CN104141025B - The method of electro-aluminothermic process vanadium iron casting dealuminzation - Google Patents
The method of electro-aluminothermic process vanadium iron casting dealuminzation Download PDFInfo
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Abstract
The method that the present invention relates to electro-aluminothermic process vanadium iron casting dealuminzation, belongs to field of metallurgy. The technical problem to be solved in the present invention is to provide a kind of method of electro-aluminothermic process vanadium iron casting dealuminzation. The method of electro-aluminothermic process vanadium iron casting dealuminzation, comprises the step of reduction, refining and casting, and reduction and refinement step can adopt art methods; Before aluminium alloy casting, the mixture of iron oxide and lime composition is put into ingot mould, and then cast, cooling, obtain vanadium iron; Wherein, in iron oxide and lime mixture, in mass ratio, iron oxide: lime=2～3:1. The method step of electro-aluminothermic process vanadium iron casting dealuminzation of the present invention is simple, strong operability; Aluminium content < 0.2wt% in the vanadium iron that production obtains. There is dealuminzation efficiency high, avoid the advantages such as dealuminzation is grown in stove duration of heat.
Description
Technical field
The method that the present invention relates to electro-aluminothermic process vanadium iron casting dealuminzation, belongs to field of metallurgy.
Background technology
Vanadium iron product is divided into middle vanadium iron (FeV50) and high vanadium ferroalloy (FeV80), and mainly as steel-making additive, it can improve steelCombination property. Whole world vanadium output more than 80% for steel and iron industry, and join in iron and steel mainly with the form of vanadium iron.Vanadium can with steel in carbon and nitrogen react, generate little and hard refractory carbide and nitride, these compounds can playThe effect of fining agent and precipitation strength agent, the tissue of refinement steel and crystal grain, improve the Coarsening Temperature of crystal grain, thereby reduced temperature-sensitivePerception, toughness, intensity and the wearability of raising steel-product. High because thering is intensity containing vanadium steel, toughness, wearability, corrosion resistantThe good feature of erosion property and be widely used in the industries such as manufacture, building, Aero-Space, railway, bridge.
Domestic vanadium iron producer all produces in strict accordance with the vanadium iron quality standard of GB/T4139-2004. In recent years, China's yearOutput of steel is keeping the situation growing steadily, but constantly soaring fast containing special steel output proportion in steel total output of vanadium,This must cause the demand of vanadium to increase. Under this overall situation, vanadium industry development is both at home and abroad very fast, causes vanadium iron product in cityThe competition of the aspects such as field, technology. Client to the requirement of vanadium iron quality except outside the regulation clause in national standard,It is good also to include such as homogeneity of ingredients, and aluminium content is low, and crystal habit is good, the new requirements such as the convenient fragmentation of product, sample preparation.This forces the technological development of vanadium iron manufacturing enterprise towards more meticulous future development.
What most domestic vanadium iron producer adopted at present is the hot smelting process of one-step method electrit, and the aluminium content in alloy cannot effectively be controlledSystem, when client need to low aluminium vanadium iron, can only meet with the yield of sacrificing vanadium, and it is difficult in vanadium iron, between the composition of aluminium and yield, to existWith the contradiction solving. Meanwhile, its vanadium recovery of one-step method smelting ferrovanadium is also restricted, and smelting recovery is difficult to further lifting,Product quality depends on batching completely, and smelting process can not effectively be controlled alloy composition. How under the condition that keeps high yield, to haveThe removing excessive aluminium and become a new developing direction of vanadium iron smelting technique of effect.
Generally speaking, in smelting process, adding sheet vanadium to carry out dealuminzation is a selection preferably, but because the proportion of sheet vanadium is followed vanadiumIron is smelted slag system and is approached, and causes sedimentation difficulty in slag, makes the dynamic conditions of dealuminzation poor, and reaction rate is slower, directlyCause the increase of smelting cost. Because vanadium iron smelting history is longer, technique is fairly perfect, and patent is in this respect less, innovationMore difficult, at present, the patent that vanadium iron is smelted all focuses on the selection of raw material and reducing agent and how effectively to improve the rate of recovery of vanadiumOn.
