CN104762488A - Direct alloying method of vanadium in electroslag remelting process - Google Patents
Direct alloying method of vanadium in electroslag remelting process Download PDFInfo
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- CN104762488A CN104762488A CN201510219962.0A CN201510219962A CN104762488A CN 104762488 A CN104762488 A CN 104762488A CN 201510219962 A CN201510219962 A CN 201510219962A CN 104762488 A CN104762488 A CN 104762488A
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Abstract
The invention discloses a direct alloying method of vanadium in an electroslag remelting process, and belongs to the technical field of electroslag remelting. The characteristic that the temperature in a furnace is higher in the electroslag remelting process is used by the method, direct reduction and oxidation are conducted on the vanadium by using carbon replacing aluminum, an injection feeding technology is combined tactfully, the adding amount of alloying elements can be controlled accurately, and impurities are reduced. The method includes the steps that firstly, an alloy wire is formed by aluminum oxide and graphite, secondly, the electroslag furnace is started to conduct the electroslag remelting, the alloy wire is fed subsequently, diffusible desoxydation is conducted by adding aluminum particles, after the electroslag remelting process is completed, injection feeding is stopped, and a feeding stage is started until the feeding is completed. By means of the method, the yielding rate of the vanadium is greatly improved, a slag system used in the electroslag remelting process can be prevented from being polluted, the phenomenon that consumable electrodes are scrapped due to the fact that the vanadium content of the consumable electrodes oversteps, and the raw material resource is saved.
Description
Technical field
The present invention relates to electroslag remelting technique field, more particularly, relate to a kind of method of direct vanadium alloying in esr process.
Background technology
Esr, as a kind of New Technology in Special Metallurgy, occupies very important effect in special steel industry.Through the steel ingot of electroslag smelting, purity is high, sulphur content is low, non-metallic inclusion is few, surface of steel ingot is smooth, crystallization even compact, metallographic structure and chemical composition are even, and this technology is obtaining and applying more and more widely.At present, electroslag remelting technique is mainly used in the production of the production of steel alloy, particularly die steel, tool steel, and in these steel, the overwhelming majority all contains Alloying Element Vanadium.But produce these vanadium steels with electro-slag re-melting method and have following two problems:
(1) esr process needs metal consumable electrode.Consumable electrode is made up of first furnace melt iron, steel scrap and ferro-vanadium.But produce ferro-vanadium and need smelting ferrovanadium, and vanadium iron smelting process is complicated, productivity is low, labour intensity is large, energy consumption is higher, and environmental pollution is serious; And the recovery rate of vanadium iron smelting process vanadium is not high, waste resource.
(2) in consumable electrode manufacturing processed, once the vanadium in consumable electrode does not reach target content, so consumable electrode just can not carry out esr, but just furnace refuse, smelting must be returned, cause the waste of a large amount of energy consumptions, resource (alloying element), and contaminate environment.
Current esr enterprise is in the production process of vanadium steel, and mainly qualified to vanadium composition metal consumable electrode carries out remelting melting.The measure of any vanadium alloying is not taked in esr process.Therefore, if can carry out the alloying of vanadium at Electroslag Process, for improving quality product, energy efficient has great importance.
Through the Searches of Patent Literature, find the patent that two relate to vanadium oxide DIRECT ALLOYING, its publication number is respectively CN101798618A, CN101067182.Publication number is the patent of CN101798618A, and it utilizes vanadium slag in the reduction of LF stove, thus makes molten steel increase vanadium, and the mode of alloying for first directly will add in stove containing vanadium slag, and then adds reductive agent reduction vanadium slag.But its reductive agent is aluminium powder, calcium carbide, reduzate is aluminum oxide.This method can cause the LF refining process quantity of slag to roll up, thus increases energy consumption, pollutes molten steel.Publication number is the patent of CN101067182, mainly utilizes V
2o
5in electric arc furnace reduction, molten steel is made to increase vanadium.Alloying mode is first add V equally
2o
5, then add reductive agent reduction.Adopt reductive agent to be silicon and Al, reduzate is silicon-dioxide and aluminum oxide, and the quantity of slag to be caused in stove equally to increase.
According to existing vanadium DIRECT ALLOYING technology, how in esr process, effectively adding vanadium, and control the quantity of slag in stove, is the key technical problem that the present invention will solve.
