CN104141025A - Method for casting and dealuminizing ferrovanadium by electro-aluminothermic process - Google Patents
Method for casting and dealuminizing ferrovanadium by electro-aluminothermic process Download PDFInfo
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Abstract
The invention relates to a method for casting and dealuminizing ferrovanadium by an electro-aluminothermic process, belongs to the field of metallurgy, and aims to solve the technical problem of providing the method for casing and dealuminizing ferrovanadium by the electro-aluminothermic process. The method comprises the steps of reducing, refining and casting, wherein existing technical methods are adopted in the reducing and refining steps; before alloy liquid is cast, a mixture composed of ferric oxide and lime is put into an ingot module, and then is cast and cooled to obtain ferrovanadium; the mass ratio of ferric oxide to lime in the mixture of ferric oxide and lime is (2-3) to 1. The method for casting and dealuminizing ferrovanadium by the electro-aluminothermic process is simple in steps and strong in operability; and the content of aluminum in the produced ferrovanadium is less than 0.2wt%. The method has the advantages that the dealuminzation efficiency is high, the smelting time for dealuminization in a furnace can be shortened, and the like.
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 the over-all properties of steel.Whole world vanadium output more than 80% for Iron And Steel Industry, and join in iron and steel mainly with the form of ferro-vanadium.Vanadium can with steel in carbon and nitrogen react, generate little and hard refractory carbide and nitride, these compounds can play the effect of fining agent and precipitation strength agent, the tissue of refinement steel and crystal grain, improve the Coarsening Temperature of crystal grain, thereby reduction superheated susceptivity, toughness, intensity and the wear resistance of raising steel-product.High because thering is intensity containing vanadium steel, the feature of toughness, wear resistance, good corrosion resistance and be widely used in the industries such as manufacture, building, aerospace, 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 year output of steel is keeping the situation growing steadily, but constantly soaring fast containing special steel output proportion in steel ultimate production 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 at the competition of the aspects such as market, technology.Client is to the requirement of vanadium iron quality except outside the regulation clause in national standard, and 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 technology of single stage method electrit, aluminium content in alloy cannot effectively be controlled, when client need to low aluminium vanadium iron, can only meet to sacrifice the yield of vanadium, in vanadium iron, between the composition of aluminium and yield, have insoluble contradiction.Meanwhile, its vanadium recovery of single stage method smelting ferrovanadium is also restricted, and smelting recovery is difficult to further lifting, and quality product depends on batching completely, and smelting process can not effectively be controlled alloy ingredient.How under the condition that keeps high yield, effectively to remove the new developing direction that excessive aluminium becomes vanadium iron smelting technology.
Generally speaking, in smelting process, adding sheet vanadium to carry out dealuminzation is a selection preferably, but because the proportion of sheet vanadium approaches with vanadium iron smelting slag system, cause sedimentation difficulty in slag, make the dynamic conditions of dealuminzation poor, speed of reaction is slower, directly causes the increase of smelting cost.Because vanadium iron smelting history is longer, technique is fairly perfect, and patent is in this respect less, and it is more difficult to innovate, and at present, the patent that vanadium iron is smelted all focuses on the selection of raw material and reductive agent and how effectively to improve in the rate of recovery of vanadium.
Publication number is that the Chinese patent application of patent CN101100720A discloses vanadic acid calcium, aluminium powder, irony material are smelted according to a certain weight ratio and obtained vanadium iron: vanadic acid calcium: 100 parts, and aluminium powder: 23～28 parts, irony material: 23～27 parts; Wherein, described vanadic acid calcium is at least one in metavanadic acid calcium, pyrovanadic acid calcium, positive vanadic acid calcium, and it is 24%～43% containing vanadium grade.The vanadium iron quality that this invented technology is smelted is good, and vanadium recovery is high, does not produce contaminated wastewater in smelting process, adapts to the infant industry needs of high economic worth, low environment pollution.
Publication number is that the Chinese patent application of CN101148733A discloses a kind of vanadium iron spraying powder refining technique, key step is in electro-aluminothermic process smelting ferrovanadium process, when furnace charge fully completes thermite reaction, slag and alloy realize separated after, stop heated by electrodes, to molten slag layer, insert spray gun winding-up reduction powder immediately, while rotating furnace body, reduction powder is fully mixed with slag under winding-up gas shock and body of heater Stirring dual function, and then electrode insertion continues to add hot smelting 20～25 minutes, allow in slag residual vanadium further reduce generation vanadium iron.This invention can make the reacting dynamics condition of refining furnace charge effectively be improved, and best 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 reduce production costs.
