CN105838970B - A kind of preparation method of high nitrogen vanadium nitride - Google Patents
A kind of preparation method of high nitrogen vanadium nitride Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C35/00—Master alloys for iron or steel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
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Abstract
The invention provides a kind of preparation method of high nitrogen vanadium nitride, the preparation method comprises the following steps：(1) vanadium oxide, carbonaceous reducing agent and water are subjected to mixing pressure ball and pelletizing is made；(2) obtained pelletizing is put into vertical intermediate frequency furnace, it is 80~200m to be passed through flow3/ h nitrogen, pelletizing are moved from top to bottom in vertical intermediate frequency furnace, are reacted in the bringing-up section of vertical intermediate frequency furnace, and cooling section is cooled down, and vanadium nitride is made.The present invention is by using vertical intermediate frequency furnace, stable reaction atmosphere and course of reaction can be provided using shaft furnace, based on Vanadium valence in vanadium oxide, so as to the phosphorus content in precisely control product, carbon proportion in product can be reduced to greatest extent, ensure the room for promotion of nitrogen content in product；Again by controlling the process conditions such as quality of green pellets, each elementary reaction temperature and nitrogen flow, high nitrogen vanadium nitride is produced.
Description
Technical field
The invention belongs to steel alloy production field, is related to a kind of preparation method of vanadium nitride, more particularly to a kind of high nitrogen
The preparation method of vanadium nitride.
Background technology
The intensity of steel can be improved after vanadium is added in low-alloy high-strength steel, improves the recrystallization temperature of material and high temperatures
Energy.And nitrogen pick-up can improve the creep rupture strength of steel in steel, improve the toughness and plasticity of steel, while also improve heat resistanceheat resistant intensity and resist
Short creep ability, often increases 10ppm nitrogen in vanadium steel, and the intensity of steel can improve 6MPa.Vanadium nitride can be simultaneously to molten steel
Middle increase vanadium and nitrogen, and the production of high nitrogen vanadium nitride product, can reduce vanadium dosage on the basis of steel strength is not reduced, so as to
Reduce steel-making cost.
Vanadium nitride is to protect raw material ball (being pressed into after being mixed in proportion by graphite, vanadium oxide and binding agent) in nitrogen atmosphere
Under High-temp. kiln in, after reducing, nitrogenizing, the VN alloy containing vanadium, nitrogen that is prepared.So-called high nitrogen vanadium nitride refers to
Nitrogen content is more than 16% vanadium nitride, is provided according to VN alloy standard GB/T/T 20567-2006, and VN alloy divides VN12
With two trades mark of VN16, V in wherein VN12：77~81%, N：10~14%, C≤10%, P≤0.06%, S≤0.1%；
V in VN16：77~81%, N：14~18%, C≤6%, P≤0.06%, S≤0.1%, according further to examine product in also about
There is 1% or so oxygen, according to VN16 product compositions, impurity capping, vanadium removes the limit, the quality shared by other essential elements in addition to N
Fraction and for 84.16%, it is assumed that all N of remaining composition, its mass fraction is also only 15.84%, but actual conditions are remaining
Also 2~2.5% other elements, therefore product nitrogen content can only be to 14% or so in C cappings.
Therefore high nitrogen vanadium nitride is produced, it is necessary to the impurity level in addition to V, N in product is controlled, in the certain situation of raw material
Under, can only be by being precisely controlled phosphorus content in product (quantity of graphite being incorporated when being precisely controlled dispensing), to improve the N in product
Content.In addition also need to ensure nitridation reaction of the vanadium nitride in sintering procedure, that is, control reaction condition (including material week in kiln
Nitrogen partial pressure, reaction temperature and reaction time for enclosing etc.).Nitrogen partial pressure therein is mainly determined by nitrogen flow, but and nitrogen
Circulation style also have an important relationship, and reaction temperature is then determined with the reaction time by temperature setting and discharging speed.
