CN102560131B - Premelted refining slag and preparation method thereof - Google Patents

Premelted refining slag and preparation method thereof Download PDF

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CN102560131B
CN102560131B CN201110446271.6A CN201110446271A CN102560131B CN 102560131 B CN102560131 B CN 102560131B CN 201110446271 A CN201110446271 A CN 201110446271A CN 102560131 B CN102560131 B CN 102560131B
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refining slag
slag
preparation
melted refining
molten bath
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CN102560131A (en
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陈炼
李龙
陈永
戈文荪
王永钢
向丽
杨森祥
杜利华
翁建军
何为
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Pangang Group Panzhihua Steel and Vanadium Co Ltd
Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
Pangang Group Xichang Steel and Vanadium Co Ltd
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Pangang Group Panzhihua Steel and Vanadium Co Ltd
Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
Pangang Group Xichang Steel and Vanadium Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P10/20—Recycling

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  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

The invention provides a premelted refining slag and preparation method thereof. The preparation method comprises the following steps of: adding ferrovanadium slag and arc striking iron to the electric furnace to melt and form a molten bath; adding aluminum to the molten bath to reduce the vanadium oxide in the ferrovanadium slag; adding lime to the molten bath and stirring the bath with inert gases so as to form the slag containing 12Cao.7Al2O3 and/ or 3CaO.Al2O3; and separating the slag from the metal liquid in the molten bath to obtain premelted refining slag and metal liquid. The method of the invention can make an effective use of the ferrovanadium slag to obtain premelted refining slag that meets the requirements of metallurgical process like steel making.

