CN106834728A - Process the method and system of vanadium chromium slag - Google Patents
Process the method and system of vanadium chromium slag Download PDFInfo
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- CN106834728A CN106834728A CN201710210968.0A CN201710210968A CN106834728A CN 106834728 A CN106834728 A CN 106834728A CN 201710210968 A CN201710210968 A CN 201710210968A CN 106834728 A CN106834728 A CN 106834728A
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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
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
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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
- C22B1/248—Binding; Briquetting ; Granulating of metal scrap or 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
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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 the method and system for the treatment of vanadium chromium slag, wherein, method includes：Vanadium chromium slag, reduction coal, binding agent and flux are mixed, to obtain mixed material；Mixed material is molded, to obtain pelletizing；Pelletizing is carried out into reduction treatment, to obtain metallized pellet；Metallized pellet is carried out into separating treatment, to obtain ferrochrome and rich vanadium slag；Rich vanadium slag is mixed with sodium salt and sodium oxide baking treatment is carried out, to obtain water-soluble sodium vanadate clinker；Water-soluble sodium vanadate clinker is carried out into water logging vanadium extraction treatment, to obtain vanadic anhydride and tailings.The comprehensive reutilization of iron, chromium and v element in vanadium chromium slag can be realized using the method, the ferrochrome and vanadic anhydride product of high-quality is obtained, and technological process is short, is adapted to industrialization promotion.
Description
Technical field
The present invention relates to metal smelt field, specifically, the method and system the present invention relates to process vanadium chromium slag.
Background technology
China is a chromium depleted country, and 97% chrome ore all relies on import.It is worth noting that, the red lattice ground of Panzhihua
Chromium content is up to 9,000,000 tons in the high-chromic vanadium-titanium ferroferrite in area, and content of the chromium with vanadium in raw ore is suitable.The country is to this red
The processing method of lattice vanadium titano-magnetite is aoxidized to blow out to first pass around blast furnace process into containing vanadium and chromium molten iron, then in converter and turned
Stove vanadium chromium slag (abbreviation vanadium chromium slag).Converter vanadium chromium slag is vanadium, chromium content is suitable or the chromium type high vanadium slag of low vanadium Gao Ge, its chromium content
About 5~13%, it is nearly 10 times of common vanadium slag, with larger application value.Prior art is directly carried out to the vanadium chromium slag
High-temperature oxydation sodium roasting-Soaking treatment, obtains low vanadium chromium solution high, wherein containing impurity such as more silicon, iron, aluminium, phosphorus, after
The purity of continuous precipitation products obtained therefrom is not high, and a small amount of vanadium contained in the chromium solution high for obtaining is difficult to remove, using prior art
Qualified chromium product cannot be obtained.
Chinese patent CN103924096A discloses a kind of method for reclaiming vanadium chromium resource, and the method first passes through vanadium chromium slag
Oxidation roasting with calcium compounds-acidleach carries chromium, and acid leaching residue passes through sodium oxide baking-water logging vanadium extraction again.The method does not account for oxidation
Vanadium in calcification baking in vanadium chromium slag can form acid soluble calcium vanadate with calcium oxide, and calcium vanadate and calcium chromate can be together during acidleach
Into in pickle liquor, the purpose of vanadium chromium separation is not reached at all actually, and without the iron resource reclaimed in vanadium chromium slag.
Chinese patent CN104357671 obtains vanadium, chromium solution using sulfuric acid to leach vanadium chromium slag, is subsequently added NaOH and obtains
Vanadium chromium sediment slurry, vanadium, the chromium for adding hydrogen peroxide or being passed through in oxygen, air oxidation slurries, regulation pH value carry out precipitation,
Calcining obtains vanadic anhydride；Mother liquor elder generation Crystallization Separation after precipitation goes out sodium sulphate, then removes chromium solution with sodium hydroxide solution
In impurity, finally concentration obtain crystals of sodium chromate.It is capable of reducing energy consumption that the method is not required to roasting, but has that technological process is long, sulphur
The problems such as acid is serious to equipment corrosion.
