CN105087994A - Method for preparing high-nitrogen high-purity vanadium-nitrogen alloy - Google Patents
Method for preparing high-nitrogen high-purity vanadium-nitrogen alloy Download PDFInfo
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- CN105087994A CN105087994A CN201510558272.8A CN201510558272A CN105087994A CN 105087994 A CN105087994 A CN 105087994A CN 201510558272 A CN201510558272 A CN 201510558272A CN 105087994 A CN105087994 A CN 105087994A
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Abstract
The invention relates to a method for preparing high-nitrogen high-purity vanadium-nitrogen alloy, and belongs to the technical field of metallurgy. According to the method disclosed by the invention, a self-propagating high-temperature synthesis technique is utilized; coarse ammonium metavanadate is used as a raw material; the hydrogen is directly supplied; nitrogen synthesis is promoted by using NH4+ in NH4VO3; nitridation is performed under high temperature. According to the method disclosed by the invention, no other materials for assisting revivification or heating are added during synthesis, so that the impurities in products can be greatly reduced; three wastes are not emitted, so that the quality of products is high. The vanadium-nitrogen alloy prepared by the method disclosed by the invention is compact; the specific gravity of the vanadium-nitrogen alloy is large, and can reach 6.5g/cm<3>; the nitrogen distribution of the vanadium-nitrogen alloy is even; the content of V in the vanadium-nitrogen alloy is equal to or greater than 78%; the content of N in the vanadium-nitrogen alloy is equal to or greater than 17%; the content of C in the vanadium-nitrogen alloy is equal to or smaller than 5%; the content of S in the vanadium-nitrogen alloy is equal to or smaller than 0.1%; the content of silicon in the vanadium-nitrogen alloy is equal to or smaller than 0.1%.
Description
Technical field
The present invention relates to a kind of method preparing the high-purity VN alloy of high nitrogen, belong to metallurgical technology field.
Background technology
China is Iron and Steel Production state maximum in the world, is also steel consumption state maximum in the world.But using maximum in steel is low carbon-structural steel, accounts for 70% of steel usage quantity, the intensity therefore improving straight carbon steel promotes China's Iron And Steel Industry technical progress, carries out the important directions of iron structure adjustment.Its method solved strengthens alloying steel-add the high-purity VN alloy of high nitrogen.Adopt VN alloy, do not need to add other valuable alloying element again, under general hot-rolled condition, just can obtain the high-strength steel that yield strength is 550 ~ 600Mpa level, therefore obtain a wide range of applications in the exploitation of the products such as the isometric material of high strength cast iron and steel plate (band), slab, heavy wall shaped steel, weldless steel tube, CSP.
American strategy mineral company in 1998 carries out applying of VN alloy technological development and patented product VN alloy thereof at the steel industry of China, more domestic steel mills have carried out application test in production HRB400 level reinforcing bar is produced, domestic research unit and some large steel mills have carried out large quantity research on adding VN alloy in steel to the impact of steel mechanics performance and strengthening mechanism, result shows: the nitrogen in VN alloy adds after in steel as the alloying element of cheapness together with vanadium, not only performance can be produced better, more stable HRB400MpaIII level Twisted Steel and V-N steel, the add-on of 30-40% vanadium can also be saved simultaneously, greatly reduce steel product cost.American side declares, the U.S. is uniquely can the country of commercial production VN alloy, but technique not unofficial biography.Domestic enterprise is after tackling key problem test, and can be mass-produced VN alloy at present, but the output of China's vanadium-nitrogen alloy product can not meet needed for the steel such as domestic production high strength cast iron at present.We adopted SHS technology R&D and production ferrovanadium nitride from 2003, and some large steel mills are successfully applied to the production of V-N steel at home, and result of use quite or be better than U.S.'s VN alloy.