Description

Pre-melted refining slag and preparation method thereof
Technical field
The present invention relates to metallurgical industry solid waste resource recovery and utilize technical field, more particularly, relate to a kind of pre-melted refining slag and preparation method thereof.
Background technology
At present, aspect the utilizing of vanadium, there is multinomial technology, for example, the V that utilizes vanadium slag to prepare 2o 5produce ferro-vanadium.Conventionally, the production method of ferro-vanadium comprises silicothermic process and thermite process.Wherein, thermite process is when preparing ferro-vanadium, owing to having added in process of production aluminum shot to reduce, so contain a large amount of Al in vanadium iron smelted furnace cinder 2o 3thereby, cause this vanadium iron smelted furnace cinder to there is high, the difficult feature of utilizing of fusing point.In the prior art, to the treatment process of vanadium iron smelted furnace cinder, be to be mainly used as crushed stone for paving the way after fragmentation, or stack.
In general, in vanadium iron smelted furnace cinder, contain by weight the CaO of 20% left and right, the Al of 60% left and right 2o 3, the MgO of 15% left and right, the V of the Fe of 0.6% left and right, 1.5% left and right, trace Cr and impurity element.If vanadium iron smelted furnace cinder is not used and is directly deposited in environment, the heavy metal elements such as the V in vanadium iron smelted furnace cinder, Cr can, to environment, also cause the waste of V resource simultaneously.Therefore, the recycling of vanadium iron smelted furnace cinder is significant for the Sustainable development that alleviates carrying capacity of environment and metallurgical industry.
Summary of the invention
The problems referred to above that exist for prior art, the invention provides a kind of pre-melted refining slag and preparation method thereof.
One of object of the present invention is to provide a kind of method that can effectively utilize vanadium iron smelted furnace cinder, to solve the environmental problem of piling up generation because of slag.
Another object of the present invention is to provide a kind of method of utilizing vanadium iron smelted furnace cinder to prepare pre-melted refining slag, a kind of containing 12CaO7Al to produce 2o 3and/or 3CaOAl 2o 3the pre-melted refining slag of phase.
An aspect of of the present present invention provides a kind of preparation method of pre-melted refining slag.Described preparation method comprises step: vanadium iron smelted furnace cinder and the electric furnace starting the arc are added to electric furnace with iron, and fusing forms molten bath; In molten bath, add the barium oxide of aluminium to reduce in described vanadium iron smelted furnace cinder; In molten bath, add lime and use stirring of inert gas molten bath, to form containing 12CaO7Al 2o 3and/or 3CaOAl 2o 3the slag of phase; Slag and molten metal in separated molten bath, obtain pre-melted refining slag and molten metal.
According in the preparation method of pre-melted refining slag of the present invention embodiment, described in add in the step of lime, lime is added to molten bath in batches.
According in the preparation method of pre-melted refining slag of the present invention embodiment, the slag that described vanadium iron smelted furnace cinder produces when adopting thermite process smelting ferrovanadium alloy.
According in the preparation method of pre-melted refining slag of the present invention embodiment, described vanadium iron smelted furnace cinder comprises by weight: 55%～70% Al 2o 3, 15%～25% CaO, 12%～20% MgO, be less than 0.5 SiO 2, 0.5%～2.5% V, 0.5%～1% TFe and trace impurity.
According in the preparation method of pre-melted refining slag of the present invention embodiment, the add-on of described vanadium iron smelted furnace cinder is 30%～60% by weight, and the add-on of described lime is 39.5%～69.5% by weight.
Another aspect of the present invention provides a kind of pre-melted refining slag, and described pre-melted refining slag adopts preparation method as above to make.
According in pre-melted refining slag of the present invention embodiment, described pre-melted refining slag composition comprises by weight: 21%～45% Al 2o 3, 44%～71% CaO, 7%～11% MgO, the SiO lower than 0.3% 2, the TFe lower than 0.5% and trace impurity.This pre-melted refining slag can be used as steel-making pre-melted refining slag.
Compared with prior art, beneficial effect of the present invention comprises: (1) can effectively utilize vanadium iron smelted furnace cinder, is conducive to resource recycling; (2) use vanadium iron smelted furnace cinder to make the pre-melted refining slag that meets processing requirement.For example, it is stable and can form fast the feature of the good high alkalinity refining slag of mobility, reductibility that described pre-melted refining slag has uniform ingredients, thereby can efficiently complete the refining task of desulfurization, deoxidation, removal of inclusions.
Accompanying drawing explanation
Fig. 1 shows the preparation method's of pre-melted refining slag process route chart according to an exemplary embodiment of the present invention.
Embodiment
Hereinafter, describe with reference to the accompanying drawings exemplary embodiment of the present invention in detail.
