and mass percentages thereof: V is 99.5%, oxygen is 0.11%, and the balance is an unavoidable impurity, and the particle size is 42 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the vanadium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain vanadium oxide powder after drying.
  • the temperature was controlled at 750 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 25 ° C, and the leaching time is 90 min, and the leaching solution is obtained. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide V x O precursor; wherein the molar concentration of hydrochloric acid is 3 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 40% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature, high-melting-point metal oxide V x O precursor contains a component and a mass percentage thereof: O: 8%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 20 min, the filtrate and the filter residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen vanadium powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 30% hydrochloric acid;
  • the low-oxygen vanadium powder contains components and mass percentages thereof: V is 99.2%, oxygen is 0.41%, and the balance is an unavoidable impurity, and the particle size is 46 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the vanadium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain vanadium oxide powder after drying.
  • the temperature was controlled at 550 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-melting-point metal Me x O of the high-melting-point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 25 ° C, and the leaching time is 80 min, and the leaching solution is obtained.
  • the low-temperature high-melting-point metal oxide V x O precursor contains a component and a mass percentage thereof: O: 12%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 30 ° C, the leaching time was 15 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen vanadium powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 30% hydrochloric acid;
  • the low-oxygen vanadium powder contains components and mass percentages thereof: V is 99.2%, oxygen is 0.22%, and the balance is an unavoidable impurity, and the particle size is 51 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain cerium oxide powder after drying.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 20 ° C, and the leaching time is 180 min, and the leaching solution is obtained. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide Hf x O precursor; wherein the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 40% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-melting and high-melting-point metal oxide Hf x O precursor contains components and mass percentages thereof: O: 15%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 25 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 30% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Hf is 99.4%, oxygen is 0.12%, and the balance is an unavoidable impurity, and the particle size is 5 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 20 ° C, and the leaching time is 120 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 24 ° C for 24 h to obtain a low-temperature high-melting metal oxide Hf x O precursor; wherein the molar concentration of hydrochloric acid is 2 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 40% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-melting and high-melting-point metal oxide Hf x O precursor contains components and mass percentages thereof: O: 15%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 20 min, the filtrate and the filter residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 30 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 20% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Hf is 99.2%, oxygen is 0.27%, and the balance is an unavoidable impurity, and the particle size is 40 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 30 ° C, and the leaching time is 60 min, and the leaching solution is obtained.
  • the low-melting and high-melting-point metal oxide Hf x O precursor contains a component and a mass percentage thereof: O: 18%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 30 ° C, the leaching time was 15 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 24 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 20% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Hf is 99.4%, oxygen is 0.21%, and the balance is an unavoidable impurity, and the particle size is 60 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the zirconia powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried zirconia powder.
  • the temperature is controlled at 650 ° C, and after cooling, a high melting point metal is obtained.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 30 ° C, and the leaching time is 180 min, and the leaching solution is obtained. And leaching the product, removing the leachate, and leaching the product by dynamic washing at 22 ° C for 24 h to obtain a low-temperature high melting point metal oxide Zr x O precursor; wherein, the molar concentration of hydrochloric acid is 1 mol / L, dilute hydrochloric acid The amount of the intermediate product added is 40% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Zr x O precursor contains components and mass percentages thereof: O: 12%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 24 ° C for 24 h under vacuum to obtain a low-oxygen zirconium powder; wherein, the molar concentration of hydrochloric acid is 1 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 30% hydrochloric acid;
  • the low-oxygen zirconium powder contains components and mass percentages thereof: Zr is 99.5%, oxygen is 0.12%, and the balance is an unavoidable impurity, and the particle size is 36 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the zirconia powder is placed in an oven and dried at 100-150 ° C for 24 h to obtain a dried zirconia powder.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, and the leaching time is 120 min to obtain a leachate And leaching the product, removing the leachate, and leaching the product by dynamic washing at 20 ° C for 24 h to obtain a low-temperature high-melting metal oxide Zr x O precursor; wherein the molar concentration of hydrochloric acid is 2 mol / L, dilute hydrochloric acid The amount of addition with the intermediate product is 26% of the excess of hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Zr x O precursor contains components and mass percentages thereof: O: 5 to 20%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal.
  • the particle size is between 0.8 and 15 ⁇ m.
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 20 min, the filtrate and the filter residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 22 ° C for 24 h under vacuum to obtain a low-oxygen zirconium powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 15% hydrochloric acid;
  • the low-oxygen zirconium powder contains components and mass percentages thereof: Zr is 99.1%, oxygen is 0.35%, and the balance is an unavoidable impurity, and the particle size is 40 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the zirconia powder is placed in an oven and dried at 100-150 ° C for 24 h to obtain dried zirconia powder.
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 30 ° C, and the leaching time is 60 min, and the leaching solution is obtained.
  • the low-temperature high-melting-point metal oxide Zr x O precursor contains components and mass percentages thereof: O: 15%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the deep reduction product was placed in a closed reaction vessel, and the deep reduction product was leached with hydrochloric acid as a leachate, the leaching temperature was 30 ° C, the leaching time was 15 min, the filtrate and the residue were obtained, the filtrate was removed, and the filter residue was dynamically washed. Drying at 24 ° C for 24 h under vacuum to obtain a low-oxygen zirconium powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 25% hydrochloric acid;
  • the low-oxygen zirconium powder contains components and mass percentages thereof: Zr is 99.3%, oxygen is 0.21%, and the balance is an unavoidable impurity, and the particle size is 47 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 650 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 30 ° C, and the leaching time is 180 min, and the leaching solution is obtained.