Therefore, the means of existing treatment vanadium chromium slag still have much room for improvement.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, of the invention
One purpose is the method and system for proposing treatment vanadium chromium slag.Iron, chromium and vanadium unit in vanadium chromium slag can be realized using the method
The comprehensive reutilization of element, obtains the ferrochrome and vanadic anhydride product of high-quality, and technological process is short, is adapted to industrialization
Promote.
In the first aspect of the present invention, the present invention proposes a kind of method for processing vanadium chromium slag.Implementation of the invention
Example, the method includes：Vanadium chromium slag, reduction coal, binding agent and flux are mixed, to obtain mixed material；Will be described
Mixed material is molded, to obtain pelletizing；The pelletizing is carried out into reduction treatment, to obtain metallized pellet；By institute
Stating metallized pellet carries out separating treatment, to obtain ferrochrome and rich vanadium slag；The rich vanadium slag is mixed with sodium salt and is gone forward side by side
Row sodium oxide baking treatment, to obtain water-soluble sodium vanadate clinker；The water-soluble sodium vanadate clinker is carried out into flooding
Vanadium treatment, to obtain vanadic anhydride and tailings.
Thus, the method for the treatment of vanadium chromium slag according to embodiments of the present invention is by by vanadium chromium slag, reduction coal, binding agent and helping
Flux mixes, and the mixed material shaping that will be obtained obtains pelletizing, then pelletizing is carried out into reduction treatment, using reduction coal by pelletizing
In iron, chromated oxide be reduced to simple substance, obtain metallized pellet, and then metallized pellet is carried out into separating treatment, respectively
To ferrochrome product and rich vanadium slag；Further, by the way that rich vanadium slag mixed with sodium salt and sodium oxide baking treatment is carried out,
Water-soluble sodium vanadate clinker is obtained, then water logging vanadium extraction treatment is carried out by by water-soluble sodium vanadate clinker, obtain vanadic anhydride
Product and tailings.Thus, the method for the treatment vanadium chromium slag of the embodiment of the present invention by by chromium, iron and vanadium step-by-step reduction, obtaining first
Ferrochrome product, and further process rich vanadium slag, obtains vanadic anhydride product, so as to realize iron, chromium and vanadium in vanadium chromium slag
The comprehensive reutilization of element, and technological process is short, is adapted to industrialization promotion.
In addition, the method for the treatment of vanadium chromium slag according to the above embodiment of the present invention can also have following additional technology special
Levy：
In some embodiments of the invention, by the vanadium chromium slag, the reduction coal, the binding agent and the flux
According to mass ratio 100:(6~12):(2~5):(5~15) are mixed.Thus, it is possible to significantly improve sequential reduction process
The degree of metalization of the metallized pellet for arriving, improves the rate of recovery of ferrochrome.
In some embodiments of the invention, the reduction treatment is completed at a temperature of 1300~1400 degrees Celsius
's.Thus, it is possible to further improve the degree of metalization of the metallized pellet that sequential reduction treatment is obtained, the recovery of ferrochrome is improved
Rate.
In some embodiments of the invention, by the rich vanadium slag with the sodium salt according to mass ratio 100:(5~20) are entered
Row mixing.Thus, it is possible to significantly improve the quality of the vanadic anhydride product for preparing.
In some embodiments of the invention, the sodium salt include selected from sodium carbonate, sodium chloride and sodium sulphate at least
One of.Thus, it is possible to further improve the quality of the vanadic anhydride product for preparing.
In some embodiments of the invention, the sodium oxide baking treatment is at a temperature of 600~900 degrees Celsius
Carry out 1~2h completions.Thus, it is possible to further improve the quality of the vanadic anhydride product for preparing.