Summary of the invention
1. invent the technical problem that will solve
The object of the invention is to solve how to utilize V at esr process
2o
5realize the problem of the DIRECT ALLOYING of V-alloyed steel, provide a kind of method of direct vanadium alloying in esr process.The method of vanadium alloying of the present invention, V
2o
5reduction rate fast, and do not pollute molten steel, the recovery rate of vanadium is high, and technique is simple; Adopt technical scheme of the present invention can remelting containing the cold-work die steel of vanadium, hot-work die steel, cold-rolled steel steel and rapid steel etc., reflow process is stablized, and Ingot Surface Quality is good, and chemical constituents analysis is even.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The method of a kind of direct vanadium alloying in esr process of the present invention, the steps include:
Step one, by vanadium oxide and graphite according to the mixing of certain ratio, adopt iron sheet to be rolled into alloy wire; Adopt the mass percent of each composition in vanadium oxide to be V
2o
5>98%, P<0.03%, S<0.015%, granularity is not more than 100 orders; In graphite, the mass percent of each composition is C>99%, S<0.02%, P<0.01%, and granularity is not more than 100 orders; The weight ratio of vanadium oxide and graphite is 1:1 ~ 1.5:1; Alloy wire diameter is 5 ~ 10mm;
Step 2, adopt melt cinder Starting mode, start esr, namely first by remelting slag after electroslag furnace melts outward, then pour electroslag furnace into, then electrode declines, and reflow process starts; The electroslag furnace adopted is the stripping formula electroslag remelting furnace adopting T-shaped crystallizer, and wherein T-shaped crystallizer slag bath liner composition is followed successively by graphite brick-high alumina brick-steel plate from inside to outside, and steel plate is without the need to water-cooled; The temperature of melt cinder is not less than 1600 DEG C, then enters normal reflow process, and the molten speed of reflow process metal consumable electrode is (0.7 ~ 0.8) × D
steel ingot(steel ingot diameter, mm), kg/h;
Step 3, in slag bath, feed the made alloy wire of step one, feed quantity is determined according to following calculation formula:
W
alloy wire=3.04W
mw
v~ 3.65W
mw
v
In formula: W
alloy wirefor the amount of the alloy wire of per minute feeding slag bath, do not comprise the weight of iron sheet, kg/min;
W
mfor the melting rate of consumable electrode per minute, kg/min
W
vfor the content of vanadium in finished product electroslag ingot, %
The slag composition adopted is 70%CaF
2+ 30%Al
2o
3;
Step 4, in esr process, in the slag bath of step 3, add aluminum shot continuously, carry out diffusive deoxidation, aluminum shot add-on is 0.5-1.0kg/ ton steel, and granularity is at 2mm ~ 5mm;
After step 5, normal esr process, stop the feeding of alloy wire, enter the feeding stage, after the feeding stage completes, reflow process terminates, wherein feeding complete after steel ingot heart portion protrusion height be 1cm ~ 2cm.
The present invention utilizes the feature that temperature in esr process is higher, according to analysis, finds that carbon just can reduction-oxidation vanadium at such high temperatures, and the CO gas of deoxidation products, the quantity of slag can not be caused to increase.When LF stove adopts oxide compound direct Reducing and Alloying, the general refining quantity of slag is about 1.8% of Metal Weight.To smelt the steel alloy containing V 0.5 ~ 1%, the quality of steel is 1 ton, and the refining quantity of slag of employing is 18kg, and the vanadium that ton steel contains is 5 ~ 10kg.These vanadium are completely by aluminium reducing V
2o
5.According to calculating, due to reduction V
2o
5and the aluminum oxide generated is 8 ~ 16kg, these aluminum oxide enter in slag completely, and the increasing amount of slag is 44%-88%.
In esr process, the slag quality adopted generally accounts for 5% of ingot quality, and being used for the addition of aluminium of diffusive deoxidation in reflow process is 0.5-1.0kg/t.For remelting 1 ton of steel, the slag quality adopted is 50kg.Reflow process adopts 0.5 ~ 1.0kg aluminium to carry out deoxidation, and will be 0.94 ~ 1.89kg after these metallic aluminiums folding borolon (deoxidation generation aluminum oxide), the increasing amount of slag be 1.9% ~ 3.8%.As can be seen here, in common process for making, due to the restriction of steel-making temperature, be not suitable for adopting C reduction V
2o
5, and AL can only be adopted to reduce, when therefore can cause vanadium alloying, the quantity of slag increases.
