CN102910596A - Preparation method of vanadium nitride - Google Patents
Preparation method of vanadium nitride Download PDFInfo
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- CN102910596A CN102910596A CN201210291750XA CN201210291750A CN102910596A CN 102910596 A CN102910596 A CN 102910596A CN 201210291750X A CN201210291750X A CN 201210291750XA CN 201210291750 A CN201210291750 A CN 201210291750A CN 102910596 A CN102910596 A CN 102910596A
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Abstract
The invention relates to a preparation method of vanadium nitride. The preparation method comprises the following steps: uniformly mixing powdered vanadium oxide, a carbonaceous reducing agent and a binding agent aqueous solution; compacting to prepare into blocks; drying the block materials; continuously adding in a double-channel push plate kiln; carrying out reduction, sintering, nitrogenization and cooling in each temperature region in the kiln under the condition of 10Pa to 100Pa of pressure in the kiln and gas protection; and finally producing the vanadium nitride product with contents of 77-80% of V (vanadium), 11-18% of N (nitrogen) and 2-8% of C (carbon), and production density of 3.2g/cm<3> to 4.1g/cm<3> is obtained. With the adoption of the preparation method provided by the invention, the continuous production is achieved, and the preparation method has the following advantages of stable technology process, high production efficiency, high reducing efficiency, low reaction temperature, high heating efficiency, low energy consumption and so on.
Description
Technical field
The present invention relates to the non-ferrous metallurgy technology field, particularly relate to a kind of preparation method of vanadium nitride.
Background technology
Vanadium is a kind of important alloying element in Iron and Steel Production, and its application in low microalloying steel is very extensive.Studies show that and add the intensity that vanadium can significantly improve steel in the steel, for example in steel, add vanadium, its yield strength is brought up to more than the 600MPa by 350MPa.Contain vanadium steel and not only improved intensity, also improved the over-all propertieies such as thermal fatigue resistance, weldability.The compound that vanadium and carbon, nitrogen reaction generate plays precipitation hardening and grain refining in steel.The method of traditional interpolation vanadium is that vanadium iron is added in the molten steel.But recently a large amount of research and practices all show, can more effectively strengthen and crystal grain thinning material if vanadium is added to molten steel inside with the form of vanadium nitride, can reduce the add-on of vanadium and reach same effect.Compare with direct interpolation vanadium iron, the use vanadium nitride can be saved the vanadium about 20～40% in high-strength low-alloy steel, thereby greatly reduces the cost of alloying.The VN alloy is not only applicable to low-carbon (LC) building Twisted Steel, and can widely apply in middle, high-carbon yet, and development is very fast in developed country.Therefore, produce the VN alloy, improve its nitrogen content, reduce its production cost, to promoting the production of the high-end rolling shapes of China, have huge economic technology benefit and realistic meaning.
The production of existing domestic and international VN alloy generally is take gaseous ammonia, nitrogen or ammonia-nitrogen mixed gas as nitridizing agent, behind raw material blending and briquetting, strengthens nitrogenize under 1000-1800 ℃ high temperature.For example: the preparation method of US Patent No. 33349992 disclosed vanadium nitrides will be pressed into piece behind V2O3 and iron powder and the carbon dust mixing, reduction is 60 hours under 1385 ℃ and 6.7Pa vacuum tightness, get first vanadium carbide, distinguish down nitriding 2 hours and 6 hours at 1100 ℃ and 1000 ℃ respectively again, make and contain V78.7%, N 7.3%, the vanadium nitride of C10.5%; The production method of the disclosed a kind of vanadium nitride of CN1422800, that pulverous barium oxide, carbonaceous pulvis and binding agent are mixed rear briquetting, moulding, again the material after the moulding is added continuously in the preparation stove, pass into nitrogen or the reaction of ammonia do and shielding gas to the preparation stove simultaneously, the preparation stove need to be heated to 1000-1800 ℃, material is at this temperature province generation carbonization and nitrogenizing reaction, acquisition contains V77-81 %, N 10.19-14.65%, the vanadium nitride product of C 7.54-8.81%; The disclosed alloy of vanadium nitride continuous production processes of CN 1 4789 15A, its raw material composition and ratio is V
2O
560-85 %, carbonaceous reducing material 12-30 %, liquid adhesive 3-15 %, raw material in the reduction nitridation vertical electric furnace of packing into, successively by preheating, prereduction, reduction nitridation, make V after mixing, compression moulding and oven dry
2O
