CN106048284B - A kind of VN alloy and preparation method thereof - Google Patents

A kind of VN alloy and preparation method thereof Download PDF

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CN106048284B
CN106048284B CN201610414450.4A CN201610414450A CN106048284B CN 106048284 B CN106048284 B CN 106048284B CN 201610414450 A CN201610414450 A CN 201610414450A CN 106048284 B CN106048284 B CN 106048284B
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preparation
parts
alloy
alloy according
vanadium
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CN106048284A (en
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唐红建
孙朝晖
余彬
陈海军
甘信德
王乖宁
杜光超
景涵
尹丹凤
王唐林
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Sichuan Pan Yan Technology Co., Ltd.
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SICHUAN PAN YAN TECHNOLOGY Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals

Abstract

The invention belongs to metallurgical technology fields, and in particular to a kind of VN alloy and preparation method thereof.The problems such as VN alloy purity being prepared for the prior art with low-density vanadium trioxide is too low, the present invention provides a kind of preparation method of VN alloy, including abrasive material, mixing and molding, the calcining of pellet.The method of the present invention has adjusted raw material composition and ratio, joined vanadic anhydride and iron series sintering aid, reduces carbothermic reduction reaction Gibbs free energy by vanadic anhydride, promotes nitriding deoxidation process, and iron series sintering aid reacts the liquid Fe generated with graphite powder3The wetting angle of C and carbide contact is small, and wetting action is significant, intensified-sintered by liquid phase, to improve the density of VN alloy, the method for the present invention is easy to operate, and no waste significantly reduces production cost.

Description

A kind of VN alloy and preparation method thereof
Technical field
The invention belongs to metallurgical technology fields, and in particular to a kind of VN alloy and preparation method thereof.
Background technique
Vanadium can play precipitation strength and dispersion-strengtherning as important alloying element in steel, be widely used in more Kind steel, especially low-alloy high-strength steel.The size of VN alloy density directly affects the rate of recovery of its vanadium in steelmaking process, High-density vanadium-nitrogen alloy is avoided that additive floats on the surface layer of steel slag, promotes the contact with molten steel, improves vanadium and was making steel The rate of recovery in journey.
The vanadium trioxide density of prior art production is smaller, between 0.60~0.80gcm-3Between, and existing vanadium nitrogen Alloy production technique is not less than 1.00gcm to the density requirements of vanadium trioxide-3, there is a certain distance between the two. Using the low-density vanadium trioxide of prior art production as raw material, the VN alloy that existing VN alloy technology is produced is continued to use Finished product density only has 2.92gcm-3, it is less than VN alloy national standard minimum requirements 3.00gcm-3If by low-density three V 2 O is smelted for vanadium iron, and according to the production statistics at scene, vanadium recovery is 95.00% or so, lower than VN alloy 99.50%, and be unfavorable for improving the single situation of product structure currently on the market.
Liu Xiansong, Liu Zhi et al. research report:Using by the oxide or ammonium metavanadate of powdered vanadium, carbonaceous pulvis And binder, densifier is added, after mixing, briquetting, molding are continuously added to external-heating revolving in a nitrogen atmosphere Kiln burns 1000 DEG C hereinafter, the block of pre-burning being cooled to room temperature in the case where discharge port is collected through nitrogen protection in advance under nitrogen protection Shape product.Then be pushed into improved soft magnetism nitrogen atmosphere pushed bat kiln, be heated to 1000~1500 DEG C of temperature, material occur carbonization and Nitridation reaction obtains vanadium-nitrogen alloy product after coming out of the stove.VN alloy obtained:V:78-83%, N:16-21%, C≤6%max, Silicon, phosphorus and aluminium are less than:0.10%, apparent density is greater than 4.4g/cm3.Apparent density can be adjusted according to the demand of client, Maximum reachable 5.0g/cm3.The invention is not improving original manufacturing condition, by adding densifier, improves vanadium The apparent density of nitrogen alloy makes molten steel be greater than 98% or more to the absorptivity of VN alloy.
