CN102560006B - Utilization method of ferrovanadium slag and premelted refining slag - Google Patents
Utilization method of ferrovanadium slag and premelted refining slag Download PDFInfo
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- CN102560006B CN102560006B CN201110446254.2A CN201110446254A CN102560006B CN 102560006 B CN102560006 B CN 102560006B CN 201110446254 A CN201110446254 A CN 201110446254A CN 102560006 B CN102560006 B CN 102560006B
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- slag
- vanadium iron
- furnace cinder
- smelted furnace
- iron smelted
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides a utilization method of ferrovanadium slag and premelted refining slag. The utilization method of ferrovanadium slag comprises the following steps of adding ferrovanadium slag to a high-temperature furnace to melt and form a molten bath; 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 cooling the slag to obtain premelted refining slag. 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
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 that utilizes method and obtain by the method for vanadium iron smelted furnace cinder.
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 be to environment.Therefore, effective utilization 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
For the problems referred to above of prior art existence, the invention provides a kind of pre-melted refining slag that utilizes method and obtain by the method for vanadium iron smelted furnace cinder.
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 method of utilizing of vanadium iron smelted furnace cinder.The described method of utilizing comprises step: vanadium iron smelted furnace cinder is added to High Temperature Furnaces Heating Apparatus, and fusing forms molten bath; 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; Cooling described slag, obtains pre-melted refining slag.
In an embodiment who utilizes method of vanadium iron smelted furnace cinder according to the present invention, the calcium oxide alumina phase in described slag is not less than 85% by weight, and described calcium oxide alumina phase is described 12CaO7Al
2o
3and/or 3CaOAl
2o
3phase.
In an embodiment who utilizes method of vanadium iron smelted furnace cinder according to the present invention, described in add in the step of lime, lime is added to molten bath in batches.
In an embodiment who utilizes method of vanadium iron smelted furnace cinder according to the present invention, described vanadium iron smelted furnace cinder is the slag producing while adopting thermite process smelting ferrovanadium alloy.
In an embodiment who utilizes method of vanadium iron smelted furnace cinder according to 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.
In an embodiment who utilizes method of vanadium iron smelted furnace cinder according to the present invention, the add-on of described vanadium iron smelted furnace cinder is 30%～60% by weight, and the add-on of described lime is 40%～70% by weight.
Another aspect of the present invention provides a kind of pre-melted refining slag, and described pre-melted refining slag adopts the method for utilizing as above to make.
According in pre-melted refining slag of the present invention embodiment, the calcium oxide alumina phase in described slag is not less than 85% by weight, and described calcium oxide alumina phase is described 12CaO7Al
2o
3and/or 3CaOAl
2o
3phase.
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 process route chart that utilizes method of vanadium iron smelted furnace cinder 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 process route chart that utilizes method of vanadium iron smelted furnace cinder according to an exemplary embodiment of the present invention.
As shown in Figure 1, in one exemplary embodiment of the present invention, the method for utilizing of vanadium iron smelted furnace cinder comprises the following steps: vanadium iron smelted furnace cinder is added to High Temperature Furnaces Heating Apparatus, and fusing forms molten bath; 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; Cooling described slag, obtains pre-melted refining slag.Here, rare gas element can be the conventional rare gas elementes such as nitrogen or argon gas.Preferably, according to 12CaO7Al
2o
3and/or 3CaOAl
2o
3the composition of phase, adds lime with generation 12CaO7Al as much as possible
2o
3and/or 3CaOAl
2o
3phase, thus be conducive to improve quality and the result of use of pre-melted refining slag.For example, the calcium oxide alumina phase in described slag is preferably not less than 85% by weight, and described calcium oxide alumina phase is described 12CaO7Al
2o
3and/or 3CaOAl
2o
3phase.In addition, preferably, be the opportunity that adds lime after molten bath is completely molten clear, like this convenient operation and be conducive to improve reaction efficiency.
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, accelerated speed of reaction, 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, cooling, obtains pre-melted refining slag.Here, 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 40%～70% 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 is the conventional material that contains a small amount of impurity.General in the situation that, in lime, the weight percent content of CaO should be greater than 80%, 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 the vanadium iron smelted furnace cinder as raw material and lime, be 30: 70 in mass ratio, amount to 15t, weigh.
