CN105838970A - Preparation method of high-nitrogen vanadium nitride - Google Patents
Preparation method of high-nitrogen vanadium nitride Download PDFInfo
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- CN105838970A CN105838970A CN201610235157.1A CN201610235157A CN105838970A CN 105838970 A CN105838970 A CN 105838970A CN 201610235157 A CN201610235157 A CN 201610235157A CN 105838970 A CN105838970 A CN 105838970A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
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Abstract
The invention provides a preparation method of high-nitrogen vanadium nitride. The preparation method comprises the following steps: (1) vanadium oxide, a carbon reducing agent and water are mixed and pressed to prepare pellets; (2) the prepared pellets are put in a vertical medium-frequency furnace; nitrogen with a flow of 80-200 m3/h is introduced; and the pellets move in the vertical medium-frequency furnace from top to bottom, are reacted by a heating section in the vertical medium-frequency furnace, and are cooled by a cooling section to prepare vanadium nitride. The preparation method adopts the vertical medium-frequency furnace to supply the stable reaction atmosphere and reaction process, uses the valence state of vanadium in vanadium oxide as basis for precisely controlling the carbon content in the product, can reduce the ratio of carbon in the product to the greatest extent, guarantees the promotion space of the nitrogen content in the product, and prepares high-nitrogen vanadium nitride through controlling such process conditions as fresh pellet quality, reaction temperature in each phase and nitrogen flow.
Description
Technical field
The invention belongs to steel alloy production field, relate to the preparation method of a kind of vanadium nitride, particularly relate to one
Plant the preparation method of high nitrogen vanadium nitride.
Background technology
In low-alloy high-strength steel, add the intensity that can improve steel after vanadium, improve material recrystallization temperature and
High-temperature behavior.And nitrogen pick-up can improve the creep rupture strength of steel in steel, improve toughness and the plasticity of steel, simultaneously
Also improving heat resistanceheat resistant intensity and anti-short creep ability, often increase the nitrogen of 10ppm in vanadium steel, the intensity of steel is just
6MPa can be improved.Vanadium nitride can increase vanadium and nitrogen in molten steel simultaneously, and the production of high nitrogen vanadium nitride product,
Vanadium consumption can be reduced on the basis of not reducing steel strength, thus reduce steel-making cost.
Vanadium nitride is at nitrogen by raw material ball (being pressed into after being mixed in proportion by graphite, vanadium oxide and binding agent)
In High-temp. kiln under atmosphere protection, after reduction, nitridation, the vanadium nitrogen containing vanadium, nitrogen prepared closes
Gold.So-called high nitrogen vanadium nitride refers to the vanadium nitride that nitrogen content is more than 16%, according to VN alloy national standard
GB/T 20567-2006 specifies, VN alloy divides two trades mark of VN12 Yu VN16, wherein V in VN12:
77～81%, N:10～14%, C≤10%, P≤0.06%, S≤0.1%；V:77～81% in VN16,
N:14～18%, C≤6%, P≤0.06%, S≤0.1%, left according further to inspection product also there are about 1%
Right oxygen, according to VN16 product composition, impurity capping, vanadium removes the limit, other essential elements in addition to N
Shared mass fraction and be 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 has other element of 2～2.5%, and therefore when C capping, product nitrogen content can only
To about 14%.
Therefore high nitrogen vanadium nitride is produced, it is necessary to control the impurity level in addition to V, N in product, at raw material
In the case of Yi Ding, can only be by being precisely controlled (the stone allocated into when being i.e. precisely controlled dispensing of phosphorus content in product
Ink amount), improve the N content in product.Additionally need to ensure vanadium nitride nitridation in sintering procedure
Reaction, i.e. controls reaction condition and (includes nitrogen partial pressure, reaction temperature and reaction time around material in kiln
Deng).Nitrogen partial pressure therein is mainly determined by nitrogen flow, but also has important relationship with the circulation style of nitrogen,
Reaction temperature and reaction time are then set by temperature and discharging speed determines.
