CN111218557B - Casting method of ferrovanadium alloy - Google Patents
Casting method of ferrovanadium alloy Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/06—Ingot moulds or their manufacture
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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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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- 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
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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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 discloses a method for casting a ferrovanadium alloy, which belongs to the technical field of metallurgy and comprises the following steps: a, uniformly mixing smelting raw materials according to the requirements of a vanadium iron alloy product to be produced, and then adding the mixture into a tiltable electric furnace for smelting; b, after smelting is finished, tipping the molten slag into a casting ingot mold for secondary deep reduction of the molten slag, and cooling to obtain an alloy; reducing mixture is pre-added into the casting ingot mold; and c, after the slag is discharged, carrying out graded casting and cooling on the molten alloy liquid in the furnace to obtain the alloy. The method of the invention is beneficial to further recovering vanadium in the waste slag through secondary deep reduction of the slag; through the graded casting of the molten alloy, the cooling and stirring of the alloy in the casting process are facilitated, the appearance of a cast alloy cake is changed, and the later-stage crushing performance is improved.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for casting a ferrovanadium alloy.
Background
Ferrovanadium is the most widely used vanadium microalloyed master alloy in the steel industry. The vanadium-containing steel is widely applied to the industries of mechanical manufacturing, aerospace, road and bridge construction and the like, and the comprehensive performance of the steel is obviously improved due to the addition of vanadium. The industrialized ferrovanadium alloy is prepared by reducing vanadium-containing oxide and other vanadium-containing raw materials by using a reducing agent, and mutually dissolving the vanadium-containing oxide and other vanadium-containing raw materials in a solid solution state at a high temperature.
Most of the world's companies now adopt vanadium oxide (V)2O5/V2O3) Is prepared from raw materialsThe reducing agent (Al/Si) and the iron material are subjected to thermal reduction reaction to produce the ferrovanadium alloy, and part of the reduction smelting process adopts an electric heating mode to ensure the heat requirement of the reaction process. The production process also comprises a straight cylinder furnace one-step process and a tilting furnace multi-stage process respectively, and finally alloy products with qualified quality can be obtained.
CN102115821A provides a method for smelting ferrovanadium by a two-step method with metallic aluminum as a reducing agent, which comprises the steps of firstly reducing partial slag in the first smelting step, and then adding partial refining material into the primary alloy for refining to obtain a ferrovanadium alloy product. CN104532105A provides a method for producing ferrovanadium by using a large-scale tilting furnace electro-aluminothermic process, adopts a technology combining multi-stage smelting and stepped aluminum distribution, and has the characteristics of convenient operation, aluminum consumption saving and ferrovanadium yield improvement.
From the technologies disclosed above, at present, the main focus is on the preparation method and process of ferrovanadium, and few reports are made about the casting method and control method in the ferrovanadium smelting process.
Disclosure of Invention
The invention aims to provide a method for casting a ferrovanadium alloy, which can not only recover unreduced vanadium in slag, but also improve the crushing performance of the ferrovanadium alloy.
The technical scheme of the invention is as follows: a method for casting a ferrovanadium alloy comprises the following steps:
a, uniformly mixing smelting raw materials according to the requirements of a vanadium iron alloy product to be produced, and then adding the mixture into a tiltable electric furnace for smelting;
b, after smelting is finished, tipping the molten slag into a casting ingot mold for secondary deep reduction of the molten slag, and cooling to obtain an alloy; reducing mixture is pre-added into the casting ingot mold;
and c, after the slag is discharged, carrying out graded casting and cooling on the molten alloy liquid in the furnace to obtain the alloy.
In the step a of the casting method of the ferrovanadium alloy, the smelting raw materials comprise a vanadium-containing material, a reducing agent, iron and a slag former.
Wherein, the casting method of the ferrovanadium alloy comprises the following stepsThe vanadium-containing material is V2O5And/or V2O3(ii) a The reducing agent is aluminum or ferrosilicon; the slag former is calcium oxide or calcium salt.