Currently, the method for preparing standard compliant VN alloy with low-density vanadium trioxide raw material not yet.
Summary of the invention
The VN alloy density being prepared for the prior art using low-density vanadium trioxide is too low, is not able to satisfy life The problem of production needs, goal of the invention of the invention are to provide the side that a kind of mixed oxidization vanadium raw materials prepare high-density vanadium-nitrogen alloy Method.The present invention is not necessarily to pre-burning link, directly progress calcination operation, and reaction speed is fast, high-efficient, meanwhile, raw material is using three oxidations The mixture of two vanadium and vanadic anhydride can overcome three oxygen of raw material since vanadic anhydride has low melting point and high shrinkage performance Change the low density problem of two vanadium, increases product density, standard compliant VN alloy is prepared.
The scheme that the present invention solves technical problem is to provide a kind of preparation method of VN alloy, is included the following steps:
A, raw material preparation
8~16 parts of vanadic anhydride, 50~60 parts of vanadium trioxide, 20~30 parts of crystalline flake graphite, iron series in parts by weight 0.8~1.6 part of sintering aid, 0.8~2 part of liquid phase inductive agent weigh raw material, crush;
B, mixing compression moulding
Raw material in step a is mixed into 25~40min, 8~12 parts of water are added, remixes 25~40min, compression moulding, system Obtain pellet;
C, pellet is calcined
Pellet obtained by step b is reacted into 6~8h in nitrogen atmosphere protection pushed slab kiln, 400~1520 DEG C of reaction temperature, out Furnace, it is cooling, obtain VN alloy;
Iron series sintering aid described in step a is in reduced iron powder, iron oxide red, ferroso-ferric oxide or ferrous oxide It is at least one;The liquid phase inductive agent is at least one of vanadium carbide, vanadium nitride or vanadium carbide nitride.
Wherein, in the preparation method of above-mentioned VN alloy, vanadium trioxide density described in step a be 0.60~ 0.80g·cm-3
Preferably, the source of the low-density vanadium trioxide is:Clinker of the vanadium slag after calcification baking is through sulfuric acid leaching After obtain immersion liquid containing vanadic acid, obtain ammonium poly-vanadate with acid ammonium salt precipitation legal system, obtain vanadium trioxide by reduction.
Wherein, in the preparation method of above-mentioned VN alloy, vanadic anhydride described in step a be full content of vanadium 52~ The vanadic anhydride of 56wt%, vanadium trioxide are vanadium trioxide of the full content of vanadium in 63~68wt%.
Wherein, in the preparation method of above-mentioned VN alloy, grinding particle size described in step a is≤140 mesh.
Wherein, in the preparation method of above-mentioned VN alloy, iron series sintering aid described in step a is that weight ratio is 3~5 ﹕ 5 ~7 di-iron trioxide and the mixture of metallic iron.
Preferably, in the preparation method of above-mentioned VN alloy, iron series sintering aid described in step a is 1.0~1.4 Part, preferably 1.2 parts.
Preferably, in the preparation method of above-mentioned VN alloy, vanadic anhydride additive amount described in step a is 10~15 Part, preferably 12 parts.
Wherein, in the preparation method of above-mentioned VN alloy, the additional amount of water described in step b is 9.5~10.5 parts, preferably It is 10 parts.
Wherein, in the preparation method of above-mentioned VN alloy, 30~50kN of briquetting pressure when being suppressed described in step b, pressure maintaining Time 5~8 minutes.
Wherein, in the preparation method of above-mentioned VN alloy, pellet weight described in step b is 50~60g.
Wherein, in the preparation method of above-mentioned VN alloy, in step c in nitrogen atmosphere protection pushed slab kiln nitrogen oxygen content 5 ~8ppm.
The present invention also provides a kind of VN alloys, are made by above-mentioned preparation method.