  • the product and leaching, the leachate is removed, the leached product was washed with a dynamic manner, and dried in vacuo 20 °C 24h, to obtain an oxide of the low melting point metal precursor Re x O; wherein the molar concentration of hydrochloric acid is 1mol / L, diluted hydrochloric acid
  • the amount of the intermediate product added is 12% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature high-melting-point metal oxide Re x O precursor contains a component and a mass percentage thereof: O: 5%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the refractory metal oxide of low Re x O calcium powder mixed with the precursors, the lower pressing 10MPa, to obtain a massive blank, the blank block placed in a vacuum reduction furnace, heated at a degree of vacuum of ⁇ 10Pa The temperature is raised to 700 ° C, and the second deep reduction is carried out for 6 h. After the second deep reduction, the block blank is obtained, and the block blank is cooled with the furnace to obtain a deep reduction product; wherein the molar ratio is Re x O:Ca 1:1.5;
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 20 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 15% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Re is 99.5%, oxygen is 0.12%, and the balance is an unavoidable impurity, and the particle size is 37 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 650 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, and the leaching time is 100 min to obtain a leachate the product and leaching, the leachate is removed, the leached product was washed with a dynamic manner, and dried in vacuo to 30 deg.] C 24h, to obtain an oxide of the low melting point metal precursor Re x O; wherein the molar concentration of hydrochloric acid was 4mol / L, diluted hydrochloric acid The amount of the intermediate product added is 30% by weight of the hydrochloric acid required according to the reaction theory;
  • the low-temperature and high-melting-point metal oxide Re x O precursor contains a component and a mass percentage thereof: O: 12%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size thereof is Between 0.8 and 15 ⁇ m.
  • the refractory metal oxide of low Re x O calcium powder mixed with the precursors, the lower pressing 2MPa, to obtain a massive blank, the blank block placed in a vacuum reduction furnace, heated at a degree of vacuum of ⁇ 10Pa The temperature is raised to 900 ° C, subjected to secondary deep reduction for 4 h, after the second deep reduction, the block blank is obtained, and the block blank is cooled with the furnace to obtain a deep reduction product; wherein, the molar ratio is Re x O: Ca 1:2;
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 26 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 2 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 25% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Re is 99.2%, oxygen is 0.25%, and the balance is an unavoidable impurity, and the particle size is 45 ⁇ m.
  • a method for preparing a high melting point metal powder by multistage deep reduction is carried out as follows:
  • the cerium oxide powder is placed in an oven and dried at 100-150 ° C for 24 hours to obtain dried cerium oxide powder.
  • the temperature was controlled at 650 ° C, and after cooling, a high melting point was obtained.
  • metal suboxides Me x O dispersed in the MgO matrix intermediate wherein the refractory metal suboxide Me x O dispersed in the MgO matrix intermediate non-stoichiometric state low melting point a mixture of metal oxides, x having a value between 0.2 and 1;
  • the intermediate product in which the low-oxide oxide Me x O of the high melting point metal is dispersed in the MgO matrix is placed in a closed reaction vessel, and the intermediate product is leached with hydrochloric acid as a leaching solution, the leaching temperature is 30 ° C, and the leaching time is 80 min, and the leaching solution is obtained.
  • the low-temperature high-melting-point metal oxide Re x O precursor contains components and mass percentages thereof: O: 20%, unavoidable impurities ⁇ 0.5%, and the balance is a high melting point metal, and the particle size is Between 0.8 and 15 ⁇ m.
  • the refractory metal oxide of low Re x O calcium powder mixed with the precursors, the lower pressing 15MPa, to obtain a massive blank, the blank block placed in a vacuum reduction furnace, heated at a degree of vacuum of ⁇ 10Pa The temperature is raised to 1100 ° C, and the second deep reduction is carried out for 2 h. After the second deep reduction, the block blank is obtained, and the block blank is cooled with the furnace to obtain a deep reduction product; wherein the molar ratio is Re x O:Ca 1:2;
  • the deep reduction product is placed in a closed reaction vessel, and the deep reduction product is leached with hydrochloric acid as a leachate, the leaching temperature is 30 ° C, the leaching time is 30 min, the filtrate and the residue are obtained, the filtrate is removed, and the filter residue is dynamically washed. Drying at 26 ° C for 24 h under vacuum to obtain a low-oxygen tantalum powder; wherein, the molar concentration of hydrochloric acid is 3 mol / L, the amount of dilute hydrochloric acid and the deep reduction product added according to the reaction theory requires an excess of 25% hydrochloric acid;
  • the low-oxygen niobium powder contains components and mass percentages thereof: Re is 99.3%, oxygen is 0.21%, and the balance is an unavoidable impurity, and the particle size is 47 ⁇ m.