Adopt graphite as reductive agent in the present invention, itself and vanadium oxide can be mixed and made into alloy wire, utilize feeding wire machine to add vanadium oxide in T-shaped crystallizer slag bath, easy control add-on, avoid gas to bring in molten steel, and molten steel reflection is steady, evenly, yield of alloy is significantly improved.In line feeding process, C reduces V
2o
5but, according to thermodynamics ultimate principle, V
2o
5having little remnants enters in slag, and now adding diffusion deoxidizer AL is to make vanadium oxide reduce further, and one is the recovery rate that can improve vanadium further; Two is to prevent V
2o
5in oxygen enter steel ingot and cause the purity of steel to reduce.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with prior art, there is following beneficial effect:
The method of a kind of direct vanadium alloying in esr process of the present invention, temperatures as high more than 1800 DEG C in esr process, C can be utilized at these elevated temperatures to replace traditional AL to carry out reduction-oxidation vanadium, without the need to smelting ferrovanadium again, achieve the DIRECT ALLOYING of vanadium, compared with prior art, its beneficial effect is: 1, cleverly wire-feeding technique is applied in esr process, and the alloying of vanadium is combined with wire-feeding technique, adopt graphite as primary reducing agent, substantially increase the recovery rate of vanadium, and reduzate is carbon monoxide, pollution can not be produced by the slag system used to esr process, 2, in esr process, utilize the direct vanadium alloying of vanadium oxide, both the energy consumption that employing vanadium oxide smelting ferrovanadium can have been avoided to cause, environmental pollution, can avoid again because consumable electrode content of vanadium the caused consumable electrode that acts improperly scraps phenomenon, raw material resources are saved, reduce production cost, simplify production technique.
Embodiment
For understanding content of the present invention further, the present invention is described in detail in conjunction with the embodiments.
Embodiment 1
The method of a kind of direct vanadium alloying in esr process of the present embodiment, produce the 9Cr2MoV cold roll steel that content of vanadium is 0.1 ~ 0.2%, for the alloying of vanadium, the operational path adopted be esr melt cinder startups → slag bath feed in alloy wire → slag add diffusion deoxidizer Al → feeding stage → feeding completes, the power-off → demoulding → annealing.In the vanadium oxide used, the mass percent of each composition is: V
2o
5be 98.2%, P<0.03%, S<0.015%, vanadium oxide granularity is not more than 100 orders; In the graphite adopted, the mass percent of each composition is: C is 99.4%, S<0.02%, P<0.01%, and graphite particle size is not more than 100 orders.Vanadium oxide and graphite being mixed according to the ratio of 1.5:1 and making diameter is after the cored-wire of 5mm, and start electroslag furnace, reflow process starts, and the speed of melting of consumable electrode is 0.8 × D
steel ingot(steel ingot diameter, mm), kg/h.After remelting starts, the cored-wire of feeding vanadium oxide and graphite composition, feeding weight is as follows:
Select W
alloy wire=3.04W
mw
v,
The content that wish produces vanadium in cold-rolled steel is 0.1 ~ 0.2%, then:
W
alloy wire=3.04 × 10
-3w
m~ 6.08 × 10
-3w
m
In formula: W
alloy wirethe amount of the alloy wire of-per minute feeding slag bath, does not comprise the weight of iron sheet, kg/min;
W
mthe melting rate of-consumable electrode per minute, kg/min
Meanwhile, continually continuously in slag bath add diffusion deoxidizer, reductor kind is Al grain, and granularity is 2mm, Al addition is 0.5kg/ ton steel.To esr latter stage, proceed to the feeding stage.After treating feeding, power-off, the demoulding, carry out anneal.
Result of implementation shows, adopt the inventive method can obtain good effect, v element recovery rate is up to 99.1%, not only higher than the method for ferro-vanadium alloying, also higher than the recovery rate of DIRECT ALLOYING vanadium in LF or electric arc furnace, and it is little to fluctuate, stable operation.In addition, vanadium alloy element is longitudinal and horizontal being evenly distributed at steel ingot, and segregation is very little.