At present, vanadium nitride production technology the most ripe is to be loaded raw material ball using horizontal pushed bat kiln (also known as tunnel cave)
After being placed on the graphite tank on graphitic push pedal, promote push pedal make in graphite tank raw material ball have stepped through horizontal push pedal preheating section of kiln,
Discharged after high temperature section and cooling section, obtain vanadium nitride product.Need reserved 30~50mm empty in the technology between batch can and furnace chamber top
Between to ensure that graphite tank moves in stove, therefore furnace gas largely flowed away from graphite tank upper space, both include among these
Nitrogen, and include CO caused by reduction.Thus following shortcoming is produced：
(1) part nitrogen flows away from top, both wastes nitrogen, reduces the nitrogen point in lower purpose square graphite tank around material again
Pressure, if wanting, nitrogen amount can only be increased to improve the nitrogen partial pressure around material by improving product nitrogen content, but increase meeting after nitrogen amount
Nitrogen is increased to wash away the resistance to material of body of heater, converter life will certainly be reduced by producing high nitrogen vanadium nitride, therefore need to converter life with
Accepted or rejected between product nitrogen content；
(2) CO parts caused by reduction flow away from top has no chance to participate in reduction reaction, can not determine to participate in reduction
CO amounts, mixed carbon comtent needs excessive more in raw material, to ensure that vanadium oxide can be reduced fully, therefore is precisely controlled phosphorus content in product
Extremely difficult, mixed carbon comtent typically needs excessive 10~15% in raw material proportioning during production.So in product phosphorus content typically 4% with
On, in the case where the total composition of product is certain, the high nitrogen vanadium nitride using traditional pushed bat kiln production nitrogenous more than 16% is highly difficult；
(3) the nitridation reaction formula of vanadium nitride is produced according to vanadium oxide：VOx+ (x+1) C=VC+xCO；2VC+N2==2VN+
2C can be seen that in nitridation process, when simple substance carbon content is high in pelletizing, can suppress the nitridation process of vanadium carbide, therefore to obtain
To high nitrogen vanadium nitride, the phosphorus content in product need to be controlled.
CN 1422800A disclose a kind of production method of vanadium nitride, and this method is by barium oxide, graphite and 2% poly- second
After enol is well mixed pressure ball, it is added to and is connected with protection and the pushed bat kiln or tunnel cave of reacting gas nitrogen and/or ammonia,
2~6h is reacted at a temperature of 1000~1800 DEG C, is discharged after being cooled to 100~250 DEG C.But this method only discloses the original of vanadium nitride
Material composition and the parameter not specified (NS) such as broad reaction temperature and reaction time, mixed carbon comtent and nitrogen amount to key, and
Used reacting furnace is horizontal positioned pushed bat kiln or tunnel cave.
CN 102173395A disclose a kind of easy vanadium nitride production method, and this method is by V2O5Powder and graphite powder press 4:
After 1 weight ratio is sufficiently mixed on dry-mixed machine, by 100:15 weight than add content be 4% polyvinyl alcohol water solution,
Mixing, pressure ball and after drying, mixing sphere of powder layering is loaded truck, enters stove, sealing fire door, after being passed through nitrogen under vacuum condition,
After keeping 5h, 6h and the common 20h of 6~10h respectively at 800 DEG C, 1350 DEG C and 1600 DEG C, power failure is cooled to 150 DEG C and come out of the stove.The skill
Art discloses accurate raw material proportioning and reaction time, reaction temperature, but its graphite powder amount proportioning is far below normal reaction
Demand and do not announce nitrogen influence, and its production process be at times complete and reacting furnace used be vacuum drying oven.
It is a revolutionary innovation of vanadium nitride production using vertical intermediate frequency furnace production vanadium nitride, it feeds from top, thing
Material discharges after preheating, heating the stages such as reduction, high temperature reduction nitridation and nitridation cooling from bottom from top to bottom.Using vertical
Intermediate frequency furnace production vanadium nitride has the advantage that：
(1) nitrogen distribution is more reasonable in stove.Vertical intermediate frequency furnace is vertical structure, and furnace charge is uniformly distributed in furnace chamber, nitrogen
Distribution and flowing in stove are uniform, ensure nitriding reaction, are advantageous to produce that composition is uniform, nitrogenous higher high nitrogen nitridation
Vanadium；
(2) body of heater internal layer is the graphite lining of machining, and outer layer is ramming mass, and furnace lining is an entirety and good airproof performance,
Resistance to nitrogen scouring capability is strong, can ensure under big flow nitrogen on lining durability influence it is smaller, add so as to increase nitrogen partial pressure
Strong nitriding, strong guarantee is provided to produce high nitrogen vanadium nitride；
(3) in raw material ball, caused CO flows between material gap from bottom to top in reduction process, because CO is uniform
It is stable to flow through in top material and stove to parameters such as spot temperatures, therefore CO caused by reduction participates in reduction reaction again
Ratio is stable, therefore need not match somebody with somebody excessive carbon during feed proportioning, can be precisely controlled mixed carbon comtent, ensures that product is carbon containing low
In 4%.