At present, the production technology that vanadium nitride is the most ripe is to utilize horizontal pushed bat kiln (also known as tunnel cave) by raw
After pellet loads the graphite tank being placed on graphitic push pedal, in promoting push pedal to make graphite tank, raw material ball has stepped through sleeping
Discharging after formula push pedal preheating section of kiln, high temperature section and cooling section, obtains vanadium nitride product.Batch can in this technology
And needing reserved 30～50mm spaces to ensure that graphite tank moves in stove between top, kiln chamber, therefore furnace gas is big
Part flows away from graphite tank upper space, has the most both included nitrogen, has comprised again the CO that reduction produces.Thus
Produce following shortcoming:
(1) part nitrogen flows away from top, has both wasted nitrogen, reduces again in lower purpose square graphite tank around material
Nitrogen partial pressure, if wanting to improve product nitrogen content can only increase nitrogen amount to improve the nitrogen partial pressure around material,
But nitrogen material resistance to body of heater can be strengthened after increase nitrogen amount wash away, produce high nitrogen vanadium nitride and will certainly reduce stove
Body life time, therefore need to accept or reject between converter life and product nitrogen content；
(2) the CO part that reduction produces flows away from top and has no chance to participate in reduction reaction, it is impossible to determine ginseng
With the CO amount of reduction, in raw material, mixed carbon comtent needs excess more, to ensure that vanadium oxide can fully reduce, because of
It is extremely difficult that this is precisely controlled phosphorus content in product, and during production, in raw material proportioning, mixed carbon comtent typically needs excess
10～15%.So phosphorus content is typically more than 4% in product, in the case of the total composition of product is certain, profit
High nitrogen vanadium nitride with tradition pushed bat kiln production nitrogenous more than 16% is highly difficult；
(3) the nitridation reaction formula of vanadium nitride: VO is produced according to vanadium oxidex+ (x+1) C=VC+xCO；
2VC+N2==2VN+2C is it can be seen that in nitridation process, in pelletizing during simple substance carbon content height, can suppress
The nitridation process of vanadium carbide, therefore to obtain high nitrogen vanadium nitride, need to control the phosphorus content in product.
CN 1422800A discloses the production method of a kind of vanadium nitride, the method by barium oxide, graphite and
After the 2% uniform pressure ball of polyvinyl alcohol, join and be connected with protection and reacting gas nitrogen and/or the push pedal of ammonia
In kiln or tunnel cave, at a temperature of 1000～1800 DEG C, react 2～6h, discharging after being cooled to 100～250 DEG C.
But the method only discloses raw material composition and broad reaction temperature and the reaction time of vanadium nitride, to key
Mixed carbon comtent and the parameter not specified (NS) such as nitrogen amount, and the reacting furnace used is the pushed bat kiln of horizontal positioned
Or tunnel cave.
CN 102173395A discloses a kind of easy vanadium nitride production method, and the method is by V2O5Powder and stone
After ink powder is sufficiently mixed on dry-mixed machine by the weight ratio of 4:1, adding content by the weight ratio of 100:15 is 4%
Polyvinyl alcohol water solution, mixing, pressure ball and dried, by mixing sphere of powder layering loading truck, enter stove,
Seal fire door, after being passed through nitrogen under vacuum condition, keep respectively at 800 DEG C, 1350 DEG C and 1600 DEG C 5h,
After 6h and 6～10h 20h altogether, power failure is cooled to 150 DEG C and comes out of the stove.This technology discloses accurate raw material
Proportioning and reaction time, reaction temperature, but its graphite powder amount proportioning is far below normal reaction demand and public
Cloth nitrogen affects, and its production process is to complete at times and reacting furnace used is vacuum drying oven.
Utilizing vertical intermediate frequency furnace to produce vanadium nitride is the revolutionary innovation that vanadium nitride produces, and it enters from top
Material, material from top to bottom through preheating, add thermal reduction, high temperature reduction nitridation and after the nitridation stage such as cooling from
Bottom discharging.Utilize vertical intermediate frequency furnace to produce vanadium nitride to have the advantage that
(1) in stove, nitrogen distribution is more reasonable.Vertical intermediate frequency furnace is vertical structure, and furnace charge uniformly divides in furnace chamber
Cloth, nitrogen distribution in stove and flowing are uniform, it is ensured that nitriding is reacted, be conducive to producing composition uniformly,
Nitrogenous higher high nitrogen vanadium nitride；
(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 close
Envelope property is good, and resistance to nitrogen scouring capability is strong, can be guaranteed under big flow nitrogen lining durability impact less, from
And nitrogen partial pressure can be increased and strengthen nitriding, provide strong guarantee for producing high nitrogen vanadium nitride；
(3) CO produced in reduction process at raw material ball flows from bottom to top between material gap, due to
It is stable that CO flows uniformly through in top material and stove to parameters such as spot temperature, and therefore reduction produces
It is stable that CO participates in the ratio of reduction reaction again, therefore need not join the carbon of excess during feed proportioning, can
To be precisely controlled mixed carbon comtent, it is ensured that product carbon containing is less than 4%.
