CN109576558A - The recovery method of valuable constituent element in a kind of vanadium slag - Google Patents
The recovery method of valuable constituent element in a kind of vanadium slag Download PDFInfo
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- CN109576558A CN109576558A CN201811366091.5A CN201811366091A CN109576558A CN 109576558 A CN109576558 A CN 109576558A CN 201811366091 A CN201811366091 A CN 201811366091A CN 109576558 A CN109576558 A CN 109576558A
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- vanadium slag
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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
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Environmental & Geological Engineering (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of recovery methods of valuable constituent element in vanadium slag, belong to field of metallurgy, it is a kind of method that the Fe-V-Mn alloy in recycling melting vanadium slag is restored using aluminium ash, the present invention can be such that vanadium slag, the valuable resources such as iron, vanadium, manganese in aluminium ash is effectively recycled, the tailings generated simultaneously can also recycle, the comprehensive utilization for realizing vanadium slag resource takes into account " resource+energy " ecology characteristic, has the advantages that low simple process, production cost, energy-saving and emission-reduction, no pollution.
Description
Technical field
The present invention relates to the comprehensive utilization of metallurgical solid waste resource, especially a kind of processing method of vanadium slag belongs to
Field of metallurgy.
Background technique
Vanadium is important strategic materials, is widely used in the industrial circles such as steel, chemistry, aerospace.As the whole world passes through
The quickening for the process of integration of helping and the rapid development of China market economy, the demand of vanadium product are further strong.China's vanadium resource exists
Mainly account for about the 45% of China's vanadium resource in vanadium titano-magnetite with elements association, preservations such as iron in nature.China's vanadium at present
The treatment process of titanomagnetite is mainly the extraction that will contain vanadium iron concentrate and realize vanadium by blast furnace-converter-vanadium process, wherein
Concentrate containing vanadium iron enters blast furnace and restores to form the molten iron containing vanadium 0.3% or so, and vanadium-bearing hot metal obtains V through bessemerizing oxidation2O3For
12%~18% vanadium slag.For to vanadium smelting and extracting, the energy consumption of the quality of vanadium slag and postorder wet process process for extracting vanadium is smelted
Efficiency, the quality of product, the discharge etc. of waste are closely bound up.Vanadium slag tapping temperature is at 1450~1500 DEG C, physical sensible heat
About 0.70GJ/ tons, and the non-barium oxide that contains has negative effect to wet process vanadium extraction in slag, therefore needs to the greatest extent in wet process vanadium extraction
Amount improves v slag grade, reduces other oxide contents, to improve the leaching rate and recovery rate of vanadium, reduces the dosage of sodium salt and gives up
The discharge amount of gurry.In consideration of it, vanadium extraction by converter blowing technique is optimized in a large number of researchers, the development of these work, to China
The progress of vanadium extractive technique has very important reference value and directive significance, and part research achievement industrially carries out
Application, reduces costs, improves efficiency and vanadium recovery rate, but produce little effect to the raising of Converter Vanadium-bearing Slag grade, together
When slag in other valuable elements such as iron, manganese, vanadium do not recycled effectively.
Aluminium ash is electrolytic aluminium or casts product of the slag generated in aluminium production technology after cooling processing, and ingredient is
15%~30% metallic aluminium, 30~60% Al2O3And a small amount of SiO2, the oxides such as CaO, MgO.In aluminium fusion process, often
Ton molten aluminum about generates 11~12kg aluminium ash.It is fluctuated according to ingredient, the price of aluminium ash at 1000 yuan/ton or so, use by aluminum current ash
In recycling metallic aluminium, synthetic material (such as aluminium polychloride, Brown Alundum, construction material), electric furnace smelting desulfurization.But these are handled
Method will not only increase additional facility, wherein metallic aluminium and Al2O3Fail to make full use of.
Therefore, carry out a kind of vanadium slag, the new technology that valuable constituent element and physical thermal recycle in aluminium ash, sufficiently recycling wherein
Iron, manganese, vanadium resource, not only improve the development and utilization of secondary resource, and are conducive to the green of built environment close friend, sustainable development
Harmonious smelter provides a kind of new method for the resource utilization of enterprise's vanadium slag, aluminium ash.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of recovery methods of valuable constituent element in vanadium slag, can make vanadium slag
In iron, manganese, vanadium resource effectively recycled, while the tailings generated can also recycle, and realize vanadium slag, aluminium ash resource
Comprehensive utilization, takes into account " resource+energy " ecology characteristic, and with simple process, production cost is low, energy-saving and emission-reduction, no pollution
Advantage.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
The method for restoring valuable constituent element in recycling melting vanadium slag using aluminium ash.