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Abstract

一种多级深度还原制备高熔点金属粉的方法，包括：将烘干后的高熔点金属氧化物粉和镁粉混合，进行自蔓延反应，高熔点金属Me，具体为W、Mo、Ta、Nb、V、Zr、Hf或Re中的一种或几种；将中间产物置于密闭反应釜中，以盐酸为浸出液进行浸出，得到低价高熔点金属的低价氧化物MexO前驱体；与钙粉混合均匀，压制，置于真空还原炉中，加热升温至700～1200℃，深度还原1～6h，以盐酸为浸出液对深度还原产物进行浸出，经处理，得到高熔点金属粉。

Description

一种多级深度还原制备高熔点金属粉的方法 技术领域
本发明属于粉末冶金工艺中的制粉技术领域，特别涉及了一种多级深度还原制备高熔点金属粉的方法。
背景技术
高熔点金属，亦称“难熔金属”。通常指钨、钼、铌、钽、钒、锆，也可以包括铪和铼。这类金属的特点为熔点高、强度大、抗蚀性强，多数能同碳、氮、硅、硼等生成高熔点、高硬度并具有良好化学稳定性的化合物。
锆是一种高熔点金属，其热中子俘获截面小，有突出的核性能，是发展原子能工业不可缺少的材料。钽是稀有金属资源之一，其硬度适中，富有延展性，其热膨胀系数很小并具有极高的抗腐蚀性，是电子工业和空间技术发展不可缺少的战略原料。钨、钼熔点高、质硬，钨粉是加工粉末冶金钨制品和钨合金的主要原料，钼粉广泛应用油漆、涂料、聚合物添加剂领域。铌粉作为半导体领域的溅射靶材添加剂，其需求量也日益增加。钒粉用于快中子反应堆包套材料、制作超导材料和特种合金的添加剂。铪粉可作火箭的推进器，在电器工业上可制造X射线管的阴极。铪是高熔点合金最重要的添加剂，其合金可作火箭喷嘴和滑翔式重返大气层的飞行器的前沿保护层。铼是一种重要的高熔点金属，用来制造电灯丝、人造卫星和火箭的外壳、原子反应堆的防护板等，化学上用做催化剂。
目前锆粉的大规模生产仍以氢化-脱氢法为主，该方法要以海绵锆、钛或锆屑为原料，原料成本较高且制备高品级锆粉受原料影响大；而以钒块、锆块、铪块为原料，以球磨破碎和雾化法等机械法生产的金属粉体生产成本高、粒度不均匀，限制了钒粉、锆粉、铪粉的大规模应用。目前钽粉的工业生产以钠热法为主，即在有Mg、Ca、Sr、Ba的卤化物中，采用碱金属Na、K还原氧化钽制取钽粉。但生产成本高、产品对温度敏感性大，因此在金属构件直接制造技术的高温区熔后，产生的热应力严重影响构件的强度。目前钨粉、钼粉的制备工艺还以氢还原氧化物的方法制备，对设备的要求高。铌粉的生产以碳或金属还原法为主，须先将铌块氢化破碎，工艺复杂，流程长。铼粉目前以KReO 4和Re 2O 7为原料，添加KCl为添加剂，用氢气还原制备。氢气的引入使工艺对设备和安全的要求高。
针对现有钨、钼、钽、铌、锆、钒、铪、铼等高熔点金属粉体制备方法存在的技术难题，本方法在系统分析钨、钼、钽、铌、锆、钒、铪、铼等高熔点金属的氧化物还原过程中价态演变规律，提出了多级深度热还原直接制备钨、钼、钽、铌、锆、钒、铪、铼等高熔点金属 粉的新思路，即首先以自蔓延快速反应进行一次还原得到中间产物(燃烧产物)，然后将中间产物进行多级深度还原得到深度还原产物，最后将深度还原产物进行酸浸除杂提纯得到钨、钼、钽、铌、锆、钒、铪、铼等高熔点金属粉。
同时以多级深度还原法制取钨、钼、钽、铌、锆、钒、铪、铼等高熔点金属粉，以金属氧化物为原料，原料易获得，成本低。同时具有工艺流程短、无中间工序、成本低、产品性能好的优点，因此更易实现连续化。多级金属热还原法制备钨、钼、钽、铌、锆、钒、铪、铼等高熔点金属粉是最具发展潜力的难熔金属粉体制备工艺之一，符合降低原材料成本、节约能源的国民经济发展战略，这一技术的工业化经济效益和社会效益都十分可观。
发明内容
针对现有技术制备难熔金属粉体的缺点，本发明提供一种多级深度还原制备高熔点金属粉的方法，通过自蔓延高温合成、深度还原及稀酸浸出获得低氧高熔点金属粉产品。该方法是一种制备高纯度、微细、低氧高熔点金属粉的方法。该方法原料成本低，操作简单，对工艺条件和仪器设备要求低，为工业化生产奠定了基础，所得的低氧高熔点金属粉具有纯度高，粒度分布可控，粉末活性高等优点。
本发明的一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将高熔点金属氧化物粉，烘干，得到烘干后的高熔点金属氧化物粉，将烘干后的高熔点金属氧化物粉和镁粉混合，得到混合物料，将混合物料加入自蔓延反应炉中，进行自蔓延反应，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
所述的高熔点金属Me，具体为W、Mo、Ta、Nb、V、Zr、Hf或Re中的一种或几种；
所述的高熔点金属氧化物为WO 3、MoO 3、Ta 2O 5、Nb 2O 5、V 2O 5、ZrO 2、HfO 2、Re 2O 7中的一种或几种混合；
当高熔点金属的氧化物为WO 3时，物料混合比例按摩尔比为WO 3:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为MoO 3时，物料混合比例按摩尔比为MoO 3:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为Ta 2O 5时，物料混合比例按摩尔比为Ta 2O 5:Mg＝1:(2.7～3.3)；当高熔点金属的氧化物为Nb 2O 5时，物料混合比例按摩尔比为Nb 2O 5:Mg＝1:(2.7～3.3)；当高熔点金属的氧化物为V 2O 5时，物料混合比例按摩尔比为V 2O 5:Mg＝1:(2.7～3.3)；当高熔点金属的氧化物为ZrO 2时，物料混合比例按摩尔比为ZrO 2:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为HfO 2时，物料混合比例按摩尔比为HfO 2:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为Re 2O 7时， 物料混合比例按摩尔比为Re 2O 7:Mg＝1:(2.7～3.3)；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，得到浸出液和浸出产物，去除浸出液，将浸出产物洗涤、真空干燥，得到低价高熔点金属的低价氧化物Me xO前驱体；其中，盐酸的摩尔浓度为1～6mol/L；
步骤3，多级深度还原
将低价高熔点金属的低价氧化物Me xO前驱体与钙粉混合均匀，在2～20MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，加热升温至700～1200℃，进行二次深度还原1～6h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Me xO：Ca＝1：(1.5～3)；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，得到滤液和滤渣，除去滤液，将滤渣洗涤、真空干燥，得到低氧的高熔点金属粉；其中，盐酸的摩尔浓度为1～6mol/L；
所述的低氧高熔点金属粉，含有的成分及其质量百分比为：O≤0.8％，高熔点金属Me≥99％，余量为不可避免的杂质，其粒度在5～60μm之间。
所述的步骤1中，所述的烘干，其具体操作步骤为：将高熔点金属氧化物粉置于烘箱中在100～150℃烘干24h以上。
所述的步骤1中，当为几种混合时，物料混合比例按照加入的高熔点金属氧化物的种类按上述比例与Mg单独进行计算。
所述的步骤1中，所述的混合物料加入自蔓延反应炉前，经以下两种方式之一进行处理：
第一种：将混合物料在10～60MPa下压制，得到块状坯料，将块状坯料加入自蔓延反应炉中，进行自蔓延反应；
第二种：不经过处理，直接加入自蔓延反应炉中，进行自蔓延反应。
所述的步骤1中，以自蔓延形式体现的一次还原反应过程，得到难熔金属一氧化物为主的中间产物，这样做节约能耗，同时能抑制还原反应过程中，复合金属氧化物杂质的生成。
所述的步骤1中，所述的自蔓延反应的引发方式分别局部点火法和整体加热法，局部点火法是指在自蔓延反应炉中用电热丝加热混合物料局部，引发自蔓延反应；整体加热法是指在自蔓延反应炉中将混合物料整体升温，直至自蔓延反应发生为止，温度控制在500～750℃。
所述的步骤2中，所述的对中间产物进行浸出时，稀盐酸与中间产物的加入量根据反应 理论需要的盐酸过量10～40％配比，反应所依据的化学方程式为MgO+2H +＝Mg 2++H 2O。
所述的步骤2中，浸出中间产物的浸出温度为20～30℃，浸出时间为60～180min。
所述的步骤2中，所述的低价高熔点金属的低价氧化物Me xO前驱体，其含有的成分及其质量百分比为：O：5～20％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度为0.8～15μm。
所述的步骤2中，所述的洗涤、真空干燥的具体步骤为：将去除浸出液的浸出产物用水洗涤至洗液为中性，然后在真空烘箱中在真空条件下烘干，温度为20～30℃，时间至少为24h；
所述洗涤为用水洗涤，具体为采用动态洗涤，即洗涤过程中洗涤槽中洗液保持恒定水位，有多少洗液排出就有多少新鲜水补充，洗涤至中性。
所述的步骤3中，所述的二次深度还原，其反应参数为，在真空度≤10Pa的条件下升温。
所述的步骤4中，所述的浸出深度还原产物时，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量5～30％配比，反应所依据的化学方程式为CaO+2H +＝Ca 2++H 2O。
所述的步骤4中，所述的浸出深度还原产物的浸出温度为20～30℃，浸出时间为15～90min。
所述的步骤4中，所述的洗涤、真空干燥的具体步骤为：将去除浸出液的浸出产物用水洗涤至洗液为中性，然后在真空烘箱中在真空条件下烘干，温度为20～30℃，时间至少为24h；
所述洗涤为用水洗涤，具体为采用动态洗涤，即洗涤过程中洗涤槽中洗液保持恒定水位，有多少洗液排出就有多少新鲜水补充，洗涤至中性。
本发明的一种多级深度还原制备高熔点金属粉的方法，其原理及优势在于：
(1)利用高熔点金属的氧化物在还原过程中的价态演变规律，将自蔓延高温合成过程作为一次还原反应，充分利用化学反应的化学能。自蔓延高温合成过程将化学能转化为热能，反应一经引发自行蔓延，无需外加能量即可自我维持，同时反应的温度梯度高，产物的活性高，产品的粒度可控。由于自蔓延反应温度很高，在反应过程中Mg会发生气化，造成Mg的损失。通过调控镁的配料量，可以控制Me xO产物的成分和物相。
自蔓延高温合成反应的方程式为：
Me aO b+yMg＝a/x Me xO+(b-a/x)MgO+(y+a/x-b)Mg
其中，Me为高熔点金属，a、b根据高熔点金属Me的不同取不同的值，x、y为化学反应配平过程中，化学计量数中的参数，x为0.2～1，y根据x的数进行调整。