Publication number is that the Chinese patent application of patent CN101100720A discloses vanadic acid calcium, aluminium powder, irony material by certain weightAmount proportioning is smelted and is obtained vanadium iron: vanadic acid calcium: 100 parts, and aluminium powder: 23～28 parts, irony material: 23～27 parts; Wherein, described inVanadic acid calcium be at least one in metavanadic acid calcium, pyrovanadic acid calcium, positive vanadic acid calcium, it is 24%～43% containing vanadium grade. ThisThe vanadium iron quality that bright technique is smelted is good, and vanadium recovery is high, does not produce contaminated wastewater in smelting process, adapts to high economic worth, lowThe infant industry of environmental pollution needs.
Publication number is that the Chinese patent application of CN101148733A discloses a kind of vanadium iron spraying powder refining technique, key step beIn electro-aluminothermic process smelting ferrovanadium process, when furnace charge fully completes thermit reaction, slag and alloy stop electrode and add after realizing and separatingHeat, inserts spray gun winding-up reduction powder to molten slag layer immediately, rotating furnace body simultaneously, and reduction powder is at winding-up gas shock and stoveFully mixed with slag under body Stirring double action, and then electrode insertion continues to add hot smelting 20～25 minutes, allow slagIn residual vanadium further reduce generation vanadium iron. This invention can make the reacting dynamics condition of refining furnace charge effectively be improved,Good component proportioning and winding-up amount can make the reaction of refining furnace charge more abundant, realize and improve the vanadium recovery that vanadium iron is smelted, and reduction is produced intoThis.
From above-mentioned disclosed technology, the existing research to electro-aluminothermic process production vanadium iron all concentrates on the reduction process of vanadium iron,Research to dealuminzation casting cycle has no report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of electro-aluminothermic process vanadium iron casting dealuminzation.
The method of electro-aluminothermic process vanadium iron casting dealuminzation, comprises the step of reduction, refining and casting, and reduction and refinement step can adoptArt methods; Before aluminium alloy casting, the mixture of iron oxide and lime composition is put into ingot mould, and then waterCasting, cooling, obtains vanadium iron; Wherein, in iron oxide and lime mixture, in mass ratio, iron oxide: lime=2～3:1.
Further, as preferred version, in iron oxide and lime mixture, in mass ratio, iron oxide: lime=2.3～2.7:1.
Further, preferably, Fe > 65wt% in above-mentioned iron oxide, Si < 1.5wt%, P < 0.02wt%, S < 0.02wt%,Mn < 0.5wt%, C < 0.5wt%, Al < 0.5wt%, the granularity of iron oxide is 0.5～1mm; CaO content > 85wt% in lime,S＜0.02wt％，C＜0.30wt％，P＜0.02wt％，SiO2< 1wt%, the granularity of lime is 2～5mm.
Further, as preferred version, before aluminium alloy casting, also the ingot mould that adds iron oxide and lime mixture is carried outBaking, baking temperature is 300～400 DEG C, baking time is 120～240min; As more preferably scheme, baking temperature is 350～400 DEG C, baking time is 180～240min.
Further, when casting, the temperature of aluminium alloy is 1950～2000 DEG C.
Further, the invention also discloses the method for electro-aluminothermic process production vanadium iron, comprise the steps:
A, batching: according to the chemical equation batching of electro-aluminothermic process, join aluminium amount and be theoretical value 1.1～1.3 times;
B, reduction;
C, refining;
D, casting: before aluminium alloy casting, the mixture of iron oxide and lime composition is put into ingot mould, and to adding iron oxideToast with the ingot mould of lime mixture, baking temperature is 300～400 DEG C, and baking time is 120～240min; Band alloyWhen liquid temp is 1950～2000 DEG C, casting, cooling, to obtain final product; In iron oxide and lime mixture, in mass ratio, iron oxide:Lime=2～3:1.
As preferred version, baking temperature is 350～400 DEG C, and baking time is 180～240min; As more preferably scheme, oxygenChange in iron and lime mixture, in mass ratio, iron oxide: lime=2.3～2.7:1.
Beneficial effect of the present invention:
(1), the method step of electro-aluminothermic process vanadium iron of the present invention casting dealuminzation is simple, strong operability;
(2), produce aluminium content < 0.2wt% in the vanadium iron obtaining;
(3), dealuminzation efficiency is high, avoided the duration of heat that in stove, dealuminzation is grown.
