CN105063398B - A kind of technique for preparing nitrogen VN alloy high - Google Patents
A kind of technique for preparing nitrogen VN alloy high Download PDFInfo
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- CN105063398B CN105063398B CN201510558273.2A CN201510558273A CN105063398B CN 105063398 B CN105063398 B CN 105063398B CN 201510558273 A CN201510558273 A CN 201510558273A CN 105063398 B CN105063398 B CN 105063398B
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Abstract
The present invention relates to a kind of technique for preparing nitrogen VN alloy high, belong to metallurgical technology field.The present invention utilizes SHS technology, with thick level ammonium metavanadate as raw material, mixes moderator, directly leads to hydrogen, by NH4VO3In NH4 +Nitrogen is promoted to close, nitriding at high temperature；After reaction completely, nitrogen VN alloy high takes out after leading to nitrogen cooling in graphite crucible, crushes blocking.Use air bleeding valve of the invention controls the synthesis pressure in closed synthesising container and controls the surface air cleft of final products VN alloy；The product strength for preparing combustion synthesis process is larger, almost without broken in transport of materials and use, so as to reduce the proportion of goods damageds of material.Sintetics is fine and close, than great, up to 6.5g/cm3, nitrogen content is evenly distributed.
Description
Technical field
The present invention relates to a kind of technique for preparing nitrogen VN alloy high, belong to metallurgical technology field.
Background technology
China is steel producing country maximum in the world, is also steel consumption state maximum in the world.But in steel
Using it is most be low carbon-structural steel, account for the 70% of steel usage amount, therefore it is to promote China's steel to improve the intensity of straight carbon steel
Iron industrial technological advancement, carries out the important directions of iron structure adjustment.Its method for solving is to increase alloying steel-addition height
Nitrogen VN alloy.Using VN alloy, it is not necessary to add other valuable alloying elements again, can under general hot-rolled condition
It is 550~600MPa grades of high strength steel to obtain yield strength, thus the isometric material of high strength cast iron and steel plate (band), slab,
Obtained a wide range of applications in the exploitation of the products such as heavy wall shaped steel, seamless steel pipe, CSP.
American strategy mineral company in 1998 carries out VN alloy technological development and its patent in the steel industry of China
The popularization and application of product VN alloy, domestic some steel mills have carried out application test, state in HRB400 grades of reinforcing bar production of production
Interior research unit and some big steel mills are carried out to adding influence and strengthening mechanism of the VN alloy to steel mechanics performance in steel
Numerous studies, as a result show：After nitrogen in VN alloy is added in steel as cheap alloying element together with vanadium, not only may be used
To produce performance more preferably, HRB400MPaIII grades of more stable spiral and V-N steel, while 30- can also be saved
The addition of 40% vanadium, greatly reduces steel product cost.American side declares, the U.S. be uniquely can commodity production VN alloy state
Family, but technique not unofficial biography.After tackling key problems and testing, can be mass-produced VN alloy at present for domestic enterprise, but at present
The yield of China's vanadium-nitrogen alloy product can not meet needed for the steel such as domestic production high strength cast iron.We adopted since 2003
With SHS technology development and production ferrovanadium nitride, and some big steel mills are successfully applied to the life of V-N steel at home
Produce, using effect is quite or better than U.S.'s VN alloy.
When SHS technology is exploration rocket solid fuel in 1967 where the academy of sciences of former Soviet Union Chemical Physics
It was found that, its composition principle is, first with the outside few energy for being provided, to induce foreign peoples's material in powder or powdered compact
Between highly exothermic chemical reaction, with formed reaction leading edge combustion wave, synthetic reaction hereafter under the support of self-heat generation again
The continuation chemical reaction self-sustaining burning of neighbouring material is induced, required composition and structure are synthesized until whole material reactions are finished
Compound-material.The advantage of SHS technology is energy-conservation (building-up process is not required to external energy), efficiently (aggregate velocity
Be exceedingly fast), environmentally friendly (discharge of building-up process contamination-free), high-quality (stable components, purity are high).SHS technology is to work as
The high-tech in preceding synthesis field, at the end of the eighties in last century, many units of China have carried out the research of this respect.