SHS technology finds when being USSR (Union of Soviet Socialist Republics) academy of sciences chemical physics place exploration rocket solid fuel in 1967, its composition principle first utilizes the outside minute quantity energy provided, bring out the high heat-producing chemical reaction in powder or powdered compact between foreign peoples's material, with the combustion wave of forming reactions leading edge, after this building-up reactions brings out the continuation chemical reaction self-sustaining burning of contiguous material again under the support of self-heat generation, until whole complete and compound-materials of the required composition and structure of synthesis of material reaction.The advantage of SHS technology is energy-conservation (building-up process does not need external energy), efficient (resultant velocity is exceedingly fast), environmental protection (discharge of building-up process contamination-free), high-quality (stable components, purity are high).SHS technology is the hi-tech in current synthesis field, and 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 the need to external heat source, therefore calculation of thermodynamics focus on discuss its reaction possibility, it is the basis that Combination Process of SHS is discussed, and according to this building-up reactions adiabatic combustion temperature (Tad) that Thermodynamics Formulas directly calculates, again characterize the important parameter of conbustion synthesis, for the theoretical investigation of SHS process and application all significant.To realize the most reliable method of possibility be the adiabatic combustion temperature calculating given mixed system to prediction Combination Process of SHS, and it judges that can combustion synthesis reaction the qualitative foundation of self―sustaining.Self-propagating High-temperature Synthesis Process originator Merzhanov etc. propose some general experience judge methods [" conbustion synthesis " 1999:P.56]: when only having Tad > 1800K, and SHS process reaction could continue to carry out certainly.For the nitrogenize of vanadium metal or vanadium alloy raw material, mainly calculate adiabatic combustion temperature by the reaction of vanadium and nitrogen, the adiabatic combustion temperature of vanadium nitrogen compound building-up reactions is 3500K, even its adiabatic combustion temperature of vanadium iron raw material also proposes the requirement of Tad > 1800K empirical value close to Merzhanov etc.Such as on 09 08th, 2010, Chinese invention patent application publication No. CN101824556A, disclose a kind of method adopting Self-propagating High-temperature Synthesis Process to produce ferrovanadium nitride, raw material is vanadium iron and nitrogen, first raw material vanadium iron is broken in abrasive blast equipment, to be bulked in crucible after vanadium iron raw material drying good for fragmentation, crucible to be placed in high-pressure synthesis device and to be filled with the nitrogen of 6-12MPa, the starting ignition device raw material that ignites carries out building-up reactions, combustion synthesis reaction is from continuing to carry out, the ferrovanadium nitride of conbustion synthesis cools rear taking-up in nitrogen, is broken into block.But nitrogen content is only 9.0 ~ 17.0% in sintetics, there is nitrogen content low (≤17%), the problems such as the foreign matter contents such as carbon sulphur silicon are high, have a strong impact on steel nitrogen increased amount and performance.And the performance such as intensity, toughness, ductility, fatigue resistance that nitrogen content (>=17%) VN alloy more effectively can promote to improve steel compared with common low nitrogen VN alloy and the usage quantity that reduces vanadium further save cost.Reduce when the impurity such as the carbon sulphur silicon in VN alloy then can be reduced in steel-making interpolation VN alloy and bring too much external impurity into, affect the performance of steel.
Summary of the invention
Technical problem to be solved by this invention is: propose a kind of method preparing the high-purity VN alloy of high nitrogen, by thick level ammonium meta-vanadate directly for vanadium-nitrogen alloy raw material and not with the high price such as vanadium iron vanadium product for raw material, utilize self-propagating low-temperature burning to react self-heat generation and carry out nitrogenize, reaction times is short, energy consumption and cost low, the nitrogen-vanadium alloy height nitrogen produced is high-purity, nitrogen content >=17%.Nitrogen content is better than U.S. VN alloy.