Detailed description of the invention
The method of electro-aluminothermic process vanadium iron casting dealuminzation of the present invention, operating procedure is: before aluminium alloy casting, by iron oxide and limeComposition mixture put into ingot mould, and then cast, cooling, to obtain final product; In iron oxide and lime mixture, by qualityRatio, iron oxide: lime=2～3:1.
Electro-aluminothermic process is produced vanadium iron, comprises the step of reduction, refining and casting, and described reduction and refinement step can adopt existing skillArt method, raw material need to carry out proportioning according to the calculated value of the chemical reaction of electro-aluminothermic process and slag making, and joining aluminium amount is theoretical value1.1～1.3 times, raw material addition, depending on heat size, enters standard electric arc furnaces after being mixed, through reduction, refinement step itAfter obtain vanadium iron liquid; Technical solution of the present invention is the improvement to casting step.
In the time that vanadium iron liquid is cast in ingot mould, will there is following reaction in the aluminium in the iron oxide in ingot mould and vanadium iron liquid:
Fe2O3+2Al＝2Fe+Al2O3
The iron restoring enters vanadium iron, enters in slag, thereby reach the object of dealuminzation and aluminium becomes aluminium oxide. Utilize rushing of castingBrush and stirring action, significantly improve the dynamic conditions of this reaction, can fast and effeciently remove the aluminium in alloy.
Wherein, if the ratio of iron oxide is too high in iron oxide and lime mixture, easily increase the quantity of slag, thereby increase vanadium loss; StoneThe effect of ash is residue adjustment, ensures vanadium iron metallurgical slag good mobility, if do not have very little residue adjustment effect, too highly easily invadesErosion ingot mould liner, can cause the loss of vanadium equally, therefore, selects in mass ratio iron oxide: lime=2～3:1.
Further, as preferred version, in iron oxide and lime mixture, in mass ratio, iron oxide: lime=2.3～2.7:1.
Further, for fear of because the introducing of other impurity causes alloy product defective, need to be to iron oxide and limeComposition is strictly controlled, as preferred version, and Fe content > 65wt% in iron oxide, Si < 1.5wt%, P < 0.02wt%,S < 0.02wt%, Mn < 0.5wt%, C < 0.5wt%, Al < 0.5wt%, the granularity of iron oxide is 0.5～1mm; CaO in limeContent > 85wt%, S < 0.02wt%, C < 0.30wt%, P < 0.02wt%, SiO2< 1wt%, the granularity of lime is 2～5mm.
Further, in order to reduce the temperature difference between lime, iron oxide and ingot mould and vanadium iron liquid, offer dealumination reactionTime enough, as preferred version, also toasts the ingot mould that adds iron oxide and lime mixture before casting, baking temperatureDegree is 300～400 DEG C, and baking time is 120～240min; As more preferably scheme, baking temperature is 350～400 DEG C, driesThe roasting time is 180～240min.
Further, in order to save time, the operation of also ingot mould of iron oxide and lime mixture being toasted before casting is passableIn smelting, carry out.
Further, when in the time that slag depletion is extremely lower containing vanadium, vanadium iron liquid has been cast at the high temperature that is greater than 1950 DEG CIn the ingot mould of aforesaid operations. Because vanadium iron smelting slag system melting temperature is very high, be about 1800 DEG C of left and right, therefore adopt and be greater than 1950 DEG CCast temperature be mainly to keep the liquid time in order to extend alloy melt, thereby make dealumination reaction carry out more thoroughly.
Preferably, when casting, the temperature of vanadium iron liquid is 1950～2000 DEG C, the too high erosion that can aggravate furnace lining of temperature.
Further, electro-aluminothermic process of the present invention is produced the method for vanadium iron, and step is as follows:
A, batching: according to the chemical equation batching of electro-aluminothermic process, join aluminium amount and be theoretical value 1.1～1.3 times;
B, reduction;
C, refining;
D, casting: before aluminium alloy casting, the mixture of iron oxide and lime composition is put into ingot mould, and to adding iron oxideToast with the ingot mould of lime mixture, baking temperature is 300～400 DEG C, and baking time is 120～240min; Treat alloyWhen liquid temp is 1950～2000 DEG C, casting, cooling, to obtain final product; In iron oxide and lime mixture, in mass ratio, iron oxide:Lime=2～3:1.
