CN103303880A - Production process for preparing high-nitrogen vanadium nitride by using vacuum furnace method - Google Patents
Production process for preparing high-nitrogen vanadium nitride by using vacuum furnace method Download PDFInfo
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- CN103303880A CN103303880A CN2013102524011A CN201310252401A CN103303880A CN 103303880 A CN103303880 A CN 103303880A CN 2013102524011 A CN2013102524011 A CN 2013102524011A CN 201310252401 A CN201310252401 A CN 201310252401A CN 103303880 A CN103303880 A CN 103303880A
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Abstract
The invention discloses a production process for preparing high-nitrogen vanadium nitride by using a vacuum furnace method, and relates to a production process for producing a high-nitrogen vanadium nitride product in a vacuum resistance furnace by taking high-purity vanadium pentoxide powder as the raw material through a nitridation sintering method. According to the production process, the process procedures of reduction, nitridation and sintering are carried out in a vacuum furnace, so that the energy consumption is low, the process control is accurate, the production efficiency of the product is high and stable, and the environment is not polluted.
Description
Technical field
The present invention relates to a kind of production technology of producing vanadium nitride, refer more particularly to the standby high nitrogen vanadium nitride production technology of vacuum oven legal system.
Background technology
Vanadium nitride is good steel-making additive, can be used for structure iron, tool steel, reinforcing bar and cast iron, can significantly improve the comprehensive mechanical performances such as wear resistance, rotproofness, toughness, intensity, hardness, ductility and thermal fatigue resistance of steel, and make steel have good weldability energy, and play effects such as eliminating the inclusion extension.The increase of nitrogen content has reduced grow up trend with alligatoring of precipitated phase in the vanadium steel, and the precipitated phase particle attenuates, more give full play to the effect of vanadium.Especially in high-strength low-alloy steel, vanadium nitride has more effective precipitation strength and Grain Refinement Effect than vanadium iron, can save the vanadium of 20 %-40 % simultaneously in high-strength low-alloy steel, thereby reduces the STEELMAKING PRODUCTION cost, has good using value.The production of domestic all the high-quality steel of country's clear must be added vanadium nitride.
At present, in producing the existing technology of vanadium nitride, all adopt nitriding process, traditional preparation method is that compound ammonium vanadate (NH4VO3), ammonium poly-vanadate take oxide compound V203, the V205 of vanadium or vanadium etc. is as raw material, take carbonaceous, hydrogen, ammonia, CO etc. as reductive agent, under high temperature or vacuum, reduce, pass into again afterwards nitrogen or ammonia and carry out nitrogenize and prepare.The method for preparing vanadium nitride can be divided into high-temperature vacuum method and the antivacuum method two large classes of high temperature by the difference of preparation condition, and the mode of production is divided into continous way production and batch production.
The method that U.S. combinating carbide company prepares vanadium nitride has following three kinds: (1) with V2O3, iron powder and carbon dust mixing after compound stalk forming, in vacuum oven, behind 1385 ℃ of lower insulation 60h, obtain vanadium carbide, respectively nitriding 2 hours and 6 hours when cooling the temperature to again 1100 ℃ and 1000 ℃, make and contain 78.7% V, 7.3 % N, the vanadium nitride of 10.5 % C; (2) in vacuum oven, be heated to 1100-1500 ℃ with V2O5 and carbon mixture, vacuumize and pass into nitrogen nitriding, repeat such process for several times, obtain at last vanadium nitride; (3) take high price barium oxide V2O5 or compound (NH4VO3) etc. as raw material, take mixed gas (N2+NH3 or N2+H2) as reductive agent and nitridizing agent, first at 675-700 ℃ of lower prereduction 1h, low-melting high price barium oxide is reduced into dystectic Low Valent Vanadium oxide compound, under 950 ℃, reduce simultaneously afterwards and nitriding 3-4h, can obtain to contain the nitrogen vanadyl product that the oxygen massfraction is 3 %-, 20 %, again it is mixed with carbonaceous material, 1400 ℃ of pyroprocessing under inertia or nitrogen atmosphere or in the vacuum oven, obtain at last basic composition is of vanadium nitride: 80 % V, 12 % N, 7 % C, 2 % O.
