CN111286610B - Method for shortening ferrovanadium smelting time - Google Patents
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- CN111286610B CN111286610B CN202010236688.9A CN202010236688A CN111286610B CN 111286610 B CN111286610 B CN 111286610B CN 202010236688 A CN202010236688 A CN 202010236688A CN 111286610 B CN111286610 B CN 111286610B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/06—Alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
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Abstract
The invention relates to a method for shortening ferrovanadium smelting time, and belongs to the technical field of vanadium metallurgy. The invention relates to a method for preparing a high-temperature-resistant ceramic material. According to the method for smelting ferrovanadium, vanadium trioxide, vanadium-containing dust and lime are mixed according to a certain proportion to prepare a mixture; adding water to prepare a wet material, and preparing wet granules through molding; drying the wet pellets to obtain cold-bonded melt type vanadium-containing pellets; and adding the dried cold-bonded melt type vanadium-containing pellets and the vanadium, aluminum particles, scrap iron and lime into a ferrovanadium furnace for electrifying smelting to obtain the ferrovanadium alloy. The invention can achieve the purpose of shortening the smelting time without changing the follow-up conventional stirring method, the product quality is not affected, and the dust emission effect in the charging process and the smelting process field environment is reduced.
Description
Technical Field
The invention belongs to the technical field of vanadium metallurgy, and particularly relates to a method for shortening ferrovanadium smelting time.
Background
The ferrovanadium alloy is used as an alloy additive to improve the quality of steel products, and is mainly used for producing vanadium-containing alloy steel and cast iron. The preparation principle of ferrovanadium is as follows: the vanadium-containing oxide is reduced by a reducing agent, and is obtained by mutual solid solution with an iron raw material in a high-temperature melting state, and smelting is generally carried out in an electric arc furnace. The method is divided into an electro-aluminothermic method and an electro-silicothermic method according to the difference of reducing agents, and the electric furnace plays a role in providing extra energy required by reaction, wherein the electro-aluminothermic method can obtain vanadium iron with high vanadium content due to short smelting period, so that the method is more and more widely applied
The vanadium oxide for smelting ferrovanadium mainly comprises vanadium flakes and vanadium powder. Although the vanadium content of the powder vanadium is high, the melting point of vanadium trioxide is high, the powder granularity is fine, the bulk density is small, the reduction effect in the smelting process is unstable and incomplete, the mass transfer dynamic condition of materials in a ferrovanadium furnace without a stirring device is worse, the vanadium loss in slag is high easily, and the target residual vanadium value for finishing smelting can be reached by prolonging the electrifying time. And the powdery material is easy to generate raised dust with inorganized emission, and the material spreading and leaking are common, so the method is not friendly to the field environment. Although the vanadium-containing materials are physically agglomerated and then added into a ferrovanadium smelting furnace for smelting by the existing ferrovanadium smelting manufacturers, the granular vanadium-containing materials prepared by the physical agglomeration mainly comprise vanadium trioxide, the melting point is higher, after the dried granules are added into the furnace, the granules firstly absorb heat and then are gradually melted, dissolved and reduced from the edge to the middle, and the good smelting index can be obtained only by prolonging the electrifying time.
With the increasing environmental protection and recycling economy, the improvement of the charging state and the optimization of the charging structure according to the raw material characteristics and the smelting requirements is one of the important development directions for promoting the smelting technical progress. However, in the existing ferrovanadium smelting, the powdery material flies and floats on the surface layer of the slag in the smelting process, so that the efficient smelting without powder or with less powder cannot be realized.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for smelting ferrovanadium, which comprises the following steps:
a. mixing vanadium trioxide, vanadium-containing dust mud and lime according to a certain proportion to prepare a mixture;
b. b, adding water into the mixture obtained in the step a to prepare a wet material, and preparing wet granules through molding;
c. drying the wet pellets obtained in the step b to obtain cold-bonded melt type vanadium-containing pellets;
d. adding the dried cold-bonded melt type vanadium-containing pellets and the vanadium flakes, the aluminum particles, the scrap iron and the lime into a ferrovanadium furnace for electrification smelting;
e. and standing and cooling after smelting, and separating slag from gold to obtain ferrovanadium and slag.
Wherein the mass ratio of the vanadium trioxide to the vanadium-containing dust mud to the lime in the step a is 2-104: 22-56: 5-15. Wherein the cold-bonded pellet in the molten form in the step d accounts for 2-20% of the total amount of the rest of the reference materials in terms of weight fraction.
