CN109576558B - Method for recovering valuable components in vanadium slag - Google Patents
Method for recovering valuable components in vanadium slag Download PDFInfo
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- CN109576558B CN109576558B CN201811366091.5A CN201811366091A CN109576558B CN 109576558 B CN109576558 B CN 109576558B CN 201811366091 A CN201811366091 A CN 201811366091A CN 109576558 B CN109576558 B CN 109576558B
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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
- 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
- C22B7/001—Dry processes
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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
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
Abstract
The invention discloses a method for recovering valuable components in vanadium slag, belongs to the field of metallurgy, and relates to a method for recovering Fe-V-Mn alloy in molten vanadium slag by using aluminum ash through reduction.
Description
Technical Field
The invention relates to comprehensive utilization of metallurgical solid waste resources, in particular to a vanadium slag treatment method, and belongs to the field of metallurgy.
Background
Vanadium is an important strategic material and is widely applied to the industrial fields of steel, chemistry, aerospace and the like. With the acceleration of the global economy integration process and the rapid development of the market economy of China, the demand of vanadium products is increasingly strong. The vanadium resource in China is mainly associated with elements such as iron and the like in nature and is present in vanadium titano-magnetite, and the vanadium resource in China accounts for about 45 percent. At present, the vanadium-titanium magnetite processing technology in China mainly realizes vanadium extraction of vanadium from vanadium-containing iron concentrate through a blast furnace-converter-vanadization process, wherein the vanadium-containing iron concentrate is reduced in a blast furnace to form molten iron containing about 0.3 percent of vanadium, and the vanadium-containing molten iron is blown and oxidized by a converter to obtain V2O312 to 18 percent of vanadium slag. For vanadium smelting and extraction, the quality of vanadium slag is closely related to the energy consumption, smelting efficiency, product quality, waste discharge and the like of a subsequent wet vanadium extraction process. The slag temperature of the vanadium slag is 1450-1500 ℃, the physical sensible heat of the vanadium slag is about 0.70 GJ/ton, and non-vanadium-containing oxides in the slag have negative effects on wet-process vanadium extraction, so that the grade of the vanadium slag needs to be improved as much as possible during the wet-process vanadium extraction, the content of other oxides needs to be reduced, the leaching rate and the yield of vanadium are improved, and the consumption of sodium salt and the discharge amount of wastes are reduced. In view of this, a large number of researchers have optimized the converter vanadium extraction process, and the development of the work has very important reference value and guiding significance for the progress of the vanadium extraction technology in China, and part of research results are applied in industry, so that the cost is reduced, the smelting efficiency and the vanadium yield are improved, but the improvement effect on the grade of the converter vanadium slag is very slight, and meanwhile, other valuable elements such as iron, manganese, vanadium and the like in the slag are not effectively recycled.
The aluminum ash is a product of cooling slag generated in the production process of electrolytic aluminum or cast aluminum, and comprises 15-30% of metallic aluminum and 30-60% of Al2O3And a small amount of SiO2Oxygen such as CaO and MgOAnd (4) melting the mixture. In the aluminum smelting process, about 11-12 kg of aluminum ash is generated in each ton of aluminum liquid. According to the fluctuation of components, the price of the aluminum ash is about 1000 yuan/ton, and the aluminum ash is currently used for recovering metal aluminum, synthetic materials (such as polyaluminium chloride, brown fused alumina and building materials), electric furnace smelting desulfurization and the like. However, these treatments require additional facilities, such as aluminum and Al2O3And is not fully utilized.
Therefore, a new technology for recycling valuable components and physical heat in the vanadium slag and the aluminum ash is developed, iron, manganese and vanadium resources in the vanadium slag and the aluminum ash are fully recycled, development and utilization of secondary resources are facilitated, environment-friendly and sustainable-development green and harmonious metallurgical enterprises are built, and a new method is provided for resource utilization of the vanadium slag and the aluminum ash of the enterprises.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for recovering valuable components in vanadium slag, which can effectively recover iron, manganese and vanadium resources in the vanadium slag, can recycle the generated tailings, realizes the comprehensive utilization of the vanadium slag and aluminum ash resources, takes the ecological characteristics of resources and energy into consideration, and has the advantages of simple process, low production cost, energy conservation, emission reduction and zero pollution.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for recovering valuable components in molten vanadium slag by aluminum ash reduction.