CN 101963446A disclose a kind of VN alloy full-automatic vertical Medium Frequency Induction Heating Furnace, and the heating furnace is by stone
Black circle alms bowl (batch can) is stacked together, upper endfeed, lower end discharging, but is designed as a result of batch can, and raw material are burnt till ripe in tank
After material, shrinkage factor is in 30% even more high, therefore idle furnace chamber area is up to more than 30% in stove, largely effects on yield.And
Due to being fed using batch can, nitrogen need to be by could contact after the hole on batch can with vanadium nitride pelletizing so that nitrogen can not be certainly
By being circulated between vanadium nitride pelletizing, vanadium nitride nitriding reaction is influenceed, is unfavorable for producing high nitrogen vanadium nitride.
As can be seen here, the means of production of vanadium nitride is many at present, but is concentrated mainly on common vanadium nitride production field, can use
Not yet found in the technology of high nitrogen vanadium nitride production.
The content of the invention
Nitrogen is wasted existing for vanadium nitride for existing prepared with horizontal pushed bat kiln, converter life reduces, and is precisely controlled production
Phosphorus content is extremely difficult in product, and shaft (tower) furnace production vanadium nitride yields poorly, and nitrogen circulation is difficult, it is difficult to prepares high nitrogen (nitrogen content
The problems such as more than 16%) vanadium nitride, the invention provides a kind of preparation method of vanadium nitride.The present invention is by using vertical intermediate frequency
Stove, based on Vanadium valence in vanadium oxide, so as to the phosphorus content in precisely control product, carbon proportion in product is reduced, is protected
Demonstrate,prove the room for promotion of nitrogen content in product；And by controlling the temperature of bringing-up section and cooling section, product nitrogen content is further improved,
Produce high nitrogen vanadium nitride.
To use following technical scheme up to this purpose, the present invention：
The invention provides a kind of preparation method of vanadium nitride, the preparation method comprises the following steps：
(1) vanadium oxide, carbonaceous reducing agent and water are subjected to mixing pressure ball and pelletizing is made；
(2) obtained pelletizing is put into vertical intermediate frequency furnace, it is 80~200m to be passed through flow3/ h nitrogen, pelletizing is vertical
Move in intermediate frequency furnace, reacted in the bringing-up section of vertical intermediate frequency furnace from top to bottom, cooling section is cooled down, and vanadium nitride is made.
Wherein, the flow of nitrogen can be 80m3/h、85m3/h、90m3/h、95m3/h、100m3/h、110m3/h、120m3/h、
130m3/h、140m3/h、150m3/h、160m3/h、170m3/h、180m3/h、190m3/ h or 200m3/ h etc., it is not limited to
Cited numerical value, other interior numerical value of listed scope are feasible.
Currently preferred technical scheme is used as below, but not as the limitation of technical scheme provided by the invention, is passed through
Following technical scheme, it can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, the vanadium oxide is vanadium trioxide, vanadic anhydride or multivalent state oxygen
Change any one in vanadium or at least two combination, more preferably multivalent state vanadium oxide.
Preferably, the valence state of vanadium is+3~+5 valencys in the multivalent state vanadium oxide, such as+trivalent ,+3.5 valencys ,+4 valencys ,+4.5
Valency or+5 valencys etc., it is not limited to cited numerical value, other interior numerical value of listed scope are feasible.
In the present invention, dispensing is carried out on the basis of the valence state of vanadium in vanadium oxide, can more accurately be controlled needed for reaction
The dosage of carbonaceous reducing agent, so as to be precisely controlled phosphorus content in product, carbon proportion in product is reduced, ensure that in product
Nitrogen content.Also, because the production process control of the vanadium oxide of single valence is more difficult, cost is higher, and multivalent state vanadium oxide
Mixture simple production process, production cost can be reduced.
In the present invention, the synthesis valence state of vanadium oxide be by determining the content of vanadium and oxygen in vanadium oxide after, pass through vanadium
With the amount ratio-dependent of oxygen species.
As currently preferred technical scheme, carbonaceous reducing agent is any in graphite, carbon dust or coke blacking in step (1)
It is a kind of or at least two combination, the combination typical case but non-limiting examples have the combination of graphite and carbon dust, carbon dust and coke
The combination of powder, the combination of graphite, carbon dust and coke blacking etc., more preferably graphite.
As currently preferred technical scheme, the weight of vanadium oxide and carbonaceous reducing agent ratio is 1 in step (1):(0.24
, such as 1~0.33):0.24、1:0.25、1:0.26、1:0.27、1:0.28、1:0.29、1:0.30、1:0.31、1:0.32 or
1:0.33 etc., it is not limited to cited numerical value, other interior numerical value of listed scope are feasible.