From above-mentioned disclosed technology, the existing research to electro-aluminothermic process production vanadium iron all concentrates on the reduction process of vanadium iron, and the research of dealuminzation casting cycle is had no to 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 adopt art methods; Before aluminium alloy casting, the mixture that ferric oxide and lime are formed is put into ingot mould, and then cast, cooling, obtain vanadium iron; Wherein, in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2～3:1.
Further, as preferred version, in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2.3～2.7:1.
Further, preferably, Fe > 65wt% in above-mentioned ferric oxide, Si < 1.5wt%, P < 0.02wt%, S < 0.02wt%, Mn < 0.5wt%, C < 0.5wt%, Al < 0.5wt%, the granularity of ferric oxide is 0.5～1mm; CaO content > 85wt% in lime, S < 0.02wt%, C < 0.30wt%, P < 0.02wt%, SiO
2< 1wt%, the granularity of lime is 2～5mm.
Further, as preferred version, before aluminium alloy casting, also, to adding the ingot mould of ferric oxide and lime mixture to toast, storing temperature is 300～400 ℃, and baking time is 120～240min; As more preferably scheme, storing temperature is 350～400 ℃, and baking time is 180～240min.
Further, during casting, the temperature of aluminium alloy is 1950～2000 ℃.
Further, the invention also discloses the method that electro-aluminothermic process is produced 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 ferric oxide and lime composition is put into ingot mould, and to adding the ingot mould of ferric oxide and lime mixture to toast, storing temperature is 300～400 ℃, baking time is 120～240min; When band aluminium alloy temperature is 1950～2000 ℃, casting, cooling, obtain; In ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2～3:1.
As preferred version, storing temperature is 350～400 ℃, and baking time is 180～240min; As more preferably scheme, in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2.3～2.7:1.
Beneficial effect of the present invention:
(1), the method steps 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 in stove dealuminzation longer tap to tap time.
Embodiment
The method of electro-aluminothermic process vanadium iron of the present invention casting dealuminzation, operation steps is: before aluminium alloy casting, the mixture that ferric oxide and lime are formed is put into ingot mould, and then cast, cooling, obtain; In ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2～3:1.
Electro-aluminothermic process is produced vanadium iron, the step that comprises reduction, refining and casting, described reduction and refinement step can adopt art methods, raw material need to carry out proportioning according to the calculated value of the chemical reaction of electro-aluminothermic process and slag making, join aluminium amount and be theoretical value 1.1～1.3 times, raw material add-on, depending on heat size, enters standard electric arc furnace after being mixed, through obtaining ferro-vanadium liquid after reduction, refinement step; Technical solution of the present invention is the improvement to casting step.
When ferro-vanadium liquid is cast in ingot mould, will there is following reaction in the aluminium in the ferric oxide in ingot mould and ferro-vanadium liquid:
Fe
2O
3+2Al＝2Fe+Al
2O
3
The iron restoring enters ferro-vanadium, enters in slag, thereby reach the object of dealuminzation and aluminium becomes aluminum oxide.Utilize washing away and stirring action of casting, significantly improve the dynamic conditions of this reaction, can fast and effeciently remove the aluminium in alloy.
Wherein, if the ratio of ferric oxide is too high in ferric oxide and lime mixture, easily increase the quantity of slag, thereby increase vanadium loss; The effect of lime is residue adjustment, guarantees the good mobility of vanadium iron metallurgical slag, if do not have very little residue adjustment effect, the too high ingot mould liner that easily corrodes, can cause the loss of vanadium equally, therefore, selects in mass ratio ferric oxide: lime=2～3:1.
Further, as preferred version, in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2.3～2.7:1.
Further, for fear of the introducing because of other impurity, cause alloy product defective, need to strictly control ferric oxide and stone ash composition, as preferred version, Fe content > 65wt% in ferric oxide, Si < 1.5wt%, P < 0.02wt%, S < 0.02wt%, Mn < 0.5wt%, C < 0.5wt%, Al < 0.5wt%, the granularity of ferric oxide is 0.5～1mm; CaO content > 85wt% in lime, S < 0.02wt%, C < 0.30wt%, P < 0.02wt%, SiO
2< 1wt%, the granularity of lime is 2～5mm.