According to requirement of the present invention, the technical solution adopted in the present invention is:
Prepare a method for the high-purity VN alloy of high nitrogen, utilize SHS technology; It is characterized in that with thick level ammonium meta-vanadate for raw material, directly logical hydrogen, by NH
4vO
3in NH
4 +promote that nitrogen closes, at high temperature nitriding, NH
4vO
3+ H
2=VN+3H
2o;
Concrete steps are: be first respectively charged into by thick level ammonium meta-vanadate one by one in plumbago crucible, then become laminated arrangement to put into airtight synthesising container these plumbago crucibles, pass into hydrogen from the bottom position of orlop plumbago crucible; The starting ignition device raw material that ignites carries out building-up reactions, the high-purity VN alloy of conbustion synthesis height nitrogen; H
2o discharges from the top of airtight synthesising container through vent valve; When vanadium nitrogenizing reaction temperature reaches 1500 DEG C-1520 DEG C; Regulable control vent valve makes the water vapour pressure in airtight synthesising container be 2-3Mpa, and combustion synthesis reaction is from continuing to carry out; After reacting completely, the high-purity VN alloy of high nitrogen is taken out after logical nitrogen cooling in plumbago crucible, is broken into block.
Innovative point of the present invention and beneficial effect are:
The present invention is that the production of the high-purity VN alloy of high nitrogen provides a kind of selection newly, and the present invention directly utilizes thick level ammonium meta-vanadate to be raw material, directly logical hydrogen, by NH
4vO
3in NH
4 +promote that nitrogen closes, at high temperature nitriding; The synthesis pressure that the present invention utilizes vent valve to control in airtight synthesising container is 2-3Mpa, the H in building-up process in VN alloy
2o discharges limited, and becomes slow, and can not gush out from VN alloy surface same position continuously and form air cleft, therefore the surface crack of the finished product VN alloy of the present invention be few, improves its surface quality, thus improves its quality product.
Compared with CN101824556A technique, the inventive method tool has the following advantages:
1, the present invention is by thick level NH
4vO
3it is directly vanadium-nitrogen alloy raw material and not with V
2o
5be raw material Deng high price vanadium product, raw material sources more easily obtain; Both NH can be utilized
4vO
3in NH
4 +promote that nitrogen closes, save great amount of cost again;
2, help the material of reduction or heating to add without other in building-up process of the present invention, greatly can reduce the impurity in product, and three-waste free discharge, quality product is high;
3, the present invention utilize self-propagating low-temperature burning to react self-heat generation can to realize vanadium and nitrogen two material reaction abundant, thus realize the high nitrogen content of alloy, and ensure uniform in quality, stablize.And whole Reactive Synthesis process is without electrically heated and insulation, has saved the energy and operation, be easy to control, apparatus processing and easy for installation.Use self-propagating low-temperature burning new technology that synthesis cycle can also be made less than 50 minutes, be far shorter than the prior art reaction times, greatly enhance productivity;
4, the present invention adopts vent valve to control the synthesis pressure in airtight synthesising container and controls the surperficial air cleft of the finished product VN alloy; Product strength prepared by combustion synthesis process is comparatively large, almost without broken in transportation of materials and use, thus reduces the wastage rate of material;
5, employing combustion synthesis process, synthesizes furnace charge at the beginning of being or final product does not need briquetting.Sintetics is fine and close, than great, can reach 6.5g/cm
3, nitrogen content is evenly distributed, and this product height nitrogen high purity vanadium nitrogen alloy composition is: VN alloy V content>=78%, VN alloy leaded wastewater>=17%, VN alloy C content≤5%, VN alloy S content≤0.1%, VN alloy silicone content≤0.1%.