In the present invention, the consumption proportion of carbonaceous reducing agent is determined by the synthesis valence state of vanadium oxide used.Meanwhile to produce
High nitrogen vanadium nitride, it is necessary to be precisely controlled raw material proportioning, therefore raw material proportioning is determined with the synthesis valence state of vanadium oxide, it is ensured that match somebody with somebody
Material is accurate, and then prepares high nitrogen vanadium nitride.
Preferably, when vanadium oxide is vanadium trioxide in step (1), the weight ratio of vanadium oxide and carbonaceous reducing agent is 1:
0.24。
Preferably, when vanadium oxide is vanadic anhydride in step (1), the weight ratio of vanadium oxide and carbonaceous reducing agent is 1:
0.33。
In the present invention, when vanadium oxide is multivalent state vanadium oxide, i.e., the valence state of vanadium is between+3~+5 valencys in vanadium oxide
When, the weight ratio of vanadium oxide and carbonaceous reducing agent is between 1:Between (0.24~0.33).
As currently preferred technical scheme, the dosage of step (1) reclaimed water is vanadium oxide and carbonaceous reducing agent gross mass
8~12wt%, such as 8wt%, 9wt%, 10wt%, 11wt% or 12wt% etc., it is not limited to cited numerical value,
Other numerical value are feasible in listed scope, more preferably 10~11wt%.
In the present invention, it can ensure that green pellets passes through dried pellet strength in the amount ranges of the water.Water adds
Entering amount has decisive influence to pressure ball quality, the addition of water within this range when can guarantee to be pressed into ball, and can ensures
The intensity of ball is extruded, green-ball is non-breakable during ensureing follow-up dress ball and drying etc..
Obtained pelletizing is put into after drying and screening as currently preferred technical scheme, in step (2) vertical
In intermediate frequency furnace.
In the present invention, dry and screening is to remove the moisture in pelletizing, fragment and chip.
As currently preferred technical scheme, the central temperature of bringing-up section described in step (2) is 1400~1500 DEG C,
Such as 1400 DEG C, 1410 DEG C, 1420 DEG C, 1430 DEG C, 1440 DEG C, 1450 DEG C, 1460 DEG C, 1470 DEG C, 1480 DEG C, 1490 DEG C or
1500 DEG C etc., it is not limited to cited numerical value, other interior numerical value of listed scope are feasible, more preferably 1450~
1500℃。
Preferably, reaction time of the pelletizing in bringing-up section is 16~30h in step (2), for example, 16h, 18h, 20h,
22h, 24h, 26h, 28h or 30h etc., it is not limited to cited numerical value, other interior numerical value of listed scope are feasible, enter one
Step is preferably 24~28h.
In the present invention, ensure reaction time of the pelletizing in bringing-up section by controlling discharging speed.Meanwhile ensure reaction
Time is in order to which nitridation reaction is complete in 16~30h, improves product nitrogen content.
As currently preferred technical scheme, cooling section divides upper and lower part in step (2), and upper temp is 800~
1000 DEG C, such as 800 DEG C, 830 DEG C, 850 DEG C, 870 DEG C, 900 DEG C, 930 DEG C, 950 DEG C, 970 DEG C or 1000 DEG C etc., but simultaneously not only
It is limited to cited numerical value, other numerical value are feasible in listed scope, more preferably 900~950 DEG C；Temperature of lower ＜
200 DEG C, such as 190 DEG C, 180 DEG C, 170 DEG C, 150 DEG C, 130 DEG C, 100 DEG C, 70 DEG C or 50 DEG C and lower temperature, but not
Cited numerical value is only limitted to, other numerical value are feasible in listed scope, more preferably 150 DEG C of ＜.
In the present invention, it is 800~1000 DEG C to define cooling section upper temp, and this is the temperature that nitridation reaction can be carried out
Lower limit, because the nitridation process of vanadium nitride is exothermic reaction, nitriding temperature is reduced in the case of nitrogen content is higher, although reducing
Nitridation reaction speed but nitridation process can be promoted, further improve product nitrogen content.Meanwhile define cooling section temperature of lower ＜
200 DEG C, because vanadium nitride can be oxidized when temperature is more than 200 DEG C, therefore, 200 DEG C of cooling section temperature of lower ＜ is limited, can be kept away
Exempt from product oxidation.
As currently preferred technical scheme, nitrogen is passed through in step (2) to be passed through from cooling section bottom.