自蔓延反应过程中生成的MgO杂质疏松，产物易于破碎，MgO杂质反应活性高，中间产物Me xO为颗粒或颗粒骨架形式存在，MgO杂质包裹在Me xO表面或填充在Me xO骨架中，利于稀盐酸的浸出。
(2)在浸出过程中为保证MgO完全去除，需将盐酸过量，同时为保证洗涤效果，在洗涤过程中采用动态循环洗涤，即洗涤过程中洗涤槽中洗液保持恒定水位，有多少洗液排出就有 多少新鲜水补充，洗涤至中性。为了保证浸出效率并防止中间产物氧化，浸出过程需在密闭釜中进行。
(3)为保证彻底脱氧，得到低氧高纯还原钛粉，提出了多级深度还原脱氧的理念，即采用比自蔓延高温还原时采用的镁还原剂还原性更强的钙对自蔓延高温还原得到的低价金属氧化物前驱体进行深度还原脱氧，保证了还原脱氧效果。
深度还原反应的化学反应方程式为：Me xO+xCa＝Me+xCaO；其中，x为0.2～1。
(4)本工艺高效、节能、流程短、对设备要求低，是清洁高效安全的生产工艺，易于工业推广。该方法同样可以用来制备其他高熔点变价金属粉体。
附图说明
图1为本发明多级深度还原制备高熔点金属粉方法的工艺流程图。
具体实施方式
下面结合实施例对本发明作进一步的详细说明。
以下实施例中采用的高熔点金属氧化物粉、镁粉、钙粉、盐酸均为工业级产品。高熔点金属氧化物粉、镁粉、钙粉的粒度均≤0.5mm。
以下实施例中采用的自蔓延反应炉为专利“ZL200510047308.2”公开的自蔓延反应炉，该反应炉由反应容器、加热器、窥视镜、变压器、函数记录仪、热电偶、通气阀门构成。
以下实施例中自蔓延反应的时间为5～90s。
以下实施例中烘干时间为至少24h。
以下实施例中，多级深度还原制备高熔点金属粉方法的工艺流程图见图1。
实施例1
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钨粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钨粉，将烘干后的氧化钨粉和镁粉按摩尔比为WO 3：Mg＝1：1混合，得到混合物料，将混合物料在20MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在500℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为120min，得到浸出液和浸 出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物W xO前驱体；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量10～40％配比；
所述的低价高熔点金属的氧化物W xO前驱体，其含有的成分及其质量百分比为：O：12％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物W xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为W xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为25℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在30℃真空干燥24h，得到低氧的钨粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量5～30％配比；
所述的低氧的钨粉，含有的成分及其质量百分比为：W为99.3％，氧为0.34％，余量为不可避免的杂质，其粒度在38μm。
实施例2
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钨粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钨粉，将烘干后的氧化钨粉和镁粉按摩尔比为WO 3：Mg＝1：1.2混合，得到混合物料，将混合物料在10MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在750℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物W xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入 量根据反应理论需要的盐酸过量10％配比；
所述的低价高熔点金属的氧化物W xO前驱体，其含有的成分及其质量百分比为：O：20％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物W xO前驱体与钙粉混合均匀，在10MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为W xO：Ca＝1：2.2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为25℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在30℃真空干燥24h，得到低氧的钨粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量10％配比；
所述的低氧的钨粉，含有的成分及其质量百分比为：W为99.5％，氧为0.13％，余量为不可避免的杂质，其粒度在28μm。
实施例3
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钨粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钨粉，将烘干后的氧化钨粉和镁粉按摩尔比为WO 3：Mg＝1：0.8混合，得到混合物料，将混合物料在60MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为60min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在30℃真空干燥24h，得到低价高熔点金属的氧化物W xO前驱体；其中，盐酸的摩尔浓度为6mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量10％配比；
所述的低价高熔点金属的氧化物W xO前驱体，其含有的成分及其质量百分比为：O：5％， 不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物W xO前驱体与钙粉混合均匀，在15MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1100℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为W xO：Ca＝1：3；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钨粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低氧的钨粉，含有的成分及其质量百分比为：W为99.6％，氧为0.09％，余量为不可避免的杂质，其粒度在41μm。
实施例4
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钼粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钼粉，将烘干后的氧化钼粉和镁粉按摩尔比为MoO 3：Mg＝1：1.1混合，得到混合物料，将混合物料在20MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在550℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为90min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在30℃真空干燥24h，得到低价高熔点金属的氧化物Mo xO前驱体；其中，盐酸的摩尔浓度为4mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量10％配比；
所述的低价高熔点金属的氧化物Mo xO前驱体，其含有的成分及其质量百分比为：O：10％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Mo xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Mo xO：Ca＝1：2.4；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为20min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钼粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量5～30％配比；
所述的低氧的钼粉，含有的成分及其质量百分比为：Mo为99.0％，氧为0.31％，余量为不可避免的杂质，其粒度在28μm。
实施例5
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钼粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钼粉，将烘干后的氧化钼粉和镁粉按摩尔比为MoO 3：Mg＝1：0.8混合，得到混合物料，将混合物料在40MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在700℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为100min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Mo xO前驱体；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量10％配比；
所述的低价高熔点金属的氧化物Mo xO前驱体，其含有的成分及其质量百分比为：O：10％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Mo xO前驱体与钙粉混合均匀，在15MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二 次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Mo xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20～30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将浸出产物采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钼粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量5～30％配比；
