CN113897507B - Preparation method of VN19 vanadium-nitrogen alloy and box-shaped bowl device - Google Patents
Preparation method of VN19 vanadium-nitrogen alloy and box-shaped bowl device Download PDFInfo
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- CN113897507B CN113897507B CN202111170142.9A CN202111170142A CN113897507B CN 113897507 B CN113897507 B CN 113897507B CN 202111170142 A CN202111170142 A CN 202111170142A CN 113897507 B CN113897507 B CN 113897507B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
Abstract
The invention relates to the technical field of metallurgy, and provides a preparation method of VN19 vanadium-nitrogen alloy. The VN19 vanadium-nitrogen alloy is prepared by mixing powdery vanadium oxide, silicon dioxide powder, a carbonaceous reducing agent, iron powder and a binder, and then sequentially carrying out ball pressing, drying, vacuum carbonization reduction and nitridation. According to the invention, the silicon dioxide powder is added into the raw materials, and is reduced to generate silicon nitride in the nitridation process, so that the nitrogen content of the product is improved. The method disclosed by the invention can be used for carrying out carbonization reduction under a vacuum condition and carrying out nitridation under a high nitrogen pressure, so that the energy-saving, efficient and rapid preparation of the VN19 vanadium-nitrogen alloy can be realized. Furthermore, the invention optimizes the trend of nitrogen gas flow in the nitriding process, and adopts the sectional cooling mode of weak cooling and strong cooling in the cooling process, thereby improving the nitrogen content of the product, fully utilizing heat energy and reducing the preparation cost.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a preparation method of VN19 vanadium-nitrogen alloy and a box bowl device.
Background
The nitrogen is an effective and cheap alloy element in the vanadium-containing microalloyed steel, the nitrogen has stronger affinity than carbon for vanadium, the content of the nitrogen element in the vanadium-nitrogen alloy is improved, the precipitation strengthening and fine crystal precipitation strengthening effects of the vanadium in the steel are more obvious, the addition of the high-nitrogen vanadium-nitrogen alloy can save the addition amount of the vanadium under the condition of reaching the same strength, and further the cost is reduced. Therefore, the method has very important significance for improving the content of nitrogen elements in the vanadium-nitrogen alloy.
The mainstream process for producing vanadium-nitrogen alloy at present is a push plate kiln method, wherein the push plate kiln method is used for producing vanadium-nitrogen alloy, two reactions of carbonization reduction and nitridation are simultaneously carried out in the production process, and CO generated by carbonization reduction around a material ball2The vanadium-nitrogen alloy can not be discharged in time, the furnace of the pushed slab kiln is slightly pressurized, and the partial pressure of nitrogen around the material balls is low, so that the nitrogen content of the vanadium-nitrogen alloy produced by the pushed slab kiln is low and hardly reaches more than 17%. The relevant information describes the use of vacuum furnaces for the production of vanadium-nitrogen alloys (for example, patents CN 103243254A, CN 101787456 a and CN 104004934 a), which have nitrogen contents of only up to 18%.
The patent with publication number CN 103305739A discloses a production method of a high-nitrogen vanadium-nitrogen alloy, which can obtain a vanadium-nitrogen alloy with nitrogen content of 16-20%, and the method comprises the steps of pressing vanadium oxide, carbon powder, a catalyst, a guiding agent, a nitrogen fixing agent, a densifier and an adhesive as raw materials into balls, then discharging the materials after a reduction stage, a deoxidation and carbonization stage, a fluffing stage, a nitridation stage and a cooling stage, wherein the temperatures of the carbonization stage and the fluffing stage are as high as 1600 ℃. This method is costly and complicated to operate.
Disclosure of Invention
In view of this, the invention provides a preparation method of VN19 vanadium-nitrogen alloy and a cartridge device. The preparation method provided by the invention is simple to operate and low in cost, and can be used for obtaining the vanadium-nitrogen alloy with high nitrogen content.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of VN19 vanadium-nitrogen alloy comprises the following steps:
mixing powdery vanadium oxide, silicon dioxide powder, a carbonaceous reducing agent, iron powder and a binder, and then sequentially performing ball pressing, drying, vacuum carbonization reduction and nitridation to obtain VN19 vanadium-nitrogen alloy; the temperature of the vacuum carbonization reduction is less than or equal to 1450 ℃, and the time is less than or equal to 2.5 hours; the nitridation is carried out under the condition of nitrogen, the nitrogen pressure of the nitridation is more than or equal to 0.3MPa, and the time is less than or equal to 3 h; the mass ratio of the powdery vanadium oxide to the silicon dioxide powder to the graphite powder to the iron powder to the binder is 90-100: 2-4: 27-31: 0-0.8: 0-4.