In the method for casting the ferrovanadium alloy, the addition amount of the reducing agent is 0.9-1.05 times of the theoretical addition amount; the addition amount of the iron is 0.85-0.95 times of the theoretical addition amount; the addition amount of the slagging agent is 5-15% of the total slag weight.
In the step b, the smelting is finished by taking the reduction range of the vanadium content in the slag to be less than or equal to 0.2%/10min as a standard; or, the vanadium content in the slag is less than or equal to 3.5 percent.
In the casting method of the ferrovanadium alloy, in the step b, the reducing mixture is a mixture of a reducing agent and a slagging constituent; the reducing agent is aluminum or ferrosilicon; the slag former calcium oxide or calcium salt; the weight ratio of the slagging agent to the reducing agent is 1-2: 1.
in the step b, the addition amount of the reducing agent in the reduction mixture is 1.0-1.2 times of the theoretical addition amount.
In the step c of the method for casting the ferrovanadium alloy, the superheat degree of the molten alloy casting is more than or equal to 300 ℃.
In the step c, the step casting equipment is an iron ingot mold with an overflow port, and the ratio of the diameter to the height of the ingot mold is not less than 5: 1; preferably, the diameter-height ratio of the ingot mold is 5-9: 1.
in the step c, the step of casting the ferrovanadium alloy is that the ferrovanadium alloy is cast from one side of an upper layer ingot mold through an electric furnace, the ferrovanadium alloy gradually overflows from the other side of the upper layer ingot mold to one side of a second layer ingot mold along with the increase of the molten alloy in the upper layer ingot mold, the molten alloy overflows from the other side of the second layer ingot mold to one side of a third layer ingot mold after the capacity is increased, and the process is repeated until all the alloy in the furnace is cast.
Compared with the prior art, the invention has the beneficial effects that:
the method of the invention is beneficial to further recovering vanadium in the waste slag through secondary deep reduction of the slag; through the graded casting of the molten alloy, the cooling and stirring of the alloy in the casting process are facilitated, the appearance of a cast alloy cake is changed, and the later-stage crushing performance is improved. Meanwhile, the method is suitable for all raw materials and processes for preparing the ferrovanadium alloy by adopting thermal reduction.
Detailed Description
Specifically, the casting method of the ferrovanadium alloy comprises the following steps:
a, uniformly mixing smelting raw materials according to the requirements of a vanadium iron alloy product to be produced, and then adding the mixture into a tiltable electric furnace for smelting;
b, after smelting is finished, tipping the molten slag into a casting ingot mold for secondary deep reduction of the molten slag, and cooling to obtain an alloy; reducing mixture is pre-added into the casting ingot mold;
and c, after the slag is discharged, carrying out graded casting and cooling on the molten alloy liquid in the furnace to obtain the alloy.
Firstly, when smelting is finished, reducing mixture is pre-added in a casting ingot mould, and secondary mixing and dissolving of molten slag are carried out in the casting process, so that deep reduction of the reducing mixture and the molten alloy excess reducing agent with the molten slag is realized, the content of vanadium in casting slag is reduced, and reduction and efficient recovery of vanadium in the slag are realized; secondly, after slag discharging is finished, the molten alloy liquid in the furnace is subjected to graded casting and cooling, so that the appearance and the cooling effect of the cast alloy cake are changed, and the crushing performance of the alloy is favorably improved.
The slag discharging amount of the tilting slag discharging of the invention accounts for more than 100 percent of the total slag amount, namely, part of molten alloy is allowed to be discharged through the slag hole in the slag discharging process.
The theoretical addition amount of the vanadium-containing material is the theoretical reducing agent (aluminum and silicon iron) required by a unit vanadium-containing material (vanadium oxide) and the theoretical iron addition amount required to be added correspondingly when a certain standard grade of vanadium-iron alloy is obtained.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The fractional casting referred to in the following examples is mainly carried out from one side of the upper layer ingot mold through an electric furnace, gradually overflows from the other side of the ingot mold to one side of the second layer ingot mold as the molten alloy in the upper layer ingot mold increases, overflows from the other side of the second layer ingot mold to one side of the third layer ingot mold as the capacity increases, and the process is repeated until all the alloy in the furnace is cast.