As preferred version, baking temperature is 350～400 DEG C, and baking time is 180～240min; As more preferably scheme, oxygenChange in iron and lime mixture, in mass ratio, iron oxide: lime=2.3～2.7:1.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention to instituteAmong the scope of embodiments of stating.
In the iron oxide using in the embodiment of the present invention: Fe68wt%, Si0.5wt%, P0.01wt%, S0.01wt%, Mn0.1wt%, C0.1wt%, Al0.05wt%, the granularity of iron oxide is 0.6mm; CaO90wt% in lime, S0.01wt%, C0.2wt％，P0.01wt％，SiO20.5wt%, the granularity of lime is 3mm.
Embodiment 1
Raw material: sheet vanadium (V2O5Mass content 98.0%) 200kg, V2O31600kg (containing vanadium 65.1%), joins aluminium 830kg,Iron 900kg, lime 200kg. After raw material is mixed, add in stove, the secondary voltage 190V striking of switching on, after furnace chargeization is clearSecondary voltage is selected 135V. During this time 300kg iron oxide and 100kg lime are joined in ingot mould and toasted, baking temperature350 DEG C, baking time 180min. Smelt after energising 90min, in rapid analysis slag, residual vanadium is 0.38%, and tapping casting, waters1980 DEG C of casting temperature, are cooled to room temperature with ingot mould afterwards, get the analysis of alloy sample, and aluminium content is 0.07%, and the vanadium iron obtaining is containing vanadium50.6%, vanadium yield 97.5%.
Embodiment 2
Raw material: sheet vanadium (V2O5Mass content 98.5%) 200kg, V2O31600kg (containing vanadium 65.5%), joins aluminium 800kg,Iron 970kg, lime 200kg. After material is mixed, add in stove, the secondary voltage 190V striking of switching on, after furnace chargeization is clear twoInferior voltage is selected 135V. During this time 200kg iron oxide and 100kg lime are joined in ingot mould and toasted, 400 DEG C of baking temperatures,Baking time 150min. Smelt after energising 85min, in rapid analysis slag, residual vanadium is 0.43%, tapping casting, cast temperature1960 DEG C, be cooled to room temperature with ingot mould afterwards, get the analysis of alloy sample, aluminium content is 0.09%, the vanadium iron obtaining contains vanadium 50.8%,Vanadium yield 97.0%.
Embodiment 3
Raw material: sheet vanadium (V2O5Mass content 97.8%) 200kg, V2O31600kg (containing vanadium 65.3%), joins aluminium 820kg,Iron 930kg, lime 200kg. After material is mixed, add in stove, the secondary voltage 190V striking of switching on, after furnace chargeization is clear twoInferior voltage is selected 135V. During this time 250kg iron oxide and 100kg lime are joined in ingot mould and toasted, 300 DEG C of baking temperatures,Baking time 240min. Smelt after energising 95min, in rapid analysis slag, residual vanadium is 0.63%, tapping casting, cast temperature1970 DEG C, be cooled to room temperature with ingot mould afterwards, get the analysis of alloy sample, aluminium content is 0.15%, the vanadium iron obtaining contains vanadium 50.2%,Vanadium yield 97.2%.
Embodiment 4
Raw material: sheet vanadium (V2O5Mass content 98.2%) 200kg, V2O31600kg (containing vanadium 64.9%), joins aluminium 810kg,Iron 120kg, lime 200kg. After material is mixed, add in stove, the secondary voltage 190V striking of switching on, after furnace chargeization is clear twoInferior voltage is selected 135V. During this time 250kg iron oxide and 100kg lime are joined in ingot mould and toasted, 350 DEG C of baking temperatures,Baking time 200min. Smelt after energising 90min, in rapid analysis slag, residual vanadium is 0.56%, tapping casting, cast temperature1990 DEG C, be cooled to room temperature with ingot mould afterwards, get the analysis of alloy sample, aluminium content is 0.18%, the vanadium iron obtaining contains vanadium 80.2%,Vanadium yield 96.8%.