The thick grade of the Wang Gong of University of Science ﹠ Technology, Beijing people was in " laboratory study of vanadium carbide, carbon vanadium nitride manufacturing condition " in 1988, the preparation method of vanadium nitride has been proposed, namely to use V2O5 and gac compound stalk forming, under experiment condition, carry out carbothermic reduction, in 1673K and 1. first reduction generates VC under the 333Pa vacuum, pass into subsequently nitrogen, nitriding 1 under 101325Pa. 5 hours, can obtain 86 % V, 7 % C, 9. 069-9.577 % N, the sample of 2 % O.In order to improve the intensity of vanadium nitride, in raw material, add 3 % iron powders.
2008; the people such as Liu Xiansong patent " a kind of production method of high-density vanadium-nitrogen alloy " (application number: 200810022372. 9) in; employing is external-heating rotary kiln under nitrogen atmosphere; under nitrogen protection, burn in advance below 1000 ℃, collect the bulk product that under nitrogen protection, is cooled to the pre-burning of room temperature at discharge port.Then push in the improved soft magnetism nitrogen atmosphere stove, be heated to 1000-1500 ℃ of temperature, material generation carbonization and nitrogenizing reaction, the rear acquisition vanadium-nitrogen alloy product of coming out of the stove.
Chinese patent 200710054260.7 " a kind of production method of VN alloy ", be Vanadium Pentoxide in FLAKES is levigate after, add iron powder, carbon dust, after mixing, makes by binding agent globe, globe is sent in the horizontal pushed bat kiln, pass into nitrogen in the pushed bat kiln, and make and remain pressure-fired in the kiln, globe carries out carbonization and nitrogenizing reaction in kiln, the temperature of carburizing reagent is 1350-1500 ℃, reaction times 2-3. 5 hours, the temperature of nitrogenizing reaction is 1000-1150 ℃, the reaction times 0. 5-1. and 5 hours, be cooled to gradually below 100 ℃ and come out of the stove.
The ubiquitous main drawback of method of producing at present vanadium nitride is: speed of response is slow, production cycle is long, productivity is low, energy consumption is high, technique is complicated, and the reliability of equipment is lower, and controllability is relatively poor, and, the product nitrogen content is low, and general nitrogen content exists: about 7%--14%, can not be referred to as high nitrogen vanadium nitride, foreign matter content is high, carbon content exists: between the 4%--10%, can not satisfy the client to the requirement of product low-carbon (LC), therefore, studying a kind of high nitrogen vanadium nitride production method, is the present technical issues that need to address.
Summary of the invention
For above-mentioned technological deficiency, the purpose of this invention is to provide a kind ofly take the high purity vanadic anhydride powder as raw material, adopt nitridation sintered method in vacuum resistance furnace, to produce the production technique of high nitrogen vanadium nitride product.