Preferably, the vacuum degree of the vacuum carbonization reduction is less than or equal to 100 Pa; the temperature of the vacuum carbonization reduction is 1350-1450 ℃, and the time is 2-2.5 h; the nitrogen pressure of the nitridation is 0.3-0.4 MPa, and the time is 2.5-3 h; the nitriding temperature is 1300-1350 ℃.
Preferably, the vacuum carbonization-reduction and nitridation are performed in a vacuum furnace;
the vacuum carbonization-reduction comprises: placing the dried material balls into a sagger, placing the sagger into a vacuum furnace, vacuumizing the vacuum furnace, heating, raising the temperature of the furnace to a vacuum carbonization-reduction temperature, and preserving the heat;
the nitriding comprises: and after the heat preservation, closing the vacuum pump, controlling the furnace temperature at the nitriding temperature, and introducing nitrogen into the vacuum furnace, wherein the nitrogen pressure is kept above 0.3MPa for nitriding.
Preferably, the bottom of the sagger is provided with a plurality of through holes, and the nitrogen is introduced from bottom to top through the through holes in the bottom of the sagger.
Preferably, the sagger is placed on the bottom plate, the surface of the bottom plate is provided with strip-shaped grooves, the bottoms of the grooves are provided with gas access holes, the bottom of the sagger covers the surface of the bottom plate, and nitrogen is introduced from the gas access holes at the bottoms of the grooves and enters the sagger from bottom to top along the strip-shaped grooves.
Preferably, CO and CO are generated in the vacuum carbonization reduction process2The drying uses the CO as a heat source.
Preferably, the nitriding further comprises: cooling the nitrided material balls; the cooling was performed under nitrogen.
Preferably, the cooling comprises: carrying out weak cooling and strong cooling in sequence;
the weak cooling is carried out from the nitriding temperature to 800-900 ℃, and the nitrogen flow of the weak cooling is 5-10 m3/h；
The forced cooling is carried out from 800-900 ℃ to the discharge temperature, and the nitrogen flow of the forced cooling is 15-20 cm3/h。
Preferably, the vanadium oxide comprises one or more of vanadium pentoxide, vanadium tetraoxide and vanadium trioxide; the silicon dioxide powder comprises quartz powder and/or white carbon black.
The invention also provides a sagger device with the vent holes, which comprises a bottom plate and a sagger arranged on the surface of the bottom plate, wherein a plurality of through holes are formed in the bottom of the sagger, strip-shaped grooves are formed in the surface of the bottom plate, and gas access holes are formed in the bottoms of the grooves.
The invention provides a preparation method of VN19 vanadium-nitrogen alloy, which comprises the following steps: mixing powdery vanadium oxide, silicon dioxide powder, a carbonaceous reducing agent, iron powder and a binder, and then sequentially carrying out ball pressing, drying, vacuum carbonization reduction and nitridation to obtain VN19 vanadium-nitrogen alloy; the temperature of the vacuum carbonization reduction is less than or equal to 1450 ℃, and the time is less than or equal to 2.5 hours; the nitridation is carried out under the condition of nitrogen, the nitrogen pressure of the nitridation is more than or equal to 0.3MPa, and the time is less than or equal to 3 h; the mass ratio of the powdery vanadium oxide to the silicon dioxide powder to the graphite powder to the iron powder to the binder is 90-100: 2-4: 27-31: 0-0.8: 0-4. According to the invention, the silicon dioxide powder is added into the raw material for preparing the vanadium-nitrogen alloy, and is reduced by the carbonaceous reducing agent, so that silicon nitride is generated in the nitriding process, beneficial metal nitrogen fixing elements are added, and the nitrogen content of the product is favorably improved.