Beneficial effects of the present invention are:When preparing VN alloy using low-density vanadium trioxide, vanadium nitrogen is be easy to cause to close Phenomena such as density of gold is too low, the present invention forms by adjusting raw material and its mutual proportion, in single three oxygen of low-density Change with addition of a certain amount of vanadic anhydride in two vanadium, while adding a certain amount of graphite, iron series sintering aid and liquid phase inductive Agent, vanadic anhydride advantageously reduce carbothermic reduction reaction Gibbs free energy, promote nitriding deoxidation process, iron series sintering aid The liquid Fe generated is reacted with graphite powder3The wetting angle of C and carbide contact is small, and wetting action is significant, is strengthened by liquid phase Sintering, that is, under sufficiently high sintering temperature, additive or the fusing of additive product form liquid phase, fill hole, with Liquid phase flow particles occur sliding, rotation, reset, and are wet at particles bridge, particle is re-placed in discrete state, separation Particle further slides, and under the driving of liquid phase capillary force, the particle of sliding forms solid matter, so that densification degree is improved, The density of final product VN alloy is increased, conversion of the low-density vanadium trioxide to high-density vanadium-nitrogen alloy is realized, has Effect has saved production cost, provides a kind of completely new method for high-density vanadium-nitrogen alloy.Preparation method technique of the invention Process is simple, does not generate any trade waste;Reduce investment of production cost:Do not increase grinding pellet forming process, technique and sets It is standby to be further simplified, significantly reduce cost of investment;The higher value application of low-density vanadium trioxide raw material is realized, is enterprise Create significant economic benefit.
Specific embodiment
The present invention provides a kind of preparation methods of VN alloy, include the following steps:
A, abrasive material:8~16 parts of vanadic anhydride, 50~60 parts of vanadium trioxide, 20~30 parts of crystalline flake graphite, iron series are burnt Tie 0.8~2 part of 0.8~1.6 part of auxiliary agent, liquid phase inductive agent abrasive material extremely -140 mesh or less;
B, mixing and molding:All raw materials are first subjected to 25-40min dry-blending operations, are subsequently added into 8~12 parts of water, into The wet mixing of row 25-40min operates, and the compression moulding after mixing obtains molding pellet;
C, pellet obtained by step b is reacted into nitrogen atmosphere protection pushed slab kiln 6~8h, at 400~1520 DEG C, come out of the stove, it is cold But to 200~250 DEG C, VN alloy is obtained;
Liquid phase inductive agent described in step a is at least one of vanadium carbide, vanadium nitride or vanadium carbide nitride, and the iron series are burnt Knot auxiliary agent is at least one of reduced iron powder, iron oxide red, ferroso-ferric oxide or ferrous oxide.
Wherein, in the preparation method of above-mentioned VN alloy, vanadic anhydride described in step a is preferably full content of vanadium 52 The vanadic anhydride of~56wt%, vanadium trioxide are preferably vanadium trioxide of the full content of vanadium in 63~68wt%, three oxidations Two vanadium density are 0.60~0.80gcm-3, it is that clinker of the vanadium slag after calcification baking obtains soaking containing vanadic acid after sulfuric acid leaching Liquid obtains ammonium poly-vanadate with acid ammonium salt precipitation legal system, obtains vanadium trioxide by reduction.
Wherein, in the preparation method of above-mentioned VN alloy, iron series sintering aid described in step a is reduced iron powder, oxygen Change at least one of iron oxide red, ferroso-ferric oxide or ferrous oxide;The preferably mixture of di-iron trioxide and metallic iron, more preferably , iron series sintering aid is the mixture of the di-iron trioxide that weight ratio is 3~5 ﹕ 5~7 and metallic iron.
In order to increase the density size of product VN alloy, a certain proportion of vanadic anhydride and iron series are added in step a Sintering aid, the addition of vanadic anhydride advantageously reduce carbothermic reduction reaction Gibbs free energy, promote nitriding deoxidation process; Iron series sintering aid reacts the liquid Fe generated with graphite powder3The wetting angle of C and carbide contact is small, and wetting action is significant, It is intensified-sintered by liquid phase, increase product density.Iron series sintering aid is preferably the mixture of di-iron trioxide and metallic iron, with The mass fraction of percentage meter is preferably 0.8~1.6 part, more preferably 1.0~1.4 parts, most preferably 1.2 parts;Five oxidations two Mass fraction of the vanadium in terms of percentage is preferably 8~16 parts, and more preferably 10~15 parts, optimal is 12 parts.
