CN104404333B - 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 - Google Patents
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 Download PDFInfo
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Abstract
The present invention relates to field of steel metallurgy more particularly to a kind of feedstock composition for being used to prepare superelevation vanadium nitride and using the method for raw material preparation superelevation vanadium nitride.A kind of feedstock composition being used to prepare superelevation vanadium nitride, the composition include vanadium-containing compound, carbonaceous reducing agent and binder, and the binder is melamine.The present invention realizes the mass production of VN19 alloy product under the conditions of low cost.The vanadium nitride of the superelevation nitrogen content of production has carried out the pilot production of high-strength deformed steel bar climbing steel.Product quality indicator: nitrogen content: 17-21%, carbon content < 2.0%, oxygen content < 2.0%, content of vanadium 75-78%.
Description
Technical field
The present invention relates to field of steel metallurgy more particularly to a kind of feedstock composition for being used to prepare superelevation vanadium nitride and adopt
With the method for raw material preparation superelevation vanadium nitride.
Background technique
Vanadium nitrogen 19 is the high-level product in VN alloy series of products, belongs to high added value vanadium deep processed product, can be with
The production that vanadium iron is used for micro alloyed steel is substituted, intensity, toughness, ductility and thermal fatigue resistance of steel etc. can be improved by adding in steel
Comprehensive mechanical performance effectively improves the welding performance of steel.Under same intensity, alloy of vanadium nitride is added, vanadium addition can be saved
30-40% is measured, steel making working procedure cost is greatly lowered.
Since output of steel sharply expands in recent years, profile output increases, and casting and rolling process is using increasingly extensive, rolling
Speed and finish to gauge speed greatly improve, and many of these is all the new grade III steel containing vanadium.Exist it is therefore desirable to reduce vanadium carbide nitride
Solubility in ferrite improves its speed from ferrite Precipitation Temperature and precipitation, maximumlly to reach precipitating using vanadium
The effect of reinforcing.
Some researches show that ferritic formation is primarily due in austenite precipitate with the presence of vanadium nitride in crystal.Even if
In the technique using vanadium iron, vanadium is all to start to be precipitated inside austenite in the form of almost pure vanadium nitride, and be precipitated
Start temperature sharply increased with the raising of nitrogen content, only when nitrogen is soon used up, ability gradual change formed vanadium carbide nitride
The isomorphous precipitating.From austenite into ferritic phase transition process carbon under the size of precipitation enhancement and given phase transition temperature
The solvability of vanadium nitride is inversely proportional.And solvability of the vanadium carbide in austenite is more much higher than vanadium nitride, pure vanadium carbide
Precipitating will not even be generated inside austenite.In addition, for vanadium micro alloyed steel, every nitrogen for increasing 10ppm can to surrender
Intensity increases 6MPa, this relationship is almost linear.In conclusion nitrogen takes on important angle in terms of precipitation strength
Color.It in terms of promoting the formation of vanadium carbide nitride of a large amount of and even dispersion, improve rolling temperature and in terms of from
Important role so that nitrogen becomes control precipitation enhancement and becomes preferred element in terms of improving the yield strengths of steel.
Chinese invention patent (application number: 200910194234.3 applyings date: 2009-11-27) discloses a kind of vanadium nitride
Preparation method, which is to mix vanadium-containing compound with organic nitrogen compound, calcines, is nitrogenized in nitrogenous gas
Vanadium.
Chinese invention patent (application number: the 201210291750.X applying date: 2012-08-16) discloses a kind of vanadium nitride
Preparation method, which is to press powdery vanadium oxide, carbonaceous reducing agent and bonding agent aqueous solution after mixing
Bulk is made, then is added continuously in binary channels pushed bat kiln after block material is dried, in kiln inner pressure 10-100Pa and gas
Under protective condition, reduction, sintering, nitridation reaction and cooling occur for each temperature region in kiln, and final production, which goes out, has obtained content
For 77-80%V, 11-18%N, 2-8%C, product density 3.2-4.1g/cm3Vanadium nitride product.The method achieve continuous raw
It produces, is easy to get with raw material, stable technical process, high production efficiency, reduction efficiency is high, and reaction temperature is low, and the thermal efficiency is high, and low energy consumption
The advantages that.