In some embodiments of the invention, the water logging vanadium extraction treatment is further included：By the water-soluble sodium vanadate
Clinker carries out Soaking treatment, to obtain containing vanadium solution；Precipitation treatment is carried out containing vanadium solution by described, to obtain poly vanadic acid
Ammonium is precipitated；Poly ammonium vanadate precipitation is carried out into calcination processing, to obtain vanadic anhydride.Thus, it is possible to further carry
The quality of the vanadic anhydride product that height is prepared.
In the second aspect of the present invention, the present invention proposes a kind of method of the treatment vanadium chromium slag for implementing preceding embodiment
System.Embodiments in accordance with the present invention, the system includes：Mixing device, the mixing device has vanadium chromium slag entrance, reduction coal
The outlet of entrance, binding agent entrance, flux entrance and mixed material；There is shaped device, the shaped device mixed material to enter
Mouth and pelletizing outlet, the mixed material entrance are connected with pelletizing outlet；Reduction apparatus, the reduction apparatus have pelletizing
Entrance and metallized pellet are exported, and the pelletizing entrance is connected with pelletizing outlet；Separator, the separator has
Metallized pellet entrance, ferrochrome outlet and rich vanadium slag outlet, the metallized pellet entrance go out with the metallized pellet
Mouth is connected；Sodium oxide baking device, the sodium oxide baking device has rich vanadium slag entrance, sodium salt entrance, air intake
Exported with water-soluble sodium vanadate clinker, the rich vanadium slag entrance is connected with the rich vanadium slag outlet；Water logging vanadium extraction device, the water
Leaching and vanadium extraction device has water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and tailings outlet, the water-soluble sodium vanadate
Clinker entrance is connected with the water-soluble sodium vanadate clinker outlet.
Thus, the system for the treatment of vanadium chromium slag according to embodiments of the present invention is by using shaped device by vanadium chromium slag, reduction
The mixing of coal, binding agent and flux, and the mixed material shaping that will be obtained obtains pelletizing, then pelletizing is supplied into reduction apparatus
Reduction treatment is carried out, the iron in pelletizing, chromated oxide are reduced to simple substance using reduction coal, obtain metallized pellet, Jin Erli
Metallized pellet is carried out into separating treatment with separator, ferrochrome product and rich vanadium slag is respectively obtained；Further, pass through
Rich vanadium slag and sodium salt are supplied to carry out mixing and sodium oxide baking treatment into sodium oxide baking device, obtains water-soluble vanadium
Sour sodium clinker, then water-soluble sodium vanadate clinker is carried out by water logging vanadium extraction treatment by water logging vanadium extraction device, obtain vanadic anhydride
Product and tailings.Thus, the system of the treatment vanadium chromium slag of the embodiment of the present invention by by chromium, iron and vanadium step-by-step reduction, obtaining first
Ferrochrome product, and further process rich vanadium slag, obtains vanadic anhydride product, so as to realize iron, chromium and vanadium in vanadium chromium slag
The comprehensive reutilization of element, and technological process is short, is adapted to industrialization promotion.
In addition, the system for the treatment of vanadium chromium slag according to the above embodiment of the present invention can also have following additional technology special
Levy：
In some embodiments of the invention, the reduction apparatus are tunnel cave or rotary hearth furnace, and the separator is mill
Ore deposit concentration equipment or molten separating device；Preferably, the mill ore magnetic selection device is the linkage of ball mill and magnetic separator, described molten
Packing is set to molten point of stove of combustion gas.
In some embodiments of the invention, the sodium oxide baking device is multihearth roaster.
Additional aspect of the invention and advantage will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by practice of the invention.