CN 101963446A discloses a kind of VN alloy full-automatic vertical Medium Frequency Induction Heating Furnace, this heating
Graphite circle alms bowl (batch can) is stacked together by stove, upper endfeed, lower end discharging, but owing to have employed batch can
Design, after in tank, raw material burn till grog, shrinkage factor is the highest 30%, therefore idle furnace chamber area in stove
It is up to more than 30%, largely effects on yield.And owing to using batch can charging, nitrogen need to be by batch can
Could contact with vanadium nitride pelletizing after hole so that nitrogen cannot freely circulate between vanadium nitride pelletizing, impact
Vanadium nitride nitriding is reacted, and is unfavorable for producing high nitrogen vanadium nitride.
As can be seen here, the means of production of current vanadium nitride is a lot, but is concentrated mainly on common vanadium nitride and produces neck
Territory, the technology that can be used for the production of high nitrogen vanadium nitride not yet finds.
Summary of the invention
Preparing, with horizontal pushed bat kiln, the waste nitrogen that vanadium nitride exists for existing, converter life reduces, precisely
Controlling phosphorus content in product extremely difficult, shaft (tower) furnace produces yielding poorly of vanadium nitride, nitrogen circulation difficulty, difficulty
To prepare the problems such as high nitrogen (nitrogen content is more than 16%) vanadium nitride, the invention provides the system of a kind of vanadium nitride
Preparation Method.The present invention, by using vertical intermediate frequency furnace, in vanadium oxide based on Vanadium valence, thus is accurately controlled
Phosphorus content in product processed, reduces carbon proportion in product, it is ensured that the room for promotion of nitrogen content in product；
And by controlling bringing-up section and the temperature of cooling section, improve product nitrogen content further, produce the nitridation of high nitrogen
Vanadium.
For reaching this purpose, the present invention by the following technical solutions:
The invention provides the preparation method of a kind of vanadium nitride, described preparation method comprises the following steps:
(1) vanadium oxide, carbonaceous reducing agent and water being carried out mixes pressure ball and makes pelletizing；
(2) being put in vertical intermediate frequency furnace by prepared pelletizing, being passed through flow is 80～200m3/ h nitrogen, ball
Group moves in vertical intermediate frequency furnace from top to bottom, and the bringing-up section at vertical intermediate frequency furnace is reacted, and cooling section enters
Row cooling, prepares vanadium nitride.
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, listed in the range of other numerical value the most feasible.
Following as currently preferred technical scheme, but the restriction of the technical scheme provided not as the present invention,
By the following technical programs, can preferably reach and realize technical purpose and the beneficial effect of the present invention.
As currently preferred technical scheme, described vanadium oxide is vanadium trioxide, vanadic anhydride or many
Any one or the combination of at least two, more preferably multivalent state vanadium oxide in valence state vanadium oxide.
Preferably, in described multivalent state vanadium oxide, the valence state of vanadium is+3～+5 valencys, such as+trivalent ,+3.5 valencys,
+ 4 valencys ,+4.5 valencys or+5 valencys etc., it is not limited to cited numerical value, listed in the range of other numerical value equal
Feasible.
In the present invention, in vanadium oxide, on the basis of the valence state of vanadium, carry out dispensing, can control anti-more accurately
The consumption of carbonaceous reducing agent needed for should, thus it is precisely controlled phosphorus content in product, reduce carbon institute accounting in product
Example, it is ensured that the nitrogen content in product.Further, control relatively due to the production process of the vanadium oxide of single valence
Difficulty, relatively costly, and the mixture production technology of multivalent state vanadium oxide is simple, can reduce production cost.
In the present invention, after the comprehensive valence state of vanadium oxide is the content of the vanadium by determining in vanadium oxide and oxygen,
By the amount ratio-dependent of vanadium and oxygen species.