According to the invention, the carbonization-reduction and the nitridation are carried out step by step, wherein the carbonization-reduction process is carried out under vacuum, and the advantages of low temperature and high reaction speed of the vacuum carbonization-reduction reaction are fully utilized to quickly complete the carbonization-reduction reaction at a lower temperature; the nitrogen pressure is kept above 0.30Mpa, and the nitrogen reaction can be completed within less than or equal to 3 h. The method disclosed by the invention can be used for carrying out carbonization reduction under a vacuum condition and carrying out nitridation under a high nitrogen pressure, so that the energy-saving, efficient and rapid preparation of the VN19 vanadium-nitrogen alloy can be realized. Compared with the pushed slab kiln method, the method provided by the invention greatly shortens the time required by production, reduces the carbonization temperature and reduces the preparation cost of the vanadium-nitrogen alloy.
Furthermore, the invention optimizes the trend of nitrogen gas flow in the nitriding process, so that nitrogen gas flows upwards from the bottom of the sagger, is discharged from the upper part after fully contacting the material ball, and can discharge CO and CO generated around the material ball2Timely discharge, reduce CO and CO2Compared with the conventional process that nitrogen enters from the side surface of the sagger in the horizontal direction, the partial pressure of the nitrogen is better in nitriding effect.
Furthermore, the cooling process is carried out under the condition of nitrogen, small-flow nitrogen is continuously introduced for weak cooling when the temperature is higher, and the product is continuously nitrided by utilizing the waste heat when the temperature of the product is reduced to 800-900 ℃ from high temperature, so that the heat energy is fully utilized, the energy consumption is reduced, and the nitrogen content of the product is improved; after the temperature is reduced to 800-900 ℃, strong cooling is carried out by adopting large-flow nitrogen, the product is quickly reduced to the discharging temperature, and the production efficiency is improved.
Detailed Description
The invention provides a preparation method of VN19 vanadium-nitrogen alloy, which comprises the following steps:
mixing powdery vanadium oxide, silicon dioxide powder, a carbonaceous reducing agent, iron powder and a binder, and then sequentially carrying out ball pressing, drying, vacuum carbonization reduction and nitridation to obtain VN19 vanadium-nitrogen alloy; the temperature of the vacuum carbonization reduction is less than or equal to 1450 ℃, and the time is less than or equal to 2.5 hours; the nitridation is carried out under the condition of nitrogen, the nitrogen pressure of the nitridation is more than or equal to 0.3MPa, and the time is less than or equal to 3 h.
In the invention, the VN19 vanadium-nitrogen alloy is specifically VN19 grade vanadium-nitrogen alloy in GB/T20567-2020, and the specific component indexes are shown in Table 1:
TABLE 1VN19 vanadium-nitrogen alloy chemistry
The invention mixes the powder vanadium oxide, silicon dioxide powder, carbonaceous reducing agent, iron powder and binder to obtain the mixture. In the invention, the vanadium oxide preferably comprises one or more of vanadium pentoxide, vanadium tetraoxide and vanadium trioxide; the silicon dioxide powder preferably comprises quartz powder and/or white carbon black; the mass fraction of silicon dioxide in the quartz powder is preferably more than 98%; the carbonaceous reducing agent is preferably graphite powder, and specifically can be artificial graphite powder and/or natural graphite powder; the iron powder plays a role of a catalyst, the melting point of the iron powder is low, a liquid phase is formed during heating, contact between vanadium and carbon can be promoted, and the reduction rate is improved; the binder is preferably a water-soluble binder, and the water-soluble binder preferably comprises one or more of starch, dextrin, polyvinyl alcohol and carboxymethyl cellulose.
In the invention, the mass ratio of the powdery vanadium oxide to the silicon dioxide powder to the graphite powder to the iron powder to the binder is 90-100: 2-4: 27-31: 0-0.8: 0-4 (namely the amount of the iron powder to the binder can be 0), preferably 93-100: 2.5-3.5: 28-30: 0.1-0.6: 0.1-3, and more preferably 93-96: 2.8-3.2: 28.5-29.5: 0.2-0.5: 0.5-2.5.
The invention has no special requirements on the mixing method, and can uniformly mix all the raw materials.