Wherein the specific surface area of the vanadium trioxide in the step a is 1000-4000 cm2/g。
Wherein the specific surface area of the vanadium-containing dust mud in the step a is 500-3000 cm2/g。
Wherein the specific surface area of the lime in the step a is 1000-5000 cm2/g。
Wherein the water adding amount in the step b is 4-7% of the total amount of the mixture
Wherein, the particle size of the wet agglomerate in the step b is made to be 0.5-25 mm.
Wherein, the residual moisture of the cold-bonded molten vanadium-containing pellets in the step c is less than 0.05 percent, and the density is 3.1-3.4 g/cm3。
Specifically, the drying temperature in the step c is 100-300 ℃, and the drying time is 2-8 hours.
And d, preparing materials according to the mass ratio, wherein the vanadium flake: aluminum particles: iron particles: and lime is 800-1000: 386-502: 83-103: 69 to 95.
And d, charging the cold-consolidation flux type vanadium-containing pellets into a furnace, wherein the cold-consolidation flux type vanadium-containing pellets in the step d are added as a bedding material independently, are added together with the reference material but are not mixed with the reference material or are added together with the reference material after being mixed.
The invention has the beneficial effects that:
(1) in the vanadium iron smelting process by taking vanadium flakes and powder vanadium as raw materials, the powder vanadium, the vanadium-containing dust mud and lime are prepared into a cold-consolidation melt type vanadium-containing pellet, the pellet can be quickly melted after being added into a furnace, the reduction and slagging are accelerated, the purpose of shortening the smelting time can be achieved on the premise of not changing a subsequent conventional stirring method, the product quality is not influenced, and the dust raising effect in the charging process and the smelting process field environment is reduced;
(2) the invention can recycle the vanadium-containing dust mud recovered by the dust removal device in the process of producing vanadium oxide from ammonium polyvanadate and the process of smelting ferrovanadium, and the vanadium-containing dust mud is mixed, mixed and pelletized with vanadium trioxide and lime, thereby having very high environmental protection value and economic value, minimizing environmental pollution and maximizing the utilization of vanadium resources;
(3) the heat release amount of the sheet vanadium in the initial stage of the reduction of the sheet vanadium in the smelting process is large, the cold-consolidation flux type vanadium-containing pellets can be used as a coolant, the effect of absorbing surplus heat in a furnace is achieved, the volatilization loss of vanadium oxides after the sheet vanadium is melted in materials is reduced, and the vanadium yield can be improved by 0.1-0.5 percent;
(4) the invention can realize the graded utilization of lime with different particle sizes, namely, fine-particle lime is used for preparing flux type pellets, coarse-particle lime is directly fed into a furnace as a slagging agent, the realization of step-by-step addition of the flux is favorable for improving the slagging effect, the slag system components can be flexibly adjusted, and the possibility of particle pollution caused by the fact that fine-particle lime enters air during feeding is also reduced.
Detailed Description
The present invention provides a brand new method for modifying the state of a furnace charge and optimizing the structure of the furnace charge, which is realized by controlling the melting and dissolving processes of a high melting point initial charging material. The invention prepares the cold consolidation fusing agent type vanadium-containing pellet before the pellet is put into the furnace, and then the pellet and other raw materials are put into the furnace for smelting, so that the vanadium-containing material can be more quickly melted and participate in aluminothermic reaction. The novel furnace charge structure is endowed with a certain metallurgical function, and the smelting time can be further shortened and the smelting efficiency can be improved while other advantages are kept.
Specifically, the invention provides a method for smelting ferrovanadium, which comprises the following steps:
a. mixing vanadium trioxide, vanadium-containing dust mud and lime according to a certain proportion to prepare a mixture;
b. b, adding water into the mixture obtained in the step a to prepare a wet material, and preparing wet granules through molding;
c. drying the wet pellets obtained in the step b to obtain cold-bonded melt type vanadium-containing pellets;
d. adding the dried cold-bonded melt type vanadium-containing pellets and the vanadium flakes, the aluminum particles, the scrap iron and the lime into a ferrovanadium furnace for electrification smelting;
e. and standing and cooling after smelting, and separating slag from gold to obtain ferrovanadium and slag.
The invention optimizes the components of the granular vanadium-containing material, adds calcium oxide, plays a role in fluxing, and simultaneously, according to the comprehensive consideration of the cold basic property, the demoulding effect and the pellet strength of the material in many aspects, through a large number of experiments, preferably, the vanadium trioxide in the step a: vanadium-containing dust and mud: the mass ratio of lime is 2-104: 22-56: 5-15.