Preferably, the flow of nitrogen is 110~150m in step (2)3/h。
As currently preferred technical scheme, the preparation method comprises the following steps：
(1) multivalent state vanadium oxide, graphite and water are subjected to mixing pressure ball and pelletizing, wherein multivalent state vanadium oxide and graphite is made
Weight ratio be 1:(0.24~0.33), the dosage of water is vanadium oxide and 10~11wt% of carbonaceous reducing agent gross mass；
(2) obtained pelletizing is put into vertical intermediate frequency furnace after drying and screening, stream is passed through from cooling section bottom
Measure as 110~150m3/ h nitrogen, pelletizing move from top to bottom in vertical intermediate frequency furnace, vertical intermediate frequency furnace bringing-up section in
1450~1500 DEG C carry out 24~28h of reaction, and cooling section is cooled down, and cooling section upper temp is 900~950 DEG C, bottom temperature
150 DEG C of ＜ is spent, vanadium nitride is made.
In the method for the invention, with the best performance of vanadium nitride made from above-mentioned raw material proportioning and process conditions.
Compared with prior art, the invention has the advantages that：
(1) present invention can ensure that nitrogen and reduction produce the steady of gas in stove using vertical intermediate frequency furnace production vanadium nitride
Fixed and uniformly circulation, in the case where ensureing that raw material proportioning is stable, product quality can be made stable, so as to accurately control production
Phosphorus content in product；Also, the present invention carries out dispensing on the basis of the valence state of vanadium in vanadium oxide, can more accurately control anti-
Quantity of graphite needed for answering, so as to be precisely controlled product phosphorus content.Make the control of the weight of vanadium oxide and carbonaceous reducing agent ratio 1:(0.24
~0.33) when, vanadium oxide is vanadium trioxide, the weight ratio of vanadium oxide and carbonaceous reducing agent is 1:0.24；Vanadium oxide is five oxygen
When changing two vanadium, the weight ratio of vanadium oxide and carbonaceous reducing agent is 1:0.33.Carbon proportion in product is reduced, ensures to contain in product
The room for promotion of nitrogen quantity.
(2) in raw material of the present invention, the addition of water is controlled in proper range, it is ensured that green pellets passes through dried ball
Group's intensity, green-ball is non-breakable during ensureing follow-up dress ball and drying etc., and then improves yield；Meanwhile green pellets passes through
The intensity of green pellets can be improved after drying, after screening, fragment and chip in green pellets are all screened out, it is ensured that material in stove
Gas permeability, ensure material where nitrogen atmosphere, beneficial to nitriding react carry out.
(3) define that cooling section upper temp is maintained in 800~1000 DEG C in the present invention, this is that nitridation reaction can enter
Limited at capable temperature, although nitridation process can be promoted by reducing nitridation reaction speed, further improve product nitrogen content；Cooling
Pars infrasegmentalis defines 200 DEG C of temperature ＜, then product can be avoided to aoxidize.
(4) the method for the invention can produce high nitrogen vanadium nitride, in the vanadium nitride nitrogen content in 17~19wt%,
Far above N16 products nitrogen content in national standard, for improving vanadium utilization rate and invigoration effect of the vanadium nitride in follow-up steel making working procedure
It is highly beneficial.And using the method for the invention production vanadium nitride, its yield can reach 93%, for improving product price,
It is significant to improve product competitiveness in the market.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provides a kind of preparation method of vanadium nitride, and the preparation method includes following step
Suddenly：
(1) vanadium oxide, carbonaceous reducing agent and water are subjected to mixing pressure ball and pelletizing is made；
(2) obtained pelletizing is put into vertical intermediate frequency furnace, it is 80~200m to be passed through flow3/ h nitrogen, pelletizing is vertical
Move in intermediate frequency furnace, reacted in the bringing-up section of vertical intermediate frequency furnace from top to bottom, cooling section is cooled down, and vanadium nitride is made.
The typical but non-limiting example is as follows：
Embodiment 1：
(1) 1000kg vanadium trioxides, 240kg graphite and 99.2kg water are subjected to mixing pressure ball and pelletizing is made, wherein three
The weight of V 2 O and graphite ratio is 1:0.24, the dosage of water is vanadium trioxide and the 8wt% of graphite gross mass；
(2) obtained pelletizing is put into vertical intermediate frequency furnace after drying and screening, stream is passed through from cooling section bottom
Measure as 200m3/ h nitrogen, pelletizing move from top to bottom in vertical intermediate frequency furnace, and bringing-up section central temperature is maintained at 1500 DEG C, ball
Group is cooled down, it is 1000 to control cooling section upper temp after the bringing-up section reaction 30h of vertical intermediate frequency furnace into cooling section
DEG C, temperature of lower is 80 DEG C, discharging, obtains high nitrogen vanadium nitride.