After the mixture is obtained, the invention presses the mixture into balls to obtain green balls. The method for pressing the balls is not particularly required, and the ball pressing method well known to those skilled in the art can be adopted.
And after the ball pressing is finished, drying the obtained green ball to obtain the material ball. In the present invention, the drying is preferably performed in a drying kiln; the temperature of the hot air for drying in the drying kiln is preferably 180-220 ℃, more preferably 190-210 ℃, the drying time is preferably more than or equal to 10 hours, and the water content of the pellets obtained after drying is preferably less than or equal to 1 wt%; in the present invention, the drying is preferably performed using CO generated in the vacuum carbonization-reduction process as a heat source, and will be described in detail later.
After drying, the invention carries out vacuum carbonization and reduction on the obtained pellets. In the invention, the temperature of the vacuum carbonization reduction is less than or equal to 1450 ℃, preferably 1350-1450 ℃, more preferably 1380-1420 ℃, and the time of the vacuum carbonization reduction is less than or equal to 2.5h, preferably 2-2.5 h, more preferably 2.1-2.3 h; the vacuum degree of the vacuum carbonization reduction is preferably less than 100Pa, and more preferably 50-95 Pa.
In the present invention, the vacuum carbonization-reduction is preferably performed in a vacuum furnace, and in a specific embodiment of the present invention, the vacuum carbonization-reduction preferably includes: placing the dried material balls into a sagger, placing the sagger into a vacuum furnace, vacuumizing the vacuum furnace, heating, raising the temperature of the furnace to a vacuum carbonization-reduction temperature, and preserving the heat; in the invention, the temperature in the vacuum furnace is preferably increased to the temperature of vacuum carbonization reduction within 2-3 h, and the heating rate is preferably 3-10 ℃/min; the sagger is preferably a graphite sagger.
In the vacuum carbo-reduction process, vanadium oxide is reduced to vanadium carbide while silicon dioxide is reduced to silicon carbide, the reactions that take place are as follows:
2V2O5(s)+C(s)＝2V2O4(s)+CO(g)；
2V2O4(s)+C(s)＝V2O3(s)+2CO(g)；
V2O3(s)+5C(s)＝2VC(s)+3CO(g)；
SiO2+C＝Si+CO2；
specifically, when the raw material is vanadium pentoxide, the vanadium pentoxide is gradually reduced to vanadium tetraoxide, vanadium trioxide, and vanadium carbide in vacuum carbonization reduction, when the raw material is vanadium tetraoxide, the vanadium tetraoxide is gradually reduced to vanadium trioxide and vanadium carbide in vacuum carbonization reduction, and when the raw material is vanadium trioxide, the vanadium trioxide is reduced to vanadium carbide in vacuum carbonization reduction.
In the present invention, CO and CO are generated in the vacuum carbonization-reduction process2In the foregoing, the drying preferably uses the CO as a heat source, specifically, as a fuel gas for a drying kiln, for baking green pellets, thereby achieving full utilization of chemical energy and reducing energy consumption.
After the vacuum carbonization reduction is finished, the invention nitrifies the obtained raw material ball. In the invention, the nitrogen pressure of the nitridation is more than or equal to 0.3MPa, preferably 0.3-0.4 MPa, more preferably 0.35-0.38 MPa, the temperature of the nitridation is preferably 1300-1350 ℃, more preferably 1320-1330 ℃, and the time of the nitridation is less than or equal to 3h, preferably 2.5-3 h, more preferably 2.6-2.8 h.
In the present invention, the nitriding is preferably performed in a vacuum furnace, and in a specific embodiment of the present invention, the nitriding preferably comprises: and after the vacuum carbonization reduction heat preservation is finished, closing the vacuum pump, controlling the furnace temperature at the nitriding temperature, introducing nitrogen into the vacuum furnace, and keeping the nitrogen pressure at more than 0.3MPa for nitriding. In the embodiment of the present invention, it is preferable that the vacuum pump is turned off when the degree of vacuum in the furnace is 200Pa or less.