The amount of the cold-bonded melt type vanadium-containing pellets can be adjusted according to actual production requirements, and a large number of experiments show that the cold-bonded melt type pellets can achieve better effects when accounting for 2-20% of the total amount of the rest reference materials.
As a specific implementation mode, the vanadium oxide powder is adopted, and the specific surface area can be 1000-4000 cm2Per g, composition in weight fraction V2O380-90% of V2O5The content is 10-20%.
The vanadium-containing dust mud refers to a fine particle dust reclaimed material obtained by a dry method or a wet method in the industrial production process of vanadium. As a specific implementation mode, the vanadium-containing dust mud can be one or a mixture of two of dust generated in the production process of vanadium oxide or dust obtained by smelting ferrovanadium, and the specific surface area can be 500-3000 cm2The component per gram comprises 5-50% of V element in weight fraction, and the balance of CaO and Al2O3And MgO.
And b, when the wet material is prepared in the step b, the material is held by a hand and can be kept in a ball shape, and the material can be dispersed by slight stirring. Preferably, the water adding amount is 4-7% of the total amount of the mixture.
The forming equipment in the step b can consider three types of compression forming, extrusion forming and rolling forming, the materials have certain viscosity, and generally have certain shape and strength by means of rolling, extrusion, compression and the like, and the shapes of the obtained materials are different due to different molds and forming modes of the adopted equipment, and can be cylindrical, flying saucer-shaped, ellipsoidal, spherical and the like. Under the normal condition, the proportion of the materials under the powder sieve with the granularity below 0.5cm after wet agglomerate control sieving is only 0-5%, and the mass percentage of the materials which are adhered to the equipment and can not be aggregated is 1-10% of the total materials, namely the requirements are met. Preferably, the particle size of the wet agglomerate in the step b is controlled to be 0.5-25 mm.
Step (ii) ofAnd c, drying the ingot mould in a drying mode to remove water, wherein the drying temperature is 100-300 ℃, and the drying time is 2-8 hours. The wet pellets can be baked and dried along with the furnace lining, the cold-bonded fusing agent type vanadium-containing pellets can also continuously improve the strength in the drying process, on one hand, the shrinkage of capillary tubes and the compactness of the pellets are caused by the evaporation of water, and on the other hand, the coal gas combustion product CO in the drying process2Reacting with free CaO in the surface material of the pellets to form a small amount of network calcium carbonate whiskers, the natural mineralization process is favorable for pellet consolidation, and the drying temperature is lower than the decomposition temperature (about 530 ℃) of calcium carbonate, so that high CO is selected in the baking process of the furnace lining2Drying under a content environment.
In order to reduce the phenomena of splashing, blasting, dust raising and the like in the smelting process, the lower the moisture in the charged material is, the better the moisture is, and the higher the density is, the better the moisture is. Therefore, considering the drying limit and the pellet pressing strength limit, it is preferable that the cold-bonded melt type vanadium-containing pellets have a residual moisture of less than 0.05% and a density of 3.1 to 3.4g/cm3。
The vanadium flakes, the aluminum particles, the scrap iron, the lime and the like are mixed before entering a furnace according to the requirements of chemical component constraint and slag system component constraint of a ferrovanadium brand, and a mixture is obtained and mixed uniformly after mixing. Preferably, the materials are mixed according to the mass ratio of sheet vanadium: aluminum particles: iron particles: and lime is 800-1000: 386-502: 83-103: 69 to 95.
The invention relates to selection of lime, fine-particle lime is used for preparing flux type pellets, and coarse-particle lime is used as a slagging agent and is directly fed into a furnace. D, coarse-particle lime is preferably selected, the granularity of the lime is preferably 5-40 mm, the activity is 310-380 mL, and a large number of holes and cracks exist on the surface of the active lime, so that the penetration of molten slag into the lime is facilitated, and the reduction product Al is reduced2O3Activity of (d) to help the reaction proceed to the right.
The invention is further illustrated and described by the following examples.