As currently preferred technical scheme, in step (1), carbonaceous reducing agent is graphite, carbon dust or coke
Any one or the combination of at least two in powder, described combination typical case but limiting examples has graphite and carbon dust
Combination, carbon dust and the combination of coke blacking, the combination etc. of graphite, carbon dust and coke blacking, more preferably
Graphite.
As currently preferred technical scheme, in step (1), the weight ratio of vanadium oxide and carbonaceous reducing agent is
1:(0.24～0.33), such as 1:0.24,1:0.25,1:0.26,1:0.27,1:0.28,1:0.29,1:0.30,1:0.31,
1:0.32 or 1:0.33 etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
In the present invention, the consumption proportion of carbonaceous reducing agent is determined by the comprehensive valence state of vanadium oxide used.Meanwhile,
Produce high nitrogen vanadium nitride, it is necessary to be precisely controlled raw material proportioning, therefore determine former with the comprehensive valence state of vanadium oxide
Material proportioning, it is ensured that dispensing is accurate, and then prepares high nitrogen vanadium nitride.
Preferably, when in step (1), vanadium oxide is vanadium trioxide, vanadium oxide and the weight of carbonaceous reducing agent
Ratio is 1:0.24.
Preferably, when in step (1), vanadium oxide is vanadic anhydride, vanadium oxide and the weight of carbonaceous reducing agent
Ratio is 1:0.33.
In the present invention, when vanadium oxide is multivalent state vanadium oxide, i.e. in vanadium oxide the valence state of vanadium between+3～+5
Time between valency, the weight ratio of vanadium oxide and carbonaceous reducing agent is between 1:(0.24～0.33) between.
As currently preferred technical scheme, in step (1), the consumption of water is vanadium oxide and carbonaceous reducing agent
The 8～12wt% of gross mass, such as 8wt%, 9wt%, 10wt%, 11wt% or 12wt% etc., but not
Be only limitted to cited numerical value, listed in the range of other numerical value the most feasible, more preferably 10～11wt%.
In the present invention, can ensure that in the amount ranges of described water green pellets is through dried pellet strength.
The addition of water has decisive influence to pressure ball quality, the addition of water in this range time can guarantee
It is pressed into ball, can guarantee that again the intensity extruding ball, it is ensured that during follow-up dress ball and drying etc., green-ball is the most fragile
Broken.
As currently preferred technical scheme, step (2) is put after prepared pelletizing drying and screening
Enter in vertical intermediate frequency furnace.
In the present invention, it be dried and screening be moisture, fragment and the chip in order to remove in pelletizing.
As currently preferred technical scheme, described in step (2), the central temperature of bringing-up section 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, listed scope
Other numerical value interior are the most feasible, more preferably 1450～1500 DEG C.
Preferably, in step (2), the pelletizing reaction time in bringing-up section is 16～30h, such as 16h, 18h,
20h, 22h, 24h, 26h, 28h or 30h etc., it is not limited to cited numerical value, listed scope
In other numerical value the most feasible, more preferably 24～28h.
In the present invention, ensure the pelletizing reaction time in bringing-up section by controlling discharging speed.Meanwhile,
Ensure that the reaction time is in order to nitridation reaction is complete 16～30h, improve product nitrogen content.
As currently preferred technical scheme, in step (2), cooling section divides upper and lower, upper temp
Be 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., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible,
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, it is not limited to cited numerical value, institute
In the range of row, other numerical value are the most feasible, more preferably ＜ 150 DEG C.
In the present invention, defining that cooling section upper temp is 800～1000 DEG C, this is that nitridation reaction can be carried out
At a temperature of limit, owing to the nitridation process of vanadium nitride is exothermic reaction, in the case of nitrogen content is higher reduce nitrogen
Change temperature, although reduce nitridation reaction speed but nitridation process can be promoted, improve product nitrogen content further.
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, limit cooling section temperature of lower ＜ 200 DEG C, product can be avoided to aoxidize.
As currently preferred technical scheme, being passed through nitrogen in step (2) is to be passed through bottom cooling section.