In the invention, the bottom of the sagger is preferably provided with a plurality of through holes, and the nitrogen is introduced from bottom to top through the through holes at the bottom of the sagger; in a specific embodiment of the present invention, the sagger is preferably placed on a bottom plate, the surface of the bottom plate is provided with a strip-shaped groove, the bottom of the groove is provided with a gas access hole, the bottom of the sagger covers the surface of the bottom plate, and the nitrogen gas is introduced from the gas access hole at the bottom of the groove and enters the sagger from bottom to top along the strip-shaped groove. In the present invention, the bottom of the sagger preferably covers the strip-shaped grooves on the surface of the bottom plate, and the groovesIs not communicated with the periphery of the bottom plate so as to avoid gas leakage from the edge of the bottom plate; according to the invention, the strip-shaped groove is formed in the bottom plate, the bottom of the sagger covers the surface of the bottom plate, the bottom surface of the sagger is combined with the groove to form the strip-shaped air passage, and nitrogen flows from the strip-shaped air passage and enters the sagger from bottom to top through the through hole under the action of air pressure after being introduced. The method for arranging the strip-shaped grooves has no special requirement, one strip groove can be arranged, a plurality of mutually communicated grooves can be arranged, and the gas can pass through the grooves. In the invention, the diameter of the through hole at the bottom of the groove is preferably 12-20 mm; the sagger and the bottom plate are both preferably made of graphite; in an embodiment of the present invention, it is preferable that the bottom plate is first placed in a vacuum furnace, and the nitrogen gas inlet hole of the bottom plate is connected to the nitrogen gas inlet port of the vacuum furnace, and then the sagger is placed on the upper surface of the graphite bottom plate. The invention optimizes the trend of nitrogen flow, so that the nitrogen flows upwards from the bottom of the sagger, is fully contacted with the material balls and is discharged from the upper part, and CO generated around the material balls can be discharged2Timely discharge to reduce CO and CO2The partial pressure of (2) and the nitriding effect are improved.
In the present invention, the inventive reaction of the nitridation process is as follows:
2VC(s)+N2(g)＝2VN(s)+2C(s)；
3Si+2N2＝Si3N4。
after the nitriding is finished, the invention preferably also comprises the steps of cooling the nitrided material ball; the cooling is preferably carried out under nitrogen; in the present invention, the cooling preferably includes weak cooling and strong cooling performed in this order; the weak cooling is carried out from the nitriding temperature to 800-900 ℃, and the nitrogen flow of the weak cooling is preferably 5-10 m3More preferably 6 to 8m3The strong cooling is carried out from 800-900 ℃ to the discharging temperature, and the discharging temperature is preferably below 160 ℃; the flow rate of the strong cold nitrogen is preferably 15-20 cm3More preferably 16 to 18 cm/h3H is used as the reference value. In the embodiment of the present invention, after the nitridation is completed, it is preferable to stop the heating and then adjust the flow rate of the nitrogen gas flow to perform the weak cooling and the strong cooling in this order. The invention introduces nitrogen at a small flow rate in the weak cooling process,the nitriding reaction is still carried out in the cooling process, nitrogen is introduced at a large flow rate in the forced cooling process, the nitrogen is fully contacted with hot materials, and heat is taken away quickly, so that the rapid cooling is realized, and the production efficiency is improved.
The invention also provides a sagger device with the vent holes, which comprises a bottom plate and a sagger arranged on the surface of the bottom plate, wherein a plurality of through holes are formed in the bottom of the sagger, strip-shaped grooves are formed in the surface of the bottom plate, and gas access holes are formed in the bottoms of the grooves. In the present invention, the materials of the sagger and the bottom plate, the size of the gas access hole, etc. are the same as those of the above scheme, and are not described herein again. The sagger device is applied to the nitriding process of vanadium-nitrogen alloy, the trend of nitrogen can be optimized, and CO generated around the material ball can be optimized2Timely discharge to reduce CO and CO2The partial pressure of (2) and the nitriding effect are improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Mixing vanadium pentoxide powder, 98% quartz powder, graphite powder and iron powder according to the mass ratio of 100:3:29:0.4, uniformly mixing, pressing into balls and drying. The dry balls are put into a graphite sagger, and a plurality of through holes are formed in the bottom of the graphite sagger; placing a graphite bottom plate in a vacuum furnace, wherein the surface of the graphite bottom plate is provided with strip-shaped grooves, the bottom of each groove is provided with a nitrogen inlet, and the nitrogen inlet is connected with a nitrogen inlet of the vacuum furnace; and putting the graphite sagger into a vacuum furnace, placing the graphite sagger on the surface of the graphite bottom plate, and covering the grooves on the surface of the graphite bottom plate by the bottom of the graphite sagger.