Fig. 1 shows the preparation method's of pre-melted refining slag process route chart according to an exemplary embodiment of the present invention.
As shown in Figure 1, in one exemplary embodiment of the present invention, the preparation method of pre-melted refining slag comprises the following steps: vanadium iron smelted furnace cinder and the electric furnace starting the arc are added to electric furnace with iron, and fusing forms molten bath; In molten bath, add the barium oxide of aluminium to reduce in described vanadium iron smelted furnace cinder; In molten bath, add lime and use stirring of inert gas molten bath, to form containing 12CaO7Al 2o 3and/or 3CaOAl 2o 3the slag of phase; Slag and molten metal in separated molten bath, obtain pre-melted refining slag and molten metal.Here, rare gas element can be the conventional rare gas elementes such as nitrogen or argon gas.Adding the iron in electric furnace together with vanadium iron smelted furnace cinder is that its add-on can be set according to practical situation in order to play the effect of striking.Adding aluminium is the barium oxide in order to reduce in described vanadium iron smelted furnace cinder, and therefore, the add-on of aluminium can draw according to the cubage of the barium oxide in vanadium iron smelted furnace cinder.Preferably, be the opportunity that adds aluminium after molten bath is completely molten clear, like this convenient operation and be conducive to improve the utilization ratio of metallic aluminium.Molten metal mainly contains vanadium metal and ferro element, and it returns to ferro-vanadium smelting technology and utilize after can die casting being piece; Or also can directly with liquid form, return to ferro-vanadium smelting technology utilizes.
In one exemplary embodiment of the present invention, the described step of lime that adds can add molten bath by lime in batches, the amount of every batch can equate also can not wait, thereby be conducive to make to add the lime in molten bath to melt in time, and improve reacting between slag phase and metal liquid phase, but also can promote the formation of refining slag desired substance, improve the quality of pre-melted refining slag.For example, in the present embodiment, lime can be added to molten bath in three batches, and with nitrogen gas stirring, after stirring, standing 20～30min takes slag and the molten metal in separated molten bath.Here, in molten metal, mainly contain vanadium metal and iron.Stirring of inert gas can promote to conduct heat and mass transfer, is conducive to promote containing 12CaO7Al2O 3and/or 3CaOAl 2o 3the generation of the slag of phase.
In one exemplary embodiment of the present invention, the slag that described vanadium iron smelted furnace cinder can produce when adopting thermite process smelting ferrovanadium alloy.Yet described vanadium iron smelted furnace cinder of the present invention is not limited to this.Because method of the present invention has been utilized aluminum oxide and the calcium oxide in slag, therefore those skilled in the art should know the slag producing while adopting other method smelting ferrovanadium alloy, as long as wherein contain the aluminum oxide of predetermined amount, can be used as vanadium iron smelted furnace cinder of the present invention.
In one exemplary embodiment of the present invention, described vanadium iron smelted furnace cinder comprises by weight: 55%～70% Al 2o 3, 15%～25% CaO, 12%～20% MgO, be less than 0.5 SiO 2, 0.5%～2.5% V, 0.5%～1% TFe and trace impurity.Now, the add-on of described vanadium iron smelted furnace cinder can be 30%～60% by weight, and the add-on of described lime can be 39.5%～69.5% by weight, thereby can obtain, contains 12CaO7Al 2o 3and/or 3CaOAl 2o 3the pre-melted refining slag of phase.For example, the composition of the pre-melted refining slag of acquisition is as shown in table 2, and it can comprise by weight: 21%～45% Al 2o 3, 44%～71% CaO, 7%～11% MgO, the SiO lower than 0.3% 2, the TFe lower than 0.5% and trace impurity.Pre-melted refining slag of the present invention has uniform ingredients, low, the molten speed of fusing point is fast and Sulfur capacity high, it can realize quick slag making and deep desulfuration, promote the absorption of non-metallic inclusion, shorten refining cycle, be especially suitable as steel-making pre-melted refining slag.When pre-melted refining slag of the present invention is used for to the secondary refining operation of process for making, can form fast mobility, the good high alkalinity refining slag of reductibility, thereby the refining task that can efficiently complete desulfurization, deoxidation, removal of inclusions, meets need of production.For example, using this pre-melted refining slag as refining slag, add ladle refining furnace (, LF stove) time, this pre-melted refining slag forms mobility, the good high alkalinity refining slag of reductibility fast at LF refining process, make LF can efficiently complete the refining task of desulfurization, deoxidation, removal of inclusions, meet need of production.
In one exemplary embodiment of the present invention, lime, aluminium, iron all can be for containing the conventional material of a small amount of impurity.General in the situation that, in lime, the weight percent content of CaO should be greater than 80%, and in aluminium, the weight percent content of aluminium element should be greater than 95%, otherwise can reduce the quality that pre-melted refining slag is used in the steel-making making.