Chinese invention patent (application number: 201310614215.8 applyings date: 2013-11-28) is disclosed with five oxygen of powdery
Change two vanadium and carbon black is raw material, powdery vanadic anhydride and carbon black is mixed according to 1 ︰ of mass ratio (0.33 ~ 0.35), then additional original
Expect the water of 4 ~ 6wt%, mix, be pressed into autoreduction ball, autoreduction ball is packed into electric furnace, 620 are warming up in nitrogen atmosphere
~ 650 DEG C, keep the temperature 1.5 ~ 2.5 hours；1250 ~ 1300 DEG C are then heated to, keeps the temperature 2 ~ 3 hours, furnace cooling；It will finally come out of the stove
Vanadium nitride afterwards is broken, and the polyvinyl alcohol water solution that the concentration of additional 2 ~ 3wt% of raw material is 4% after being crushed stirs and evenly mixs, with strength
Ball press suppresses balling-up, obtains alloy of vanadium nitride.The pressure of the compacting balling-up is 12 ~ 14MPa, repeats compacting 2 ~ 3 times.The party
Method has the characteristics that simple process, strong operability, with short production cycle, low energy consumption low with production cost, prepared vanadium nitride
Alloy quality is stable, nitrogen content is high and apparent density is higher.
Chinese invention patent (application number: 201410289772.1 applyings date: 2014-06-26) discloses molten using liquid phase
Agent thermal method prepares vanadium nitride, and liquid phase uses aqueous solution or alcohols solvent, and vanadium source is the divalent, trivalent or tetravalence chloride, sulphur of vanadium
Hydrochlorate, nitrate and acetate, nitrogen source are ammonia, urea, hydrazine, ammonium chloride, ammonium carbonate, ammonium acetate, ammonium sulfate.Party's legal system
Standby process does not need to eliminate the discharge of preparation process percent of greenhouse gases as reducing agent using carbon or hydrogen, while eliminating yet
Impurity carbon in vanadium nitride, alloy synthesis temperature is lower than 400 DEG C in this method；The vanadium nitride nitrogen content of this method synthesis
Highest can achieve 21% theoretical content.
Chinese invention patent (application number: 201410309698.5 applyings date: 2014-07-01) discloses a kind of vanadium nitride
Iron and preparation method thereof, method includes the following steps: barium oxide, carbonaceous powder, iron powder, aqueous binders and nitridation are promoted
It mixes and is compacted into agent, form material block；Material block is dried, then block is expected in heating in a nitrogen atmosphere in the reactor,
It is cooling after heating, to obtain ferrovanadium nitride.This method passes through reasonable ingredient and the exact operations to equipment, can significantly mention
The apparent density of high ferrovanadium nitride, and improve the nitrogen content in ferrovanadium nitride.
Currently, vanadium nitrogen 19 is the high-level product in VN alloy series of products, belong to high added value vanadium deep processed product,
Production of the vanadium iron for micro alloyed steel can be substituted, the intensity, toughness, ductility and thermal fatigue resistance that can improve steel in steel are added
The comprehensive mechanical performances such as property, effectively improve the welding performance of steel.Under same intensity, alloy of vanadium nitride is added, vanadium can be saved
Steel making working procedure cost is greatly lowered in additional amount 30-40%, currently, market sale is ensuring vanadium mostly based on 16 alloy of vanadium nitrogen
Under the premise of 16 alloy yield of nitrogen and sales volume are occupied an leading position, accelerates the new-product development dynamics of higher level, make full use of elder generation
Into shaft furnace production technique, adjust formula and processing technology, studied repeatedly and pilot production, realized under the conditions of low cost
The mass production of VN19 alloy product.
Summary of the invention
It is an object of the present invention to provide a kind of feedstock compositions for being used to prepare superelevation vanadium nitride, using the raw material group
It closes object and produces vanadium nitride, the nitrogen content in vanadium nitride is high, reduces the time required for nitridation, has saved energy consumption, extended furnace
The service life of son.A second object of the present invention is to provide the methods using above-mentioned raw materials composition preparation superelevation vanadium nitride.