Closing the door of the vacuum furnace, starting the vacuum pump, vacuumizing the furnace to 95Pa, starting to transmit power for rapid heating, heating the furnace to 1400 ℃ within 2.8 hours, carrying out carbonization reduction for 2.2 hours, keeping the vacuum degree in the furnace at 169Pa, stopping pumping the vacuum pump, starting to fill nitrogen into the furnace, keeping the furnace temperature at 1300 ℃ for carrying out nitridation reaction, keeping the nitrogen pressure at 0.37MPa, and carrying out nitridation time for 2.8 hours. The heating was stopped and a nitrogen flow of 7.0m was applied during the furnace temperature was decreased from 1300 ℃ to 900 ℃3The furnace temperature is reduced to 900 ℃ in 2h, and the nitrogen gas supply flow is adjusted to 20m3The furnace temperature is reduced to 5.2hDischarging at 160 ℃ to obtain a vanadium-nitrogen alloy product, wherein the V content in the vanadium-nitrogen alloy is 76.7 percent, and the N content in the vanadium-nitrogen alloy is 19.1 percent.
Example 2
Mixing vanadium trioxide powder, 98% of quartz powder, graphite powder and starch according to the mass ratio of 100:3:26.5:3, uniformly mixing, pressing into balls and drying. The dry balls are put into a graphite sagger, and a plurality of through holes are formed in the bottom of the graphite sagger; placing a graphite bottom plate in a vacuum furnace, wherein the surface of the graphite bottom plate is provided with strip-shaped grooves, the bottom of each groove is provided with a nitrogen inlet, and the nitrogen inlet is connected with a nitrogen inlet of the vacuum furnace; and putting the graphite sagger into a vacuum furnace, placing the graphite sagger on the surface of the graphite bottom plate, and covering the grooves on the surface of the graphite bottom plate by the bottom of the graphite sagger.
Closing the furnace door of the vacuum furnace, starting the vacuum pump, vacuumizing the furnace to 88Pa, starting to transmit power for rapid heating, heating the furnace to 1380 ℃ within 2.7h, carrying out carbonization reduction for 2.2h at the temperature, keeping the vacuum degree in the furnace at 180Pa, stopping the vacuum pump, starting to fill nitrogen into the furnace, keeping the furnace temperature at 1320 ℃ for carrying out nitridation reaction, keeping the nitrogen pressure at 0.35MPa, and carrying out nitridation time for 2.7 h. The heating was stopped and a nitrogen flow of 6.9m was applied during the furnace temperature was reduced from 1320 ℃ to 800 ℃3The furnace temperature is reduced to 800 ℃ within 2.8h, and the nitrogen gas supply flow is adjusted to 19.5m3And h, reducing the furnace temperature to 160 ℃ within 5.0h, discharging to obtain a vanadium-nitrogen alloy product, wherein the V content in the vanadium-nitrogen alloy is 76.2 percent, and the N content in the vanadium-nitrogen alloy is 19.4 percent.
Example 3
Mixing vanadium pentoxide powder, vanadium trioxide powder, 98% quartz powder, graphite powder, iron powder and starch according to the mass ratio of 50:43:4:27.5:0.3:2, uniformly mixing, pressing into balls and drying. The dry balls are put into a graphite sagger, and a plurality of through holes are formed in the bottom of the graphite sagger; placing a graphite bottom plate in a vacuum furnace, wherein the surface of the graphite bottom plate is provided with strip-shaped grooves, the bottom of each groove is provided with a nitrogen inlet, and the nitrogen inlet is connected with a nitrogen inlet of the vacuum furnace; and putting the graphite sagger into a vacuum furnace, placing the graphite sagger on the surface of the graphite bottom plate, and covering the grooves on the surface of the graphite bottom plate by the bottom of the graphite sagger.