Example 1
Mixing vanadium-containing powder (powdery vanadium trioxide, vanadium-containing dust mud and the like) and lime according to a certain proportion to prepare a mixtureMixing materials, wherein the vanadium-containing dust mud is dust removed by ferrovanadium, and the specific surface area is 500-3000 cm2The component is 5 percent of V element, and the rest components are CaO and Al2O3And MgO. According to the mass ratio, vanadium trioxide: vanadium-containing dust and mud: lime 2:22:5, obtaining cylindrical wet aggregates by means of extrusion molding, and finding that the ratio of the powdery undersize materials with the particle size below 0.5cm is only 2.5% through screening inspection, and the mass percentage of the materials which are adhered to the equipment and cannot be integrated is 5.5% of the total materials. The drying temperature is 100-300 ℃, the drying time is 2h, the pellet block loses 5% weight due to dehydration, the residual moisture in the dried pellet block is less than 0.05%, and the density of the pellet block is about 3.1g/cm3。
The method is characterized in that the reference materials, namely 800kg of vanadium flakes, 386kg of aluminum particles, 83kg of iron particles and 69kg of lime are preferably selected, 267.6kg of cold-bonded flux type pellets are added on the basis of the reference materials, and the cold-bonded flux type pellets are added as a coolant in the charging process, so that the smelting time can be shortened by 10min, the obtained alloy product is qualified in quality, and the field dust emission is reduced. Meanwhile, the vanadium yield can be improved by 0.1 percent.
Example 2
Mixing vanadium-containing powder (powdery vanadium trioxide, vanadium-containing dust mud and the like) and lime according to a certain ratio to prepare a mixture, wherein the vanadium-containing dust mud is dust generated in the reduction process of ammonium polyvanadate, and the specific surface area of the vanadium-containing dust mud is 500-3000 cm2Per g, the component is V element content of 50 percent, and the rest components are CaO and Al2O3And MgO. According to the mass ratio, vanadium trioxide: vanadium-containing dust and mud: lime 104:56:15, obtaining spherical wet granules by a rolling forming mode, and screening and checking to find that the ratio of powdery undersize materials with the granularity of below 0.5cm is only 5 percent, and the mass percent of the materials which are adhered to equipment and can not be aggregated into an integrated type is 10 percent of the total materials. The drying temperature is 100-300 ℃, the drying time is 5h, the pellet mass loses 10 percent of weight due to dehydration, the residual moisture in the dried pellet mass is less than 0.05 percent, and the density of the pellet mass is about 3.4g/cm3。
The method is characterized in that the reference materials, namely 1000kg of vanadium flakes, 502kg of aluminum particles (powder), 103kg of iron particles and 95kg of lime are preferably selected, 170kg of cold-bonded melt type pellets are additionally added on the basis of the reference materials, and the cold-bonded melt type pellets are added as a coolant in the feeding process, so that the smelting time can be shortened by 15min, the obtained alloy product is qualified in quality, and the field dust emission is reduced. Meanwhile, the vanadium yield can be improved by 0.5 percent.
Example 3
Mixing vanadium-containing powder (powdery vanadium trioxide, vanadium-containing dust mud and the like) and lime according to a certain ratio to prepare a mixture, wherein the vanadium-containing dust mud is a mixture of dust generated in the reduction process of ammonium polyvanadate and dust obtained from ferrovanadium, and the specific surface area of the mixture is 500-3000 cm2The component per gram is that the content of the V element is 27.5 percent, and the rest components are CaO and Al2O3And MgO. According to the mass ratio, vanadium trioxide: vanadium-containing dust and mud: the lime is mixed according to the ratio of 52:39:10, the spherical wet granules are obtained in a rolling forming mode, the ratio of the powdery undersize materials with the granularity of below 0.5cm is only 2.5 percent through screening inspection, and the mass percent of the materials which are adhered to equipment and cannot be integrated is 1 percent of the total materials. The drying temperature is 100-300 ℃, the drying time is 5h, the pellet mass loses 10 percent of weight due to dehydration, the residual moisture in the dried pellet mass is less than 0.05 percent, and the pellet mass has the rapid density of about 3.1g/cm3。
The method is characterized in that the reference materials, namely 900kg of vanadium flakes, 444kg of aluminum particles, 93kg of iron particles and 82kg of lime are preferably selected, 151.9kg of cold-bonded flux type pellets are additionally added on the basis of the reference materials, and the cold-bonded flux type pellets are added as a coolant in the charging process, so that the smelting time can be shortened by 15min, the obtained alloy product is qualified in quality, and the field dust emission is reduced. Meanwhile, the vanadium yield can be improved by 0.1 percent.