In order to realize first above-mentioned purpose, present invention employs technical solutions below:
A kind of feedstock composition being used to prepare superelevation vanadium nitride, the composition include vanadium-containing compound, carbonaceous reducing agent
And binder, the binder are melamine.
Preferably, the feedstock composition is mainly made of following component by weight: 100 parts of vanadium-containing compound, powder
10 ~ 40 parts of last shape carbonaceous reducing agent, 1 ~ 15 part of melamine.
As further preferably, which is mainly made of following component by weight: 100 parts of vanadium-containing compound,
18 ~ 25 parts of powdered carbonaceous reducing agent, 3 ~ 8 parts of melamine.
Preferably, the feedstock composition further includes 2% weight ratio of feedstock composition water below.
Preferably, the vanadium-containing compound is ammonium metavanadate, poly ammonium vanadate, vanadic anhydride, vanadium dioxide, three
At least one of V 2 O.
As further preferably, the vanadium-containing compound is the mixture of vanadic anhydride or vanadium trioxide or both.
Preferably, the carbonaceous reducing agent is active carbon, carbon black, natural graphite, graphous graphite powder and crystalline flake graphite
One of or it is a variety of.
As further preferably, the carbonaceous reducing agent is powdered graphous graphite powder, and granularity is 80 ~ 150 mesh.
In order to realize second above-mentioned purpose, present invention employs technical solutions below:
A kind of preparation method of superelevation vanadium nitride, this method include the following steps:
1) being pressed into diameter after mixing a kind of above-mentioned feedstock composition for being used to prepare superelevation vanadium nitride is 30 ~ 60mm
Semi-finished product ball, then naturally dry；
2) the semi-finished product ball after drying continuously puts into middle-end equipped in the shaft kiln of intermediate frequency furnace, and material first passes around vertical
The upper end preheating and drying of kiln, drying temperature are 400 ~ 600 DEG C, and the time is 1 ~ 2 hour, then arrive the Medium frequency induction of shaft kiln middle-end
Furnace, intermediate frequency furnace are passed through high pure nitrogen, keep 0.01 ~ 0.03MPa of micro-positive pressure in furnace, 900 ~ 1150 DEG C of temperature, are carbonized
It nitridation reaction 4 ~ 6 hours, finally arrives shaft kiln lower end and carries out cooling 1 ~ 2 hour, be cooled to 150 DEG C with bottom discharge, in this way every 6 ~ 8
Hour feeds intake once, and discharging is primary.
Preferably, the intermediate frequency furnace is to heat loop diameter in the Medium frequency induction shaft furnace of 500mm-1000mm.
The present invention due to the adoption of the above technical solution, using melamine as binder, during the reaction three
The decomposition of poly cyanamid does not remain any impurity, and the nitrogen for decomposing generation can be used as cryogenic nitrogen agent, decomposes the protium of generation
It can be used as low-temperature reduction agent, the oxygen element content in vanadium oxide be substantially reduced；Melamine, which is formed by hole after decomposing, to be made
The raising of the specific surface area of low price barium oxide significantly is obtained, this improves the contact area of high-temperature ammonolysis stage and nitrogen, because
The nitrogen content of this vanadium nitride is high, reduces the time required for nitridation, has saved energy consumption, extended the service life of stove.
The present invention realizes the mass production of VN19 alloy product under the conditions of low cost.The superelevation nitrogen content of production
Vanadium nitride carried out the pilot production of high-strength deformed steel bar climbing steel.Product quality indicator: nitrogen content: 17-21%, carbon content
< 2.0%, oxygen content < 2.0%, content of vanadium 75-78%.
Specific embodiment
Embodiment 1
By 100kg purity be 98% powdery vanadic anhydride, the graphite powder that 22kg granularity is 100 mesh and 6kg trimerization
Cyanamide after mixing, the semi-finished product ball of diameter 50mm ± 0.5mm is made of high-pressure ball press, spare after spontaneously drying 3 ~ 5 days.