所述的低氧的钼粉，含有的成分及其质量百分比为：Mo为99.2％，氧为0.34％，余量为不可避免的杂质，其粒度在33μm。
实施例6
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钼粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钼粉，将烘干后的氧化钼粉和镁粉按摩尔比为MoO 3：Mg＝1：1混合，得到混合物料，将混合物料在30MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在520℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Mo xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量35％配比；
所述的低价高熔点金属的氧化物Mo xO前驱体，其含有的成分及其质量百分比为：O：12％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Mo xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1100℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Mo xO：Ca＝1：3；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20～30℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钼粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量5～30％配比；
所述的低氧的钼粉，含有的成分及其质量百分比为：Mo为99.4％，氧为0.37％，余量为不可避免的杂质，其粒度在44μm。
实施例7
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钽粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钽粉，将烘干后的氧化钽粉和镁粉按摩尔比为Ta 2O 5：Mg＝1：3混合，得到混合物料，将混合物料在20MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在720℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为20℃，浸出时间为60min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Ta xO前驱体；其中，盐酸的摩尔浓度为6mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量15％配比；
所述的低价高熔点金属的氧化物Ta xO前驱体，其含有的成分及其质量百分比为：O：10％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Ta xO前驱体与钙粉混合均匀，在20MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至800℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Ta xO：Ca＝1：1.5；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出 温度为30℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钽粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量25％配比；
所述的低氧的钽粉，含有的成分及其质量百分比为：Ta为99.1％，氧为0.45％，余量为不可避免的杂质，其粒度在22μm。
实施例8
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钽粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钽粉，将烘干后的氧化钽粉和镁粉按摩尔比为Ta 2O 5：Mg＝1：3.2混合，得到混合物料，将混合物料在40MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在600℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为24℃，浸出时间为90min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Ta xO前驱体；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量15％配比；
所述的低价高熔点金属的氧化物Ta xO前驱体，其含有的成分及其质量百分比为：O：10％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Ta xO前驱体与钙粉混合均匀，在10MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Ta xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在20℃真空干燥24h，得到低氧的钽粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还 原产物的加入量根据反应理论需要的盐酸过量20％配比；
所述的低氧的钽粉，含有的成分及其质量百分比为：Ta为99.3％，氧为0.25％，余量为不可避免的杂质，其粒度在34μm。
实施例9
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钽粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钽粉，将烘干后的氧化钽粉和镁粉按摩尔比为Ta 2O 5：Mg＝1：2.8混合，得到混合物料，将混合物料在20MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为24℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Ta xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低价高熔点金属的氧化物Ta xO前驱体，其含有的成分及其质量百分比为：O：20％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Ta xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Ta xO：Ca＝1：2.5；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在20℃真空干燥24h，得到低氧的钽粉；其中，盐酸的摩尔浓度为6mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量5％配比；
所述的低氧的钽粉，含有的成分及其质量百分比为：Ta为99.5％，氧为0.25％，余量为 不可避免的杂质，其粒度在44μm。
实施例10
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铌粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铌粉，将烘干后的氧化铌粉和镁粉按摩尔比为Nb 2O 5：Mg＝1：3混合，得到混合物料，将混合物料在10MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在580℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为24℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Nb xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低价高熔点金属的氧化物Nb xO前驱体，其含有的成分及其质量百分比为：O：5％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Nb xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Nb xO：Ca＝1：2.2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在30℃真空干燥24h，得到低氧的铌粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量20％配比；
所述的低氧的铌粉，含有的成分及其质量百分比为：Nb为99.5％，氧为0.16％，余量为不可避免的杂质，其粒度在42μm。
实施例11
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铌粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铌粉，将烘干后的氧化铌粉和镁粉按摩尔比为Nb 2O 5：Mg＝1：2.8混合，得到混合物料，将混合物料在30MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在700℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为24℃，浸出时间为90min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Nb xO前驱体；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低价高熔点金属的氧化物Nb xO前驱体，其含有的成分及其质量百分比为：O：7％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Nb xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Nb xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为20℃，浸出时间为90min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的铌粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量20％配比；