Example 1
Adding aluminum and iron in an amount of 0.9 times and 0.85 times the theoretical amount, respectively, adding lime in an amount of 15% of the total amount of slag, and mixing with vanadium oxide (V)2O5And V2O3The weight ratio of 1:1) are evenly mixed and then added into a smelting electric furnace, and electrode arc striking is adopted for smelting operation; when the vanadium content in the slag is reduced to 1.5 percent, the smelting is finished, the slag in the electric furnace is overturned to a casting ingot mold which is pre-added with a reducing mixture (the weight ratio of aluminum to lime is 1:1, and the dosage of aluminum is 1.0 time of the theoretical addition), the secondary deep reduction of the slag is carried out, and the obtained primary alloy cake is recovered; after deslagging, carrying out graded casting and cooling on molten alloy liquid in the electric furnace by adopting an ingot mold with a diameter-height ratio of 5:1 under the condition that the superheat degree is 300 ℃ to obtain a plurality of alloy thin cakes; and after the casting is finished, collecting the primary alloy cakes obtained by secondary reduction and the alloy cakes obtained by fractional casting, and transferring all the alloy cakes to a cooling crushing area for rapid cooling and crushing to obtain alloy finished products with qualified sizes and components.
Through the operation, the vanadium content in the ferrovanadium smelting waste slag is 2.5 percent, the primary alloy cake accounts for 1:4 of the total alloy by weight, and the ferrovanadium fine powder rate is 16.8 percent.
Example 2
Adding aluminum and iron according to the theoretical addition amount of 1.0 time and 0.90 time respectively, adding lime according to 10% of the total slag amount, and mixing with vanadium oxide (V)2O5And V2O3The weight ratio of 2:1) are evenly mixed and then added into a smelting electric furnace, and electrode arc striking is adopted for smelting operation; when the vanadium content in the slag is reduced to 3.5 percent, the smelting is finished, the slag in the electric furnace is overturned to a casting ingot mold which is pre-added with a reducing mixture (the weight ratio of aluminum to lime is 1:1, and the dosage of aluminum is 1.1 times of the theoretical addition), the secondary deep reduction of the slag is carried out, and the obtained primary alloy cake is recovered; after the slag discharge is finished, the diameter is adoptedCarrying out graded casting and cooling on molten alloy liquid in an electric furnace by an ingot mould with a height ratio of 7:1 under the condition that the superheat degree is 300 ℃ to obtain a plurality of alloy wafers; and after the casting is finished, collecting the primary alloy cakes obtained by secondary reduction and the alloy cakes obtained by fractional casting, and transferring all the alloy cakes to a cooling crushing area for rapid cooling and crushing to obtain alloy finished products with qualified sizes and components.
Through the operation, the vanadium content in the ferrovanadium smelting waste slag is 0.8 percent, the primary alloy cake accounts for 1:9 of the total alloy by weight, and the ferrovanadium fine powder rate is 13.5 percent.
Example 3
Adding aluminum and iron according to the theoretical addition amount of 1.05 times and 0.95 time respectively, adding lime according to 5 percent of the total slag amount, and mixing with V2O5After being uniformly mixed, the mixture is added into a smelting electric furnace, and smelting operation is carried out by adopting electrode arc striking; when the vanadium content in the slag is reduced to 1.5 percent, the smelting is finished, the slag in the electric furnace is overturned to a casting ingot mold which is pre-added with a reducing mixture (the weight ratio of aluminum to lime is 1:2, and the dosage of aluminum is 1.2 times of the theoretical addition), the secondary deep reduction of the slag is carried out, and the obtained primary alloy cake is recovered; after deslagging, carrying out graded casting and cooling on molten alloy liquid in the electric furnace by adopting an ingot mold with a diameter-height ratio of 9:1 under the condition that the superheat degree is 300 ℃ to obtain a plurality of alloy thin cakes; and after the casting is finished, collecting the primary alloy cakes obtained by secondary reduction and the alloy cakes obtained by fractional casting, and transferring all the alloy cakes to a cooling crushing area for rapid cooling and crushing to obtain alloy finished products with qualified sizes and components.