Semi-finished product ball is continuously put into middle-end equipped in the shaft kiln of intermediate frequency furnace when feeding intake, material first passes around the upper end preheating of shaft kiln
Dry, drying temperature is 500 DEG C, and the time is 1 hour, then arrives the intermediate frequency furnace of shaft kiln middle-end, intermediate frequency furnace is with 14m3/
H is passed through high pure nitrogen, keeps micro-positive pressure 0.02MPa in furnace, 1000 DEG C ± 100 DEG C of temperature, carries out carbonization nitridation reaction 4 hours,
The storing cooling chamber of shaft kiln lower end is finally arrived, cooling chamber jacketed is water-cooled, and it is 1 hour cooling, it is cooled to 150 DEG C or less and goes out
Material fed intake primary every 6 hours, and discharging is primary, fed upper end furnace body temperature for the second time at 500 DEG C, continuous production is available
Product V:75.96%, N:18.54%, C:1.16%, density 3.5g/cm3.
Embodiment 2
By 100kg purity be 98% powdery vanadic anhydride, the melamine that 20kg granularity is the graphite powder of 100 mesh, 6kg
Amine after mixing, the semi-finished product ball of diameter 50mm ± 0.5mm is made of high-pressure ball press, spare after spontaneously drying 3 ~ 5 days.It throws
Semi-finished product ball is continuously put into middle-end equipped in the shaft kiln of intermediate frequency furnace when material, the upper end preheating that material first passes around shaft kiln is dry
Dry, drying temperature is 550 DEG C, and the time is 1 hour, then arrives the intermediate frequency furnace of shaft kiln middle-end, intermediate frequency furnace is with 14m3/h
It is passed through high pure nitrogen, micro-positive pressure 0.02MPa in furnace is kept, 1000 DEG C ± 100 DEG C of temperature, carries out carbonization nitridation reaction 4 hours,
The storing cooling chamber of shaft kiln lower end is finally arrived, cooling chamber jacketed is water-cooled, and it is 1 hour cooling, it is cooled to 150 DEG C or less and goes out
Material fed intake primary every 6 hours, and discharging is primary, fed upper end furnace body temperature for the second time at 550 DEG C, continuous production is available
Product V:77.17%, N:19.29, %C:1.53, density 3.15g/cm3.
Embodiment 3
By 100kg purity be 98% powdery vanadic anhydride, the melamine that 24kg granularity is the graphite powder of 100 mesh, 6kg
Amine after mixing, the semi-finished product ball of diameter 50mm ± 0.5mm is made of high-pressure ball press, spare after spontaneously drying 3 ~ 5 days.It throws
Semi-finished product ball is continuously put into middle-end equipped in the shaft kiln of intermediate frequency furnace when material, the upper end preheating that material first passes around shaft kiln is dry
Dry, drying temperature is 450 DEG C, and the time is 1 hour, then arrives the intermediate frequency furnace of shaft kiln middle-end, intermediate frequency furnace is with 14m3/h
It is passed through high pure nitrogen, micro-positive pressure 0.02MPa in furnace is kept, 1000 DEG C ± 100 DEG C of temperature, carries out carbonization nitridation reaction 4 hours,
The storing cooling chamber of shaft kiln lower end is finally arrived, cooling chamber jacketed is water-cooled, and it is 1 hour cooling, it is cooled to 150 DEG C or less and goes out
Material fed intake primary every 6 hours, and discharging is primary, fed upper end furnace body temperature for the second time at 450 DEG C, continuous production is available
Product V:78.27%, N:20.69, %C:1.06, density 3.1g/cm3.