Closing the door of the vacuum furnace, starting the vacuum pump, vacuumizing the furnace to 82Pa, and starting power transmissionRapidly heating, and raising the furnace temperature to 1410 ℃ for 2.9h, and carrying out carbonization and reduction for 2.5h at the temperature. And (3) closing the vacuum pump, stopping exhausting, starting to charge nitrogen into the furnace, keeping the furnace temperature at 1345 ℃ to perform nitridation reaction, wherein the nitrogen pressure is 0.40Mpa, and the nitridation time is 3.0 h. The heating was stopped and a nitrogen flow of 7.1m was applied during the furnace temperature had decreased from 1345 ℃ to 850 DEG C3The furnace temperature is reduced to 850 ℃ within 2.4h, and the nitrogen gas supply flow is adjusted to 19m3And h, reducing the furnace temperature to 160 ℃ within 5.5h, discharging to obtain a vanadium-nitrogen alloy product, wherein the V content in the vanadium-nitrogen alloy is 76.4%, and the N content in the vanadium-nitrogen alloy is 19.3%.
Example 4
Mixing vanadium pentoxide powder, vanadium tetraoxide, vanadium trioxide powder, 98% quartz powder, graphite powder, iron powder and starch according to a ratio of 60:20:16:3:27:0.2:2, uniformly mixing, pressing into balls and drying. The dry balls are put into a graphite sagger, and a plurality of through holes are formed in the bottom of the graphite sagger; placing a graphite bottom plate in a vacuum furnace, wherein the surface of the graphite bottom plate is provided with strip-shaped grooves, the bottom of each groove is provided with a nitrogen inlet, and the nitrogen inlet is connected with a nitrogen inlet of the vacuum furnace; and putting the graphite sagger into a vacuum furnace, placing the graphite sagger on the surface of the graphite bottom plate, and covering the grooves on the surface of the graphite bottom plate by the bottom of the graphite sagger.
And closing the furnace door of the vacuum furnace, starting a vacuum pump, vacuumizing the furnace to 79Pa, starting to supply power for rapid heating, heating the furnace to 1408 ℃ within 2.9 hours, and carrying out carbonization-reduction for 2.4 hours at the temperature. And (3) closing the vacuum pump, stopping exhausting, starting to fill nitrogen into the furnace, keeping the furnace temperature at 1342 ℃ for nitridation reaction, keeping the nitrogen pressure at 0.38Mpa, and keeping the nitridation time at 3.0 h. The heating was stopped and a nitrogen flow of 7.1m was applied during the furnace temperature had decreased from 1342 ℃ to 900 ℃3The furnace temperature is reduced to 900 ℃ within 2.11h, and the nitrogen gas supply flow is adjusted to 19m3And h, reducing the furnace temperature to 160 ℃ within 5.49h, discharging to obtain a vanadium-nitrogen alloy product, wherein the V content in the vanadium-nitrogen alloy is 76.5%, and the N content in the vanadium-nitrogen alloy is 19.3%.
Example 5
Mixing vanadium tetraoxide, 98% quartz powder and graphite powder according to the mass ratio of 100:3:27.5, uniformly mixing, pressing balls and drying. The dry balls are put into a graphite sagger, and a plurality of through holes are formed in the bottom of the graphite sagger; placing a graphite bottom plate in a vacuum furnace, wherein the surface of the graphite bottom plate is provided with strip-shaped grooves, the bottom of each groove is provided with a nitrogen inlet, and the nitrogen inlet is connected with a nitrogen inlet of the vacuum furnace; and putting the graphite sagger into a vacuum furnace, placing the graphite sagger on the surface of the graphite bottom plate, and covering the grooves on the surface of the graphite bottom plate by the bottom of the graphite sagger.
