CN112250080A - Method for preparing refractory metal boride in two steps - Google Patents
Method for preparing refractory metal boride in two steps Download PDFInfo
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- CN112250080A CN112250080A CN202010991505.4A CN202010991505A CN112250080A CN 112250080 A CN112250080 A CN 112250080A CN 202010991505 A CN202010991505 A CN 202010991505A CN 112250080 A CN112250080 A CN 112250080A
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- C01—INORGANIC CHEMISTRY
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- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/04—Metal borides
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Abstract
A method for preparing refractory metal boride in two steps belongs to the field of inorganic non-metallic materials. The refractory metal boride generally has the characteristics of high melting point, high hardness, good wear resistance, good oxidation resistance and the like, and the current industrial preparation method of the refractory metal boride has the problems of low product purity, large granularity, high preparation cost and the like. Generally, the elementary powder of the metal is not easy to prepare and has higher price. The method uses refractory metal oxide, carbonaceous reducing agent, boron carbide and metallic calcium as raw materials, and comprises the steps of carrying out high-temperature carbothermic reduction reaction, carrying out high-temperature boronization reaction under certain conditions to generate corresponding refractory metal boride, carrying out acid leaching on a final reaction product to remove soluble impurities, and carrying out filtering, rinsing and drying to obtain the high-purity refractory metal boride. The invention relates to a new method for synthesizing refractory metal boride powder, which has the advantages that: the method has universal applicability, high purity of reaction products, low cost, controllable granularity of products and easy large-scale production.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials, discloses a method for preparing refractory metal boride in two steps, and particularly relates to a method for preparing refractory metal boride by using refractory metal oxide, a carbonaceous reducing agent, boron carbide and metallic calcium as raw materials.
Background
The refractory metal boride has the characteristics of high melting point, high hardness, good electrical and thermal conductivity, high corrosion resistance and the like due to a special chemical bond structure, and is a material applicable to extreme service conditions. Refractory metal borides may be used as heat shields, ceramic armor, specialty tools, wear resistant ceramics, and the like. There have been proposed a number of methods for producing a refractory metal boride powder, such as direct elemental synthesis, borothermic reduction, carbothermic reduction, magnesiothermic reduction, electrolytic and gas phase synthesis. However, these methods often do not compromise economics, reliability and high product quality.
Disclosure of Invention
The invention aims to provide a method for preparing refractory metal boride by using refractory metal oxide, a carbonaceous reducing agent, boron carbide and metallic calcium as raw materials.
A method for preparing refractory metal boride in two steps comprises the following specific steps:
(1) according to different kinds of target boride products, the carbonaceous reducing agent and the refractory metal oxide are proportioned and mixed according to the stoichiometric ratio of the chemical reaction (the carbonaceous reducing agent can be excessive);
(2) under the protection of inert atmosphere, reacting the mixed powder raw material obtained in the step (1) in a high-temperature furnace, wherein the process can be carried out under the vacuum condition;
(3) mixing the reaction product obtained by calcining in the step (2) with boron carbide and metal calcium according to a reaction stoichiometric ratio (the metal calcium can be excessive), and uniformly mixing;
(4) placing the uniformly mixed material in the step (3) in a high-temperature furnace under the protection of inert atmosphere for reaction; and performing acid leaching, filtering, rinsing and drying on the product after reaction to obtain the refractory metal boride.
Further, the refractory metal oxide is oxides of various valence states of Ti, Zr, Hf, V, Nb, Ta and Cr, the carbonaceous reducing agent includes but is not limited to graphite, carbon black, activated carbon and petroleum coke, and the boron carbide is various boron-carbon compounds including but not limited to B4C、B13C2。
Further, refractory metal borides of different particle size grades may be prepared when using different particle size feedstocks, such as different particle size refractory metal oxides or ultra fine carbonaceous feedstocks.
Further, the high-temperature carbothermic reduction reaction process in the step (2) is carried out at 1200-1800 ℃ for 2-8 hours.
Further, the high-temperature reaction process in the step (4) is carried out for 2-6 hours at the temperature of 1000-1500 ℃.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) the refractory metal oxide, the carbonaceous reducing agent, the boron carbide and the calcium metal are used as raw materials, the raw materials are general metallurgical and chemical products, and the raw materials are low in cost;
(2) the invention can produce the adjustment of the proportioning according to different kinds of transition metal borides, and the method has universality.
(3) The invention can select the raw materials according to the transition metal borides with different granularity levels, and the method is flexible and convenient.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first embodiment is as follows:
(1) mixing a refractory metal oxide powder (TiO)2、ZrO2、HfO2、V2O3、Nb2O5、Ta2O5And Cr2O3) And weighing and mixing the graphite and the carbon according to the reaction stoichiometric ratio of 20% excess carbon, and uniformly mixing.
(2) Placing the mixture obtained in (1) in a crucible under an argon protective atmosphere, and carrying out vacuum treatment at 1800 ℃ for 4 hours.
(3) Reacting the reaction product in (2) with B4C, uniformly mixing according to the reaction metering ratio, and adding excessive metal calcium with the reaction metering ratio of 20%;
(4) and (3) placing the mixture obtained in the step (3) in a crucible to be treated at 1300 ℃ for 4 hours under the argon protective atmosphere.
(5) And (4) after the heat preservation is finished, cooling the reaction product to room temperature in an argon atmosphere, and performing acid leaching, filtering, rinsing and drying on the reaction product to obtain the refractory metal boride.
Example two:
(1) oxidizing a refractory metalCompound powder (TiO)2、ZrO2、HfO2、V2O3、Nb2O5、Ta2O5And Cr2O3) And weighing and mixing the carbon black and the carbon black according to the reaction stoichiometric ratio of 20% excess carbon.