5Add the final reduction nitridation of carbon-containing material and generate alloy of vanadium nitride, the alloy of vanadium nitride that makes contains V77.46%, N10.46-12.65%, C3.82-5.10%; The production method of the disclosed vanadium nitride of CN1562770A, to contain barium oxide and activated carbon or Graphite Powder 99, binding agent is mixing in proportion, briquetting, moulding, material after the moulding is inserted in the special industrial microwave heating oven, constantly bleed, keep vacuum tightness, prereduction, carbonization, nitrogenize, coming out of the stove behind the naturally cooling is the vanadium nitride product, the temperature in this technique prereduction stage is 600-700 ℃, the temperature of carbonation stage is 1300-1500 ℃, and the temperature in nitrogenize stage is 900-1250 ℃, and the alloy of vanadium nitride that makes contains V 76-80 %, N 7-14 %, C 6-12 %; The disclosed vanadium nitride production method of CN1587064; the method be first with the powdery vanadic acid by; the carbonaceous pulvis is mixed and carries out pre-treatment in the rear adding rotary kiln; rotary kiln keeps little negative pressure; rotary kiln is heated to 600-800 ℃; and move 2-3 hours; then with behind the adding additives compound stalk forming behind the said mixture porphyrize; put into the vertical tube kiln; described pipe kiln inner with nitrogenous neutrality or reducing gas as reacting and shielding gas; under 1100-1900 ℃; move 4-6 hour and carbonization occurs and nitrogenizing reaction, final production goes out the vanadium nitride product, and its vanadium nitride product contains 81% V; the N of 9-16%; the C of 2-8%.
The high temperature of needs more than 1800 ℃ that above several method has, what have has particular requirement to raw material, and the N content that has is low, has more difficulty in producing and using.
Summary of the invention
Purpose of the present invention just is to provide a kind of raw material to be easy to get, stable technical process, and the vanadium valence state can keep on the go for a long time greater than the vanadium raw materials of tetravalence, can realize continuous production, and temperature of reaction is low, and reduction efficiency is high, the preparation method of the vanadium nitride that nitrogen content is high.
Another object of the present invention provides the production equipment of above-mentioned vanadium nitride.
A kind of preparation method of vanadium nitride; it is characterized in that: be pressed into bulk after powdery vanadium oxide compound, carbonaceous reducing agent and caking agent aqueous solution is even; to join continuously in the two channels pushed bat kiln after the lumpy material oven dry again; under kiln inner pressure 10-100pa and gas protective condition; in kiln each temperature province reduce, sintering, nitrogenizing reaction and cooling, final production goes out vanadium nitride.
Described powdery vanadium oxide compound and carbonaceous reducing agent mix according to the weight ratio of 3.4-3:1, and the caking agent aqueous solution accounts for the 8-25% of above-mentioned two kinds of material gross weights, and this aqueous solution mass concentration is 2.0-3.0%.
The granularity requirements of described powdery vanadium oxide compound is crossed 80 mesh sieves.
Described barium oxide is V
2O
5, V
2O
3, NH
4VO
3Or a kind of or any several mixture of ammonium poly-vanadate.
Described carbonaceous reducing agent is one or more in carbon black, graphite, gac, pitch and the refinery coke.
Described caking agent is one or more in starch, polyvinyl alcohol, acrylic resin, sucrose and the Mierocrystalline cellulose.
The compression ratio of described lumpy material is 1.8-2.3, pressing pressure 100-150Mpa.
Described lumpy material was dried 8-24 hour under 100 ℃-250 ℃ of temperature.
Described gas is NH
3, N
2Or N
2-H
2Mixed gas, wherein N
2-H
2N in the mixed gas
2Content 20-70%.
Have four temperature provinces in the described kiln at least, top temperature is less than 1600 ℃.
Described kiln temperature zone is comprised of preheating zone, heating zone, reduction zone, sintering zone, nitrogenize district, cooling area and cooling zone, and the sintering zone temperature is greater than 1350 ℃.
Described two channels pushed bat kiln adopts PID control.
Compared with prior art, the present invention has following features:
1, the present invention adopts the polycomponent carbonaceous reducing agent, improves reduction efficiency, reduces reduction temperature.
2, the present invention adopts two channels pushed bat kiln device to produce continuously, and production efficiency is high, long service life.
3, adopt upper and lower layer heating, the heating chamber thermograde is little, temperature is even, and thermo-efficiency is high, and energy consumption is low.
4, adopt forced exhaust, be conducive to corrosives and discharge, reduce corrosion, service life of equipment is long.
5, two channels pushed bat kiln device has the gentle flow point cloth of unique seal structure, prevents that corrosive gases from permeating to outer lagging material along the heating chamber window.