Table 1 shows the major ingredient (ignoring foreign matter content) of vanadium iron smelted furnace cinder, and wherein, described vanadium iron smelted furnace cinder is the slag producing while adopting thermite process smelting ferrovanadium alloy.
The major ingredient of table 1 vanadium iron smelted furnace cinder ((wt%) meter by weight percentage)
Composition Al 2O 3 CaO MgO SiO 2 V TFe
Ratio/wt% 55～70 15～25 12～20 ＜0.5 0.5～2.5 0.5～1
Table 2 is according to the major ingredient of the pre-melted refining slag of exemplary embodiment
Composition Al 2O 3 CaO MgO SiO 2 TFe
Ratio/wt% 21～45 44～71 7～11 ＜0.3 ＜0.5
In order to understand better the present invention, below in conjunction with concrete example, further illustrate the present invention.
Process route chart shown in example 1 to 3 employing Fig. 1 operates.Vanadium iron smelted furnace cinder in example 1 to 3 has the composition shown in table 1.
Example 1
Using vanadium iron smelted furnace cinder, lime and aluminum shot as raw material, be 30: 69.5: 0.5 in mass ratio, amount to 15t, weigh.
Vanadium iron smelted furnace cinder and 300kg iron block are put into electric furnace to be melted.After melting clearly completely, add aluminum shot to continue molten clear.Then add in three batches lime and use nitrogen gas stirring, standing 10min after stirring first slags tap and taps a blast furnace afterwards after the separation of slag iron, and resulting slag is pre-melted refining slag, obtains the molten metal containing vanadium, ferro element simultaneously.Pre-melted refining slag is packed after being broken into the particle of 6mm～12mm.Pre-melted slag composition is by weight: Al 2o 321.45%, CaO 70.63%, and MgO 7.65%, SiO 20.27%, TFe 0.43%, and surplus is impurity.Molten metal containing vanadium, ferro element is molded into after piece, returns to ferro-vanadium smelting technology and utilize.
Example 2
Using vanadium iron smelted furnace cinder, lime and aluminum shot as raw material, be 60: 39.5: 0.5 in mass ratio, amount to 10t, weigh.
Vanadium iron smelted furnace cinder and 200kg iron block are put into electric furnace to be melted.After melting clearly completely, add aluminum shot to continue molten clear.Then add in three batches lime and use nitrogen gas stirring, standing 20min after stirring first slags tap and taps a blast furnace afterwards after the separation of slag iron, and resulting slag is pre-melted refining slag, obtains the molten metal containing vanadium, ferro element simultaneously.Pre-melted refining slag is packed after being broken into the particle of 6mm～12mm.Pre-melted slag composition is by weight: Al 2o 345.51%, CaO 44.03%, MgO10.22%, SiO 20.24%, TFe 0.48%, and surplus is impurity.Molten metal containing vanadium, ferro element is molded into after piece, returns to ferro-vanadium smelting technology and utilize.
Example 3
Using vanadium iron smelted furnace cinder, lime and aluminum shot as raw material, be 35: 64.5: 0.5 in mass ratio, amount to 20t, weigh.
Vanadium iron smelted furnace cinder and 400kg iron block are put into electric furnace to be melted.After melting clearly completely, add aluminum shot to continue molten clear.Then add in three batches lime and use nitrogen gas stirring, standing 15min after stirring first slags tap and taps a blast furnace afterwards after the separation of slag iron, and resulting slag is pre-melted refining slag, obtains the molten metal containing vanadium, ferro element simultaneously.Pre-melted refining slag is packed after being broken into the particle of 6mm～12mm.Pre-melted slag composition is by weight: Al 2o 335.78%, CaO 54.98%, and MgO 9.05%, SiO 20.19%, TFe 0.45%, and surplus is impurity.Molten metal containing vanadium, ferro element is molded into after piece, returns to ferro-vanadium smelting technology and utilize.
In sum, the present invention can effectively utilize vanadium iron smelted furnace cinder to prepare pre-melted refining slag, not only realize the effective utilization to the vanadium iron smelted furnace cinder as Using Metallurgical Solid Wastes, and the pre-melted refining slag making to have uniform ingredients stable and can form fast the feature of the good high alkalinity refining slag of mobility, reductibility, thereby the refining task that can efficiently complete desulfurization, deoxidation, removal of inclusions, has met need of production.Visible; the present invention can guarantee on the basis of refining effect; used the slag charge of vanadium iron in producing as raw material; both natural Mineral resources had been protected; widened again the recycling approach of vanadium iron smelted furnace cinder; for example realized vanadium iron smelted furnace cinder, in inner the recycling of metallurgical technology flow process (, ferrous metallurgy flow process).
Although described pre-melted refining slag of the present invention and preparation method thereof in conjunction with exemplary embodiment above, but above description be only illustrating property and nonrestrictive, those of ordinary skills should be clear, in the situation that do not depart from the spirit and scope that claim limits, can change foregoing description.