Closing a furnace door of the vacuum furnace, starting a vacuum pump, vacuumizing the furnace to 80Pa, starting to transmit power for rapid heating, heating the furnace to 1390 ℃ within 2.75 hours, carrying out carbonization reduction for 2.8 hours at the temperature, keeping the vacuum degree in the furnace at 180Pa, stopping vacuumizing the vacuum pump, starting to fill nitrogen into the furnace, keeping the furnace temperature at 1340 ℃ for carrying out nitridation reaction, keeping the nitrogen pressure at 0.35MPa, and keeping the nitridation time at 2.9 hours. The heating was stopped and a nitrogen flow of 7.0m was fed during the time the furnace temperature was decreased from 1340 ℃ to 880 ℃3The furnace temperature is reduced to 880 ℃ within 2.2h, and the nitrogen gas supply flow is adjusted to 19.5m3And h, reducing the furnace temperature to 160 ℃ within 5.4h, discharging to obtain a vanadium-nitrogen alloy product, wherein the V content in the vanadium-nitrogen alloy is 76.3%, and the N content in the vanadium-nitrogen alloy is 19.2%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A VN19 vanadium-nitrogen alloy preparation method is characterized by comprising the following steps:
mixing powdery vanadium oxide, silicon dioxide powder, a carbonaceous reducing agent, iron powder and a binder, and then sequentially carrying out ball pressing, drying, vacuum carbonization reduction and nitridation to obtain VN19 vanadium-nitrogen alloy;
the temperature of the vacuum carbonization reduction is less than or equal to 1450 ℃, and the time is less than or equal to 2.5 hours; the nitridation is carried out under the condition of nitrogen, the nitrogen pressure of the nitridation is more than or equal to 0.3MPa, and the time is less than or equal to 3 h; the mass ratio of the powdery vanadium oxide to the silicon dioxide powder to the graphite powder to the iron powder to the binder is 90-100: 2-4: 27-31: 0-0.8: 0-4; the nitriding temperature is 1300-1350 ℃; the cooling comprises the following steps: carrying out weak cooling and strong cooling in sequence; the weak cooling is carried out from the nitriding temperature to 800-900 ℃, and the nitrogen flow rate of the weak cooling isIs 5 to 10m3H; the forced cooling is carried out from 800-900 ℃ to the discharge temperature, and the nitrogen flow of the forced cooling is 15-20 cm3/h。
2. The production method according to claim 1, wherein a degree of vacuum of the vacuum carbonization reduction is 100Pa or less; the temperature of the vacuum carbonization reduction is 1350-1450 ℃, and the time is 2-2.5 h; the nitrogen pressure of the nitridation is 0.3-0.4 MPa, and the time is 2.5-3 h.
3. The production method according to claim 1, wherein the vacuum carbo-reduction and nitriding are performed in a vacuum furnace;
the vacuum carbonization-reduction comprises: placing the dried material balls into a sagger, placing the sagger into a vacuum furnace, vacuumizing the vacuum furnace, heating, raising the temperature of the furnace to a vacuum carbonization-reduction temperature, and preserving the heat;
the nitriding comprises: and after the heat preservation, closing the vacuum pump, controlling the furnace temperature at the nitriding temperature, and introducing nitrogen into the vacuum furnace, wherein the nitrogen pressure is kept above 0.3MPa for nitriding.
4. The manufacturing method according to claim 3, wherein the bottom of the saggar is provided with a plurality of through holes, and the nitrogen gas is introduced from bottom to top through the through holes in the bottom of the saggar.
5. The manufacturing method according to claim 4, wherein the sagger is placed on a bottom plate, a surface of the bottom plate is provided with a strip-shaped groove, a bottom of the groove is provided with a gas inlet hole, the sagger bottom covers the surface of the bottom plate, and the nitrogen gas is introduced from the gas inlet hole at the bottom of the groove and enters the sagger along the strip-shaped groove from bottom to top.
6. The production method according to claim 1 or 3, wherein CO and CO are produced in the vacuum carbonization-reduction process2The drying uses the CO as a heat source.
7. The method of claim 1, 4 or 5, wherein the nitriding further comprises: cooling the nitrided material balls; the cooling was performed under nitrogen.
8. The preparation method according to claim 1, wherein the vanadium oxide comprises one or more of vanadium pentoxide, vanadium tetraoxide and vanadium trioxide; the silicon dioxide powder comprises quartz powder and/or white carbon black.
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| CN201664605U (en) * | 2010-04-08 | 2010-12-08 | 江阴市长兴钒氮新材料有限公司 | Sagger special for vanadium nitrogen alloy |
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