6, temperature control system adopts PID control, and numeral shows to have control accurately and temperature curve characteristics easy to adjust.
7, operational process adopts PLC control, carries out Full-automatic circulation, and analog information.
Can obtain the vanadium nitride of V content 77-80%, N content 11-18%, C content 2-8%, its product density 3.2-4.1g/cm3 by method of the present invention.
Description of drawings
Fig. 1 is the structural representation sketch of two channels pushed bat kiln of the present invention;
Fig. 2 is the mounting plane synoptic diagram of two channels pushed bat kiln of the present invention.
Embodiment
The used two channels pushed bat kiln of the present invention is conventional equipment, its structural principle as shown in Figure 1, the kiln body is built by laying bricks or stones by lagging material 1 and is formed, heat up in the kiln by heating unit 4, add thermal window 5 heated sealed elements 4, upper, middle and lower three places carry out temperature detection and temperature control in 6 pairs of kilns of thermopair, and nitrogen is entered in the kiln by admission 7, crucible 3 above push pedal 2, crucible 3 material of packing into.
Fig. 2 is the mounting plane synoptic diagram of two channels pushed bat kiln, the 8 tiling push pedals of outer circulation track, and the above places crucible, by hydraulic efficiency system 9 material is pushed kiln body 10 interior sintering.Have four temperature provinces in the kiln at least, top temperature is less than 1600 ℃.Described two channels pushed bat kiln adopts PID control.
The preparation technology of vanadium nitride is:
Powdery vanadium oxide compound (the V of 80 mesh sieves will be crossed
2O
5, V
2O
3, NH
4VO
3Or ammonium poly-vanadate a kind of or any several mixture) and carbonaceous reducing agent (one or more in carbon black, graphite, gac, pitch and the refinery coke) according to the weight ratio mixing of 3.4-3:1, the binding agent (one or more in starch, polyvinyl alcohol, acrylic resin, sucrose, the Mierocrystalline cellulose) that adds concentration 2.0-3.0%, add-on is the 8-25%(weight percent), mix; Then be pressed into the diamond block of 45mm * 455mm * 35mm size, pressing pressure is controlled at 100-150Mpa, and compression ratio is 1.8-2.3; Oven for drying, temperature are 100-250 ℃, time 8-24 hour; The plumbago crucible of packing into after the oven dry is sent into the two channels pushed bat kiln.The two channels pushed bat kiln adopts and to pass into nitrogen protection, has designed respectively gas-tight silo and purge chamber in the import and export of kiln body.The outlet in inlet seal storehouse is connected with kiln body import resistance to air loss.The kiln body is divided into by preheating zone (less than 400 ℃), heating zone (less than 900 ℃), reduction zone (less than 1200 ℃), sintering zone (greater than 1350 ℃), nitrogenize district (less than 1350 ℃), cooling area and cooling zone (less than 200 ℃) and forms.Material passes through regional step by step automatically, finishes reduction, sintering, nitridation process.
Utilize the vanadium nitride product of technology of the present invention, equipment scheme preparation to contain 77-80%V, 10-18%N, 0.1-0.8%O, density reaches 3.2-4.1g/cm
3
1000kg vanadium pentoxide powder and 325kg carbon black are mixed, adding concentration is 2.5% polyvinyl alcohol water solution, solution proportion 8%, mix rear at pressure 120Mpa lower lock block, material compression is than 1.8, dried 12 hours for 125 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 6h 1500 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 78.32%V, 15.2%N, 4.7%C, 0.83%O, the vanadium nitride of 0.01%S, its product density 3.8g/cm
3
With the 1000kg Vanadium Pentoxide in FLAKES, the 335kg carbon black mixes, adding concentration is 2% polyvinyl alcohol water solution, solution proportion 15%, mix rear at pressure 150Mpa lower lock block, material compression is than 2.0, dried 12 hours for 150 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 6h 1480 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 78.22%V, 13.8%N, 5.9%C, 0.72%O, the vanadium nitride of 0.01%S, its product density 3.8g/cm
3
With the 1000kg Vanadium Pentoxide in FLAKES, 335kg graphite mixes, adding concentration is 3% polyvinyl alcohol water solution, solution proportion 15%, mix rear at pressure 120Mpa lower lock block, material compression is than 1.8, dried 12 hours for 150 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 6h 1450 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 78.63%V, 11.7%N, 7.2%C, 0.64%O, the vanadium nitride of 0.01%S, its product density 3.2g/cm
3
