CN102115821B - Method for smelting ferrovanadium - Google Patents
Method for smelting ferrovanadium Download PDFInfo
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- CN102115821B CN102115821B CN2010102794892A CN201010279489A CN102115821B CN 102115821 B CN102115821 B CN 102115821B CN 2010102794892 A CN2010102794892 A CN 2010102794892A CN 201010279489 A CN201010279489 A CN 201010279489A CN 102115821 B CN102115821 B CN 102115821B
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Abstract
The invention provides a method for smelting ferrovanadium, which comprises the following steps of: preparing a mixture from 10 to 35 weight percent of lime, 15 to 35 weight percent of aluminum and the balance of V2O3 and/or V2O5; adding the mixture into an electric furnace and adding a predetermined amount of iron according to the requirement simultaneously; electrifying to melt materials in the electric furnace so as to reduce the V2O3 and/or the V2O5 by using the aluminum, and discharging 80 to 95 weight percent of slag when the content of all vanadium in the slag is less than 0.2 weight percent; adding refined materials consisting of 15 to 35 weight percent of lime, 0 to 30 weight percent of iron oxide and the balance of V2O5 into the electric furnace according to the proportion of 10 to 80kg per ton of ferrovanadium, refining, and discharging alloy liquid and refined slag when the content of the aluminum and vanadium in the ferrovanadium alloy liquid meets the requirement of a ferrovanadium alloy product to be produced on the content of the aluminum and the vanadium; and casting to obtain the ferrovanadium alloy product. By the method, 97 to 99 percent of vanadium recovery rate can be achieved, and energy consumption can be reduced.
Description
Technical field
The present invention relates to the ferroalloy smelting technical field, particularly a kind of method that adopts electrit thermal reduction method to produce ferro-vanadium by reduction and two sections series-operations of refining.
Background technology
Vanadium iron is very important alloy addition, can improve intensity, toughness, ductility and the thermotolerance of steel.The main representative products of vanadium iron is FeV50 and FeV80.
At present, the method for production vanadium iron mainly comprises carbothermic method, silicothermic process and thermit reduction.To cause producing in the vanadium iron that obtains carbon content too high because easily forming carbide for carbothermic method, uses so that its product can not be most of vanadium steels.Be difficult to production higher-grade vanadium iron although the silicothermic process cost is lower, and its smelting cycle is relatively long.
Usually, thermit reduction is different by the raw material of its use, can be divided into Vanadium Pentoxide in FLAKES thermit reduction and vanadous oxide electrit hot reducing method.Different from the Vanadium Pentoxide in FLAKES thermit reduction is that vanadous oxide electrit hot reducing method generally carries out in electric furnace, and can save the consumption as the aluminium of reductive agent, has reduced to a certain extent cost.Usually, the process flow sheet of vanadous oxide electrit hot reducing method as shown in Figure 1.The main deficiency of this technique is that vanadium recovery is not high, is about 91%-95%.
Publication number is that the Chinese invention patent of CN1343794 discloses a kind of V
2O
3Electro-aluminothermic process is smelted the method for FeV50, and its raw material is by V
2O
3, aluminium powder, abrasive grit and lime consists of, technological process is: with V
2O
3, put into electrosmelting behind aluminium powder, abrasive grit and the lime batch mixing; Then come out of the stove and carry out shrend after isolating slag smelting the alloy mixture that, carry out at last break-iron, fragmentation, screening, packing and process.The FeV50 smelting technology of this invention has reduced product cost, and technological process is relatively simple, and the finished product vanadium recovery has reached more than 94.5%.As seen, also there is the not high deficiency of vanadium recovery in this patent.
In sum, need the method for the high smelting ferrovanadium of a kind of vanadium recovery badly.
Summary of the invention
Problem for the prior art existence, the invention provides a kind of two step of employing electrit heat method of reducing, that is: the method for producing ferro-vanadium by reduction and two sections continuous smelting procedures of refining uses method of the present invention can realize improving the effect of vanadium recovery.