Brief description of the drawings
Of the invention above-mentioned and/or additional aspect and advantage will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the method flow schematic diagram for the treatment of vanadium chromium slag according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram of the treatment vanadium chromium slag according to further embodiment of the present invention；
Fig. 3 is the system structure diagram for the treatment of vanadium chromium slag according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
It is exemplary to scheme the embodiment of description, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In the present invention, unless otherwise clearly defined and limited, term " connected " should be interpreted broadly, for example, can be with
It is to be fixedly connected, or be detachably connected, or integrally；Can mechanically connect, or electrically connect；Can be straight
Connect connected, it is also possible to be indirectly connected to by intermediary, can be two element internals connection or two phase interactions of element
With relation, unless otherwise clearly restriction.For the ordinary skill in the art, on can understanding as the case may be
State term concrete meaning in the present invention.
In the first aspect of the present invention, the present invention proposes a kind of method for processing vanadium chromium slag.Implementation of the invention
Example, the method includes：Vanadium chromium slag, reduction coal, binding agent and flux are mixed, to obtain mixed material；Will mixing
Material is molded, to obtain pelletizing；Pelletizing is carried out into reduction treatment, to obtain metallized pellet；By metallized pellet
Separating treatment is carried out, to obtain ferrochrome and rich vanadium slag；Rich vanadium slag is mixed and carried out at sodium oxide baking with sodium salt
Reason, to obtain water-soluble sodium vanadate clinker；Water-soluble sodium vanadate clinker is carried out into water logging vanadium extraction treatment, to obtain five oxidations
Two vanadium and tailings.
Method below with reference to Fig. 1~2 pair treatment vanadium chromium slag according to embodiments of the present invention is described in detail.According to this
Inventive embodiment, the method includes：
S100：Batch mixing
In the step, vanadium chromium slag, reduction coal, binding agent and flux are mixed, to obtain mixed material.Specifically
Ground, vanadium chromium slag is the mine tailing that red lattice vanadium titano-magnetite is obtained after blast furnace process and converter oxidation blowing, and its main thing is mutually
FeO·(Cr,V,Ti)2O3And 2FeOSiO2, vanadium, chromium and part iron are main to be existed in the form of vanadium iron and chromohercynite, also
Some iron exists in the form of fayalite.Converter vanadium chromium slag is vanadium, chromium content is suitable or the high-chromic vanadium of low vanadium Gao Ge
Slag, wherein Cr2O3Mass fraction is about 8~16%, Fe mass fractions and is about 20~35%, V2O5Mass fraction be about 8~
16%, it is worth with larger recycling.Active degree according to different metal is different, with reduction coal as reducing agent, can be with
The step-by-step reduction of different metal is realized, and before reduction treatment is carried out, in advance by vanadium chromium slag, reduction coal, binding agent and flux
Carry out being mixed to get mixed material, the efficiency of sequential reduction treatment can be significantly improved.
Embodiments in accordance with the present invention, the proportioning of vanadium chromium slag, reduction coal, binding agent and flux for mixing is not received
Especially limitation, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, can be by
Vanadium chromium slag, reduction coal, binding agent and flux are according to mass ratio 100:(6~12):(2~5):(5~15) are mixed.By
This, can significantly improve the degree of metalization of the metallized pellet that sequential reduction treatment is obtained, and improve the rate of recovery of ferrochrome.Inventor
It was found that, if the amount of allocating of reduction coal is too high, by Cr in pelletizing2O3After being reduced to Cr, side reaction 3Cr+7C will further occur
=Cr3C7, causing the rate of recovery of Cr reduces.In addition, by allocating flux into, chromium and iron in sequential reduction treatment can also be improved
Reduction effect.
S200：Shaping
In the step, the mixed material that S100 is obtained is molded, to obtain pelletizing.Specifically, can be using circle
Disk pelletizer enters to be about to mixed material to be molded.