Obtained vanadium nitride composition is：V:77.29%, N:19%, C:0.89%, P:0.013%, S:0.014%, it is produced
Rate is 97.6%.
Embodiment 2：
(1) 1000kg vanadic anhydrides, 330kg graphite and 160kg water are subjected to mixing pressure ball and pelletizing is made, wherein five oxygen
The weight ratio for changing two vanadium and graphite is 1:0.33, the dosage of water is vanadic anhydride and the 12wt% of graphite gross mass；
(2) obtained pelletizing is put into vertical intermediate frequency furnace after drying and screening, stream is passed through from cooling section bottom
Measure as 120m3/ h nitrogen, pelletizing move from top to bottom in vertical intermediate frequency furnace, and bringing-up section central temperature is maintained at 1400 DEG C, ball
Group is cooled down after the bringing-up section reaction 20h of vertical intermediate frequency furnace into cooling section, and it is 800 DEG C to control cooling section upper temp,
Temperature of lower is 150 DEG C, discharging, obtains high nitrogen vanadium nitride.
Obtained vanadium nitride composition is：V:77.10%, N:18.35%, C:0.79%, P:0.013%, S:0.012%,
Its yield is 95.3%.
Embodiment 3：
(1) vanadium oxide of 1000kg tetravalences, 318kg graphite and 131.8kg water are subjected to mixing pressure ball and pelletizing is made, wherein
The vanadium oxide of tetravalence and the weight ratio of graphite are 1:0.318, the dosage of water is the vanadium oxide and graphite gross mass of tetravalence
10wt%；
(2) obtained pelletizing is put into vertical intermediate frequency furnace after drying and screening, stream is passed through from cooling section bottom
Measure as 80m3/ h nitrogen, pelletizing move from top to bottom in vertical intermediate frequency furnace, and bringing-up section central temperature is maintained at 1450 DEG C, pelletizing
After the bringing-up section reaction 16h of vertical intermediate frequency furnace, cooled down into cooling section, it is 900 DEG C to control cooling section upper temp, under
Portion's temperature is 199 DEG C, discharging, obtains high nitrogen vanadium nitride.
Obtained vanadium nitride composition is：V:77.28%, N:17%, C:1.76%, P:0.011%, S:0.013%, it is produced
Rate is 94.1%.
Embodiment 4：
(1) vanadium oxide of the valencys of 1000kg 3.5,292kg graphite and 130kg water are subjected to mixing pressure ball and pelletizing is made, wherein
The vanadium oxide of 3.5 valencys and the weight ratio of graphite are 1:0.292, the dosage of water is the vanadium oxide and graphite gross mass of 3.5 valencys
10wt%；
(2) obtained pelletizing is put into vertical intermediate frequency furnace after drying and screening, stream is passed through from cooling section bottom
Measure as 100m3/ h nitrogen, pelletizing move from top to bottom in vertical intermediate frequency furnace, and bringing-up section central temperature is maintained at 1480 DEG C, ball
Group is cooled down after the bringing-up section reaction 24h of vertical intermediate frequency furnace into cooling section, and it is 950 DEG C to control cooling section upper temp,
Temperature of lower is 100 DEG C, discharging, obtains high nitrogen vanadium nitride.
Obtained vanadium nitride composition is：V:77.85%, N:18.21%, C:1.20%, P:0.012%, S:0.013%,
Its yield is 96.6%.
Embodiment 5：
In the present embodiment, in addition to carbonaceous reducing agent used is carbon dust, each material amounts and preparation process with embodiment 1
It is identical.
Embodiment 6：
In the present embodiment, in addition to carbonaceous reducing agent used is coke blacking, each material amounts and preparation process with embodiment 1
In it is identical.
Comparative example 1：
Except the mass ratio of vanadium oxide and graphite is more than 1 in this comparative example:0.24, it is 1:Outside 0.15, other each materials are used
Amount is in the same manner as in Example 1 with preparation process.
Vanadium nitride composition made from this comparative example is V:72.23%, N:6.21%, C:0.51%, P:0.012%, S:
0.013%, because mixed carbon comtent is not enough to complete reduction reaction, product is unqualified.