所述的低氧的铌粉，含有的成分及其质量百分比为：Nb为99.2％，氧为0.41％，余量为不可避免的杂质，其粒度在46μm。
实施例12
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铌粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铌粉，将烘干后的氧化铌粉和镁粉按摩尔比为Nb 2O 5：Mg＝1：3.1混合，得到混合物料，将混合物料在50MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在700℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为24℃，浸出时间为80min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Nb xO前驱体；其中，盐酸的摩尔浓度为4mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低价高熔点金属的氧化物Nb xO前驱体，其含有的成分及其质量百分比为：O：18％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Nb xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Nb xO：Ca＝1：3；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在20℃真空干燥24h，得到低氧的铌粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量20％配比；
所述的低氧的铌粉，含有的成分及其质量百分比为：Nb为99.3％，氧为0.22％，余量为不可避免的杂质，其粒度在51μm。
实施例13
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钒粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钒粉，将烘干后的氧化钒粉和镁粉按摩尔比为V 2O 5：Mg＝1：3混合，得到混合物料，将混合物料在10MPa下压 制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在500℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为24℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在25℃真空干燥24h，得到低价高熔点金属的氧化物V xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量40％配比；
所述的低价高熔点金属的氧化物V xO前驱体，其含有的成分及其质量百分比为：O：6％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物V xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为V xO：Ca＝1：2.2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在20℃真空干燥24h，得到低氧的钒粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低氧的钒粉，含有的成分及其质量百分比为：V为99.5％，氧为0.11％，余量为不可避免的杂质，其粒度在42μm。
实施例14
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钒粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钒粉，将烘干后的氧化钒粉和镁粉按摩尔比为V 2O 5：Mg＝1：2.7混合，得到混合物料，将混合物料在30MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在750℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其 中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为90min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物V xO前驱体；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量40％配比；
所述的低价高熔点金属的氧化物V xO前驱体，其含有的成分及其质量百分比为：O：8％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物V xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为V xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为20min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钒粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低氧的钒粉，含有的成分及其质量百分比为：V为99.2％，氧为0.41％，余量为不可避免的杂质，其粒度在46μm。
实施例15
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化钒粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化钒粉，将烘干后的氧化钒粉和镁粉按摩尔比为V 2O 5：Mg＝1：2.8混合，得到混合物料，将混合物料在50MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在550℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为25℃，浸出时间为80min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物V xO前驱体；其中，盐酸的摩尔浓度为4mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量40％配比；
所述的低价高熔点金属的氧化物V xO前驱体，其含有的成分及其质量百分比为：O：12％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物V xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为V xO：Ca＝1：3；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的钒粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低氧的钒粉，含有的成分及其质量百分比为：V为99.2％，氧为0.22％，余量为不可避免的杂质，其粒度在51μm。
实施例16
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铪粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铪粉，将烘干后的氧化铪粉和镁粉按摩尔比为HfO 2：Mg＝1：1混合，得到混合物料，将混合物料在30MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在600℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以 盐酸为浸出液对中间产物进行浸出，浸出温度为20℃，浸出时间为180min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Hf xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量40％配比；
所述的低价高熔点金属的氧化物Hf xO前驱体，其含有的成分及其质量百分比为：O：15％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Hf xO前驱体与钙粉混合均匀，在10MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Hf xO：Ca＝1：1.6；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在25℃真空干燥24h，得到低氧的铪粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低氧的铪粉，含有的成分及其质量百分比为：Hf为99.4％，氧为0.12％，余量为不可避免的杂质，其粒度在5μm。
实施例17
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铪粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铪粉，将烘干后的氧化铪粉和镁粉按摩尔比为HfO 2：Mg＝1：1.2混合，得到混合物料，将混合物料在10MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在600℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为20℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在24℃真空干燥24h，得到低价高熔 点金属的氧化物Hf xO前驱体；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量40％配比；