S300：Reduction treatment
In the step, pelletizing is carried out into reduction treatment, to obtain metallized pellet.Inventor has found, according to metal
Active degree is different, and using reduction coal as reducing agent, what preferential reduction was obtained in reduction treatment is iron, followed by chromium, is finally
Vanadium, so that the condition by controlling reduction treatment, can realize iron, chromium by the selective step-by-step reduction of iron, chromium and vanadium in pelletizing
Separated with vanadium.Specifically, the reduction to iron compound mainly includes following reaction：
2FeO·SiO2+ 2C=2Fe+SiO2+2CO；
2FeO·SiO2+ 2CO=2Fe+SiO2+2CO2；
FeO·(Cr,V,Ti)2O3+ C=(Cr, V, Ti)2O3+Fe+CO；
FeO·(Cr,V,Ti)2O3+ CO=(Cr, V, Ti)2O3+Fe+CO2。
Reduction to chromium compound mainly includes following reaction：
Cr2O3+ 3C=2Cr+3CO；
Cr2O3+ 3CO=2Cr+3CO2。
According to a particular embodiment of the invention, reduction treatment is completed at a temperature of 1300~1400 degrees Celsius.Hair
A person of good sense has found, if temperature is too high and reduction coal allocates excess into, side reaction may occur：V2O3+ 3C=2V+3CO and V2O3
+ 5C=2VC+3CO；So that vanadium is reduced in reduction treatment with chromium and iron simultaneously, vanadium is caused to be separated with chromium and iron.Together
When, the reduction of chromium needs uniform temperature, if temperature is too low, the reduction effect of chromium is bad.
S400：Separating treatment
In the step, metallized pellet is carried out into separating treatment, to obtain ferrochrome and rich vanadium slag, so as to realize vanadium
Separated with chromium, iron.After testing, the mass fraction of Cr is reached for the rate of recovery of 15~22%, Cr in the ferrochrome product for obtaining
More than 80%, Cr in rich vanadium slag2O3Mass fraction be not higher than 2%, V2O5Mass fraction be 12~22%.
Embodiments in accordance with the present invention, the condition of separating treatment is not particularly restricted, and those skilled in the art can be with root
Selected according to being actually needed, according to a particular embodiment of the invention, can be processed using mill ore magnetic selection or melt office reason to gold
Category pellet carries out separating treatment.
A specific embodiment of the invention, when separating treatment is carried out to metallized pellet using molten office reason,
Molten office reason can be carried out in non-reducing atmosphere at a temperature of 1500~1600 degrees Celsius, thus, it is possible to further improve
The grade of chromium and iron in isolated ferrochrome product.
A specific embodiment of the invention, contains O in the preferred atmosphere of non-reducing atmosphere2Volumetric concentration 3~
25%, it is possible thereby to ensure that metal is preferably separated during molten point.
S500：Sodium oxide baking treatment
In the step, rich vanadium slag is carried out into sodium oxide baking treatment in atmosphere, it is ripe to obtain water-soluble sodium vanadate
Material, wherein, water-soluble sodium vanadate clinker can be at least one of sodium vanadate, sodium pyrovanadate or sodium metavanadate.Specifically,
Sodium oxide baking treatment is main to include following reaction：
Na2O+V2O3+O2=2NaVO3Sodium metavanadate；
2Na2O+V2O3+O2=Na4V2O7Sodium pyrovanadate；
3Na2O+V2O3+O2=Na3VO4Sodium vanadate.
After testing, the ratio that positive pentavalent vanadium accounts for full vanadium in gained water solubility sodium vanadate clinker is not less than 90%.
Embodiments in accordance with the present invention, rich vanadium slag is not particularly restricted with the proportioning of sodium salt, and those skilled in the art can
To be selected according to actual needs, according to a particular embodiment of the invention, rich vanadium slag can be 100 with the mass ratio of sodium salt:
(5~20), thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the species of sodium salt is not particularly restricted, and those skilled in the art can be according to reality
Border needs to be selected, and according to a particular embodiment of the invention, sodium salt can be included selected from sodium carbonate, sodium chloride and sodium sulphate
At least one of.Thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the condition of sodium oxide baking treatment is not particularly restricted, people in the art
Member can be selected according to actual needs, according to a particular embodiment of the invention, sodium oxide baking treatment be 600~
1~2h completions are carried out under 900 degrees Celsius.Thus, it is possible to positive pentavalent in ensureing to be calcined the water-soluble sodium vanadate clinker for obtaining
The ratio that vanadium accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
S600：Water logging vanadium extraction is processed
In the step, water-soluble sodium vanadate clinker is carried out into water logging vanadium extraction treatment, to obtain vanadic anhydride and tailings.