The invention provides a kind of method of smelting ferrovanadium, said method comprising the steps of:
(1) with the lime of 10wt%～35wt%, the aluminium of 15wt%～35wt% and the V of surplus
2O
3And/or V
2O
5Be made into compound; (2) compound is added electric furnace, add simultaneously the iron of predetermined amount according to the requirement of the ferro-vanadium product that will produce; (3) material in the energising smelting electrical furnace is to reduce V by aluminium
2O
3And/or V
2O
5, when treating that full content of vanadium is lower than 0.2wt% in the slag, go out the slag of 80wt%～95wt%; (4) will be V by lime 15wt%～35wt%, ferriferous oxide 0wt%～30wt% and surplus again
2O
5The refining material that forms adds in the electric furnace, the add-on of refining material is pressed 10kg/t vanadium iron～80kg/t vanadium iron and is determined, carry out refining, when treating that aluminium content in the ferro-vanadium liquid and content of vanadium meet the ferro-vanadium product that will produce to the requiring of aluminium content and content of vanadium, go out aluminium alloy and refining slag; (5) cast with aluminium alloy, obtain the ferro-vanadium product.
The method of smelting ferrovanadium according to the present invention, the compound in the step (1) can also comprise be less than or equal to 15wt% contain the rich slag of vanadium, the described rich slag of vanadium that contains obtains after by the method for finishing described smelting ferrovanadium.
The method of smelting ferrovanadium according to the present invention, in step (3), reduction temperature can be 1800 ℃～2100 ℃, the recovery time can be 30min～90min.
The method of smelting ferrovanadium according to the present invention, in step (4), refining temperature can be 1600 ℃～1900 ℃, refining time can be 3min～80min.
The method of smelting ferrovanadium according to the present invention, in step (4), the ferro-vanadium product that produce can be for being lower than 0.8wt% to the requirement of aluminium content.
The method of smelting ferrovanadium according to the present invention in step (1), adds V when simultaneously
2O
3And V
2O
5The time, V
2O
3And V
2O
5Weight ratio can carry out proportioning according to 2: 1 ratio.
Compared with prior art, the present invention has following beneficial effect:
(1) vanadium recovery is high.In the present invention, vanadium recovery is 97%～99%, and is higher 2～8 percentage points than existing thermite process smelting ferrovanadium technique.
(2) energy consumption is low.In refinement step of the present invention, because the adding of refining material, so the furnace temperature of refining process is reduced to 1600～1900 ℃.Compare with 1800～2100 ℃ reduction furnace temperature in the prior art, the furnace temperature among the present invention in the refining process can reduce at most 500 ℃.
Description of drawings
Fig. 1 shows the technical process of the vanadous oxide electrit hot reducing method of prior art.
Fig. 2 shows the technical process according to the electrit hot reducing method of the embodiment of the invention.
Embodiment
Hereinafter, describe with reference to the accompanying drawings embodiments of the invention in detail.
Fig. 2 shows the technical process according to the electrit hot reducing method of the embodiment of the invention.
As shown in Figure 2, the technical process of the electrit hot reducing method of the embodiment of the invention can may further comprise the steps:
(1) batching
According to lime 10wt%～35wt%, contain the rich slag 0wt%～15wt% of vanadium and aluminium 15wt%～35wt%, surplus are V
2O
3And/or V
2O
5Prepare burden, after raw material mixes, tinning.
(2) reinforced
The furnace charge of tinning is added in the stove, simultaneously, require and electric furnace nominal capacity size according to the ferro-vanadium composition such as FeV50 or FeV80, add the iron of predetermined amount.
(3) fusing and reduction
Send electric rapid melting furnace charge.After the furnace charge fusing, in stove by aluminium with V
2O
3And/or V
2O
5Reduction, recovery time 30min～90min, the reduction furnace temperature can in 1800 ℃～2100 ℃ scope, treat that full content of vanadium (also can be expressed as TV content) goes out the lean slag of 80wt%～95wt%, then the body of heater return when being lower than 0.2wt% in the slag.Slag tap after the operation in reduction, can make refining procedure refining slag quantity of slag minimizing and the composition of refining slag is more easily regulated.TV content is lower than 0.2wt% in the reducing slag, can guarantee the rate of recovery of vanadium; And the going out the quantity of slag and should be controlled between 80wt%～95wt% of reducing slag, if it goes out the quantity of slag greater than 95wt%, then the loss of ferro-vanadium liquid increases when slagging tap, thereby has reduced the rate of recovery of vanadium; If it goes out the quantity of slag less than 80wt%, then can increase the quantity of slag of cost and the refining slag of residue adjustment in the refining procedure, also increased difficulty and the rhythm of organization of production.