Preferably, in step (2), the flow of nitrogen is 110～150m3/h。
As currently preferred technical scheme, described preparation method comprises the following steps:
(1) multivalent state vanadium oxide, graphite and water being carried out mixes pressure ball and makes pelletizing, wherein multivalent state oxidation
The weight ratio of vanadium and graphite is 1:(0.24～0.33), the consumption of water is vanadium oxide and carbonaceous reducing agent gross mass
10～11wt%；
(2) put in vertical intermediate frequency furnace after prepared pelletizing drying and screening, be passed through bottom cooling section
Being passed through flow is 110～150m3/ h nitrogen, pelletizing moves in vertical intermediate frequency furnace from top to bottom, in vertical
Frequently the bringing-up section of stove carries out reacting 24～28h in 1450～1500 DEG C, and cooling section cools down, cooling section top
Temperature is 900～950 DEG C, temperature of lower ＜ 150 DEG C, prepares vanadium nitride.
In the method for the invention, with the best performance of the vanadium nitride that above-mentioned raw materials proportioning and process conditions prepare.
Compared with prior art, the method have the advantages that
(1) present invention uses vertical intermediate frequency furnace to produce vanadium nitride, it is possible to ensure nitrogen and reduction generation gas in stove
Stablizing and uniformly circulating of body, in the case of ensureing that raw material proportioning is stable, can make constant product quality,
It is thus possible to the phosphorus content in precisely control product；Further, the present invention is in vanadium oxide on the basis of the valence state of vanadium
Carry out dispensing, can control to react required quantity of graphite more accurately, thus be precisely controlled product phosphorus content.
The weight ratio making vanadium oxide and carbonaceous reducing agent controls at 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；When vanadium oxide is vanadic anhydride, vanadium oxide and carbon
The weight ratio of matter reducing agent is 1:0.33.Reduce carbon proportion in product, it is ensured that in product, nitrogen content carries
Rise space.
(2), in raw material of the present invention, the addition of water controls in proper range, it is ensured that green pellets is through overdrying
Pellet strength after dry, it is ensured that during follow-up dress ball and drying etc., green-ball is the most broken, and then improve product
Rate；Meanwhile, green pellets is through improving the intensity of green pellets after drying, after screening, and broken in green pellets
Block and chip are all screened out, it is ensured that the gas permeability of material in stove, it is ensured that the nitrogen atmosphere at material place, profit
Carry out in nitriding reaction.
(3) defining in the present invention that cooling section upper temp is maintained in 800～1000 DEG C, this is that nitridation is anti-
Limit at a temperature of should carrying out, although reduce nitridation reaction speed but nitridation process can be promoted, further
Improve product nitrogen content；Cooling section bottom defines temperature ＜ 200 DEG C, then product can be avoided to aoxidize.
(4) the method for the invention can produce high nitrogen vanadium nitride, and in described vanadium nitride, nitrogen content exists
17～19wt%, far above N16 product nitrogen content in GB, for improving vanadium nitride in follow-up steel making working procedure
Vanadium utilization rate and invigoration effect highly beneficial.And using the method for the invention to produce vanadium nitride, it produces
Rate can reach 93%, for improving product price, improves product competitiveness in the market significant.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, further to the present invention below
Describe in detail.But following embodiment is only the simple example of the present invention, does not represent or limits the present invention
Rights protection scope, scope is as the criterion with claims.
Specific embodiment of the invention part provides the preparation method of a kind of vanadium nitride, and described preparation method includes
Following steps:
(1) vanadium oxide, carbonaceous reducing agent and water being carried out mixes pressure ball and makes pelletizing；
(2) being put in vertical intermediate frequency furnace by prepared pelletizing, being passed through flow is 80～200m3/ h nitrogen, ball
Group moves in vertical intermediate frequency furnace from top to bottom, and the bringing-up section at vertical intermediate frequency furnace is reacted, and cooling section enters
Row cooling, prepares vanadium nitride.
Described typical case but non-limiting example is as follows:
Embodiment 1:
(1) 1000kg vanadium trioxide, 240kg graphite and 99.2kg water being carried out mixes pressure ball and makes ball
Group, wherein the weight ratio of vanadium trioxide and graphite is 1:0.24, and the consumption of water is vanadium trioxide and graphite
The 8wt% of gross mass；
(2) put in vertical intermediate frequency furnace after prepared pelletizing drying and screening, be passed through bottom cooling section
Being passed through flow is 200m3/ h nitrogen, pelletizing moves in vertical intermediate frequency furnace from top to bottom, bringing-up section center temperature
Degree is maintained at 1500 DEG C, and pelletizing, after the bringing-up section of vertical intermediate frequency furnace reacts 30h, enters cooling section and carries out cold
But, controlling cooling section upper temp is 1000 DEG C, and temperature of lower is 80 DEG C, discharging, obtains high nitrogen vanadium nitride.