The electroslag furnace adopted in the present embodiment is the stripping formula electroslag remelting furnace adopting T-shaped crystallizer, and wherein T-shaped crystallizer slag bath liner composition is followed successively by graphite brick-high alumina brick-steel plate from inside to outside.Current crystallizer liner adopts copper, and price is high, and copper heat conduction is fast, and cause calorific loss comparatively large, energy consumption is higher; Adopt graphite brick-high alumina brick-inner steel lining in the present embodiment, graphite mainly plays high-temperature corrosion resistance effect, and high alumina brick then plays the high temperature resistant effect of insulation, and steel plate plays a supportive role, and this liner cost is low, calorific loss is little, can save power consumption.
Embodiment 2
The method of a kind of direct vanadium alloying in esr process of the present embodiment, produce the 4Cr5MoSiV hot-work die steel that content of vanadium is 0.3 ~ 0.6%, for the alloying of vanadium, the operational path adopted be esr melt cinder startups → slag bath feed in alloy wire → slag add diffusion deoxidizer Al → feeding stage → feeding completes, the power-off → demoulding → annealing.Wherein in the vanadium oxide that uses of DIRECT ALLOYING, the mass percent of each composition is: 98.1% is V
2o
5, P<0.03%, S<0.015%, vanadium oxide granularity is not more than 100 orders; During graphite contains, the mass percent of each composition is: C is 99.5%, S<0.02%, P<0.01%, and graphite particle size is not more than 100 orders.Vanadium oxide and graphite being mixed according to the ratio of 1.25:1 and making diameter is after the cored-wire of 10mm, starts electroslag furnace.Enabling of electroslag furnace adopts melt cinder to start, namely first by remelting slag after electroslag furnace melts outward, then pour electroslag furnace into, then electrode declines, and the temperature of melt cinder is not less than 1600 DEG C, and reflow process starts, and consumable electrode melting speed is 0.75 × D
steel ingot(steel ingot diameter, mm), kg/h.After remelting starts, the cored-wire of feeding vanadium oxide and graphite composition, feeding weight is as follows:
Select W
alloy wire=3.28W
mw
v,
The content that wish produces vanadium in cold-rolled steel is 0.3 ~ 0.6%, then:
W
alloy wire=9.84 × 10
-3w
m~ 1.968 × 10
-2w
m
In formula: W
alloy wirethe amount of the alloy wire of-per minute feeding slag bath, does not comprise the weight of iron sheet, kg/min;
W
mthe melting rate of-consumable electrode per minute, kg/min
Meanwhile, continually continuously in slag bath add diffusion deoxidizer, reductor kind is Al, and granularity is 0.8kg/ ton steel at 5mm, Al addition.To esr latter stage, proceed to the feeding stage.After treating feeding, power-off, the demoulding, carry out anneal.
Embodiment 3
The method of a kind of direct vanadium alloying in esr process of the present embodiment, produce the 6Cr4W3Mo2VNb cold-work die steel that content of vanadium is 0.8 ~ 1.2%, for the alloying of vanadium, the operational path adopted be esr melt cinder startups → slag bath feed in alloy wire → slag add diffusion deoxidizer Al → feeding stage → feeding completes, the power-off → demoulding → annealing.The vanadium oxide that wherein DIRECT ALLOYING uses contains the V of 98.5%
2o
5, P<0.03%, S<0.015% in vanadium oxide, vanadium oxide granularity is not more than 100 orders; Graphite contains the C of 99.2%, and S<0.02%, P<0.01 in graphite, graphite particle size is not more than 100 orders.Vanadium oxide and graphite being mixed according to the ratio of 1:1 and making diameter is after the cored-wire of 8mm, starts electroslag furnace.Enabling of electroslag furnace adopts melt cinder to start, namely first by remelting slag after electroslag furnace melts outward, then pour electroslag furnace into, then electrode declines, and the temperature of melt cinder is not less than 1600 DEG C, and reflow process starts, and the speed of melting of consumable electrode is 0.7 × D
steel ingot(steel ingot diameter, mm), kg/h.After remelting starts, the cored-wire of feeding vanadium oxide and graphite composition, feeding weight is as follows:
Select W
alloy wire=3.65W
mw
v,
The content that wish produces vanadium in cold-rolled steel is 0.8 ~ 1.2%, then:
W
alloy wire=2.92 × 10
-2w
m~ 4.38 × 10
-2w
m
In formula: W
alloy wirethe amount of the alloy wire of-per minute feeding slag bath, kg/min (not comprising the weight of iron sheet);
W
mthe melting rate of-consumable electrode per minute, kg/min
Meanwhile, continually continuously in slag bath add diffusion deoxidizer, reductor kind is Al grain, and granularity is 1kg/ ton steel at 3mm, Al addition.To esr latter stage, proceed to the feeding stage.After treating feeding, power-off, the demoulding, carry out anneal.