Comparative example 2：
Except the mass ratio of vanadium oxide and graphite is less than 1 in this comparative example:0.24, it is 1:Outside 0.4, other each material amounts
It is in the same manner as in Example 1 with preparation process.
Vanadium nitride composition made from this comparative example is V:74.12%, N:5.21%, C:8.54%, P:0.011%, S:
0.011%, due to seriously excessive with carbon, product is unqualified.
Comparative example 3：
It it is 1300 DEG C outer, other each material amounts are with preparing except 1000 DEG C of cooling section upper temp ＞ in this comparative example
Process is in the same manner as in Example 1.
Vanadium nitride composition made from this comparative example is V:77.18%, N:18.63%, C:0.90%, P:0.013%, S:
0.013%, its yield is 97.5%.
Comparative example 4：
It it is 500 DEG C outer, other each material amounts were with preparing except 800 DEG C of cooling section upper temp ＜ in this comparative example
Cheng Jun is in the same manner as in Example 1.
Vanadium nitride composition made from this comparative example is V:77.31%, N:17.93%, C:0.89%, P:0.013%, S:
0.014%, its yield is 97.3%.
Comparative example 5：
It it is 300 DEG C outer, other each material amounts were with preparing except 200 DEG C of cooling section temperature of lower ＞ in this comparative example
Cheng Jun is in the same manner as in Example 1.
Vanadium nitride composition made from this comparative example is V:77.30%, N:18.45%, C:0.89%, P:0.013%, S:
0.013%, its yield is 98%, but there is oxidative phenomena on individual product surface.
Comparative example 6：
It is 5wt% except the dosage of water is less than vanadium oxide and 8~12wt% of carbonaceous reducing agent gross mass in this comparative example
Outside, other each material amounts and preparation process are in the same manner as in Example 1.
The yield of vanadium nitride made from this comparative example is 96.5%.
Comparative example 7：
Except the dosage of water is higher than vanadium oxide and 8~12wt% of carbonaceous reducing agent gross mass in this comparative example, it is
Outside 15wt%, other each material amounts and preparation process are in the same manner as in Example 1.
The yield of vanadium nitride made from this comparative example is 96.8%.
Integrated embodiment 1-6 and comparative example 1-7 result can be seen that the present invention and produces high nitrogen nitrogen using vertical intermediate frequency furnace
Change vanadium, can ensure that nitrogen and reduction produce the stabilization of gas and uniformly circulation in stove, are ensureing the stable feelings of raw material proportioning
Under condition, product quality can be made stable, so as to the phosphorus content in precisely control product；Also, the present invention is with vanadium in vanadium oxide
Valence state on the basis of carry out dispensing, can more accurately control reaction needed for quantity of graphite, so as to be precisely controlled product phosphorus content,
Make the control of the weight of vanadium oxide and carbonaceous reducing agent ratio 1:(0.24~0.33), when vanadium oxide is vanadium trioxide, vanadium oxide
Weight ratio with carbonaceous reducing agent is 1:0.24；When vanadium oxide is vanadic anhydride, the weight ratio of vanadium oxide and carbonaceous reducing agent
For 1:0.33.Carbon proportion in product is reduced, ensures the room for promotion of nitrogen content in product.
In raw material of the present invention, the addition of water is controlled in proper range, it is ensured that green pellets passes through dried pelletizing
Intensity, green-ball is non-breakable during ensureing follow-up dress ball and drying etc., and then improves yield；Meanwhile green pellets is through overdrying
The intensity of green pellets can be improved after dry, after screening, fragment and chip in green pellets are all screened out, it is ensured that material in stove
Gas permeability, ensure the nitrogen atmosphere where material, react and carry out beneficial to nitriding.
Define that cooling section upper temp is maintained in 800~1000 DEG C in the present invention, this is that nitridation reaction can be carried out
At a temperature of limit, although nitridation process can be promoted by reducing nitridation reaction speed, further improve product nitrogen content；Cooling section
Bottom defines 200 DEG C of temperature ＜, then product can be avoided to aoxidize.