The vanadium nitride composition prepared is: V:77.29%, N:19%, C:0.89%, P:0.013%, S:0.014%,
Its productivity is 97.6%.
Embodiment 2:
(1) 1000kg vanadic anhydride, 330kg graphite and 160kg water being carried out mixes pressure ball and makes ball
Group, wherein the weight ratio of vanadic anhydride and graphite is 1:0.33, and the consumption of water is vanadic anhydride and graphite
The 12wt% of gross mass；
(2) put in vertical intermediate frequency furnace after prepared pelletizing drying and screening, be passed through bottom cooling section
Being passed through flow is 120m3/ h nitrogen, pelletizing moves in vertical intermediate frequency furnace from top to bottom, bringing-up section center temperature
Degree is maintained at 1400 DEG C, and pelletizing, after the bringing-up section of vertical intermediate frequency furnace reacts 20h, enters cooling section and carries out cold
But, controlling cooling section upper temp is 800 DEG C, and temperature of lower is 150 DEG C, discharging, obtains high nitrogen vanadium nitride.
The vanadium nitride composition prepared is: V:77.10%, N:18.35%, C:0.79%, P:0.013%, S:0.012%,
Its productivity is 95.3%.
Embodiment 3:
(1) vanadium oxide of 1000kg tetravalence, 318kg graphite and 131.8kg water carry out mix pressure ball make
Pelletizing, wherein the vanadium oxide of tetravalence and the weight ratio of graphite are 1:0.318, and the consumption of water is the vanadium oxide of tetravalence
10wt% with graphite gross mass；
(2) put in vertical intermediate frequency furnace after prepared pelletizing drying and screening, be passed through bottom cooling section
Being passed through flow is 80m3/ h nitrogen, pelletizing moves in vertical intermediate frequency furnace from top to bottom, bringing-up section central temperature
Being maintained at 1450 DEG C, pelletizing, after the bringing-up section of vertical intermediate frequency furnace reacts 16h, enters cooling section and cools down,
Controlling cooling section upper temp is 900 DEG C, and temperature of lower is 199 DEG C, discharging, obtains high nitrogen vanadium nitride.
The vanadium nitride composition prepared is: V:77.28%, N:17%, C:1.76%, P:0.011%, S:0.013%,
Its productivity is 94.1%.
Embodiment 4:
(1) vanadium oxide of 1000kg 3.5 valency, 292kg graphite and 130kg water carry out mix pressure ball make
Pelletizing, wherein the vanadium oxide of 3.5 valencys and the weight ratio of graphite are 1:0.292, and the consumption of water is the oxygen of 3.5 valencys
Change vanadium and the 10wt% of graphite gross mass；
(2) put in vertical intermediate frequency furnace after prepared pelletizing drying and screening, be passed through bottom cooling section
Being passed through flow is 100m3/ h nitrogen, pelletizing moves in vertical intermediate frequency furnace from top to bottom, bringing-up section center temperature
Degree is maintained at 1480 DEG C, and pelletizing, after the bringing-up section of vertical intermediate frequency furnace reacts 24h, enters cooling section and carries out cold
But, controlling cooling section upper temp is 950 DEG C, and temperature of lower is 100 DEG C, discharging, obtains high nitrogen vanadium nitride.
The vanadium nitride composition prepared is: V:77.85%, N:18.21%, C:1.20%, P:0.012%, S:0.013%,
Its productivity 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 are all with real
Execute in example 1 identical.
Embodiment 6:
In the present embodiment, in addition to carbonaceous reducing agent used is coke blacking, each material amounts and preparation process all with
In embodiment 1 identical.
Comparative example 1:
Except the mass ratio of vanadium oxide and graphite is more than 1:0.24 in this comparative example, for 1:0.15 outside, other are each
Material amounts is the most in the same manner as in Example 1 with preparation process.
The vanadium nitride composition that this comparative example prepares is V:72.23%, N:6.21%, C:0.51%, P:0.012%,
S:0.013%, owing to mixed carbon comtent has been not enough to reduction reaction, product is defective.