(4) refining
Behind the body of heater return, adding according to lime 15wt%～35wt%, ferriferous oxide (as: iron sheet) 0wt%～30wt%, surplus is V
2O
5It is definite that the refining material of preparing burden and mixing, the add-on of refining material are pressed 10kg/t vanadium iron～80kg/t vanadium iron, and namely the add-on of refining material is determined according to the tonnage of the ferro-vanadium product that will produce.Send electricity and carry out refining, refining time 3min～80min, the refining furnace temperature can be in 1600 ℃～1900 ℃ scope, when treating that aluminium content in the ferro-vanadium liquid and content of vanadium meet the ferro-vanadium product that will produce to the requiring of aluminium content and content of vanadium, ferro-vanadium liquid and refining slag are gone out in hot metal ladle in the lump.In refining procedure, add the refining material in the stove after, can generate the low melting point phase, thereby reduce the fusing point of refining slag; And can utilize metallic aluminium residual in the ferro-vanadium liquid that obtains of reduction operation with the V in the refining material
2O
5Partial reduction, thus realized the adjustment of content of vanadium in the alloy liquid, so that the content of vanadium in the aluminium alloy satisfies the ferro-vanadium product that will produce to the requirement of content of vanadium; Can reduce simultaneously the content of aluminium in the ferro-vanadium liquid, so that the satisfied ferro-vanadium product that will produce of aluminium content is to the requirement of aluminium content.For example, regulation in Chinese vanadium iron standard (GB4139-1987), content of vanadium is not less than 50% among the FeV50A, and aluminium content is not more than 0.5wt%; Content of vanadium is not less than 50% among the FeV50B, and aluminium content is not more than 0.8wt%.
(5) casting
Ferro-vanadium liquid goes out after hot metal ladle, hangs out hot metal ladle, and the ferro-vanadium liquid of hot metal ladle is cast in the ingot mould.Simultaneously, pour out the refining slag that refining process forms, and the residue in the cleaning ingot mould, slag in the tank formed.In the present invention, the interior slag of refining slag and tank is referred to as and contains the rich slag of vanadium.
(6) fragmentation
After ferro-vanadium liquid was cooled to room temperature, the demoulding also was crushed to customer requirements with the vanadium iron ingot, obtains 50 vanadium iron or 80 vanadium iron finished products.
Embodiment 1
According to lime 10wt%, by slag in refining slag and the tank form contain the rich slag 15wt% of vanadium and aluminium 25wt%, surplus are V
2O
3And V
2O
5(V
2O
3And V
2O
5Weight ratio be 2: 1) prepare burden, form compound.After this compound mixed, get the 10t tinning, then add in the electric furnace of electric furnace nominal capacity 10t, add the 1.5t abrasive grit in the stove simultaneously.Behind reinforced the finishing, send electric rapid melting furnace charge.After the furnace charge fusing, in stove by aluminium with V
2O
3And V
2O
5Reduction, recovery time 30min, the reduction furnace temperature is about 2100 ℃, when treating that TV content is 0.1wt% in the slag, goes out the lean slag of 95wt%, then the body of heater return.Behind the body of heater return, adding according to lime 15wt%, iron sheet 10wt%, surplus is V
2O
5Batching and the refining material 500kg that mixes send electricity and carry out refining, and refining time is 80min, and the refining furnace temperature is about 1900 ℃, when treating that aluminium content is lower than 0.8wt% in the ferro-vanadium liquid, ferro-vanadium liquid and refining slag are come in and gone out in the hot metal ladle in the lump.Obtain approximately 7.5t of ferro-vanadium liquid, product is FeV80, vanadium recovery 99%.
Ferro-vanadium liquid has gone out after hot metal ladle, hangs out hot metal ladle, and the ferro-vanadium liquid of hot metal ladle is cast in the ingot mould.After ferro-vanadium liquid was cooled to room temperature, the demoulding also was crushed to the customer requirements granularity with the vanadium iron ingot, obtains meeting 80 vanadium iron finished products of GB.The burden process that the interior slag of the refining slag that produces and tank returns compound is in the lump prepared burden, and further reclaiming has the valency v element.
Embodiment 2
Be V according to lime 35wt%, aluminium 15wt%, surplus
2O
3Prepare burden, form compound.After this compound mixed, get the 3.8t tinning, then add in the electric furnace of electric furnace nominal capacity 5t, add the 2.5t abrasive grit in the stove simultaneously.Behind reinforced the finishing, send electric rapid melting furnace charge.After the furnace charge fusing, in stove by aluminium with V
2O
3Reduction, recovery time 90min, the reduction furnace temperature is about 1800 ℃, when treating that TV content is 0.1wt% in the slag, goes out the lean slag of 80wt%, then the body of heater return.Behind the body of heater return, add according to lime 30wt% and V
2O
570wt% batching and the refining material 50kg that mixes send electricity and carry out refining, and refining time is 3min, and the refining furnace temperature is about 1600 ℃, when treating that aluminium content is lower than 0.8wt% in the ferro-vanadium liquid, ferro-vanadium liquid and refining slag are come in and gone out in the hot metal ladle in the lump.According to furnace volume, this ferro-vanadium liquid is 5.0t approximately, and product is FeV50, vanadium recovery 98%.