SHS process in building-up process without external heat source, therefore calculation of thermodynamics focus on discuss that its is anti-
The possibility answered, it is the basis that Combination Process of SHS is discussed, and the conjunction directly calculated according to Thermodynamics Formulas
It is again the important parameter for characterizing conbustion synthesis into reaction adiabatic combustion temperature (Tad), the theory for SHS process is ground
Study carefully and application is all significant.Prediction Combination Process of SHS realizes that the most reliable method of possibility is to calculate given
The adiabatic combustion temperature of mixed system, it be judge combustion synthesis reaction can self―sustaining qualitative foundation.Self propagating high temperature
Synthesis technique founder Merzhanov etc. propose some general experience judge methods [《Conbustion synthesis》1999：P.56]：Only Tad
During ＞ 1800K, SHS process reaction ability self-sustaining is carried out.For the nitridation of vanadium metal or vanadium alloy raw material, mainly
It is that adiabatic combustion temperature is calculated by the reaction of vanadium and nitrogen, the adiabatic combustion temperature of vanadium nitrogen compound synthetic reaction is 3500K,
Even its adiabatic combustion temperature of vanadium iron raw material proposes the requirement of Tad ＞ 1800K empirical values also close to Merzhanov etc..For example
On 09 08th, 2010, Chinese invention patent application publication No. CN101824556A disclosed a kind of using self propagating high temperature conjunction
Into the method for technique productions ferrovanadium nitride, raw material is vanadium iron and nitrogen, and raw material vanadium iron is crushed in abrasive blast equipment first, will be broken
It is bulked in crucible after broken good vanadium iron raw material drying, crucible is placed in high-pressure synthesis device and the nitrogen of 6-12MPa is filled with, is opened
The dynamic igniter raw material that ignites carries out synthetic reaction, and combustion synthesis reaction self-sustaining is carried out, and the ferrovanadium nitride of conbustion synthesis is in nitrogen
Taken out after being cooled down in gas, crushed blocking.But nitrogen content is only 9.0~17.0% in sintetics, there is nitrogen content low（≤
17%）, the problems such as the impurity content such as carbon sulphur silicon is high, have a strong impact on steel nitrogen increased amount and performance.And nitrogen content（≥17%）Vanadium nitrogen is closed
Golden intensity, toughness, ductility, fatigue resistance that raising steel can be more efficiently facilitated compared with common low nitrogen VN alloy etc.
The usage amount of performance and further reduction vanadium is cost-effective.And reducing the impurity such as the carbon sulphur silicon in VN alloy can then reduce in refining
Excessive external impurity is brought into during steel addition VN alloy, influence the performance of steel.
The content of the invention
The technical problems to be solved by the invention are：A kind of technique for preparing nitrogen VN alloy high is proposed, by the inclined vanadium of thick level
Sour ammonium is directly vanadium-nitrogen alloy raw material without with the high price vanadium product such as vanadium iron as raw material, itself being reacted using self- propagating low-temperature burning
Heat release is nitrogenized, and the reaction time is short, energy consumption and low cost, and the nitrogen-vanadium alloy nitrogen high of production is high-purity, nitrogen content >=17%.Nitrogen contains
Amount is better than U.S.'s VN alloys.
According to requirement proposed by the present invention, the technical solution adopted in the present invention is：
1. a kind of technique for preparing nitrogen VN alloy high, using SHS technology, be with thick level ammonium metavanadate
Raw material, mixes moderator, directly leads to hydrogen, by NH4VO3In NH4 +Nitrogen is promoted to close, nitriding at high temperature；Comprise the concrete steps that：Instead
, first be sufficiently mixed for thick level ammonium metavanadate and moderator by Ying Qian；Be distributed into graphite crucible one by one, these graphite crucibles into
Laminated arrangement is put into closed synthesising container, and hydrogen is passed through from the bottom position of orlop graphite crucible；Starting ignition device draws
Combustion raw material carries out synthetic reaction, conbustion synthesis nitrogen VN alloy high；Water vapour and Co mixed gas hold from closed synthesis
Discharged through air bleeding valve the top of device；When vanadium nitridation reaction temperature reaches 1500 DEG C -1520 DEG C；Regulation control air bleeding valve makes closed conjunction
It is 2-3MPa into the gas pressure in container, combustion synthesis reaction self-sustaining is carried out；After reaction completely, nitrogen VN alloy high exists
Taken out after leading to nitrogen cooling in graphite crucible, crushed blocking.