Vanadium iron smelted furnace cinder is put into High Temperature Furnaces Heating Apparatus to be melted.After melting clearly completely, add in three batches lime and use nitrogen gas stirring, standing 20min after stirring.High Temperature Furnaces Heating Apparatus stops heating, and liquid slag is poured in mould, and after cooling of furnace slag, resulting slag is exactly pre-melted refining slag, after being broken into the particle of 6mm～12mm, packs.Pre-melted slag composition is by weight: Al
2o
321.60%, CaO 70.15%, MgO4.7.55%, SiO
20.27%, TFe 0.43%, and surplus is impurity.
Example 2
Using the vanadium iron smelted furnace cinder as raw material and lime, be 41: 59 in mass ratio, amount to 10t, weigh.
Vanadium iron smelted furnace cinder is put into High Temperature Furnaces Heating Apparatus to be melted.After melting clearly completely, add in three batches lime and use nitrogen gas stirring, standing 15min after stirring.High Temperature Furnaces Heating Apparatus stops heating, and liquid slag is poured in mould, and after cooling of furnace slag, resulting slag is exactly pre-melted refining slag, after being broken into the particle of 6mm～12mm, packs.Pre-melted slag composition is by weight: Al
2o
335.78%, CaO 54.98%, MgO9.05%, SiO
20.19%, TFe 0.45%, and surplus is impurity.
Example 3
Using the vanadium iron smelted furnace cinder as raw material and lime, be 60: 40 in mass ratio, amount to 20t, weigh.
Vanadium iron smelted furnace cinder is put into High Temperature Furnaces Heating Apparatus to be melted.After melting clearly completely, add in three batches lime and use nitrogen gas stirring, standing 30min after stirring.High Temperature Furnaces Heating Apparatus stops heating, and liquid slag is poured in mould, and resulting slag pre-melted refining slag namely after cooling of furnace 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.
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 the present invention 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 (9)
- Vanadium iron smelted furnace cinder utilize a method, the described method of utilizing comprises the following steps:Vanadium iron smelted furnace cinder is added to High Temperature Furnaces Heating Apparatus, and fusing forms molten bath;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;Cooling described slag, obtains pre-melted refining slag, and 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.
- Vanadium iron smelted furnace cinder according to claim 1 utilize method, it is characterized in that, the calcium oxide alumina phase in described slag is not less than 85% by weight, described calcium oxide alumina phase is described 12CaO7Al 2o 3and/or 3CaOAl 2o 3phase.
- Vanadium iron smelted furnace cinder according to claim 1 utilize method, it is characterized in that, described in add in the step of lime, lime is added to molten bath in batches.
- Vanadium iron smelted furnace cinder according to claim 1 utilize method, it is characterized in that the slag that described vanadium iron smelted furnace cinder produces when adopting thermite process smelting ferrovanadium alloy.
- Vanadium iron smelted furnace cinder according to claim 4 utilize method, it 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.
- Vanadium iron smelted furnace cinder according to claim 5 utilize method, it is characterized in that, the add-on of described vanadium iron smelted furnace cinder is 30%～60% by weight, the add-on of described lime is 40%～70% by weight.
- 7. a pre-melted refining slag, is characterized in that, described pre-melted refining slag adopts and makes according to the method for utilizing of the vanadium iron smelted furnace cinder described in any one in claim 1 to 6.
- 8. pre-melted refining slag according to claim 7, is characterized in that, the calcium oxide alumina phase in described slag is not less than 85% by weight, and described calcium oxide alumina phase is described 12CaO7Al 2o 3and/or 3CaOAl 2o 3phase.
- 9. pre-melted refining slag according to claim 7, is characterized in that, described pre-melted refining slag is steel-making pre-melted refining slag.
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| CN102560006B true CN102560006B (en) | 2014-02-05 |
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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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2011
- 2011-12-28 CN CN201110446254.2A patent/CN102560006B/en active Active
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|---|---|---|---|---|
| CN101029347A (en) * | 2006-02-28 | 2007-09-05 | 宝山钢铁股份有限公司 | Pre-melt steel ladle refined slag for cryogenic desulfurization |
| CN1827792A (en) * | 2006-03-31 | 2006-09-06 | 天津钢铁有限公司 | Fluorine-free pro-molten refining slag and preparation method thereof |
| 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 |
| CN101717843A (en) * | 2009-12-24 | 2010-06-02 | 东北大学 | Method for utilizing sulfur-containing refining waste residue for refining slag |
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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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