The technical scheme of the invention is further improved as follows: the method comprises the following steps:
A. raw material preparation and charging: preparing molten vanadium slag, reducing agent aluminum ash and modifier lime, firstly, putting a certain amount of aluminum ash and lime into a heating reduction furnace according to a proportion, and then pouring the molten vanadium slag into the heating reduction furnace;
B. heating and reducing: after the charging is finished, heating and preserving heat to reduce the valuable components in the aluminum ash and the vanadium slag to obtain Fe-V-Mn alloy with high added value;
C. slagging off and alloy discharging: discharging the alloy after the tailings in the furnace are completely discharged, and closing the heating system.
The technical scheme of the invention is further improved as follows: in the step A, the adding amount of the reducing agent aluminum ash is 60-75% of the total weight of the vanadium slag, and the granularity of the aluminum ash is less than or equal to 100 meshes.
The technical scheme of the invention is further improved as follows: in the step A, the addition amount of the modifier lime is 15-20% of the total weight of the vanadium slag, and the granularity of the lime is less than or equal to 100 meshes.
The technical scheme of the invention is further improved as follows: in the step B, the heating temperature is 1450-1500 ℃, and the heat preservation time is 1.5-2 hours.
The technical scheme of the invention is further improved as follows: the vanadium slag is molten vanadium slag, and the heating and reducing furnace is an electric furnace.
Due to the adoption of the technical scheme, the invention has the technical progress that:
1. the invention provides a method for comprehensively recycling valuable components in vanadium slag and aluminum ash, which can effectively recycle iron, manganese and vanadium resources in the vanadium slag and the aluminum ash and generate Fe-V-Mn alloy with high added value, and compared with the traditional production process of ferroalloy, the method not only reduces energy consumption and reduces waste and noise pollution, but also recycles generated tailings, realizes comprehensive utilization of the vanadium slag and the aluminum ash resources, takes ecological characteristics of resources and energy into consideration, and has the advantages of simple process, low production cost, energy conservation, emission reduction and zero pollution;
2. the basicity of the vanadium slag is lower than 0.5, and a large amount of fayalite, titanium-iron spinel, vanadium-iron spinel and free SiO exist2With FeO and V in the vanadium slag2O3The reduction of MnO content, the sharp increase of melting point and viscosity of vanadium slag are not beneficial to the reaction, and the modifier lime added before reduction can generate CaO & SiO with low melting point2The physical and chemical properties of the vanadium slag are improved; in addition, the aluminum ash is used as a reducing agent, so that not only can metallic aluminum in the aluminum ash be fully utilized, but also the generated Al2O3Forming low melting point oxide (12CaO 7 Al) with CaO2O3、CaO·Al2O3·2SiO2、2CaO·Al2O3·SiO2) Can further improve the physical and chemical properties of the vanadium slag and is beneficial to the valuable oxides in the slagReduction of (2);
3. the vanadium slag is molten vanadium slag, the self physical heat of the molten slag is fully utilized, the energy consumption is low, the production efficiency is improved, the added value of the produced Fe-V-Mn alloy is higher, and the production cost is obviously reduced compared with the traditional ferroalloy production process;
4. when the particle size of the modifier and the reducer is less than or equal to 100 meshes, the contact area of solid and liquid is increased, the reaction can be rapidly carried out, valuable elements such as iron, manganese, vanadium and the like in the vanadium slag can be reduced to the maximum extent, valuable resources in the vanadium slag can be efficiently recovered, if the particle size is too large, the reaction is not facilitated, and if the particle size is too small, more energy is consumed during crushing;
5. the heating and reducing furnace adopts an electric furnace, does not need additional equipment, and has the advantages of convenience, feasibility, high heating speed, environmental protection and the like;
6. the main component in the tailings is CaO-Al2O3-SiO2-TiO2The content of the quaternary oxide is as high as more than 90 percent, and the quaternary oxide can be used as a raw material for titanium extraction and cement production and a metallurgy return material for secondary recycling, so that the problem of waste residue occupying area is effectively solved, and waste is changed into valuable;