According to the invention, the cold basic characteristics (granularity, specific surface area and hydrophilicity) and the hot basic characteristics (melting point and fluidity) of the vanadium-containing material and the vanadium-containing pellets are carried out in a laboratory, the diffusion couple experiment of calcium oxide and vanadium oxide and the thermogravimetric analysis of a dried mixture are carried out, the melting point of the cold-solidified melt type pellets is lower by 50-500 ℃ than that of the non-flux type vanadium-containing pellets without CaO, the fluidity is better, and the basic support can be provided for the above embodiment by combining with auxiliary means such as a diffusion experiment and a phase diagram.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. The method for shortening the ferrovanadium smelting time is characterized by comprising the following steps:
a. mixing vanadium trioxide, vanadium-containing dust mud and lime according to a certain proportion to prepare a mixture; the mass ratio of the vanadium trioxide to the vanadium-containing dust mud to the lime is 2-104: 22-56: 5-15; the specific surface area of the vanadium trioxide is 1000-4000 cm2(ii)/g; the specific surface area of the vanadium-containing dust mud is 500-3000 cm2(ii)/g; the specific surface area of the lime is 1000-5000 cm2/g；
b. B, adding water into the mixture obtained in the step a to prepare a wet material, and preparing wet granules through molding;
c. drying the wet pellets obtained in the step b to obtain cold-bonded melt type vanadium-containing pellets; the cold-consolidation melt type vanadium-containing pellet has residual moisture of less than 0.05% and density of 3.1-3.4 g/cm3；
d. Adding the dried cold-bonded melt type vanadium-containing pellets and the vanadium flakes, the aluminum particles, the scrap iron and the lime into a ferrovanadium furnace for electrification smelting;
e. and standing and cooling after smelting, and separating slag from gold to obtain ferrovanadium and slag.
2. The method for shortening the time for smelting ferrovanadium according to claim 1, wherein: and d, counting the cold-bonded melt type pellets in the step d by weight percent to account for 2-20% of the total amount of the rest reference materials.
3. The method for shortening the time for smelting ferrovanadium according to claim 1, wherein: the water adding amount of the step b is 4-7% of the total amount of the mixture; the particle size of the wet aggregate is controlled to be 0.5-25 mm.
4. The method for shortening the time for smelting ferrovanadium according to claim 1, wherein: and c, drying at 100-300 ℃ for 2-8 h.
5. The method for shortening the time for smelting ferrovanadium according to claim 1, wherein: d, proportioning according to the mass ratio, and slicing vanadium: aluminum particles: scrap iron: and lime is 800-1000: 386-502: 83-103: 69 to 95.
6. The method for shortening the time for smelting ferrovanadium according to claim 1, wherein: and d, controlling the granularity of the lime in the step d to be 5-40 mm.
7. The method for shortening the time for smelting ferrovanadium according to claim 1, wherein: and d, adding the cold-consolidation flux type vanadium-containing pellets into the furnace in a smelting mode that the cold-consolidation flux type vanadium-containing pellets are independently used as a bedding material, added together with a reference material but not mixed with the reference material or added together with the reference material after being mixed.
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| US4795491A (en) * | 1987-04-13 | 1989-01-03 | Quigley Joseph R | Premelted synthetic slag for ladle desulfurizing molten steel |
| JP2004035995A (en) * | 2002-07-04 | 2004-02-05 | Mettsu Corporation:Kk | Method for manufacturing ferroalloy from spent catalyst |
| CN102206754A (en) * | 2011-04-20 | 2011-10-05 | 攀枝花学院 | Method for producing ferrovanadium |
| CN107354367A (en) * | 2017-07-25 | 2017-11-17 | 攀钢集团研究院有限公司 | Shorten the smelting process of the vanadium iron duration of heat |
| CN107504828A (en) * | 2017-07-25 | 2017-12-22 | 攀钢集团研究院有限公司 | Vanadium iron smelting furnace |
| CN109750158A (en) * | 2019-03-26 | 2019-05-14 | 成都先进金属材料产业技术研究院有限公司 | Vanadium-containing material is rolled to the method for being granulated and melt down smelting |
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2020
- 2020-03-30 CN CN202010236688.9A patent/CN111286610B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4795491A (en) * | 1987-04-13 | 1989-01-03 | Quigley Joseph R | Premelted synthetic slag for ladle desulfurizing molten steel |
| JP2004035995A (en) * | 2002-07-04 | 2004-02-05 | Mettsu Corporation:Kk | Method for manufacturing ferroalloy from spent catalyst |
| CN102206754A (en) * | 2011-04-20 | 2011-10-05 | 攀枝花学院 | Method for producing ferrovanadium |
| CN107354367A (en) * | 2017-07-25 | 2017-11-17 | 攀钢集团研究院有限公司 | Shorten the smelting process of the vanadium iron duration of heat |
| CN107504828A (en) * | 2017-07-25 | 2017-12-22 | 攀钢集团研究院有限公司 | Vanadium iron smelting furnace |
| CN109750158A (en) * | 2019-03-26 | 2019-05-14 | 成都先进金属材料产业技术研究院有限公司 | Vanadium-containing material is rolled to the method for being granulated and melt down smelting |
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