Process technology scheme of the present invention is finished as follows:
The first step: high purity vanadic anhydride (V2O5 content 〉=99.5%) powder is added reductive agent, binding agent, efficient nitrogenize promotor by a certain percentage, the wherein wt ratio is: Vanadium Pentoxide in FLAKES accounts for 68%, reductive agent accounts for 16%, binding agent accounts for 12%, efficiently nitrogenize promotor accounts for 5%, in this process program, reductive agent is Graphite Powder 99, and binding agent is polyvinyl alcohol water solution, efficient nitrogenize promotor is the organic nitrogen compound class, such as: urea, hydrazine, trimeric cyanamide etc.;
Second step: the material for preparing is put into whipping device mix, put into afterwards four post hydraulic efficiency installations or pair roller type hydraulic efficiency installation, material is pressed into cake or pelletizing shape, this is the pre-treatment of material;
The 3rd step: pretreated material is positioned on the rail type material dolly, and the material dolly is pushed in the vacuum oven, and the airtight vacuum smelting furnace;
The 4th step: use the vacuum pump unit of two-stage high-power high-vacuum, with vacuum tightness in certain pumping speed control vacuum oven, the invention reside in and regulate suitable vacuum tightness index, be beneficial to provide nitrogen and vanadium sintering best atmosphere;
The 5th step: when vacuum tightness is evacuated to 200Pa in stove, begin to carry out heating in the stove.This production technique uses ULTC to send electrically heated to the molybdenum electrode of vacuum smelting furnace.Electrode voltage can many grades of pressure regulation, so that accurately control temperature required in the stove and the speed of temperature rise;
The 6th step: vacuum tightness in the stove is evacuated to 50-100Pa, heat to 800 ℃ and under this temperature, be incubated 3-4 hours, make Vanadium Pentoxide in FLAKES and carbon carry out prereduction, then continue to be warmed up to 1300 ℃ and continue to be no less than 4 hours drastic reduction and carbonization, constantly be filled with during the course purity 99. the nitrogen that 9 % are above;
The 7th step: be incubated under optimum temps and pressure, pressurize, more be conducive to infiltration and the homogeneous phase of nitrogen, this is the key that reaches high nitrogen content.In the present invention, found a suitable time value to keep state of the art, be about to temperature in the stove and be warming up to 1500 ℃ and carry out 4-6 hours nitridation sintered, this pressure process is controlled at 0 .25-0.35Mpa, and after reaction was finished, cooling had a power failure;
The 8th step: this production technique adopts best cooling chart that vacuum oven is slowly swelled temperature drop and presses, when temperature reaches between 200-250 ℃ a certain value, and unlatching vacuum oven, extract trolley.
Beneficial effect of the present invention:
1, adopts that nitrogen content can reach 15%-18% in the vanadium nitride of this explained hereafter, be higher than the nitrogen content that existing other production technique draws product far away, for other production technique the superiority that can't compare is arranged, and this product carbon-containing impurities be very low, C＜4% is much better than other like product;
2, production technique of the present invention has realized industrial sector production, adopts same transformer bank to be powered in turn two vacuum ovens, can realize continual production, and the output of every day can reach the 5-8 ton, is that other production technique is incomparable;
3, the present invention adopt that vacuum oven reduces, nitrogenize, sintering process process, energy consumption is low, technology controlling and process is accurate, products production efficient is high and stable, environmentally safe.
Description of drawings
Fig. 1 is the process flow sheet for the preparation of high nitrogen vanadium nitride of the present invention.
Embodiment
Embodiment 1
1, with 2.72 tons of high purity vanadic anhydride (V2O5 content 〉=99.5%), 0.64 ton of reductive agent Graphite Powder 99,0.48 ton of binding agent polyvinyl alcohol water solution, 0.2 ton in efficient nitrogenize promotor urea is put into whipping device and is mixed, four kinds of material gross weights are 4 tons, mixed uniformly material is put into four-column hydraulic press to be pressed, the material shapes that is pressed into is the cylindrical pie of Φ 50*30, with the material convey materials dolly of packing into, every chassis is put 1 ton, put 4 cars and amount to 4 tons, 4 dollies are pushed vacuum smelting furnace and airtight;