Preferably, in order to which the pellet density of preparation is bigger, the granularity of strict control raw material, granularity too big influence reaction phase Between heat and mass process;Granularity is meticulous, increases grinding cost, and meticulous granularity is unfavorable for the molding of raw material, inventor It is found through overtesting, when all raw materials are crushed to -140 mesh or less, VN alloy density highest obtained, effect is best.
Density is bigger, pellet of better quality in order to be prepared, in the preparation method of above-mentioned VN alloy, in step b 30~50kN of briquetting pressure when the compacting, the dwell time 5~8 minutes, control pellet quality was 50~60g.
In order to which by pellet compression moulding, a certain amount of water is added as binder in the present invention, and the additional amount of water is preferably 9.5 ~10.5 parts, most preferably 10 parts.
After being pressed into pellet, the oxidation of VN alloy is generated in order to prevent, gained pellet is put under nitrogen atmosphere and is reacted, Controlling nitrogen oxygen content in nitrogen atmosphere two pass pushed bat kiln, in 5~8ppm, reaction temperature is 400~1520 DEG C, and platform is taken to heat up Curve is by 400 DEG C of linear temperature increases to 950 DEG C;950 DEG C to 1100 DEG C;1100 DEG C afterwards~1520 DEG C, 1520 DEG C are kept for 3 hours.
Pushed bat kiln is to prepare common equipment in VN alloy method, and the setting of parameter and technique has been mature on the whole, this It invents a kind of mixed oxidization vanadium raw materials to prepare in the method for VN alloy, existing pushed bat kiln production VN alloy technique not made big The change of scale is based only on the fact that low-density vanadium trioxide can largely influence alloy density size, in low-density A certain proportion of low melting point vanadic anhydride is added in vanadium trioxide raw material, by its liquid phase invigoration effect and strong volume Contractive effect increases product density;At the same time, the addition of iron series sintering aid further enhances the effect of liquid phase reinforcing, Promote the process of reaction.
The present invention also provides a kind of VN alloys, are made by above-mentioned preparation method.Preparation method system through the invention After standby, final products (i.e. VN alloy) chemical component meets GB/T 20567-2006 requirement, density size 3.12~ 3.48g·cm-3
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention System is among the embodiment described range.
Crystalline flake graphite quality used in embodiment meets the pertinent regulations of national standard GB/T 3518-2008, and fixed carbon contains Amount >=98%, volatile matter content≤1%, liquid phase inductive agent and iron series sintering aid are general industry product;Institute in embodiment To roller hydraulic press model YYQD560 × 216, main motor current 22kw, pressure roller maximum thrust 83t, pressure roller specification 560 × 216;Pushed bat kiln used in embodiment is 36mTBY kiln, and push plate pushes away fast 17min/ block, nitrogen pressure 0.02MPa, nitrogen flow 1.440km3/h。
Embodiment 1 prepares VN alloy with technical solution of the present invention
A, abrasive material:By 12 parts of vanadic anhydride (V2O5), 52 parts of vanadium trioxide (V2O3), 24 parts of crystalline flake graphites, 1.2 parts Iron series sintering aid (0.6 part of reduced iron powder, 0.6 part of di-iron trioxide) and 0.8 part of liquid phase inductive agent VN16 alloy abrasive material to- Below 140 mesh;
B, mixing and molding:The all materials of step a are imported into batch mixer and carry out 30min dry-blending operations, are subsequently added into 10 Part tap water carries out the wet mixing operation of 30min in wet mixing equipment, after mixing, is made using ball exercise processed is carried out to roller hydraulic press, The pellet with certain shapes, some strength is made, the quality of every pellet ball is controlled in 50g or so;
C, the calcining of pellet:Pellet, which enters in nitrogen atmosphere two pass pushed bat kiln, to react at 400 DEG C~1520 DEG C with nitrogen, out Furnace cooling obtains VN alloy.