Comparative example 2:
Except the mass ratio of vanadium oxide and graphite is less than 1:0.24 in this comparative example, for 1:0.4 outside, other each things
Material consumption is the most in the same manner as in Example 1 with preparation process.
The vanadium nitride composition that this comparative example prepares is V:74.12%, N:5.21%, C:8.54%, P:0.011%,
S:0.011%, the most excessive owing to joining carbon, product is defective.
Comparative example 3:
Except cooling section upper temp ＞ 1000 DEG C in this comparative example, it is outside 1300 DEG C, other each material amounts
The most in the same manner as in Example 1 with preparation process.
The vanadium nitride composition that this comparative example prepares is V:77.18%, N:18.63%, C:0.90%, P:0.013%,
S:0.013%, its productivity is 97.5%.
Comparative example 4:
Except cooling section upper temp ＜ 800 DEG C in this comparative example, be outside 500 DEG C, other each material amounts with
Preparation process is the most in the same manner as in Example 1.
The vanadium nitride composition that this comparative example prepares is V:77.31%, N:17.93%, C:0.89%, P:0.013%,
S:0.014%, its productivity is 97.3%.
Comparative example 5:
Except cooling section temperature of lower ＞ 200 DEG C in this comparative example, be outside 300 DEG C, other each material amounts with
Preparation process is the most in the same manner as in Example 1.
The vanadium nitride composition that this comparative example prepares is V:77.30%, N:18.45%, C:0.89%, P:0.013%,
S:0.013%, its productivity is 98%, but there is oxidative phenomena on individual product surface.
Comparative example 6:
In this comparative example, the consumption except water is less than vanadium oxide and the 8 of carbonaceous reducing agent gross mass～12wt%, for
Outside 5wt%, other each material amounts are the most in the same manner as in Example 1 with preparation process.
The productivity of the vanadium nitride that this comparative example prepares is 96.5%.
Comparative example 7:
In this comparative example, the consumption except water is higher than vanadium oxide and the 8 of carbonaceous reducing agent gross mass～12wt%, for
Outside 15wt%, other each material amounts are the most in the same manner as in Example 1 with preparation process.
The productivity of the vanadium nitride that this comparative example prepares is 96.8%.
The result of integrated embodiment 1-6 and comparative example 1-7 is it can be seen that the present invention uses vertical intermediate frequency furnace to produce
High nitrogen vanadium nitride, it is possible in guarantee stove, nitrogen and reduction produce the stable of gas and uniformly circulate, and are ensureing
In the case of raw material proportioning is stable, constant product quality can be made such that it is able to the carbon containing in precisely control product
Amount；Further, the present invention carries out dispensing in vanadium oxide on the basis of the valence state of vanadium, can control more accurately
The required quantity of graphite of reaction, thus it is precisely controlled product phosphorus content, make the weight ratio of vanadium oxide and carbonaceous reducing agent
Control at 1:(0.24～0.33), when vanadium oxide is vanadium trioxide, vanadium oxide and the weight ratio of carbonaceous reducing agent
For 1:0.24；When vanadium oxide is vanadic anhydride, the weight ratio of vanadium oxide and carbonaceous reducing agent is 1:0.33.Subtract
Carbon proportion in few product, it is ensured that the room for promotion of nitrogen content in product.
In raw material of the present invention, the addition of water controls in proper range, it is ensured that green pellets is through dried
Pellet strength, it is ensured that during follow-up dress ball and drying etc., green-ball is the most broken, so improve productivity；
Meanwhile, green pellets is through improving the intensity of green pellets after drying, after screening, the fragment in green pellets and
Chip is all screened out, it is ensured that the gas permeability of material in stove, it is ensured that the nitrogen atmosphere at material place, is beneficial to ooze
Nitrogen reaction is carried out.
Defining in the present invention that cooling section upper temp is maintained in 800～1000 DEG C, this is that nitridation reaction is permissible
Limit at a temperature of carrying out, although reduce nitridation reaction speed but nitridation process can be promoted, improve product further
Product nitrogen content；Cooling section bottom defines temperature ＜ 200 DEG C, then product can be avoided to aoxidize.