Ferro-vanadium liquid has gone out after hot metal ladle, hangs out hot metal ladle, and the ferro-vanadium liquid of hot metal ladle is cast in the ingot mould.After ferro-vanadium liquid was cooled to room temperature, the demoulding also was crushed to the customer requirements granularity with the vanadium iron ingot, obtains meeting 50 vanadium iron finished products of GB.The burden process that the interior slag of the refining slag that produces and tank returns compound is in the lump prepared burden, and further reclaiming has the valency v element.
Embodiment 3
According to lime 25wt%, by slag in refining slag and the tank form contain the rich slag 15wt% of vanadium and aluminium 35wt%, surplus are V
2O
5Prepare burden, form compound.After this compound mixed, get the 3.5t tinning, then add in the electric furnace of electric furnace nominal capacity 2t, add the 0.5t abrasive grit in the stove simultaneously.Behind reinforced the finishing, send electric rapid melting furnace charge.After the furnace charge fusing, in stove by aluminium with V
2O
5Reduction, recovery time 60min, the reduction furnace temperature is about 1900 ℃, when treating that TV content is 0.2wt% in the slag, goes out the lean slag of 87wt%, then the body of heater return.Behind the body of heater return, add according to lime 30wt% and V
2O
570% batching and the refining material 30kg that mixes send electricity and carries out refining, and refining time is 80min, and the refining furnace temperature is about 1800 ℃, when treating that aluminium content is lower than 0.8wt% in the ferro-vanadium liquid, ferro-vanadium liquid and refining slag come in and gone out in the hot metal ladle in the lump.Obtain approximately 1.0t of ferro-vanadium liquid, product is FeV50, vanadium recovery 97%.
Ferro-vanadium liquid has gone out after hot metal ladle, hangs out hot metal ladle, and the ferro-vanadium liquid of hot metal ladle is cast in the ingot mould.After ferro-vanadium liquid was cooled to room temperature, the demoulding also was crushed to the customer requirements granularity with the vanadium iron ingot, obtains meeting 50 vanadium iron finished products of GB.The burden process that the interior slag of the refining slag that produces and tank returns compound is in the lump prepared burden, and further reclaiming has the valency v element.
Embodiment 4
According to lime 20wt%, by slag in refining slag and the tank form contain the rich slag 12wt% of vanadium and aluminium 30wt%, surplus are V
2O
3And V
2O
5(V
2O
3And V
2O
5Weight ratio be 2: 1) prepare burden, form compound.After this compound mixed, get the 6t tinning, then add in the electric furnace of electric furnace nominal capacity 5t, add the 2.5t abrasive grit in the stove simultaneously.Behind reinforced the finishing, send electric rapid melting furnace charge.After the furnace charge fusing, in stove by aluminium with V
2O
3And V
2O
5Reduction, recovery time 30min, the reduction furnace temperature is about 1900 ℃, when treating that TV content is 0.2wt% in the slag, goes out the lean slag of 95wt%, then the body of heater return.Behind the body of heater return, adding according to lime 20wt%, iron sheet 10wt%, surplus is V
2O
5Batching and the refining material 400kg that mixes send electricity and carry out refining, and refining time is 30min, and the refining furnace temperature is about 1700 ℃, when treating that aluminium content is lower than 0.8wt% in the ferro-vanadium liquid, ferro-vanadium liquid and refining slag are come in and gone out in the hot metal ladle in the lump.Obtain approximately 5.0t of ferro-vanadium liquid, product is FeV50, vanadium recovery 97%.