Wherein, a~b step carries out under normal temperature and pressure conditions, and the step c carries out under the non-room temperature of normal pressure.
After measured, VN alloy chemical component obtained by the present embodiment is:TV:78.48%, N:14.72%, C:4.68%, P:0.024%, S:0.036%, alloy bulk density is 3.38gcm-3
Embodiment 2 prepares VN alloy with technical solution of the present invention
A, abrasive material:By 8 parts of vanadic anhydride (V2O5), 56 parts of vanadium trioxide (V2O3), 23.4 parts of crystalline flake graphites, 1.0 parts Iron series sintering aid (0.5 part of reduced iron powder, 0.5 part of di-iron trioxide) and 1.2 parts of liquid phase inductive agent VN16 alloy abrasive materials to- Below 140 mesh;
B, mixing and molding:The all materials of step a are imported into batch mixer and carry out 30min dry-blending operations, are subsequently added into 10 Part tap water carries out the wet mixing operation of 30min in wet mixing equipment, after mixing, is made using ball exercise processed is carried out to roller hydraulic press, The pellet with certain shapes, some strength is made, the quality of every pellet ball is controlled in 50g or so;
C, the calcining of pellet:Pellet, which enters in nitrogen atmosphere two pass pushed bat kiln, to react at 400 DEG C~1520 DEG C with nitrogen, out Furnace cooling obtains VN alloy.
Wherein, a~b step carries out under normal temperature and pressure conditions, and the step c carries out under the non-room temperature of normal pressure.
After measured, VN alloy chemical component obtained by the present embodiment is:TV:77.91%, N:15.30%, C:4.58%, P:0.017%, S:0.012%, alloy bulk density is 3.26gcm-3
Embodiment 3 prepares VN alloy with technical solution of the present invention
A, abrasive material:By 10 parts of vanadic anhydride (V2O5), 56 parts of vanadium trioxide (V2O3), 24.2 parts of crystalline flake graphites, 0.9 Part iron series sintering aid (0.45 part of reduced iron powder, 0.45 part of di-iron trioxide) and 0.9 part of liquid phase inductive agent VN16 alloy abrasive material Below to -140 mesh;
B, mixing and molding:The all materials of step a are imported into batch mixer and carry out 30min dry-blending operations, are subsequently added into 8 parts Tap water carries out the wet mixing operation of 30min in wet mixing equipment, after mixing, is made using ball exercise processed is carried out to roller hydraulic press, system At the pellet with certain shapes, some strength, the quality of every pellet ball is controlled in 50g or so;
C, the calcining of pellet:Pellet, which enters in nitrogen atmosphere two pass pushed bat kiln, to react at 400 DEG C~1520 DEG C with nitrogen, out Furnace cooling obtains VN alloy.
Wherein, a~b step carries out under normal temperature and pressure conditions, and the step c carries out under the non-room temperature of normal pressure.
After measured, VN alloy chemical component obtained by the present embodiment is:TV:77.40%, N:15.78%, C:4.23%, P:0.032%, S:0.021%, alloy bulk density is 3.43gcm-3
Comparative example 4 is added without vanadic anhydride and prepares VN alloy
In addition to being added without vanadic anhydride, remaining step is with embodiment 1, and the VN alloy measurement result being prepared is such as Under:
TV:78.38%, N:14.78%, C:4.76%, P:0.026%, S:0.018%, alloy bulk density is 2.98g·cm-3
Comparative example 5 is added without iron series sintering aid and prepares VN alloy
In addition to being added without iron series sintering aid, remaining step is with embodiment 1, and the VN alloy measurement result being prepared is such as Under:
TV:79.02%, N:12.78%, C:5.73%, P:0.041%, S:0.038%, alloy bulk density is 2.83g·cm-3
VN alloy, simple process, by being added five are prepared using technical solution of the present invention it can be seen from test result V 2 O and iron series sintering aid, cooperate between raw material reaction, so that it may so that product VN alloy density improves, solution The technical issues of high-density vanadium-nitrogen alloy cannot be prepared in low-density of having determined vanadium trioxide, and greatly reduce production Cost improves economic benefit.The raw materials such as the vanadic anhydride and iron series sintering aid that are added, it is intricate to exist each other Matching relationship, the technical scheme is that technical solution works as a whole, each condition is indispensable, finally obtains A method of high-density vanadium-nitrogen alloy is prepared using low-density vanadium trioxide.