(2) Placing the mixture obtained in the step (1) in a crucible under an argon protective atmosphere, and carrying out vacuum treatment at 1500 ℃ for 4 hours.
(3) Reacting the reaction product in (2) with B4C, uniformly mixing according to the reaction metering ratio, and adding excessive metal calcium with the reaction metering ratio of 20%;
(4) and (3) placing the mixture obtained in the step (3) in a crucible to be treated at 1300 ℃ for 4 hours under the argon protective atmosphere.
(5) And (4) after the heat preservation is finished, cooling the reaction product to room temperature in an argon atmosphere, and performing acid leaching, filtering, rinsing and drying on the reaction product to obtain the refractory metal boride.
Example three:
(1) mixing certain nanometer refractory metal oxide powder (TiO)2Or ZrO2) And weighing and mixing the carbon black and the carbon black according to the reaction stoichiometric ratio of 20% excess carbon.
(2) Placing the mixture obtained in the step (1) in a crucible under an argon protective atmosphere, and carrying out vacuum treatment at 1500 ℃ for 4 hours.
(3) Reacting the reaction product in (2) with B4C, uniformly mixing according to the reaction metering ratio, and adding excessive metal calcium with the reaction metering ratio of 20%;
(4) and (3) placing the mixture obtained in the step (3) in a crucible to be treated at 1200 ℃ for 4 hours under an argon protective atmosphere.
(5) And (4) after the heat preservation is finished, cooling the reaction product to room temperature in an argon atmosphere, and performing acid leaching, filtering, rinsing and drying on the reaction product to obtain the superfine refractory metal boride.
Claims (5)
1. A method for preparing refractory metal boride in two steps is characterized by comprising the following specific preparation steps:
(1) according to different kinds of target boride products, mixing a carbonaceous reducing agent and refractory metal according to a stoichiometric ratio of a chemical reaction;
(2) under the protection of inert atmosphere, carrying out carbothermic reduction reaction on the mixed raw material obtained in the step (1) in a high-temperature furnace, wherein the process is carried out under the vacuum condition;
(3) mixing the reaction product obtained by calcining in the step (2) with boron carbide and metal calcium according to a reaction metering ratio, and uniformly mixing;
(4) placing the uniformly mixed material in the step (3) in a high-temperature furnace under the protection of inert atmosphere for carrying out a boronization reaction; and performing acid leaching, filtering, rinsing and drying on the product after reaction to obtain the refractory metal boride.
2. The method of claim 1, wherein the refractory metal oxide is an oxide of various valence states of Ti, Zr, Hf, V, Nb, Ta, Cr, the carbonaceous reducing agent includes but is not limited to graphite, carbon black, activated carbon, petroleum coke, biomass carbon, and the boron carbide includes but is not limited to B4C、B13C2A boron carbon compound of (2).
3. A two step process according to claim 1 wherein refractory metal borides of different particle size grades are produced using different particle size feedstocks, such as different particle size refractory metal oxides or different particle size carbonaceous reducing agents.
4. The method for preparing the refractory metal boride in two steps according to claim 1, wherein the high temperature carbothermic reduction process of the step (2) is carried out at 1200 to 1800 ℃ for 2 to 8 hours.
5. The method for preparing the refractory metal boride in two steps according to claim 1, wherein the boride reaction in the step (4) is carried out at 1000 to 1500 ℃ for 2 to 6 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898025A (en) * | 2021-02-02 | 2021-06-04 | 中冶节能环保有限责任公司 | Method for preparing vanadium boride ultrafine powder by carbon-thermal boron-thermal method |
| CN113772711A (en) * | 2021-08-09 | 2021-12-10 | 北京科技大学 | Method for preparing rare earth metal hexaboride through aluminothermic reduction |
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| CN103588216A (en) * | 2013-10-23 | 2014-02-19 | 航天材料及工艺研究所 | Method for preparing zirconium boride powder at low temperature according to boron/carbon thermal reduction method |
| CN108622911A (en) * | 2018-06-06 | 2018-10-09 | 山东大学 | A kind of ultra fine zirconium biboride-silicon carbide composite powder body and preparation method thereof |
| CN110029220A (en) * | 2019-04-25 | 2019-07-19 | 北京科技大学 | A kind of method that two-step method reduction-oxidation chromium prepares hafnium metal powfer |
| US20200247680A1 (en) * | 2019-02-05 | 2020-08-06 | United Technologies Corporation | Preparation of metal diboride and boron-doped powders |
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2020
- 2020-09-17 CN CN202010991505.4A patent/CN112250080B/en active Active
Patent Citations (5)
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| CA1048257A (en) * | 1975-02-03 | 1979-02-13 | Roger A. Steiger | Sub-micron carbon-containing titanium boride powder and method for preparing same |
| CN103588216A (en) * | 2013-10-23 | 2014-02-19 | 航天材料及工艺研究所 | Method for preparing zirconium boride powder at low temperature according to boron/carbon thermal reduction method |
| CN108622911A (en) * | 2018-06-06 | 2018-10-09 | 山东大学 | A kind of ultra fine zirconium biboride-silicon carbide composite powder body and preparation method thereof |
| US20200247680A1 (en) * | 2019-02-05 | 2020-08-06 | United Technologies Corporation | Preparation of metal diboride and boron-doped powders |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898025A (en) * | 2021-02-02 | 2021-06-04 | 中冶节能环保有限责任公司 | Method for preparing vanadium boride ultrafine powder by carbon-thermal boron-thermal method |
| CN113772711A (en) * | 2021-08-09 | 2021-12-10 | 北京科技大学 | Method for preparing rare earth metal hexaboride through aluminothermic reduction |
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