7. the raw material applicability is strong, the method is applicable to various types of vanadium slag and aluminum ash, the recovery rate of iron, vanadium and manganese is high and reaches more than 90%, and the high-efficiency cyclic utilization of resources is realized.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
a method for recovering valuable components in vanadium slag by utilizing aluminum ash to recover the valuable components in molten vanadium slag through reduction comprises the following steps:
A. raw material preparation and charging: preparing molten vanadium slag, reducing agent aluminum ash and modifier lime, firstly, proportionally filling a certain amount of aluminum ash and lime into a heating and reducing furnace, wherein the heating and reducing furnace is an electric furnace, does not need additional equipment, has high heating speed, and then pouring the molten vanadium slag, and is beneficial to uniformly mixing the components of the lime, the aluminum ash and the molten vanadium slag in the pouring process;
the addition amount of the reducer aluminum ash is vanadium slag60-75% of the total weight, not only can make full use of metal aluminum in the aluminum ash, but also can generate Al2O3Can generate low-melting point oxide (12CaO 7 Al) with CaO2O3、CaO·Al2O3·2SiO2、2CaO·Al2O3·SiO2) The physical and chemical properties of the vanadium slag can be improved, and the reduction of the valuable oxides in the slag is facilitated;
the addition amount of the modifier lime is 15-20% of the total weight of the vanadium slag, and the modifier lime and free SiO in the vanadium slag2Can generate CaO and SiO with low melting point2The physical and chemical properties of the vanadium slag are improved;
the following reactions occur in the vanadium slag during the whole reduction process:
CaO+SiO2＝CaO·SiO2 (1)
3CaO+Al2O3＝3CaO·Al2O3 (2)
12CaO+7Al2O3＝12CaO·7Al2O3 (3)
CaO+Al2O3+2SiO2＝CaO·Al2O3·2SiO2 (4)
2CaO+Al2O3+SiO2＝2CaO·Al2O3·SiO2 (5)
3FexO+2Al＝3xFe+Al2O3 (6)
3V2O5+10Al＝6V+5Al2O3 (7)
3MnO+2Al＝3Mn+Al2O3 (8)
the particle sizes of the lime and the aluminum ash are both less than or equal to 100 meshes, so that the solid-liquid contact area is increased, the reaction is favorably and quickly carried out, if the particle size is too large, the reaction is not favorably carried out, and if the particle size is too small, more energy is consumed during crushing;
B. heating and reducing: after the charging is finished, heating and preserving heat, wherein the heating temperature is 1450-1500 ℃, and the heat preservation time is 1.5-2 hours, so that valuable components in the aluminum ash and the vanadium slag are reduced, and the Fe-V-Mn alloy with high added value is obtained;
C. slagging off and alloy discharging: discharging the tailings in the furnace, discharging the alloy, closing the heating system, wherein the main component in the tailings is CaO-Al2O3-SiO2-TiO2The quaternary system with the quaternary oxide content of more than 90 percent can be used as raw materials and metallurgy return materials for titanium extraction, cement and glass production for secondary recycling.
Example 1:
the vanadium slag of the No. 1 melting converter comprises the following components of TFe 37.00 percent, MFe 14.00 percent, FeO 29.57 percent and V2O517.32％，SiO2 16.23％，MnO 10.28％，TiO28.43 percent, and the other 4.17 percent; the aluminum ash 1 component is SiO25.42％，Al2O3 38.53％，Al 28.25％，(FeO+Fe2O3)0.74％，CaO 1.52％，MgO 2.52％，Na2O2.82%, MnO 0.86%, others 19.34%.
The method for comprehensively recycling the valuable components of the vanadium slag and the aluminum ash comprises the following steps:
A. raw material preparation and charging: preparing molten vanadium slag, lime and aluminum ash, firstly adding the lime and the aluminum ash into an electric furnace, and then pouring the molten vanadium slag, wherein the adding amount of the lime and the aluminum ash is respectively 15 percent and 70 percent of the total weight of the vanadium slag, and the granularity is less than or equal to 100 meshes.
B. Heating and reducing: after the charging is finished, the electric furnace is heated to 1500 ℃, the temperature is kept for 1.5 hours, and the valuable components of iron, manganese and vanadium in the aluminum ash and the vanadium slag are reduced to obtain the Fe-V-Mn alloy with high added value.
C. Slagging off and alloy discharging: discharging the alloy after the tailings in the furnace are completely discharged, and closing the heating system.
Examples 1 to 3 and comparative examples 1 to 3 used a # 1 molten converter vanadium slag, examples 4 to 6 and comparative examples 4 to 6 used a # 2 molten converter vanadium slag, the composition table of the # 1 and # 2 molten converter vanadium slag is shown in table 1, examples 1, 2, 4, 5 and comparative examples 1, 2, 4, 5 used aluminum ash 1, examples 3, 6 and comparative examples 3, 6 used aluminum ash 2, the composition table of aluminum ash 1 and aluminum ash 2 is shown in table 2, and tables 3 and 4 respectively show the content and yield of different examples and different comparative examples.