Claims (7)

1. a preparation method for pre-melted refining slag, described preparation method comprises the following steps:
Vanadium iron smelted furnace cinder and the electric furnace starting the arc are added to electric furnace with iron, and fusing forms molten bath;
In molten bath, add the barium oxide of aluminium to reduce in described vanadium iron smelted furnace cinder;
In molten bath, add lime and use stirring of inert gas molten bath, to form containing 12CaO7Al 2o 3and/or 3CaOAl 2o 3the slag of phase;
Slag and molten metal in separated molten bath, obtain pre-melted refining slag and molten metal, and described pre-melted refining slag composition comprises by weight: 21%～45% Al 2o 3, 44%～71% CaO, 7%～10.22% MgO, the SiO lower than 0.3% 2, the TFe lower than 0.5% and trace impurity.
2. the preparation method of pre-melted refining slag according to claim 1, is characterized in that, described in add in the step of lime, lime is added to molten bath in batches.
3. the preparation method of pre-melted refining slag according to claim 1, is characterized in that, described vanadium iron smelted furnace cinder is the slag producing while adopting thermite process smelting ferrovanadium alloy.
4. the preparation method of pre-melted refining slag according to claim 3, is characterized in that, described vanadium iron smelted furnace cinder comprises by weight: 55%～70% Al 2o 3, 15%～25% CaO, 12%～20% MgO, be less than 0.5% SiO 2, 0.5%～2.5% V, 0.5%～1% TFe and trace impurity.
5. the preparation method of pre-melted refining slag according to claim 4, is characterized in that, the add-on of described vanadium iron smelted furnace cinder is 30%～60% by weight, and the add-on of described lime is 39.5%～69.5% by weight.
6. a pre-melted refining slag, is characterized in that, described pre-melted refining slag adopts and makes according to the preparation method described in any one in claim 1 to 5.
7. pre-melted refining slag according to claim 6, is characterized in that, described pre-melted refining slag is steel-making pre-melted refining slag.
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CN106350675A (en) * 2015-07-16 2017-01-25 东北大学 Preparation method of high-quality AlV55 alloy
CN106350674A (en) * 2015-07-16 2017-01-25 东北大学 Preparation method of high-quality AlV85 alloy
CN109338044A (en) * 2018-12-18 2019-02-15 攀枝花钢城集团有限公司 Pre-melted refining slag and preparation method thereof
CN110408779B (en) * 2019-07-25 2021-04-02 河钢股份有限公司承德分公司 Method for comprehensively recycling vanadium-containing solid waste resources
CN114264157A (en) * 2021-12-10 2022-04-01 徐州宏阳新材料科技股份有限公司 Method for prolonging service life of submerged arc furnace body

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CN101984088A (en) * 2010-11-16 2011-03-09 东北大学 Method for preparing premelted refining slag by using converter slag and aluminum slag
CN102206729A (en) * 2011-04-11 2011-10-05 东北大学 Method for recycling steel slag of LF (Low Frequency) furnace

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CN101701281A (en) * 2009-12-04 2010-05-05 石家庄钢铁有限责任公司 Premelted refining slag for refining low-oxygen steel by converter
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CN102206729A (en) * 2011-04-11 2011-10-05 东北大学 Method for recycling steel slag of LF (Low Frequency) furnace

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