Embodiment 5
According to lime 18wt%, by slag in refining slag and the tank form contain the rich slag 14wt% of vanadium and aluminium 30wt%, surplus are V
2O
3And V
2O
5(V
2O
3And V
2O
5Weight ratio be 5: 3) prepare burden, form compound.After this compound mixed, get the 6t tinning, then add in the electric furnace of electric furnace nominal capacity 5t, add the 2.5t abrasive grit in the stove simultaneously.Behind reinforced the finishing, send electric rapid melting furnace charge.After the furnace charge fusing, in stove by aluminium with V
2O
3And V
2O
5Reduction, recovery time 30min, the reduction furnace temperature is about 1950 ℃, when treating that TV content is 0.2wt% in the slag, goes out the lean slag of 95wt%, then the body of heater return.Behind the body of heater return, adding according to lime 25wt%, iron sheet 15wt%, surplus is V
2O
5Batching and the refining material 300kg that mixes send electricity and carry out refining, and refining time is 20min, and the refining furnace temperature is about 1800 ℃, when treating that aluminium content is lower than 0.8wt% in the ferro-vanadium liquid, ferro-vanadium liquid and refining slag are come in and gone out in the hot metal ladle in the lump.Obtain approximately 5.0t of ferro-vanadium liquid, product is FeV50, vanadium recovery 99%.
Ferro-vanadium liquid has gone out after hot metal ladle, hangs out hot metal ladle, and the ferro-vanadium liquid of hot metal ladle is cast in the ingot mould.After ferro-vanadium liquid was cooled to room temperature, the demoulding also was crushed to the customer requirements granularity with the vanadium iron ingot, obtains meeting 50 vanadium iron finished products of GB.The burden process that the interior slag of the refining slag that produces and tank returns compound is in the lump prepared burden, and further reclaiming has the valency v element.
In sum, the present invention adopts electrit thermal reduction method to produce ferro-vanadium by reduction and two sections series-operations of refining, can realize the effect that improves vanadium recovery and reduce energy consumption.
Although the above illustrates and has described the present invention in conjunction with the embodiments, it will be apparent to those skilled in the art that in the situation that does not break away from the spirit and scope that claim limits, can carry out various changes and modifications.
Claims (6)
1. the method for a smelting ferrovanadium is characterized in that, may further comprise the steps:
(1) with the lime of 10wt%～35wt%, the aluminium of 15wt%～35wt% and the V of surplus
2O
3And/or V
2O
5Be made into compound;
(2) compound is added electric furnace, add simultaneously the iron of predetermined amount according to the requirement of the ferro-vanadium product that will produce;
(3) material in the energising smelting electrical furnace is to reduce V by aluminium
2O
3And/or V
2O
5, when treating that full content of vanadium is lower than 0.2wt% in the slag, go out the slag of 80wt%～95wt%;
(4) will be V by lime 15wt%～35wt%, ferriferous oxide 0wt%～30wt% and surplus again
2O
5The refining material that forms adds in the electric furnace, the add-on of refining material is pressed 10kg/t vanadium iron～80kg/t vanadium iron and is determined, carry out refining, when treating that aluminium content in the ferro-vanadium liquid and content of vanadium meet the ferro-vanadium product that will produce to the requiring of aluminium content and content of vanadium, go out aluminium alloy and refining slag;
(5) cast with aluminium alloy, obtain the ferro-vanadium product.
2. the method for smelting ferrovanadium as claimed in claim 1 is characterized in that, the compound in the step (1) also comprise be less than or equal to 15wt% contain the rich slag of vanadium, the described rich slag of vanadium that contains obtains after by the method for finishing described smelting ferrovanadium.
3. the method for smelting ferrovanadium as claimed in claim 1 is characterized in that, in step (3), reduction temperature is 1800 ℃～2100 ℃, and the recovery time is 30min～90min.
4. the method for smelting ferrovanadium as claimed in claim 1 is characterized in that, in step (4), refining temperature is 1600 ℃～1900 ℃, and refining time is 3min～80min.
5. the method for smelting ferrovanadium as claimed in claim 1 is characterized in that, in step (4), the ferro-vanadium product that produce to the requirement of aluminium content for being lower than 0.8wt%.
6. the method for smelting ferrovanadium as claimed in claim 1 is characterized in that, in step (1), adds V when simultaneously
2O
3And V
2O
5The time, V
2O
3And V
2O
5Weight ratio carry out proportioning according to 2: 1 ratio.
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| CN101724752A (en) * | 2009-12-29 | 2010-06-09 | 四川省川威集团有限公司 | Method for smelting medium ferrovanadium |
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| CN101100720A (en) * | 2007-08-22 | 2008-01-09 | 攀枝花新钢钒股份有限公司 | Technique for smelting vanadium iron from calcium vanadate |
| CN101724751A (en) * | 2009-12-29 | 2010-06-09 | 四川省川威集团有限公司 | Method for smelting high vanadium ferrovanadium |
| CN101724752A (en) * | 2009-12-29 | 2010-06-09 | 四川省川威集团有限公司 | Method for smelting medium ferrovanadium |
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