所述的低价高熔点金属的氧化物Hf xO前驱体，其含有的成分及其质量百分比为：O：15％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Hf xO前驱体与钙粉混合均匀，在15MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Hf xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为20min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在30℃真空干燥24h，得到低氧的铪粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量20％配比；
所述的低氧的铪粉，含有的成分及其质量百分比为：Hf为99.2％，氧为0.27％，余量为不可避免的杂质，其粒度在40μm。
实施例18
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铪粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铪粉，将烘干后的氧化铪粉和镁粉按摩尔比为HfO 2：Mg＝1：0.9混合，得到混合物料，将混合物料在50MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为60min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Hf xO前驱体；其中，盐酸的摩尔浓度为6mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量10％配比；
所述的低价高熔点金属的氧化物Hf xO前驱体，其含有的成分及其质量百分比为：O：18％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Hf xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1200℃，进行二次深度还原1h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Hf xO：Ca＝1：1.8；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在24℃真空干燥24h，得到低氧的铪粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量20％配比；
所述的低氧的铪粉，含有的成分及其质量百分比为：Hf为99.4％，氧为0.21％，余量为不可避免的杂质，其粒度在60μm。
实施例19
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化锆粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化锆粉，将烘干后的氧化锆粉和镁粉按摩尔比为ZrO 2：Mg＝1：1混合，得到混合物料，将混合物料在30MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为180min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在22℃真空干燥24h，得到低价高熔点金属的氧化物Zr xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量40％配比；
所述的低价高熔点金属的氧化物Zr xO前驱体，其含有的成分及其质量百分比为：O：12％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Zr xO前驱体与钙粉混合均匀，在10MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1000℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Zr xO：Ca＝1：1.5；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在24℃真空干燥24h，得到低氧的锆粉；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低氧的锆粉，含有的成分及其质量百分比为：Zr为99.5％，氧为0.12％，余量为不可避免的杂质，其粒度在36μm。
实施例20
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化锆粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化锆粉，将烘干后的氧化锆粉和镁粉按摩尔比为ZrO 2：Mg＝1：1.2混合，得到混合物料，将混合物料直接加入自蔓延反应炉中，以整体加热的方式引发自蔓延反应，温度控制在550℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为120min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Zr xO前驱体；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量26％配比；
所述的低价高熔点金属的氧化物Zr xO前驱体，其含有的成分及其质量百分比为：O：5～20％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Zr xO前驱体与钙粉混合均匀，在20MPa下压制，得到块状 坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原3h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Zr xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为20min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在22℃真空干燥24h，得到低氧的锆粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量15％配比；
所述的低氧的锆粉，含有的成分及其质量百分比为：Zr为99.1％，氧为0.35％，余量为不可避免的杂质，其粒度在40μm。
实施例21
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化锆粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化锆粉，将烘干后的氧化锆粉和镁粉按摩尔比为ZrO 2：Mg＝1：0.8混合，得到混合物料，将混合物料在50MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在570℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为60min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在30℃真空干燥24h，得到低价高熔点金属的氧化物Zr xO前驱体；其中，盐酸的摩尔浓度为6mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量12％配比；
所述的低价高熔点金属的氧化物Zr xO前驱体，其含有的成分及其质量百分比为：O：15％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Zr xO前驱体与钙粉混合均匀，在5MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1100℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按 摩尔比为Zr xO：Ca＝1：1.8；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为15min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在24℃真空干燥24h，得到低氧的锆粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量25％配比；
所述的低氧的锆粉，含有的成分及其质量百分比为：Zr为99.3％，氧为0.21％，余量为不可避免的杂质，其粒度在47μm。
实施例22
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铼粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铼粉，将烘干后的氧化铼粉和镁粉按摩尔比为Re 2O 7：Mg＝1：3混合，得到混合物料，将混合物料在40MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为180min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在20℃真空干燥24h，得到低价高熔点金属的氧化物Re xO前驱体；其中，盐酸的摩尔浓度为1mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量12％配比；
所述的低价高熔点金属的氧化物Re xO前驱体，其含有的成分及其质量百分比为：O：5％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Re xO前驱体与钙粉混合均匀，在10MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至700℃，进行二次深度还原6h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Re xO：Ca＝1：1.5；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在20℃真空干燥24h，得到低氧的铼粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量15％配比；
所述的低氧的铼粉，含有的成分及其质量百分比为：Re为99.5％，氧为0.12％，余量为不可避免的杂质，其粒度在37μm。
实施例23