Moderator of the invention is to prevent nitridation reaction from excessively acutely being added with the rising of temperature.
Described moderator is graphite powder, and its addition is the 3%-5% of thick level ammonium metavanadate gross weight.
Innovative point of the invention and beneficial effect are：
The present invention provides a kind of new selection for the production of nitrogen VN alloy high, and the present invention directly utilizes thick level metavanadic acid
Ammonium is raw material, directly leads to hydrogen, by NH4VO3In NH4 +Nitrogen is promoted to close, nitriding at high temperature；The present invention is using air bleeding valve control
Synthesis pressure in closed synthesising container is 2-3MPa, the H in building-up process in VN alloy2The discharge of O and CO is limited, and becomes
Obtain slowly, will not continuously gush out from VN alloy body surface face same position and form air cleft, therefore final products vanadium nitrogen of the present invention
The face crack of alloy is few, improves its surface quality, so as to improve its product quality.
Compared with CN101824556A techniques, the inventive method has the following advantages that：
1st, it is of the invention by thick level NH4VO3Directly for vanadium-nitrogen alloy raw material without with V2O5It is raw material etc. high price vanadium product, it is former
Material source is easier to obtain；Both using NH4VO3In NH4 +Promote nitrogen to close, great amount of cost is saved again；
2nd, moderator is removed in building-up process of the present invention（Graphite powder）Outward, added without other materials for helping reduction or heating, can
The impurity in product, and three-waste free discharge are substantially reduced, product quality is high；
3rd, the present invention can realize vanadium and the material reaction of nitrogen two fully using self- propagating low-temperature burning reaction self-heat generation, from
And the high nitrogen content of alloy is realized, and ensure uniform in quality, stabilization.And process is entirely synthesized without electrical heating and
Insulation, has saved the energy and operation, it is easy to control, and equipment is processed and easy for installation.Using self- propagating low-temperature burning new technology also
Synthesis cycle can be made less than 50 minutes, considerably shorter than the prior art reaction time, production efficiency is greatly improved；
4th, the present invention controls the synthesis pressure in closed synthesising container and controls final products VN alloy using air bleeding valve
Surface air cleft；The product strength for preparing combustion synthesis process is larger, almost without broken in transport of materials and use, so that
Reduce the proportion of goods damageds of material；
5th, using combustion synthesis process, either just synthesis furnace charge or final product all do not need briquetting.Sintetics
Densification, than great, up to 6.5g/cm3, nitrogen content is evenly distributed, and product nitrogen VN alloy composition high is：VN alloy contains V
Amount >=78%, VN alloy leaded wastewater >=17%, VN alloy C content≤5%, VN alloy S content≤0.1%, VN alloy silicon contains
Amount≤0.1%.
Specific embodiment
A kind of technique for preparing nitrogen VN alloy high of the present invention：
A kind of technique for preparing nitrogen VN alloy high, using SHS technology, with thick level ammonium metavanadate as former
Material, mixes moderator, directly leads to hydrogen, by NH4VO3In NH4 +Nitrogen is promoted to close, nitriding at high temperature；
2NH4VO3+H2+C =2VN+5H2O+CO；
The present invention is solid-solid/liquid/gas reactions, and it belongs to " infiltration conbustion synthesis " type.Infiltration conbustion synthesis are that hydrogen penetrates into
NH4VO3In with nitrogen-atoms occur exothermic chemical transformation and structure transformation process.By current NH4VO3Combustion synthesis process,
NH4VO3The middle nitrogen-atoms for containing of depositing is enough to maintain vanadium nitridation reaction required.In order to prevent nitridation reaction with the rising of temperature
It is excessively violent；The present invention is in NH4VO3Middle addition graphite powder moderator；
The graphite powder that the present invention is added plays decelerating effect, and its addition is the 3%-5% of thick level ammonium metavanadate gross weight；Reaction
Before be sufficiently mixed；It is fitted into graphite crucible one by one, these graphite crucibles are put into closed synthesising container into laminated arrangement, from most
The bottom position of lower floor's graphite crucible is passed through hydrogen；The starting ignition device raw material that ignites carries out synthetic reaction, conbustion synthesis nitrogen high
VN alloy；H2O and CO is discharged from the top of closed synthesising container through air bleeding valve；When vanadium nitridation reaction temperature reach 1500 DEG C-
1520℃；Regulation control the air bleeding valve to make the gas pressure in closed synthesising container be 2-3MPa, and combustion synthesis reaction self-sustaining enters
OK；After reaction completely, nitrogen VN alloy high takes out after leading to nitrogen cooling in graphite crucible, crushes blocking.