Through the operation, the vanadium content in the ferrovanadium smelting waste slag is 0.5 percent, the primary alloy cake accounts for 1:11 of the total alloy by weight, and the ferrovanadium fine powder rate is 11.4 percent.
Example 4
Adding ferrosilicon and iron according to 0.9 time and 0.85 time of theoretical addition amount respectively, adding lime according to 5% of total slag amount, and mixing with V2O5After being uniformly mixed, the mixture is added into a smelting electric furnace, and smelting operation is carried out by adopting electrode arc striking; when the vanadium content in the slag is reduced to 1.5%, the smelting is finished, and the slag in the electric furnace is overturned to be pre-added with a reducing mixture (the weight ratio of the ferrosilicon to the lime is1:1, the dosage of the ferrosilicon is 1.0 times of the theoretical addition), carrying out secondary deep reduction on the molten slag in a casting ingot mold, and recovering the obtained primary alloy cake; after deslagging, carrying out graded casting and cooling on molten alloy liquid in the electric furnace by adopting an ingot mold with a diameter-height ratio of 5:1 under the condition that the superheat degree is 300 ℃ to obtain a plurality of alloy thin cakes; and after the casting is finished, collecting the primary alloy cakes obtained by secondary reduction and the alloy cakes obtained by fractional casting, and transferring all the alloy cakes to a cooling crushing area for rapid cooling and crushing to obtain alloy finished products with qualified sizes and components.
Through the operation, the vanadium content in the ferrovanadium smelting waste slag is 2.8 percent, the primary alloy cake accounts for 1:5 of the total alloy by weight, and the ferrovanadium fine powder rate is 18.5 percent.
Example 5
Adding ferrosilicon and iron according to the theoretical addition amount of 1.05 times and 0.95 time respectively, adding lime according to 5 percent of the total slag amount, and mixing with V2O5After being uniformly mixed, the mixture is added into a smelting electric furnace, and smelting operation is carried out by adopting electrode arc striking; when the vanadium content in the slag is reduced to 1.5 percent, the smelting is finished, the slag in the electric furnace is overturned to a casting ingot mold which is pre-added with a reducing mixture (the weight ratio of the ferrosilicon to the lime is 1:2, and the using amount of the ferrosilicon is 1.2 times of the theoretical adding amount) for secondary deep reduction of the slag, and the obtained primary alloy cake is recovered; after deslagging, carrying out graded casting and cooling on molten alloy liquid in the electric furnace by adopting an ingot mold with a diameter-height ratio of 9:1 under the condition that the superheat degree is 300 ℃ to obtain a plurality of alloy thin cakes; and after the casting is finished, collecting the primary alloy cakes obtained by secondary reduction and the alloy cakes obtained by fractional casting, and transferring all the alloy cakes to a cooling crushing area for rapid cooling and crushing to obtain alloy finished products with qualified sizes and components.
Through the operation, the vanadium content in the ferrovanadium smelting waste slag is 0.6 percent, the primary alloy cake accounts for 1:10 of the total alloy by weight, and the ferrovanadium fine powder rate is 13.1 percent.