Claims (5)
1. a kind of preparation method of superelevation vanadium nitride, it is characterised in that this method includes the following steps:
1) the semi-finished product ball that diameter is 30 ~ 60mm is pressed into after mixing the feedstock composition for being used to prepare superelevation vanadium nitride, then
Naturally dry；The feedstock composition is made of following component by weight: 100 parts of vanadium-containing compound, powdered carbonaceous reduction
18 ~ 25 parts of agent, 3 ~ 8 parts of melamine and 2% weight ratio of feedstock composition water below；
2) the semi-finished product ball after drying continuously puts into middle-end equipped in the shaft kiln of intermediate frequency furnace, and material first passes around shaft kiln
Upper end preheating and drying, drying temperature are 400 ~ 600 DEG C, and the time is 1 ~ 2 hour, then arrive the intermediate frequency furnace of shaft kiln middle-end, in
Frequency induction furnace is passed through high pure nitrogen, keeps 0.01 ~ 0.03MPa of micro-positive pressure in furnace, 900 ~ 1150 DEG C of temperature, carries out carbonization nitridation
Reaction 4 ~ 6 hours finally arrives shaft kiln lower end and carries out cooling 1 ~ 2 hour, is cooled to 150 DEG C with bottom discharge, in this way every 6 ~ 8 hours
It feeds intake primary, discharging is primary, and the vanadium-containing compound is ammonium metavanadate, poly ammonium vanadate, vanadic anhydride, vanadium dioxide, three
At least one of V 2 O.
2. a kind of preparation method of superelevation vanadium nitride according to claim 1, it is characterised in that: vanadium-containing compound is five oxygen
Change the mixture of two vanadium or vanadium trioxide or both.
3. a kind of preparation method of superelevation vanadium nitride according to claim 1 or 2, it is characterised in that: carbonaceous reducing agent is
One of active carbon, carbon black, natural graphite, graphous graphite powder and crystalline flake graphite are a variety of.
4. a kind of preparation method of superelevation vanadium nitride according to claim 3, it is characterised in that: carbonaceous reducing agent is powder
Shape graphous graphite powder, granularity are 80 ~ 150 mesh.
5. a kind of preparation method of superelevation vanadium nitride according to claim 1, it is characterised in that: intermediate frequency furnace is heating
Medium frequency induction shaft furnace of the loop diameter in 500mm-1000mm.
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| CN105671393A (en) * | 2016-01-07 | 2016-06-15 | 湖北湖大天沭新能源材料工业研究设计院有限公司 | Preparation method for micro-negative-pressure vanadium nitride and product thereof |
| CN107012385A (en) * | 2017-04-10 | 2017-08-04 | 攀钢集团研究院有限公司 | The preparation method of high nitrogen VN alloy |
| CN110923558B (en) * | 2019-10-30 | 2024-02-13 | 中色（宁夏）东方集团有限公司 | Preparation method of high-nitrogen vanadium-nitrogen alloy |
| CN114195522B (en) * | 2021-11-30 | 2023-05-26 | 松山湖材料实验室 | Method for rapidly preparing vanadium nitride ceramic powder by utilizing urea nitridation, product and application thereof |
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| CN101372321A (en) * | 2008-10-21 | 2009-02-25 | 冯良荣 | Method for preparing vanadium nitride |
| CN101693529A (en) * | 2009-10-12 | 2010-04-14 | 冯良荣 | Method for preparing vanadium nitride |
| CN102534219A (en) * | 2012-02-22 | 2012-07-04 | 浙江欣万飞科技有限公司 | Preparation method of vanadium nitride iron alloys for preventing bonding after alloy sintering |
| CN103303880A (en) * | 2013-06-24 | 2013-09-18 | 湘西自治州丰达合金科技有限公司 | Production process for preparing high-nitrogen vanadium nitride by using vacuum furnace method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372321A (en) * | 2008-10-21 | 2009-02-25 | 冯良荣 | Method for preparing vanadium nitride |
| CN101693529A (en) * | 2009-10-12 | 2010-04-14 | 冯良荣 | Method for preparing vanadium nitride |
| CN102534219A (en) * | 2012-02-22 | 2012-07-04 | 浙江欣万飞科技有限公司 | Preparation method of vanadium nitride iron alloys for preventing bonding after alloy sintering |
| CN103303880A (en) * | 2013-06-24 | 2013-09-18 | 湘西自治州丰达合金科技有限公司 | Production process for preparing high-nitrogen vanadium nitride by using vacuum furnace method |
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