Claims (6)
1. the method for electro-aluminothermic process vanadium iron casting dealuminzation, is characterized in that: before aluminium alloy casting, by iron oxide and lime compositionMixture put into ingot mould, the ingot mould that adds iron oxide and lime mixture is toasted, baking temperature is 300～400 DEG C,Baking time is 120～240min, and then cast, cooling, obtain vanadium iron; Wherein, iron oxide and lime mixtureIn, in mass ratio, iron oxide: lime=2～3:1; Wherein, when casting, the temperature of aluminium alloy is 1950～2000 DEG C; DescribedFe > 65wt% in iron oxide, Si < 1.5wt%, P < 0.02wt%, S < 0.02wt%, Mn < 0.5wt%, C < 0.5wt%Al < 0.5wt%, the granularity of iron oxide is 0.5～1mm; CaO content > 85wt% in lime, S < 0.02wt%, C < 0.30wt%,P＜0.02wt％，SiO2< 1wt%, the granularity of lime is 2～5mm.
2. the method for electro-aluminothermic process vanadium iron casting dealuminzation according to claim 1, is characterized in that: iron oxide and lime are mixedIn compound, in mass ratio, iron oxide: lime=2.3～2.7:1.
3. the method for electro-aluminothermic process vanadium iron according to claim 1 casting dealuminzation, is characterized in that: baking temperature is 350～400 DEG C, baking time is 180～240min.
4. electro-aluminothermic process is produced the method for vanadium iron, it is characterized in that, comprises the steps:
A, batching: according to the chemical equation batching of electro-aluminothermic process, join aluminium amount and be theoretical value 1.1～1.3 times;
B, reduction;
C, refining;
D, casting: before aluminium alloy casting, the mixture of iron oxide and lime composition is put into ingot mould, and to adding iron oxideToast with the ingot mould of lime mixture, baking temperature is 300～400 DEG C, and baking time is 120～240min; Treat alloyWhen liquid temp is 1950～2000 DEG C, casting, cooling, to obtain final product; In iron oxide and lime mixture, in mass ratio, iron oxide:Lime=2～3:1.
5. electro-aluminothermic process according to claim 4 is produced the method for vanadium iron, it is characterized in that: baking temperature is 350～400 DEG C, baking time is 180～240min.
6. the method for producing vanadium iron according to the electro-aluminothermic process described in claim 4 or 5, is characterized in that: iron oxide and lime are mixedIn compound, in mass ratio, iron oxide: lime=2.3～2.7:1.
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| CN104532105B (en) * | 2015-01-04 | 2016-05-18 | 攀钢集团攀枝花钢铁研究院有限公司 | The stove electro-aluminothermic process of tumbling is prepared the method for vanadium iron |
| CN106216645B (en) * | 2016-08-30 | 2018-12-28 | 成都工业学院 | The method of ferrocolumbium casting dealuminzation |
| CN106967917B (en) * | 2017-04-28 | 2019-03-19 | 攀钢集团研究院有限公司 | The control method of FeV80 alloy carbon content |
| CN107760887A (en) * | 2017-10-30 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method that vanadium iron in low aluminium is smelted using stove of tumbling |
| CN109825704B (en) * | 2019-04-12 | 2020-07-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Smelting method of ferrovanadium alloy |
| CN110283998A (en) * | 2019-08-06 | 2019-09-27 | 攀钢集团研究院有限公司 | The control method of content of vanadium and alloying component in vanadium iron metallurgical slag |
| CN111304523A (en) * | 2020-03-31 | 2020-06-19 | 西安宏信矿热炉有限公司 | Production process of low-aluminum ferrosilicon |
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| RU2166556C1 (en) * | 2000-01-10 | 2001-05-10 | ОАО "Нижнетагильский металлургический комбинат" | Method of ferrovanadium smelting |
| CN102115821B (en) * | 2010-09-13 | 2013-01-23 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN102094097B (en) * | 2011-03-04 | 2013-01-09 | 攀钢集团钢铁钒钛股份有限公司 | Production process for smelting vanadium ferro-alloy by electro-aluminothermic process |
| CN103031484B (en) * | 2011-09-30 | 2015-05-06 | 攀钢集团有限公司 | Method for smelting vanadium iron |
| CN103045928A (en) * | 2012-12-31 | 2013-04-17 | 攀钢集团西昌钢钒有限公司 | Method for producing ferrovanadium by aluminothermic process |
| CN103045929B (en) * | 2012-12-31 | 2015-12-23 | 攀钢集团西昌钢钒有限公司 | Electro-aluminothermic process produces the method for vanadium iron |
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