Claims (5)
1. the method for direct vanadium alloying in esr process, is characterized in that: the steps include:
Step one, vanadium oxide and graphite to be mixed in proportion, to adopt iron sheet to be rolled into alloy wire;
Step 2, employing melt cinder Starting mode start electroslag furnace, when melt cinder temperature is not less than 1600 DEG C, start esr;
Step 3, in slag bath, feed the made alloy wire of step one;
Step 4, in esr process, in the slag bath of step 3, add aluminum shot continuously, carry out diffusive deoxidation;
After step 5, esr process, stop the feeding of alloy wire, enter the feeding stage.
2. the method for a kind of direct vanadium alloying in esr process according to claim 1, is characterized in that: in step one, V in vanadium oxide
2o
5>98%, P<0.03%, S<0.015%, vanadium oxide granularity is not more than 100 orders; C>99%, S<0.02%, P<0.01% in graphite, graphite particle size is not more than 100 orders.
3. the method for a kind of direct vanadium alloying in esr process according to claim 1, it is characterized in that: in step one, the weight ratio of vanadium oxide and graphite is 1:1 ~ 1.5:1; Alloy wire diameter is 5 ~ 10mm.
4. the method for a kind of direct vanadium alloying in esr process according to claim 1, it is characterized in that: in step 3, alloy wire feeds slag bath by feeding wire machine, and the amount of alloy wire feeding slag bath is determined according to following formula:
W
alloy wire=3.04W
mw
v~ 3.65W
mw
v
In formula: W
alloy wirefor the amount of the alloy wire of per minute feeding slag bath, and do not comprise the weight of iron sheet, kg/min;
W
mfor the melting rate of consumable electrode per minute, kg/min
W
vfor the content of vanadium in finished product electroslag ingot, %.
5. the method for a kind of direct vanadium alloying in esr process according to claim 1, it is characterized in that: in step 3, aluminum shot add-on is 0.5 ~ 1.0kg/ ton steel, and the granularity of aluminum shot is at 2mm ~ 5mm.
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Cited By (5)
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|---|---|---|---|---|
| CN110055428A (en) * | 2019-05-31 | 2019-07-26 | 马鞍山市中桥金属材料有限公司 | A kind of method that esr process is boron alloyed |
| CN110551907A (en) * | 2019-10-12 | 2019-12-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium-titanium alloy by using refined tailings |
| CN111041157A (en) * | 2019-12-31 | 2020-04-21 | 龙南龙钇重稀土科技股份有限公司 | Electroslag furnace wire feeding method |
| WO2021134948A1 (en) * | 2019-12-31 | 2021-07-08 | 龙南龙钇重稀土科技股份有限公司 | Wire feeding device and electroslag furnace having same |
| CN115074484A (en) * | 2022-06-29 | 2022-09-20 | 山东钢铁股份有限公司 | Production process for smelting vanadium microalloyed steel by vanadium oxide self-reduction |
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| CN111041157A (en) * | 2019-12-31 | 2020-04-21 | 龙南龙钇重稀土科技股份有限公司 | Electroslag furnace wire feeding method |
| CN111041157B (en) * | 2019-12-31 | 2021-02-26 | 龙南龙钇重稀土科技股份有限公司 | Electroslag furnace wire feeding method |
| WO2021134948A1 (en) * | 2019-12-31 | 2021-07-08 | 龙南龙钇重稀土科技股份有限公司 | Wire feeding device and electroslag furnace having same |
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| CN115074484A (en) * | 2022-06-29 | 2022-09-20 | 山东钢铁股份有限公司 | Production process for smelting vanadium microalloyed steel by vanadium oxide self-reduction |
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