Specifically, embodiments in accordance with the present invention, water logging vanadium extraction treatment can further include the following steps：
S610：Soaking treatment
Embodiments in accordance with the present invention, Soaking treatment, water logging condition are carried out by water-soluble sodium vanadate clinker：Extraction temperature 80
~95 degrees Celsius, the solid mass ratio of liquid is (3~10):1, extraction time is 3~15min, and water logging terminates rear separation of solid and liquid, can obtain
To containing vanadium solution.
S620：Precipitation is processed
Embodiments in accordance with the present invention, will contain vanadium solution purification and impurity removal, and carrying out acid ammonium salt again containing vanadium solution after removal of impurities sinks
Vanadium treatment, you can obtain poly ammonium vanadate precipitation.
Wherein, the key reaction of generation is in above-mentioned precipitation treatment：
Acid adjustment degree：10VO3 -+6H+=H2V10O28 4-+2H2O
Ammonium salt precipitation：3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O。
S630：Calcination processing
Further, embodiments in accordance with the present invention, the poly ammonium vanadate precipitation that precipitation treatment is obtained is carried out at calcining
Reason, control calcining heat reacts 2h under 550 degrees Celsius carries out deamination, to obtain vanadic anhydride product.
Wherein, the key reaction of generation is in above-mentioned calcination processing：
(NH4)2V6O16=3V2O5+2NH3↑+H2O。
Thus, the method for the treatment of vanadium chromium slag according to embodiments of the present invention is by by vanadium chromium slag, reduction coal, binding agent and helping
Flux mixes, and the mixed material shaping that will be obtained obtains pelletizing, then pelletizing is carried out into reduction treatment, using reduction coal by pelletizing
In iron, chromated oxide be reduced to simple substance, obtain metallized pellet, and then metallized pellet is carried out into separating treatment, respectively
To ferrochrome product and rich vanadium slag；Further, by the way that rich vanadium slag mixed with sodium salt and sodium oxide baking treatment is carried out,
Water-soluble sodium vanadate clinker is obtained, then water-soluble sodium vanadate clinker is carried out into water logging vanadium extraction treatment, obtained containing vanadium solution, and will contain
After vanadium solution carries out acid ammonium salt precipitation treatment, the poly ammonium vanadate precipitation to obtaining carries out calcination processing, to obtain five oxygen
Change two vanadium products and tailings.It is computed, vanadium chromium slag is processed using the present processes, the rate of recovery of chromium is up to more than 85%, iron
The rate of recovery up to more than 80%, the rate of recovery of vanadium is up to more than 95%.Thus, the side of the treatment vanadium chromium slag of the embodiment of the present invention
Method further processes rich vanadium slag by by chromium, iron and vanadium step-by-step reduction, ferrochrome product being obtained first, obtains five oxidations two
Vanadium product, so as to realize the comprehensive reutilization of iron, chromium and v element in vanadium chromium slag, and technological process is short, and suitable industrialization is pushed away
Extensively.