Technical solution of the present invention further improvement lies in that: include the following steps:
A. raw material preparation and charging: preparing melting vanadium slag, reducing agent aluminium ash and modification agent lime, first by quantitative aluminium ash and
Lime is packed into Heating Reduction Furnace for Tungsten in proportion, then melting vanadium slag is poured into；
B. heating reduction: after charging, heating and keep the temperature, and makes aluminium ash, the valuable constituent element reduction in vanadium slag, obtains high attached
Value added Fe-V-Mn alloy；
C. it skims, go out alloy: after emptying the tailings in furnace, releasing alloy, close heating system.
Technical solution of the present invention further improvement lies in that: in step A the additional amount of reducing agent aluminium ash be vanadium slag total weight
60~75%, and the granularity of aluminium ash≤100 mesh.
Technical solution of the present invention further improvement lies in that: in step A the additional amount of modification agent lime be vanadium slag total weight
15%~20%, and the granularity of lime≤100 mesh.
Technical solution of the present invention further improvement lies in that: heating temperature is 1450 DEG C~1500 DEG C, when heat preservation in step B
Between be 1.5~2 hours.
Technical solution of the present invention further improvement lies in that: the vanadium slag be melting vanadium slag, Heating Reduction Furnace for Tungsten is electric furnace.
By adopting the above-described technical solution, the technological progress achieved by the present invention is:
1, the present invention provides a kind of method of valuable constituent element comprehensive reutilization in vanadium slag, aluminium ash, vanadium slag, aluminium can be made
Iron, manganese, vanadium resource in ash are effectively recycled, and the Fe-V-Mn alloy of high added value, the life relative to traditional ferroalloy are generated
Production. art not only reduces energy consumption, reduces waste and noise pollution, while the tailings generated is recycled, realizes
The comprehensive utilization of vanadium slag, aluminium ash resource, takes into account " resource+energy " ecology characteristic, have simple process, production cost it is low,
The advantages of energy-saving and emission-reduction, no pollution；
2, vanadium slag alkalinity it is lower less than 0.5, and there are a large amount of fayalite, ulvospinel, vanadium iron spinelle and
Free SiO2, with FeO, V in vanadium slag2O3, MnO content reduction, the fusing point of vanadium slag sharply increases with viscosity, is unfavorable for reacting
Progress, and the modification agent lime that is added before reduction produces the CaOSiO of low melting point2, improve the physical and chemical performance of vanadium slag；
In addition, using aluminium ash as reducing agent, the metallic aluminium in aluminium ash, and the Al generated can be not only made full use of2O3Eutectic is generated with CaO
Point oxide (12CaO7Al2O3、CaO·Al2O3·2SiO2、2CaO·Al2O3·SiO2) it can further improve the object of vanadium slag
Change performance, is conducive to the reduction of valuable oxide in slag；
3, vanadium slag is melting vanadium slag, takes full advantage of the own physical heat of slag, low energy consumption, improves production efficiency, raw
The Fe-V-Mn alloy added value of production is higher, and production cost is significantly reduced compared with conventional iron alloy production technique；
4, when the granularity of modification agent and reducing agent≤100 mesh, the contact area of solid-liquid is increased, is conducive to the quick of reaction
It carries out, the valuable elements such as iron, manganese, vanadium in vanadium slag can be reduced to the maximum extent, efficiently recycle the valuable money in vanadium slag
Source is unfavorable for the progress of reaction, granularity is too small, then more energy need to be expended when crushing if granularity is too big；
5, Heating Reduction Furnace for Tungsten uses electric furnace, does not need another oil (gas) filling device, and feasible with facilitating, heating speed is fast, and environmental protection etc. is excellent
Point；
6, the main component in tailings is CaO-Al2O3-SiO2-TiO2Quaternary system, and quaternary oxide content is up to
90% or more, it can be used as and propose titanium, the raw material of manufacture of cement and metallurgical returning charge, carry out secondary cycle utilization, effectively solve waste residue and account for
The problem of ground, realizing turns waste into wealth；
7, adaptability to raw materials is strong, is applicable to various types of vanadium slags and aluminium ash, iron, vanadium, the rate of recovery of manganese are higher, up to
90% or more, the efficient circulation for realizing resource utilizes.