With the 1000kg Vanadium Pentoxide in FLAKES, 320kg graphite mixes, adding concentration is 2.5% polyvinyl alcohol water solution, solution proportion 18%, mix rear at pressure 150Mpa lower lock block, material compression is than 2.2, dried 12 hours for 180 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 6h 1450 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 78.89%V, 15.8%N, 3.3%C, 0.93%O, the vanadium nitride of 0.01%S, its product density 3.8g/cm
3
With 700kg Vanadium Pentoxide in FLAKES and 200kg vanadous oxide, 150kg graphite and 150kg carbon black mix, adding concentration is 2.5% polyvinyl alcohol water solution, solution proportion 15%, mix rear at pressure 150Mpa lower lock block, material compression is than 2.0, dried 12 hours for 180 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 8h 1530 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 77.39%V, 17.5%N, 3.3%C, 0.86%O, the vanadium nitride of 0.01%S, its product density 3.8g/cm
3
With the 1000kg Vanadium Pentoxide in FLAKES, 100kg graphite and 200kg carbon black mix, adding concentration is 2.5% polyvinyl alcohol water solution, solution proportion 20%, mix rear at pressure 150Mpa lower lock block, material compression is than 2.2, dried 12 hours for 180 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 8h 1550 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 77.59%V, 16.6%N, 2.6%C, 1.16%O, the vanadium nitride of 0.01%S, its product density 4.1g/cm
3
With 800kg Vanadium Pentoxide in FLAKES and 200kg vanadous oxide, 210kg graphite and 100kg carbon black mix, adding concentration is 2.5% polyvinyl alcohol water solution, solution proportion 25%, mix rear at pressure 100Mpa lower lock block, material compression is than 2.0, dried 12 hours for 180 ℃, again the material after the moulding oven dry is placed in the feeding warehouse of pushed bat kiln, material is controlled by PLC, carry out Full-automatic circulation turnover pushed bat kiln, simultaneously pass into nitrogen to pushed bat kiln, keep the above 10-100pa of furnace pressure normal atmosphere, material keeps 8h 1500 ℃ of temperature provinces, be cooled to 1200 ℃ of temperature provinces and keep the 2h nitriding treatment, then continue to be cooled to 120 ℃ of automatic tappings, having obtained content is 77.62%V, 17.2%N, 3.8%C, 1.02%O, the vanadium nitride of 0.01%S, its product density 3.8g/cm
3
Top example is for explanation the present invention rather than limitation of the present invention.Scope of the present invention and core content are determined according to claims.
Claims (12)
1. the preparation method of a vanadium nitride; it is characterized in that: be pressed into bulk after powdery vanadium oxide compound, carbonaceous reducing agent and caking agent aqueous solution is even; to join continuously in the two channels pushed bat kiln after the lumpy material oven dry again; under kiln inner pressure 10-100pa and gas protective condition; in kiln each temperature province reduce, sintering, nitrogenizing reaction and cooling, final production goes out vanadium nitride.
2. according to the preparation method of vanadium nitride claimed in claim 1, it is characterized in that: described powdery vanadium oxide compound and carbonaceous reducing agent mix according to the weight ratio of 3.4-3:1, the caking agent aqueous solution accounts for the 8-25% of above-mentioned two kinds of material gross weights, and this aqueous solution mass concentration is 2.0-3.0%.
3. according to the preparation method of claim 1 or 2 described vanadium nitrides, it is characterized in that: the granularity requirements of described powdery vanadium oxide compound is crossed 80 mesh sieves.
4. according to the preparation method of vanadium nitride claimed in claim 3, it is characterized in that: described barium oxide is V
2O
5, V
2O
3, NH
4VO
3Or a kind of or any several mixture of ammonium poly-vanadate.
5. according to the preparation method of claim 1 or 2 described vanadium nitrides, it is characterized in that: described carbonaceous reducing agent is one or more in carbon black, graphite, gac, pitch and the refinery coke.
6. according to the preparation method of claim 1 or 2 described vanadium nitrides, it is characterized in that: described caking agent is one or more in starch, polyvinyl alcohol, acrylic resin, sucrose and the Mierocrystalline cellulose.
7. according to the preparation method of vanadium nitride claimed in claim 1, it is characterized in that: the compression ratio of described lumpy material is 1.8-2.3, pressing pressure 100-150Mpa.
8. according to the preparation method of vanadium nitride claimed in claim 1, it is characterized in that: described lumpy material was dried 8-24 hour under 100 ℃-250 ℃ of temperature.