2, vacuum oven is vacuumized, to 50-100Pa, heat to 800 ℃ and under this temperature the insulation 3.5 hours, make Vanadium Pentoxide in FLAKES and carbon carry out prereduction, then continue to be warmed up to 1300 ℃ of drastic reduction and carbonizations that continue 4 hours, constantly be filled with during the course the above nitrogen of purity 99.9 %;
3, temperature in the stove is warming up to 1500 ℃ and carries out 5 hours nitridation sintered, this pressure process is controlled at 0.3Mpa, and after reaction was finished, cooling had a power failure; When the slow cooling temperature is down to 246 ℃, open fire door, take out material;
4, material is cooled to room temperature, metering, packing warehouse-in, and this time production process draws product by analysis, obtains alloy of vanadium nitride, wherein following (the unit: %) of constituent content
| Element | V | N | C |
| Content (%) | 78.79 | 15.93 | 3.1 |
Embodiment 2
1, with 4.08 tons of high purity vanadic anhydride (V2O5 content 〉=99.5%), 0.96 ton of reductive agent Graphite Powder 99,0.72 ton of binding agent polyvinyl alcohol water solution, 0.9 ton in efficient nitrogenize promotor urea is put into whipping device and is mixed, four kinds of material gross weights are 6 tons, mixed uniformly material is put into the pair roller type hydraulic forming machine to be pressed, the material shapes that is pressed into be 50*35*25 with spherical, with the material convey materials dolly of packing into, every chassis is put 1.5 tons, put 4 cars and amount to 6 tons, 4 dollies are pushed vacuum smelting furnace and airtight;
2, vacuum oven is evacuated to 120Pa, heat to 850 ℃ and under this temperature the insulation 4 hours, make Vanadium Pentoxide in FLAKES and carbon carry out prereduction, then continue to be warmed up to 1350 ℃ of drastic reduction and carbonizations that continue 6 hours, constantly be filled with during the course the above nitrogen of purity 99.9 %;
3, temperature in the stove is warming up to 1500 ℃ and carries out 6 hours nitridation sintered, this pressure process is controlled at 0.35Mpa, and after reaction was finished, cooling had a power failure; When the slow cooling temperature is down to 200 ℃, open fire door, take out material;
4, material is cooled to room temperature, metering, packing warehouse-in, this time production process draws product by analysis, obtains alloy of vanadium nitride, wherein constituent content following (unit: %):
| Element | V | N | C |
| Content (%) | 78.47 | 16.32 | 2.92 |
Claims (1)
1. a vacuum oven legal system is characterized by for high nitrogen vanadium nitride production technique:
Process technology scheme of the present invention is finished as follows:
The first step: high purity vanadic anhydride (V2O5 content 〉=99.5%) powder is added reductive agent, binding agent, efficient nitrogenize promotor by a certain percentage, the wherein wt ratio is: Vanadium Pentoxide in FLAKES accounts for 68%, reductive agent accounts for 16%, binding agent accounts for 12%, efficiently nitrogenize promotor accounts for 5%, in this process program, reductive agent is Graphite Powder 99, and binding agent is polyvinyl alcohol water solution, efficient nitrogenize promotor is the organic nitrogen compound class, such as: urea, hydrazine, trimeric cyanamide etc.;
Second step: the material for preparing is put into whipping device mix, put into afterwards four post hydraulic efficiency installations or pair roller type hydraulic efficiency installation, material is pressed into cake or pelletizing shape, this is the pre-treatment of material;
The 3rd step: pretreated material is positioned on the rail type material dolly, and the material dolly is pushed in the vacuum oven, and the airtight vacuum smelting furnace;
The 4th step: use the vacuum pump unit of two-stage high-power high-vacuum, with vacuum tightness in certain pumping speed control vacuum oven, the invention reside in and regulate suitable vacuum tightness index, be beneficial to provide nitrogen and vanadium sintering best atmosphere;
The 5th step: when vacuum tightness is evacuated to 200Pa in stove, begin to carry out heating in the stove;
This production technique uses ULTC to send electrically heated to the molybdenum electrode of vacuum smelting furnace;
Electrode voltage can many grades of pressure regulation, so that accurately control temperature required in the stove and the speed of temperature rise;