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铼粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铼粉，将烘干后的氧化铼粉和镁粉按摩尔比为Re 2O 7：Mg＝1：2.9混合，得到混合物料，将混合物料在30MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为100min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在30℃真空干燥24h，得到低价高熔点金属的氧化物Re xO前驱体；其中，盐酸的摩尔浓度为4mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量30％配比；
所述的低价高熔点金属的氧化物Re xO前驱体，其含有的成分及其质量百分比为：O：12％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Re xO前驱体与钙粉混合均匀，在2MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至900℃，进行二次深度还原4h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Re xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、 在26℃真空干燥24h，得到低氧的铼粉；其中，盐酸的摩尔浓度为2mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量25％配比；
所述的低氧的铼粉，含有的成分及其质量百分比为：Re为99.2％，氧为0.25％，余量为不可避免的杂质，其粒度在45μm。
实施例24
一种多级深度还原制备高熔点金属粉的方法，按以下步骤进行：
步骤1，自蔓延反应
将氧化铼粉置于烘箱中，在100～150℃烘干24h，得到烘干后的氧化铼粉，将烘干后的氧化铼粉和镁粉按摩尔比为Re 2O 7：Mg＝1：3.3混合，得到混合物料，将混合物料在40MPa下压制，得到块状坯料，加入自蔓延反应炉中，以局部点火的方式引发自蔓延反应，温度控制在650℃，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
步骤2，一次浸出
将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，浸出温度为30℃，浸出时间为80min，得到浸出液和浸出产物，去除浸出液，将浸出产物采用动态洗涤方式、在30℃真空干燥24h，得到低价高熔点金属的氧化物Re xO前驱体；其中，盐酸的摩尔浓度为6mol/L，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量12％配比；
所述的低价高熔点金属的氧化物Re xO前驱体，其含有的成分及其质量百分比为：O：20％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
步骤3，多级深度还原
将低价高熔点金属的氧化物Re xO前驱体与钙粉混合均匀，在15MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，在真空度≤10Pa的条件下加热升温至1100℃，进行二次深度还原2h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Re xO：Ca＝1：2；
步骤4，二次浸出
将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，浸出温度为30℃，浸出时间为30min，得到滤液和滤渣，除去滤液，将滤渣采用动态洗涤方式、在26℃真空干燥24h，得到低氧的铼粉；其中，盐酸的摩尔浓度为3mol/L，稀盐酸与深度还原产物的加入量根据反应理论需要的盐酸过量25％配比；
所述的低氧的铼粉，含有的成分及其质量百分比为：Re为99.3％，氧为0.21％，余量为不可避免的杂质，其粒度在47μm。

Claims (10)

  1. 一种多级深度还原制备高熔点金属粉的方法，其特征在于，按以下步骤进行：
    步骤1，自蔓延反应
    将高熔点金属氧化物粉，烘干，得到烘干后的高熔点金属氧化物粉，将烘干后的高熔点金属氧化物粉和镁粉混合，得到混合物料，将混合物料加入自蔓延反应炉中，进行自蔓延反应，冷却后，得到高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物；其中，高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物为非化学计量比的低价态高熔点金属氧化物的混合物，x取值在0.2～1之间；
    所述的高熔点金属Me，具体为W、Mo、Ta、Nb、V、Zr、Hf或Re中的一种或几种；
    所述的高熔点金属氧化物为WO 3、MoO 3、Ta 2O 5、Nb 2O 5、V 2O 5、ZrO 2、HfO 2、Re 2O 7中的一种或几种混合；
    当高熔点金属的氧化物为WO 3时，物料混合比例按摩尔比为WO 3:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为MoO 3时，物料混合比例按摩尔比为MoO 3:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为Ta 2O 5时，物料混合比例按摩尔比为Ta 2O 5:Mg＝1:(2.7～3.3)；当高熔点金属的氧化物为Nb 2O 5时，物料混合比例按摩尔比为Nb 2O 5:Mg＝1:(2.7～3.3)；当高熔点金属的氧化物为V 2O 5时，物料混合比例按摩尔比为V 2O 5:Mg＝1:(2.7～3.3)；当高熔点金属的氧化物为ZrO 2时，物料混合比例按摩尔比为ZrO 2:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为HfO 2时，物料混合比例按摩尔比为HfO 2:Mg＝1:(0.8～1.2)；当高熔点金属的氧化物为Re 2O 7时，物料混合比例按摩尔比为Re 2O 7:Mg＝1:(2.7～3.3)；
    步骤2，一次浸出
    将高熔点金属的低价氧化物Me xO弥散在MgO基体中的中间产物置于密闭反应釜中，以盐酸为浸出液对中间产物进行浸出，得到浸出液和浸出产物，去除浸出液，将浸出产物洗涤、真空干燥，得到低价高熔点金属的低价氧化物Me xO前驱体；其中，盐酸的摩尔浓度为1～6mol/L；
    步骤3，多级深度还原
    将低价高熔点金属的低价氧化物Me xO前驱体与钙粉混合均匀，在2～20MPa下压制，得到块状坯料，将块状坯料置于真空还原炉中，加热升温至700～1200℃，进行二次深度还原1～6h，二次深度还原后，得到块坯，将块坯随炉冷却，得到深度还原产物；其中，按摩尔比为Me xO：Ca＝1：(1.5～3)；
    步骤4，二次浸出
    将深度还原产物置于密闭的反应釜中，以盐酸为浸出液对深度还原产物进行浸出，得到滤液和滤渣，除去滤液，将滤渣洗涤、真空干燥，得到低氧的高熔点金属粉；其中，盐酸的 摩尔浓度为1～6mol/L；
    所述的低氧高熔点金属粉，含有的成分及其质量百分比为：O≤0.8％，高熔点金属Me≥99％，余量为不可避免的杂质，其粒度在5～60μm之间。
  2. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤1中，所述的烘干，其具体操作步骤为：将高熔点金属氧化物粉置于烘箱中在100～150℃烘干24h以上。
  3. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤1中，所述的混合物料加入自蔓延反应炉前，经过以下两种方式之一进行处理：
    第一种：将混合物料在10～60MPa下压制，得到块状坯料，将块状坯料加入自蔓延反应炉中，进行自蔓延反应；
    第二种：不经过处理，直接加入自蔓延反应炉中，进行自蔓延反应。
  4. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤1中，所述的自蔓延反应的引发方式分别局部点火法和整体加热法，局部点火法是指在自蔓延反应炉中用电热丝加热混合物料局部，引发自蔓延反应；整体加热法是指在自蔓延反应炉中将混合物料整体升温，直至自蔓延反应发生为止，温度控制在500～750℃。
  5. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤2中，所述的对中间产物进行浸出时，稀盐酸与中间产物的加入量根据反应理论需要的盐酸过量10～40％配比；
    所述的步骤2中，浸出中间产物的浸出温度为20～30℃，浸出时间为60～180min。
  6. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤2中，所述的低价高熔点金属的低价氧化物Me xO前驱体，其含有的成分及其质量百分比为：O：5～20％，不可避免的杂质≤0.5％，余量为高熔点金属，其粒度在0.8～15μm之间。
  7. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤2中，所述的洗涤、真空干燥的具体步骤为：将去除浸出液的浸出产物用水洗涤至洗液为中性，然后在真空烘箱中在真空条件下烘干，烘干温度为20～30℃，时间至少为24h；
    所述洗涤为用水洗涤，具体为采用动态洗涤，即洗涤过程中洗涤槽中洗液保持恒定水位，有多少洗液排出就有多少新鲜水补充，洗涤至中性。
  8. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤3中，所述的二次深度还原，其反应参数为，在真空度≤10Pa的条件下升温。
  9. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤4中，所述的浸出深度还原产物时，稀盐酸与深度还原产物的加入量根据反应理论需要 的盐酸过量5～30％配比；
    所述的步骤4中，所述的浸出深度还原产物的浸出温度为20～30℃，浸出时间为15～90min。
  10. 如权利要求1中所述的多级深度还原制备高熔点金属粉的方法，其特征在于，所述的步骤4中，所述的洗涤、真空干燥的具体步骤为：将去除浸出液的浸出产物用水洗涤至洗液为中性，然后在真空烘箱中在真空条件下烘干，烘干温度为20～30℃，时间至少为24h；
    所述洗涤为用水洗涤，具体为采用动态洗涤，即洗涤过程中洗涤槽中洗液保持恒定水位，有多少洗液排出就有多少新鲜水补充，洗涤至中性。
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