9. according to the preparation method of vanadium nitride claimed in claim 1, it is characterized in that: described gas is NH
3, N
2Or N
2-H
2Mixed gas, wherein N
2-H
2N in the mixed gas
2Content 20-70%.
10. according to the preparation method of vanadium nitride claimed in claim 1, it is characterized in that: have four temperature provinces in the described kiln at least, top temperature is less than 1600 ℃.
11. the preparation method according to claim 1 or 10 described vanadium nitrides is characterized in that: described kiln temperature zone is comprised of preheating zone, heating zone, reduction zone, sintering zone, nitrogenize district, cooling area and cooling zone, and the sintering zone temperature is greater than 1350 ℃.
12. the preparation method according to vanadium nitride claimed in claim 1 is characterized in that: described two channels pushed bat kiln adopts PID control.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103925786A (en) * | 2014-04-15 | 2014-07-16 | 刁君 | Double-pushing-plate high-temperature sintering kiln for producing vanadium-nitrogen alloy |
| CN104099634A (en) * | 2014-08-07 | 2014-10-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium nitride preparing method |
| CN105087994A (en) * | 2015-09-06 | 2015-11-25 | 湖南众鑫新材料科技股份有限公司 | Method for preparing high-nitrogen high-purity vanadium-nitrogen alloy |
| CN105466210A (en) * | 2015-12-04 | 2016-04-06 | 中国电子科技集团公司第四十八研究所 | Atmosphere protection full-sealed roller kiln |
| CN106315524A (en) * | 2016-07-28 | 2017-01-11 | 河北钢铁股份有限公司承德分公司 | Method for producing vanadium nitride through pushed slab kiln |
| CN106399785A (en) * | 2016-11-25 | 2017-02-15 | 南通汉瑞新材料科技有限公司 | Method for preparing vanadium-nitrogen alloy by utilizing vanadium trioxide |
| CN109321811A (en) * | 2018-11-18 | 2019-02-12 | 湖南众鑫新材料科技股份有限公司 | Vanadium nitride powder at block method |
| CN114249306A (en) * | 2021-12-06 | 2022-03-29 | 武汉科技大学 | Vanadium nitride based on vanadium-rich liquid and preparation method thereof |
| CN115637367A (en) * | 2022-10-21 | 2023-01-24 | 武汉科技大学 | Vanadium-nitrogen alloy based on vanadium compound and preparation method thereof |
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| CN1562770A (en) * | 2004-04-06 | 2005-01-12 | 湘潭市恒新特种合金厂 | Method for preparing vanadium nitride and device |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103925786A (en) * | 2014-04-15 | 2014-07-16 | 刁君 | Double-pushing-plate high-temperature sintering kiln for producing vanadium-nitrogen alloy |
| CN104099634A (en) * | 2014-08-07 | 2014-10-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium nitride preparing method |
| CN104099634B (en) * | 2014-08-07 | 2016-08-31 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of vanadium nitride |
| CN105087994A (en) * | 2015-09-06 | 2015-11-25 | 湖南众鑫新材料科技股份有限公司 | Method for preparing high-nitrogen high-purity vanadium-nitrogen alloy |
| CN105466210A (en) * | 2015-12-04 | 2016-04-06 | 中国电子科技集团公司第四十八研究所 | Atmosphere protection full-sealed roller kiln |
| CN105466210B (en) * | 2015-12-04 | 2017-11-28 | 中国电子科技集团公司第四十八研究所 | A kind of hermetically sealed roller kilns of atmosphere protection |
| CN106315524A (en) * | 2016-07-28 | 2017-01-11 | 河北钢铁股份有限公司承德分公司 | Method for producing vanadium nitride through pushed slab kiln |
| CN106315524B (en) * | 2016-07-28 | 2019-03-15 | 河北钢铁股份有限公司承德分公司 | A kind of method of pushed bat kiln production vanadium nitride |
| CN106399785A (en) * | 2016-11-25 | 2017-02-15 | 南通汉瑞新材料科技有限公司 | Method for preparing vanadium-nitrogen alloy by utilizing vanadium trioxide |
| CN109321811A (en) * | 2018-11-18 | 2019-02-12 | 湖南众鑫新材料科技股份有限公司 | Vanadium nitride powder at block method |
| CN114249306A (en) * | 2021-12-06 | 2022-03-29 | 武汉科技大学 | Vanadium nitride based on vanadium-rich liquid and preparation method thereof |
| CN115637367A (en) * | 2022-10-21 | 2023-01-24 | 武汉科技大学 | Vanadium-nitrogen alloy based on vanadium compound and preparation method thereof |
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Application publication date: 20130206 |