TABLE 1 composition table of different vanadium slag
TABLE 2 composition of different types of aluminum ashes
Table 3 table of different embodiments
Table 4 table of different comparative examples
Comparing table 3 and table 4 one can obtain: compared with the embodiment 1, the lime accounts for 15 percent to 10 percent of the total weight of the vanadium slag, compared with the embodiment 3, the lime accounts for 20 percent to 25 percent of the total weight of the vanadium slag, and the yield of iron, manganese and vanadium is rapidly reduced, so that the proper amount of the modifier is beneficial to improving the physical and chemical properties (viscosity and melting point) of the slag, and the reaction kinetic condition is good. According to the method, when the lime accounts for 15-20% of the total weight of the vanadium slag, the yield of iron, manganese and vanadium reaches over 90%, and the best effect is obtained.
Compared with the embodiment 2, the aluminum ash accounts for 75 to 85 percent of the total weight of the vanadium slag, and compared with the embodiment 4, the aluminum ash accounts for 60 to 50 percent of the total weight of the vanadium slag, and the yield of iron, manganese and vanadium is rapidly reduced, mainly because when the content of the aluminum ash is higher, a high-melting-point compound is generated, which is not beneficial to the reaction, and when the content of the aluminum ash is lower, the reducing agent is not enough, so that the yield of iron, manganese and vanadium reaches more than 90 percent, and the obtained effect is the best when the content of the aluminum ash accounts for 60 to 75 percent of the total weight of the vanadium slag.
Compared with the example 4, when the temperature is reduced from 1450 ℃ to 1300 ℃, the yields of iron, manganese and vanadium are all rapidly reduced, which is mainly that the temperature is too low to be beneficial to the reduction of vanadium and manganese; in comparison with example 6, the temperature was increased from 1500 ℃ to 1600 ℃ and the yield of fe, mn, and v was increased, but not much, and the temperature was increased by 100 ℃ and the power consumption of the electric furnace was increased much, so that the yield of fe, mn, and v was the best and the power consumption was low at 1450 ℃ to 1500 ℃.
Claims (3)
1. A method for recovering valuable components in vanadium slag is characterized by comprising the following steps: a method for recovering Fe-V-Mn alloy in molten vanadium slag by aluminum ash reduction;
the method comprises the following steps:
A. raw material preparation and charging: preparing molten vanadium slag, reducing agent aluminum ash and modifier lime, firstly, putting a certain amount of aluminum ash and lime into a heating reduction furnace according to a proportion, and then pouring the molten vanadium slag into the heating reduction furnace;
B. heating and reducing: after the charging is finished, heating and preserving heat to reduce the valuable components in the aluminum ash and the vanadium slag to obtain Fe-V-Mn alloy with high added value;
C. slagging off and alloy discharging: discharging alloy after completely discharging the tailings in the furnace, and closing a heating system;
in the step B, the heating temperature is 1450-1500 ℃, and the heat preservation time is 1.5-2 hours;
the vanadium slag is molten vanadium slag, and the heating and reducing furnace is an electric furnace;
v in molten vanadium slag2O3The content of (A) is 12-18%, the components of the aluminum ash are 15-30% of metallic aluminum and 30-60% of Al2O3And a small amount of SiO2CaO and MgO oxides, and the recovery rate of V in the obtained Fe-V-Mn alloy is more than 92 percent.
2. The method for recovering valuable components in vanadium slag according to claim 1, which is characterized in that: in the step A, the adding amount of the reducing agent aluminum ash is 60-75% of the total weight of the vanadium slag, and the granularity of the aluminum ash is less than or equal to 100 meshes.
3. The method for recovering valuable components in vanadium slag according to claim 1, which is characterized in that: in the step A, the addition amount of the modifier lime is 15-20% of the total weight of the vanadium slag, and the granularity of the lime is less than or equal to 100 meshes.
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| RU2299921C2 (en) * | 2005-06-27 | 2007-05-27 | ОАО "Уральский институт металлов" | Method of producing complex foundry alloys from converter vanadium slag |
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| CN1026501C (en) * | 1991-10-17 | 1994-11-09 | 承德钢铁厂 | Directly alloying process in vanadium slag furnace |
| CN102115821B (en) * | 2010-09-13 | 2013-01-23 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN102094097B (en) * | 2011-03-04 | 2013-01-09 | 攀钢集团钢铁钒钛股份有限公司 | Production process for smelting vanadium ferro-alloy by electro-aluminothermic process |
| CN103045929B (en) * | 2012-12-31 | 2015-12-23 | 攀钢集团西昌钢钒有限公司 | Electro-aluminothermic process produces the method for vanadium iron |
| CN103397208B (en) * | 2013-07-11 | 2015-04-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Process for smelting ferro-vanadium through electro-aluminothermic method |
| CN106350674A (en) * | 2015-07-16 | 2017-01-25 | 东北大学 | Preparation method of high-quality AlV85 alloy |
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