The method of the invention can produce high nitrogen vanadium nitride, and in described vanadium nitride, nitrogen content exists
17～19wt%, far above N16 product nitrogen content in GB, for improving vanadium nitride in follow-up steel making working procedure
Vanadium utilization rate and invigoration effect highly beneficial.And using the method for the invention to produce vanadium nitride, it produces
Rate can reach 93%, for improving product price, improves product competitiveness in the market significant.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.
Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, each former to product of the present invention
The equivalence of material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the protection model of the present invention
Within the scope of enclosing and disclosing.
Claims (10)
1. the preparation method of a vanadium nitride, it is characterised in that described preparation method comprises the following steps:
(1) vanadium oxide, carbonaceous reducing agent and water being carried out mixes pressure ball and makes pelletizing；
(2) being put in vertical intermediate frequency furnace by prepared pelletizing, being passed through flow is 80～200m3/ h nitrogen, ball
Group moves in vertical intermediate frequency furnace from top to bottom, and the bringing-up section at vertical intermediate frequency furnace is reacted, and cooling section enters
Row cooling, prepares vanadium nitride.
Preparation method the most according to claim 1, it is characterised in that described vanadium oxide is three oxidations two
Any one or the combination of at least two in vanadium, vanadic anhydride or multivalent state vanadium oxide, more preferably
Multivalent state vanadium oxide；
Preferably, in described multivalent state vanadium oxide, the valence state of vanadium is+3～+5 valencys.
Preparation method the most according to claim 1 and 2, it is characterised in that carbonaceous in step (1)
Reducing agent is any one or the combination of at least two, more preferably stone in graphite, carbon dust or coke blacking
Ink.
4. according to the preparation method described in any one of claim 1-3, it is characterised in that in step (1)
The weight ratio of vanadium oxide and carbonaceous reducing agent is 1:(0.24～0.33)；
Preferably, when in step (1), vanadium oxide is vanadium trioxide, vanadium oxide and the weight of carbonaceous reducing agent
Ratio is 1:0.24；
Preferably, when in step (1), vanadium oxide is vanadic anhydride, vanadium oxide and the weight of carbonaceous reducing agent
Ratio is 1:0.33.
5. according to the preparation method described in any one of claim 1-4, it is characterised in that in step (1)
The consumption of water is vanadium oxide and the 8 of carbonaceous reducing agent gross mass～12wt%, and more preferably the consumption of water is
Vanadium oxide and the 10 of carbonaceous reducing agent gross mass～11wt%.
6. according to the preparation method described in any one of claim 1-5, it is characterised in that in step (2)
Put in vertical intermediate frequency furnace after prepared pelletizing drying and screening.
7. according to the preparation method described in any one of claim 1-6, it is characterised in that in step (2)
The central temperature of described bringing-up section is 1400～1500 DEG C, and more preferably central temperature is
1450～1500 DEG C；
In step (2), the pelletizing reaction time in bringing-up section is 16～30h, more preferably 24～28h.
8. according to the preparation method described in any one of claim 1-7, it is characterised in that in step (2)
Cooling section divides upper and lower, and upper temp is 800～1000 DEG C, more preferably 900～950 DEG C；Under
Portion's temperature ＜ 200 DEG C, more preferably ＜ 150 DEG C.
9. according to the preparation method described in any one of claim 1-8, it is characterised in that in step (2)
Being passed through nitrogen is to be passed through bottom cooling section；
Preferably, in step (2), the flow of nitrogen is 110～150m3/h。
10. according to the preparation method described in any one of claim 1-9, it is characterised in that described preparation side
Method comprises the following steps:
(1) multivalent state vanadium oxide, graphite and water being carried out mixes pressure ball and makes pelletizing, wherein multivalent state oxidation
The weight ratio of vanadium and graphite is 1:(0.24～0.33), the consumption of water is vanadium oxide and carbonaceous reducing agent gross mass
10～11wt%；
(2) put in vertical intermediate frequency furnace after prepared pelletizing drying and screening, be passed through bottom cooling section
Being passed through flow is 110～150m3/ h nitrogen, pelletizing moves in vertical intermediate frequency furnace from top to bottom, in vertical
Frequently the bringing-up section of stove carries out reacting 24～28h in 1450～1500 DEG C, and cooling section cools down, cooling section top
Temperature is 900～950 DEG C；Temperature of lower ＜ 150 DEG C, prepares vanadium nitride.
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| CN110923559A (en) * | 2019-12-12 | 2020-03-27 | 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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