Claims (6)
1. The casting method of the ferrovanadium alloy is characterized by comprising the following steps:
a, uniformly mixing smelting raw materials according to the requirements of a vanadium iron alloy product to be produced, and then adding the mixture into a tiltable electric furnace for smelting;
b, after smelting is finished, tipping the molten slag into a casting ingot mold for secondary deep reduction of the molten slag, and cooling to obtain an alloy; reducing mixture is pre-added into the casting ingot mold; the reducing mixture is a mixture of a reducing agent and a slagging constituent; the reducing agent is aluminum or ferrosilicon; the slag former calcium oxide or calcium salt; the weight ratio of the slagging agent to the reducing agent is 1-2: 1; the vanadium content reduction amplitude in the slag is less than or equal to 0.2%/10min as a standard after smelting is finished; or, the vanadium content in the slag is less than or equal to 3.5 percent as a standard;
c, after the slag is discharged, carrying out graded casting and cooling on the molten alloy liquid in the furnace to obtain an alloy; the equipment for graded casting is an iron ingot mould with an overflow port, and the ratio of the diameter to the height of the ingot mould is more than or equal to 5: 1; and the step casting is to carry out casting from one side of an upper layer ingot mould through an electric furnace, gradually overflow from the other side of the ingot mould to one side of a second layer ingot mould along with the increase of the molten alloy in the upper layer ingot mould, overflow from the other side of the second layer ingot mould to one side of a third layer ingot mould after the capacity is increased, and the process is circulated until all the alloy in the furnace is cast completely.
2. The method for casting a ferrovanadium alloy according to claim 1, wherein: in the step a, the smelting raw materials comprise vanadium-containing materials, reducing agents, iron and slag formers.
3. The method for casting a ferrovanadium alloy according to claim 2, wherein: the vanadium-containing material is V2O5And/or V2O3(ii) a The reducing agent is aluminum or ferrosilicon; the slag former is calcium oxide or calcium salt.
4. The method for casting a ferrovanadium alloy according to claim 2, wherein: the addition amount of the reducing agent is 0.9-1.05 times of the theoretical addition amount; the addition amount of the iron is 0.85-0.95 time of the theoretical addition amount; the addition amount of the slagging agent is 5-15% of the total slag weight.
5. The method for casting a ferrovanadium alloy according to claim 1, wherein: in the step b, the addition amount of the reducing agent in the reduced mixture is 1.0-1.2 times of the theoretical addition amount.
6. The method for casting a ferrovanadium alloy according to claim 1, wherein: in the step c, the superheat degree of the molten alloy casting is more than or equal to 300 ℃.
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| CN111778423B (en) * | 2020-08-17 | 2022-05-24 | 攀钢集团研究院有限公司 | Ferrovanadium slag refining agent, preparation method thereof and slag vanadium removal method |
| CN114293043A (en) * | 2021-11-19 | 2022-04-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for smelting ferrovanadium alloy by ferrosilicon |
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| CN109295316A (en) * | 2018-12-05 | 2019-02-01 | 盐边县向阳钒业有限公司 | The recovery process of vanadium in vanadium containing steel slag |
| AU2018247275A1 (en) * | 2017-10-13 | 2019-05-02 | TiMAG Technologies Pty Ltd | Processing of impure titanium dioxide ore |
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2020
- 2020-03-02 CN CN202010137567.9A patent/CN111218557B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| JPH0144772B2 (en) * | 1981-10-31 | 1989-09-29 | Kawasaki Steel Co | |
| CN101148733A (en) * | 2006-09-21 | 2008-03-26 | 攀枝花新钢钒股份有限公司 | Vanadium iron spraying powder refining technique |
| CN102051519A (en) * | 2011-01-21 | 2011-05-11 | 河北钢铁股份有限公司承德分公司 | Lean slag process in vanadium iron smelting and special device |
| CN105112594A (en) * | 2015-09-23 | 2015-12-02 | 攀钢集团西昌钢钒有限公司 | Method of using tilting furnace to smelt ferrovanadium |
| AU2018247275A1 (en) * | 2017-10-13 | 2019-05-02 | TiMAG Technologies Pty Ltd | Processing of impure titanium dioxide ore |
| CN109295316A (en) * | 2018-12-05 | 2019-02-01 | 盐边县向阳钒业有限公司 | The recovery process of vanadium in vanadium containing steel slag |
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