Claims (18)

1. a kind of preparation method of VN alloy, which is characterized in that include the following steps:
A, raw material preparation
8~16 parts of vanadic anhydride, 50~60 parts of vanadium trioxide, 20~30 parts of crystalline flake graphite, iron series sintering in parts by weight 0.8~1.6 part of auxiliary agent, 0.8~2 part of liquid phase inductive agent weigh raw material, crush;The vanadium trioxide density be 0.60~ 0.80g·cm-3;The vanadic anhydride is vanadic anhydride of the full content of vanadium in 52~56wt%, and vanadium trioxide is full vanadium Vanadium trioxide of the content in 63~68wt%;
B, mixing compression moulding
Raw material in step a is mixed into 25~40min, 8~12 parts of water are added, remixes 25~40min, material is made in compression moulding Ball;30~50kN of briquetting pressure when the compacting, the dwell time 5~8 minutes;
C, pellet is calcined
Pellet obtained by step b is reacted into 6~8h in nitrogen atmosphere protection pushed slab kiln, 400~1520 DEG C of reaction temperature, is come out of the stove, it is cold But, VN alloy is obtained;
Iron series sintering aid described in step a be reduced iron powder, iron oxide red, ferroso-ferric oxide or ferrous oxide at least It is a kind of;The liquid phase inductive agent is at least one of vanadium carbide, vanadium nitride or vanadium carbide nitride.
2. the preparation method of VN alloy according to claim 1, it is characterised in that:Grinding particle size described in step a For≤140 mesh.
3. the preparation method of VN alloy according to claim 1, it is characterised in that:Iron series sintering aid is in step a Weight ratio is the iron oxide red of 3~5 ﹕ 5~7 and the mixture of reduced iron powder.
4. the preparation method of VN alloy according to claim 2, it is characterised in that:Iron series sintering aid is in step a Weight ratio is the iron oxide red of 3~5 ﹕ 5~7 and the mixture of reduced iron powder.
5. the preparation method of VN alloy according to claim 1, it is characterised in that:The sintering of iron series described in step a Auxiliary agent is 1.0~1.4 parts.
6. the preparation method of VN alloy according to claim 2, it is characterised in that:The sintering of iron series described in step a Auxiliary agent is 1.0~1.4 parts.
7. the preparation method of VN alloy according to claim 3, it is characterised in that:The sintering of iron series described in step a Auxiliary agent is 1.0~1.4 parts.
8. the preparation method of VN alloy according to claim 4, it is characterised in that:The sintering of iron series described in step a Auxiliary agent is 1.0~1.4 parts.
9. the preparation method of VN alloy according to claim 1, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
10. the preparation method of VN alloy according to claim 2, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
11. the preparation method of VN alloy according to claim 3, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
12. the preparation method of VN alloy according to claim 4, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
13. the preparation method of VN alloy according to claim 5, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
14. the preparation method of VN alloy according to claim 6, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
15. the preparation method of VN alloy according to claim 7, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
16. the preparation method of VN alloy according to claim 8, it is characterised in that:The additional amount of water described in step b It is 9.5~10.5 parts.
17. the preparation method of described in any item VN alloys according to claim 1~16, it is characterised in that:Nitrogen in step c Nitrogen oxygen content is in 5~8ppm in atmosphere protection pushed bat kiln.
18. a kind of VN alloy is made by the described in any item preparation methods of claim 1~17.
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