Specific embodiment
The present invention is described in further details below with reference to embodiment:
The recovery method of valuable constituent element in a kind of vanadium slag utilizes the valuable constituent element in aluminium ash reduction recycling melting vanadium slag, packet
Include following steps:
A. raw material preparation and charging: preparing melting vanadium slag, reducing agent aluminium ash and modification agent lime, first by quantitative aluminium ash and
Lime is packed into Heating Reduction Furnace for Tungsten in proportion, and the Heating Reduction Furnace for Tungsten is electric furnace, does not need another oil (gas) filling device, and heating speed is fast, then
Melting vanadium slag is poured into, the ingredient for being conducive to lime, aluminium ash and melting vanadium slag during pouring into mixes；
The additional amount of reducing agent aluminium ash is the 60~75% of vanadium slag total weight, can not only make full use of the metal in aluminium ash
Aluminium, and the Al generated2O3Low melting point oxide (12CaO7Al is produced with CaO2O3、CaO·Al2O3·2SiO2、
2CaO·Al2O3·SiO2), the physical and chemical performance of vanadium slag can be improved, be conducive to the reduction of valuable oxide in slag；
The additional amount of modification agent lime is the 15%~20% of vanadium slag total weight, free in modification agent lime and vanadium slag
SiO2Produce the CaOSiO of low melting point2, improve the physical and chemical performance of vanadium slag；
Following reaction occurs in vanadium slag in entire reduction process:
CaO+SiO2=CaOSiO2 (1)
3CaO+Al2O3=3CaOAl2O3 (2)
12CaO+7Al2O3=12CaO7Al2O3 (3)
CaO+Al2O3+2SiO2=CaOAl2O3·2SiO2 (4)
2CaO+Al2O3+SiO2=2CaOAl2O3·SiO2 (5)
3FexO+2Al=3xFe+Al2O3 (6)
3V2O5+ 10Al=6V+5Al2O3 (7)
3MnO+2Al=3Mn+Al2O3 (8)
And the granularity of lime and aluminium ash≤100 mesh, increase the contact area of solid-liquid, be conducive to reaction it is quick into
Row is unfavorable for the progress of reaction, granularity is too small, then more energy need to be expended when crushing if granularity is too big；
B. heating reduction: after charging, heating and keep the temperature, and heating temperature is 1450 DEG C~1500 DEG C, and soaking time is
1.5~2 hours, makes aluminium ash, the valuable constituent element reduction in vanadium slag, obtain the Fe-V-Mn alloy of high added value；
C. it skims, go out alloy: after emptying the tailings in furnace, releasing alloy, close heating system, the main component in tailings
For CaO-Al2O3-SiO2-TiO2Quaternary system, and quaternary oxide content is up to 90% or more, can be used as and mentions titanium, cement and glass
The raw material of glass production and metallurgical returning charge, carry out secondary cycle utilization.
Embodiment 1:
Converter Vanadium-bearing Slag is melted using 1#, ingredient is TFe 37.00%, MFe 14.00%, FeO 29.57%, V2O5
17.32%, SiO216.23%, MnO 10.28%, TiO28.43%, other 4.17%；Aluminium 1 ingredient of ash is SiO2
5.42%, Al2O338.53%, Al 28.25%, (FeO+Fe2O3) 0.74%, CaO 1.52%, MgO 2.52%, Na2O
2.82%, MnO 0.86%, other 19.34%.
Vanadium slag, the valuable constituent element comprehensive reutilization of aluminium ash method the following steps are included:
A. raw material preparation and charging: preparing melting vanadium slag, lime and aluminium ash, first lime and aluminium ash be added in electric furnace, then
Melting vanadium slag is poured into, lime and aluminium ash additional amount are respectively the 15% and 70% of vanadium slag total weight, granularity≤100 mesh.
B. heating reduction: after charging, electric furnace is heated to 1500 DEG C, keeps the temperature 1.5 hours, makes aluminium ash, having in vanadium slag
Valence group rod iron, manganese, vanadium reduction, obtain high added value Fe-V-Mn alloy.
C. it skims, go out alloy: after emptying the tailings in furnace, releasing alloy, close heating system.
Using 1# melting Converter Vanadium-bearing Slag, embodiment 4~6 and comparative example 4~6 use 2# for Examples 1 to 3 and comparative example 1~3
Converter Vanadium-bearing Slag is melted, the component list that 1# and 2# melt Converter Vanadium-bearing Slag is as shown in table 1, embodiment 1,2,4,5 and comparative example 1,2,4,5
Using aluminium ash 1, embodiment 3,6 and comparative example 3,6 use aluminium ash 2, and the component list of aluminium ash 1 and aluminium ash 2 is as shown in table 2, table 3 and table
4 be respectively the content and yield of different embodiments and different comparative examples.