The 6th step: vacuum tightness in the stove is evacuated to 50--100Pa, heat to 800 ℃ and under this temperature, be incubated 3-4 hours, make Vanadium Pentoxide in FLAKES and carbon carry out prereduction, then continue to be warmed up to 1300 ℃ and continue to be no less than 4 hours drastic reduction and carbonization, constantly be filled with during the course purity 99. the nitrogen that 9 % are above;
The 7th step: be incubated under optimum temps and pressure, pressurize, more be conducive to infiltration and the homogeneous phase of nitrogen, this is the key that reaches high nitrogen content;
In the present invention, found a suitable time value to keep state of the art, be about to temperature in the stove and be warming up to 1500 ℃ and carry out 4--6 hours nitridation sintered, this pressure process is controlled at 0 .25-0.35Mpa, and after reaction was finished, cooling had a power failure;
The 8th step: this production technique adopts best cooling chart that vacuum oven is slowly swelled temperature drop and presses, when temperature reaches between 200-250 ℃ a certain value, and unlatching vacuum oven, extract trolley.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602814A (en) * | 2013-11-28 | 2014-02-26 | 武汉科技大学 | Method for preparing vanadium nitride alloy |
| CN104404333A (en) * | 2014-11-11 | 2015-03-11 | 应忠芳 | Raw material composition for preparing vanadium nitride with ultrahigh nitrogen content and method utilizing same to prepare ultrahigh vanadium nitride |
| CN108842107A (en) * | 2018-06-25 | 2018-11-20 | 江苏渝鑫科技股份有限公司 | A method of passing through sectional temperature-controlled raising VN alloy nitrogen content |
| CN110923557A (en) * | 2019-10-30 | 2020-03-27 | 中色（宁夏）东方集团有限公司 | Preparation method of high-density nitrided ferrovanadium |
| CN111943149A (en) * | 2020-08-25 | 2020-11-17 | 合肥工业大学 | General preparation method of transition metal nitride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4562057A (en) * | 1984-03-29 | 1985-12-31 | Union Carbide Corporation | Preparation of low-carbon vanadium nitride |
| CN101172585A (en) * | 2007-09-30 | 2008-05-07 | 冯良荣 | Method for producing vanadium nitride |
| CN101633497A (en) * | 2009-08-18 | 2010-01-27 | 石明生 | Vanadium nitride production method |
| CN101693975A (en) * | 2009-10-28 | 2010-04-14 | 攀钢集团攀枝花钢钒有限公司 | Method for increasing nitrogen content of vanadium-nitrogen alloy |
| CN102040202A (en) * | 2009-10-13 | 2011-05-04 | 冯良荣 | Method for preparing vanadium nitride |
-
2013
- 2013-06-24 CN CN2013102524011A patent/CN103303880A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4562057A (en) * | 1984-03-29 | 1985-12-31 | Union Carbide Corporation | Preparation of low-carbon vanadium nitride |
| CN101172585A (en) * | 2007-09-30 | 2008-05-07 | 冯良荣 | Method for producing vanadium nitride |
| CN101633497A (en) * | 2009-08-18 | 2010-01-27 | 石明生 | Vanadium nitride production method |
| CN102040202A (en) * | 2009-10-13 | 2011-05-04 | 冯良荣 | Method for preparing vanadium nitride |
| CN101693975A (en) * | 2009-10-28 | 2010-04-14 | 攀钢集团攀枝花钢钒有限公司 | Method for increasing nitrogen content of vanadium-nitrogen alloy |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602814A (en) * | 2013-11-28 | 2014-02-26 | 武汉科技大学 | Method for preparing vanadium nitride alloy |
| CN103602814B (en) * | 2013-11-28 | 2015-07-29 | 武汉科技大学 | A kind of preparation method of alloy of vanadium nitride |
| CN104404333A (en) * | 2014-11-11 | 2015-03-11 | 应忠芳 | Raw material composition for preparing vanadium nitride with ultrahigh nitrogen content and method utilizing same to prepare ultrahigh vanadium nitride |
| CN104404333B (en) * | 2014-11-11 | 2019-01-08 | 应忠芳 | A method of it being used to prepare the feedstock composition of superelevation vanadium nitride and superelevation vanadium nitride is prepared using the raw material |
| CN108842107A (en) * | 2018-06-25 | 2018-11-20 | 江苏渝鑫科技股份有限公司 | A method of passing through sectional temperature-controlled raising VN alloy nitrogen content |
| CN108842107B (en) * | 2018-06-25 | 2020-06-26 | 江苏渝鑫科技股份有限公司 | Method for improving nitrogen content of vanadium-nitrogen alloy through segmented temperature control |
| CN110923557A (en) * | 2019-10-30 | 2020-03-27 | 中色（宁夏）东方集团有限公司 | Preparation method of high-density nitrided ferrovanadium |
| CN111943149A (en) * | 2020-08-25 | 2020-11-17 | 合肥工业大学 | General preparation method of transition metal nitride |
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Application publication date: 20130918 |