Further, in order to reduce the temperature difference between lime, ferric oxide and ingot mould and ferro-vanadium liquid, offer dealumination reaction time enough, as preferred version, before casting also to adding the ingot mould of ferric oxide and lime mixture to toast, storing temperature is 300～400 ℃, and baking time is 120～240min; As more preferably scheme, storing temperature is 350～400 ℃, and baking time is 180～240min.
Further, in order to save time, the operation of also ingot mould of ferric oxide and lime mixture being toasted before casting can be carried out when smelting.
Further, when when slag depletion is extremely lower containing vanadium, ferro-vanadium liquid has been cast in the ingot mould of aforesaid operations at the high temperature that is greater than 1950 ℃.Due to vanadium iron, to smelt slag system melting temperature very high, is about 1800 ℃ of left and right, and therefore adopting and being greater than the pouring temperature of 1950 ℃ is mainly to keep the liquid time in order to extend alloy melt, thereby makes dealumination reaction carry out more thoroughly.
Preferably, during casting, the temperature of ferro-vanadium liquid is 1950～2000 ℃, 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 ferric oxide and lime composition is put into ingot mould, and to adding the ingot mould of ferric oxide and lime mixture to toast, storing temperature is 300～400 ℃, baking time is 120～240min; When aluminium alloy temperature is 1950～2000 ℃, casting, cooling, obtain; In ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2～3:1.
As preferred version, storing temperature is 350～400 ℃, and baking time is 180～240min; As more preferably scheme, in ferric oxide and lime mixture, in mass ratio, ferric 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 among described scope of embodiments.
In the ferric 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 ferric oxide is 0.6mm; CaO90wt% in lime, S0.01wt%, C0.2wt%, P0.01wt%, SiO
20.5wt%, the granularity of lime is 3mm.
Embodiment 1
Raw material: sheet vanadium (V
2o
5mass content 98.0%) 200kg, V
2o
31600kg (containing vanadium 65.1%), joins aluminium 830kg, iron 900kg, lime 200kg.After being mixed, raw material adds in stove, the secondary voltage 190V striking of switching on, and after furnace chargeization is clear, secondary voltage is selected 135V.During this time 300kg ferric oxide and 100kg lime are joined in ingot mould and toasted, 350 ℃ of storing temperatures, baking time 180min.Smelt after energising 90min, in real-time analysis slag, residual vanadium is 0.38%, tapping casting, and 1980 ℃ of pouring temperatures, are cooled to room temperature with ingot mould afterwards, get alloy sample analysis, and aluminium content is 0.07%, and the vanadium iron obtaining is containing vanadium 50.6%, vanadium yield 97.5%.
Embodiment 2
Raw material: sheet vanadium (V
2o
5mass content 98.5%) 200kg, V
2o
31600kg (containing vanadium 65.5%), joins aluminium 800kg, iron 970kg, lime 200kg.After being mixed, material adds in stove, the secondary voltage 190V striking of switching on, and after furnace chargeization is clear, secondary voltage is selected 135V.During this time 200kg ferric oxide and 100kg lime are joined in ingot mould and toasted, 400 ℃ of storing temperatures, baking time 150min.Smelt after energising 85min, in real-time analysis slag, residual vanadium is 0.43%, tapping casting, and 1960 ℃ of pouring temperatures, are cooled to room temperature with ingot mould afterwards, get alloy sample analysis, and aluminium content is 0.09%, and the vanadium iron obtaining is containing vanadium 50.8%, vanadium yield 97.0%.
Embodiment 3
Raw material: sheet vanadium (V
2o
5mass content 97.8%) 200kg, V
2o
31600kg (containing vanadium 65.3%), joins aluminium 820kg, iron 930kg, lime 200kg.After being mixed, material adds in stove, the secondary voltage 190V striking of switching on, and after furnace chargeization is clear, secondary voltage is selected 135V.During this time 250kg ferric oxide and 100kg lime are joined in ingot mould and toasted, 300 ℃ of storing temperatures, baking time 240min.Smelt after energising 95min, in real-time analysis slag, residual vanadium is 0.63%, tapping casting, and 1970 ℃ of pouring temperatures, are cooled to room temperature with ingot mould afterwards, get alloy sample analysis, and aluminium content is 0.15%, and the vanadium iron obtaining is containing vanadium 50.2%, vanadium yield 97.2%.