The method of the invention can produce high nitrogen vanadium nitride, and nitrogen content is in 17~19wt% in the vanadium nitride, far
Higher than N16 products nitrogen content in national standard, for improving vanadium utilization rate and invigoration effect ten of the vanadium nitride in follow-up steel making working procedure
Divide favourable.And using the method for the invention production vanadium nitride, its yield can reach 93%, for improving product price, carry
The high product market competitiveness is significant.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (11)
1. a kind of preparation method of vanadium nitride, it is characterised in that the preparation method comprises the following steps：
(1) vanadium oxide, carbonaceous reducing agent and water are subjected to mixing pressure ball and pelletizing is made；
(2) obtained pelletizing is put into vertical intermediate frequency furnace, it is 80~200m to be passed through flow3/ h nitrogen, pelletizing is in vertical intermediate frequency furnace
In move from top to bottom, reacted in the bringing-up section of vertical intermediate frequency furnace, cooling section is cooled down, be made vanadium nitride；
The dosage of step (1) reclaimed water is vanadium oxide and 8~12wt% of carbonaceous reducing agent gross mass；
Cooling section divides upper and lower part in step (2), and upper temp is 800~1000 DEG C, 200 DEG C of temperature of lower ＜；
The vanadium oxide is for any one in vanadium trioxide, vanadic anhydride or other+3~+5 valency multivalent state vanadium oxides or extremely
Few two kinds combination；
Carbonaceous reducing agent is any one in graphite, carbon dust or coke blacking or at least two combination in step (1)；
The weight of vanadium oxide and carbonaceous reducing agent ratio is 1 in step (1):(0.24~0.33)；
The central temperature of bringing-up section described in step (2) is 1400~1500 DEG C, reaction of the pelletizing in bringing-up section in step (2)
Time is 16~30h.
2. preparation method according to claim 1, it is characterised in that carbonaceous reducing agent is graphite in step (1).
3. preparation method according to claim 1, it is characterised in that when vanadium oxide is vanadium trioxide in step (1), oxygen
The weight ratio for changing vanadium and carbonaceous reducing agent is 1:0.24.
4. preparation method according to claim 1, it is characterised in that when vanadium oxide is vanadic anhydride in step (1), oxygen
The weight ratio for changing vanadium and carbonaceous reducing agent is 1:0.33.
5. preparation method according to claim 1, it is characterised in that the dosage of step (1) reclaimed water is vanadium oxide and carbonaceous
10~11wt% of reducing agent gross mass.
6. preparation method according to claim 1, it is characterised in that by obtained pelletizing through drying and sieving in step (2)
It is put into after point in vertical intermediate frequency furnace.
7. preparation method according to claim 1, it is characterised in that the central temperature of bringing-up section is described in step (2)
1450~1500 DEG C,
Reaction time of the pelletizing in bringing-up section is 24~28h in step (2).
8. preparation method according to claim 1, it is characterised in that cooling section divides upper and lower part, top in step (2)
Temperature is 900~950 DEG C；150 DEG C of temperature of lower ＜.
9. preparation method according to claim 1, it is characterised in that it is from cooling section bottom that nitrogen is passed through in step (2)
It is passed through.
10. preparation method according to claim 1, it is characterised in that the flow of nitrogen is 110~150m in step (2)3/
h。
11. according to the preparation method described in claim any one of 1-10, it is characterised in that the preparation method includes following step
Suddenly：
(1) multivalent state vanadium oxide, graphite and water are subjected to mixing pressure ball and pelletizing, the wherein weight of multivalent state vanadium oxide and graphite is made
Amount is than being 1:(0.24~0.33), the dosage of water is vanadium oxide and 10~11wt% of carbonaceous reducing agent gross mass；
(2) obtained pelletizing is put into vertical intermediate frequency furnace after drying and screening, being passed through flow from cooling section bottom is
110~150m3/ h nitrogen, pelletizing move from top to bottom in vertical intermediate frequency furnace, vertical intermediate frequency furnace bringing-up section in 1450~
1500 DEG C carry out 24~28h of reaction, and cooling section is cooled down, and cooling section upper temp is 900~950 DEG C；Temperature of lower ＜ 150
DEG C, vanadium nitride is made.
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| CN106498266B (en) * | 2016-12-01 | 2018-03-27 | 武汉科技大学 | A kind of preparation method of VN alloy |
| CN107587023A (en) * | 2017-09-19 | 2018-01-16 | 芜湖人本合金有限责任公司 | A kind of method that alloy of vanadium nitride is prepared with vanadic anhydride |
| 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 |
| CN110923559B (en) * | 2019-12-12 | 2021-10-12 | 湖南众鑫新材料科技股份有限公司 | Vanadium-nitrogen alloy and production method thereof |
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Address after: 067102 Luanhe Town, Shuangluan District, Chengde, Hebei Patentee after: River steel Limited by Share Ltd Chengde branch Address before: 067000 Luanhe Town, Shuangluan District, Chengde, Hebei Patentee before: Chengde Branch Co., Ltd. of Hebei Iron & Steel Group |