As described above, the present invention provides a kind of technique for preparing nitrogen VN alloy high, the Shen of patent of invention is now proposed in accordance with the law
Please；However, the above implementation explanation be one of present pre-ferred embodiments, the present invention is not limited to this, therefore such as with this
Feature of invention etc. is approximate, identical person, all should belong within claim of the invention.
Claims (1)
1. a kind of technique for preparing nitrogen VN alloy high, using SHS technology, it is characterized in that with thick level metavanadic acid
Ammonium is raw material, mixes moderator, directly leads to hydrogen, by NH4VO3In NH4 +Nitrogen is promoted to close, nitriding at high temperature；Specific steps
It is：Before reaction, first thick level ammonium metavanadate and moderator are sufficiently mixed；It is distributed into graphite crucible one by one, these graphite
Crucible is put into closed synthesising container into laminated arrangement, and hydrogen is passed through from the bottom position of orlop graphite crucible；Starting ignition
The device raw material that ignites carries out synthetic reaction, conbustion synthesis nitrogen VN alloy high；Water vapour and Co mixed gas are from closed
Discharged through air bleeding valve the top of synthesising container；When vanadium nitridation reaction temperature reaches 1500 DEG C -1520 DEG C；Regulation control air bleeding valve makes
Gas pressure in closed synthesising container is 2-3MPa, and combustion synthesis reaction self-sustaining is carried out；In building-up process in VN alloy
The discharge of water vapour and Co mixed gas be limited, and become slow, will not be continuously same from VN alloy body surface face
Position gushes out and forms air cleft；After reaction completely, nitrogen VN alloy high takes out after leading to nitrogen cooling in graphite crucible, is broken into
Block；Described moderator is graphite powder, and its addition is the 3%-5% of thick level ammonium metavanadate gross weight.
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| CN115927947A (en) * | 2022-12-12 | 2023-04-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of vanadium-nitrogen alloy |
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| GB1318467A (en) * | 1970-09-08 | 1973-05-31 | Hollandse Metallurg Ind Billit | Methods of preparation of a material containing vanadium carbonitride and or vanadium nitride |
| US4562057A (en) * | 1984-03-29 | 1985-12-31 | Union Carbide Corporation | Preparation of low-carbon vanadium nitride |
| CN101172585A (en) * | 2007-09-30 | 2008-05-07 | 冯良荣 | Method for producing vanadium nitride |
| CN101824556A (en) * | 2009-03-05 | 2010-09-08 | 承德金科科技开发有限责任公司 | Method for producing ferrovanadium nitride by adopting self-propagating high temperature synthesis process |
| CN103160698B (en) * | 2013-03-14 | 2015-06-10 | 西峡县中嘉合金材料有限公司 | Vanadium nitride alloy production technology |
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Application publication date: 20151118 Assignee: Zhongguancun Technology Leasing Co.,Ltd. Assignor: HUNAN ZHONGXIN NEW MATERIALS TECHNOLOGY Co.,Ltd. Contract record no.: X2022980001568 Denomination of invention: A process for preparing high nitrogen vanadium nitrogen alloy Granted publication date: 20170531 License type: Exclusive License Record date: 20220215 |
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