Embodiment 4
Raw material: sheet vanadium (V
2o
5mass content 98.2%) 200kg, V
2o
31600kg (containing vanadium 64.9%), joins aluminium 810kg, iron 120kg, lime 200kg.After being mixed, material adds in stove, the secondary voltage 190V striking of switching on, and after furnace chargeization is clear, secondary voltage is selected 135V.During this time 250kg ferric oxide and 100kg lime are joined in ingot mould and toasted, 350 ℃ of storing temperatures, baking time 200min.Smelt after energising 90min, in real-time analysis slag, residual vanadium is 0.56%, tapping casting, and 1990 ℃ of pouring temperatures, are cooled to room temperature with ingot mould afterwards, get alloy sample analysis, and aluminium content is 0.18%, and the vanadium iron obtaining is containing vanadium 80.2%, vanadium yield 96.8%.
Claims (9)
1. the method for electro-aluminothermic process vanadium iron casting dealuminzation, is characterized in that: before aluminium alloy casting, the mixture that ferric oxide and lime are formed is put into ingot mould, and then cast, cooling, obtain vanadium iron; Wherein, in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2～3:1.
2. the method for electro-aluminothermic process vanadium iron according to claim 1 casting dealuminzation, is characterized in that: in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2.3～2.7:1.
3. the method for electro-aluminothermic process vanadium iron according to claim 1 and 2 casting dealuminzation, it is characterized in that: Fe > 65wt% in ferric oxide, Si < 1.5wt%, P < 0.02wt%, S < 0.02wt%, Mn < 0.5wt%, C < 0.5wt%, Al < 0.5wt%, the granularity of ferric oxide is 0.5～1mm; CaO content > 85wt% in lime, S < 0.02wt%, C < 0.30wt%, P < 0.02wt%, SiO
2< 1wt%, the granularity of lime is 2～5mm.
4. according to the method for the electro-aluminothermic process vanadium iron casting dealuminzation described in claim 1～3 any one, it is characterized in that: before aluminium alloy casting, also, to adding the ingot mould of ferric oxide and lime mixture to toast, storing temperature is 300～400 ℃, and baking time is 120～240min.
5. the method for electro-aluminothermic process vanadium iron casting dealuminzation according to claim 4, is characterized in that: storing temperature is 350～400 ℃, and baking time is 180～240min.
6. according to the method for the electro-aluminothermic process vanadium iron casting dealuminzation described in claim 1～5 any one, it is characterized in that: during casting, the temperature of aluminium alloy is 1950～2000 ℃.
7. 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 ferric oxide and lime composition is put into ingot mould, and to adding the ingot mould of ferric oxide and lime mixture to toast, storing temperature is 300～400 ℃, baking time is 120～240min; When aluminium alloy temperature is 1950～2000 ℃, casting, cooling, obtain; In ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2～3:1.
8. electro-aluminothermic process according to claim 7 is produced the method for vanadium iron, it is characterized in that: storing temperature is 350～400 ℃, and baking time is 180～240min.
9. according to the electro-aluminothermic process described in claim 7 or 8, produce the method for vanadium iron, it is characterized in that: in ferric oxide and lime mixture, in mass ratio, ferric oxide: lime=2.3～2.7:1.
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| CN104532105A (en) * | 2015-01-04 | 2015-04-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing ferrovanadium by rollover furnace through electro-aluminothermic process |
| CN106216645A (en) * | 2016-08-30 | 2016-12-14 | 成都工业学院 | The method of ferrocolumbium casting dealuminzation |
| CN106967917A (en) * | 2017-04-28 | 2017-07-21 | 攀钢集团研究院有限公司 | The control method of FeV80 alloy carbon contents |
| 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 |
| CN109825704A (en) * | 2019-04-12 | 2019-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | The smelting process of vanadium iron |
| 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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| CN106967917A (en) * | 2017-04-28 | 2017-07-21 | 攀钢集团研究院有限公司 | The control method of FeV80 alloy carbon contents |
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| 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 |
| CN109825704A (en) * | 2019-04-12 | 2019-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | The smelting process of vanadium iron |
| 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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