1 variety classes vanadium slag component list of table
2 variety classes aluminium ash component table of table
The different embodiment tables of table 3
The different comparative example tables of table 4
Table 3 can be obtained with the comparison of table 4: comparative example 1 is compared with embodiment 1, and the total weight that lime accounts for vanadium slag is dropped to by 15%
10%, comparative example 3 is compared with embodiment 3, and the total weight that lime accounts for vanadium slag is raised to 25% by 20%, and iron, manganese, the yield of vanadium are fast
Speed decline is primarily due to physical and chemical performance (the viscosity, fusing point) improvement that suitable modification agent is conducive to slag, kinetics by this
Condition is good.This can be obtained, lime account for vanadium slag total weight be 15%~20% when, iron, manganese, vanadium yield reach 90% or more,
Obtain best effects.
Comparative example 2 is compared with embodiment 2, and aluminium ash accounts for the total weight of vanadium slag and is raised to 85% by 75%, comparative example 4 and embodiment
4 compare, and aluminium ash accounts for the total weight of vanadium slag and drops to 50% by 60%, iron, manganese, vanadium yield decline rapidly, this is mainly due to
When aluminium ash content is higher, high melting compound can be generated, is unfavorable for reaction and carries out, and reduction dosage is inadequate when content is lower, by
This can be obtained, aluminium ash account for vanadium slag total weight be 60%~75% when, iron, manganese, vanadium yield reach 90% or more, obtained effect
Fruit is best.
Comparative example 5 is compared with embodiment 4, and when temperature falls to 1300 DEG C by 1450 DEG C, iron, manganese, the yield of vanadium are rapid
Decline, this is mainly the too low reduction for being unfavorable for vanadium, manganese of temperature；Comparative example 6 is compared with embodiment 6, and temperature is risen by 1500 DEG C
It is 1600 DEG C, although the yield of iron, manganese, vanadium is promoted, what is promoted is few, and temperature improves 100 DEG C, electric furnace consumption
Electric energy but increases very much, it can thus be concluded that iron, manganese, the yield of vanadium are best, and electric energy disappears when heating temperature is 1450 DEG C~1500 DEG C
It consumes lower.
Claims (6)
1. the recovery method of valuable constituent element in a kind of vanadium slag, it is characterised in that: utilize Fe-V- in aluminium ash reduction recycling melting vanadium slag
The method of Mn alloy.
2. the recovery method of valuable constituent element in a kind of vanadium slag according to claim 1, it is characterised in that: including walking as follows
It is rapid:
A. raw material preparation and charging: preparing melting vanadium slag, reducing agent aluminium ash and modification agent lime, first by quantitative aluminium ash and lime
It is packed into Heating Reduction Furnace for Tungsten in proportion, then melting vanadium slag is poured into；
B. heating reduction: after charging, heating and keep the temperature, and makes aluminium ash, the valuable constituent element reduction in vanadium slag, obtains high added value
Fe-V-Mn alloy；
C. it skims, go out alloy: after emptying the tailings in furnace, releasing alloy, close heating system.
3. the recovery method of valuable constituent element in a kind of vanadium slag according to claim 2, it is characterised in that: restored in step A
The additional amount of agent aluminium ash is the 60~75% of vanadium slag total weight, and the granularity of aluminium ash≤100 mesh.
4. the recovery method of valuable constituent element in a kind of vanadium slag according to claim 2, it is characterised in that: modified in step A
The additional amount of agent lime is the 15%~20% of vanadium slag total weight, and the granularity of lime≤100 mesh.
5. the recovery method of valuable constituent element in a kind of vanadium slag according to claim 2, it is characterised in that: heated in step B
Temperature is 1450 DEG C~1500 DEG C, and soaking time is 1.5~2 hours.
6. the recovery method of valuable constituent element in a kind of vanadium slag according to claim 2, it is characterised in that: the vanadium slag is molten
Melt vanadium slag, Heating Reduction Furnace for Tungsten is electric furnace.
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| CN102115821A (en) * | 2010-09-13 | 2011-07-06 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN103045929A (en) * | 2012-12-31 | 2013-04-17 | 攀钢集团西昌钢钒有限公司 | Method for producing ferrovanadium by aluminothermic process |
| CN103397208A (en) * | 2013-07-11 | 2013-11-20 | 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 |
-
2018
- 2018-11-16 CN CN201811366091.5A patent/CN109576558B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071708A (en) * | 1991-10-17 | 1993-05-05 | 承德钢铁厂 | Directly alloying process in vanadium slag furnace |
| RU2299921C2 (en) * | 2005-06-27 | 2007-05-27 | ОАО "Уральский институт металлов" | Method of producing complex foundry alloys from converter vanadium slag |
| CN102115821A (en) * | 2010-09-13 | 2011-07-06 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN102094097A (en) * | 2011-03-04 | 2011-06-15 | 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 |
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| CN106350674A (en) * | 2015-07-16 | 2017-01-25 | 东北大学 | Preparation method of high-quality AlV85 alloy |
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