Embodiment
A kind of method preparing the high-purity VN alloy of high nitrogen of the present invention:
Prepare a method for the high-purity VN alloy of high nitrogen, utilize SHS technology, with thick level ammonium meta-vanadate for raw material, directly logical hydrogen, by NH
4vO
3in NH
4 +promote that nitrogen closes, at high temperature nitriding;
NH
4VO
3+H
2=VN+3H
2O；
The present invention is solid-solid/liquid/gas reactions, type that it belongs to " infiltration conbustion synthesis ".Infiltration conbustion synthesis is that hydrogen infiltrates NH
4vO
3in to change with nitrogen-atoms generation exothermic chemical and the process of structural transformation; By current NH
4vO
3combustion synthesis process, NH
4vO
3middle the nitrogen-atoms contained of depositing is enough to maintain needed for vanadium nitrogenizing reaction;
Thick level ammonium meta-vanadate of the present invention is respectively charged into one by one in plumbago crucible, becomes laminated arrangement to put into airtight synthesising container these plumbago crucibles, passes into hydrogen from the bottom position of orlop plumbago crucible; The starting ignition device raw material that ignites carries out building-up reactions, the high-purity VN alloy of conbustion synthesis height nitrogen; H
2o discharges from the top of airtight synthesising container through vent valve; When vanadium nitrogenizing reaction temperature reaches 1500 DEG C-1520 DEG C; Regulable control vent valve makes the water vapour pressure in airtight synthesising container be 2-3Mpa, and combustion synthesis reaction is from continuing to carry out; After reacting completely, the high-purity VN alloy of high nitrogen is taken out after logical nitrogen cooling in plumbago crucible, is broken into block.
As mentioned above, the invention provides a kind of method preparing the high-purity VN alloy of high nitrogen, the existing application in accordance with the law proposing patent of invention; But above implementation is one of present pre-ferred embodiments, not limit to the present invention with this, therefore approximate with feature of the present invention etc., identical person such as, all should belong within claim of the present invention.
Claims (1)
1. prepare a method for the high-purity VN alloy of high nitrogen, utilize SHS technology; It is characterized in that with thick level ammonium meta-vanadate for raw material, directly logical hydrogen, by NH
4vO
3in NH
4 +promote that nitrogen closes, at high temperature nitriding; Concrete steps are: be first respectively charged into by thick level ammonium meta-vanadate one by one in plumbago crucible, then become laminated arrangement to put into airtight synthesising container these plumbago crucibles, pass into hydrogen from the bottom position of orlop plumbago crucible; The starting ignition device raw material that ignites carries out building-up reactions, the high-purity VN alloy of conbustion synthesis height nitrogen; H
2o discharges from the top of airtight synthesising container through vent valve; When vanadium nitrogenizing reaction temperature reaches 1500 DEG C-1520 DEG C; Regulable control vent valve makes the water vapour pressure in airtight synthesising container be 2-3Mpa, and combustion synthesis reaction is from continuing to carry out; After reacting completely, the high-purity VN alloy of high nitrogen is taken out after logical nitrogen cooling in plumbago crucible, is broken into block.
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Citations (11)
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| CN102277522A (en) * | 2011-07-28 | 2011-12-14 | 四川省川威集团有限公司 | Method for producing vanadium and nitrogen alloy |
| CN102910596A (en) * | 2012-08-16 | 2013-02-06 | 中色（宁夏）东方集团有限公司 | Preparation method of vanadium nitride |
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2015
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| US4562057A (en) * | 1984-03-29 | 1985-12-31 | Union Carbide Corporation | Preparation of low-carbon vanadium nitride |
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Application publication date: 20151125 Assignee: Zhongguancun Technology Leasing Co.,Ltd. Assignor: HUNAN ZHONGXIN NEW MATERIALS TECHNOLOGY Co.,Ltd. Contract record no.: X2022980001568 Denomination of invention: A method for preparing high nitrogen and high purity vanadium nitrogen alloy Granted publication date: 20170531 License type: Exclusive License Record date: 20220215 |
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Denomination of invention: A method for preparing high nitrogen and high purity vanadium nitrogen alloy Effective date of registration: 20220216 Granted publication date: 20170531 Pledgee: Zhongguancun Technology Leasing Co.,Ltd. Pledgor: HUNAN ZHONGXIN NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: Y2022110000033 |
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