In the second aspect of the present invention, the present invention proposes a kind of method of the treatment vanadium chromium slag for implementing preceding embodiment
System.Embodiments in accordance with the present invention, with reference to Fig. 3, the system includes：Mixing device 100, shaped device 200, reduction apparatus
300th, separator 400, sodium oxide baking device 500 and water logging vanadium extraction device 600.Wherein, mixing device 100 has vanadium chromium
Slag entrance 101, reduction coal entrance 102, binding agent entrance 103, flux entrance 104 and mixed material outlet 105；Shaped device
200 have mixed material entrance 201 and pelletizing outlet 202, and mixed material entrance 201 is connected with mixed material outlet 105；Reduction
Device 300 has pelletizing entrance 301 and metallized pellet outlet 302, and pelletizing entrance 301 is connected with pelletizing outlet 202；Separate dress
Putting 400 has metallized pellet entrance 401, ferrochrome outlet 402 and a rich vanadium slag outlet 403, metallized pellet entrance 401 with
Metallized pellet outlet 302 is connected；There is sodium oxide baking device 500 rich vanadium slag entrance 501, sodium salt entrance 502, air to enter
Mouth 503 and water-soluble sodium vanadate clinker outlet 504, rich vanadium slag entrance 501 export 403 and are connected with rich vanadium slag；Water logging vanadium extraction device
600 have water-soluble sodium vanadate clinker entrance 601, vanadic anhydride outlet 602 and tailings outlet 603, and water-soluble sodium vanadate is ripe
Material entrance 601 is connected with water-soluble sodium vanadate clinker outlet 504.
The system for the treatment of vanadium chromium slag according to embodiments of the present invention is described in detail below with reference to Fig. 3：
Embodiments in accordance with the present invention, mixing device 100 has vanadium chromium slag entrance 101, reduction coal entrance 102, binding agent
Entrance 103, flux entrance 104 and mixed material outlet 105, mixing device 100 is suitable to vanadium chromium slag, reduction coal, binding agent
Mixed with flux, to obtain mixed material.Specifically, vanadium chromium slag is red lattice vanadium titano-magnetite through blast furnace process and turns
The mine tailing obtained after stove oxidation blowing, its main thing is mutually FeO (Cr, V, Ti)2O3And 2FeOSiO2, vanadium, chromium and part iron
Main to exist in the form of vanadium iron and chromohercynite, some iron exists in the form of fayalite.Converter vanadium chromium slag
For vanadium, chromium content are suitable or the chromium type high vanadium slag of low vanadium Gao Ge, wherein Cr2O3Mass fraction is about 8~16%, Fe mass fractions
About 20~35%, V2O5Mass fraction be about 8~16%, be worth with larger recycling.According to the work of different metal
The degree of sprinkling is different, with reduction coal as reducing agent, it is possible to achieve the step-by-step reduction of different metal, and before reduction treatment is carried out, in advance
First vanadium chromium slag, reduction coal, binding agent and flux are carried out being mixed to get mixed material, sequential reduction treatment can be significantly improved
Efficiency.
Embodiments in accordance with the present invention, the proportioning of vanadium chromium slag, reduction coal, binding agent and flux for mixing is not received
Especially limitation, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, can be by
Vanadium chromium slag, reduction coal, binding agent and flux are according to mass ratio 100:(6~12):(2~5):(5~15) are mixed.By
This, can significantly improve the degree of metalization of the metallized pellet that sequential reduction treatment is obtained, and improve the rate of recovery of ferrochrome.Inventor
It was found that, if the amount of allocating of reduction coal is too high, by Cr in pelletizing2O3After being reduced to Cr, side reaction 3Cr+7C will further occur
=Cr3C7, causing the rate of recovery of Cr reduces.In addition, by allocating flux into, chromium and iron in sequential reduction treatment can also be improved
Reduction effect.
Embodiments in accordance with the present invention, shaped device 200 has mixed material entrance 201 and pelletizing outlet 202, mixture
Material entrance 201 is connected with mixed material outlet 105, and shaped device 200 is suitable to enter the mixed material obtained in mixing device 100
Row shaping, to obtain pelletizing.
A specific embodiment of the invention, shaped device 200 can be disc balling machine.
Embodiments in accordance with the present invention, reduction apparatus 300 have pelletizing entrance 301 and metallized pellet outlet 302, pelletizing
Entrance 201 is connected with pelletizing outlet 202, and reduction apparatus 300 are suitable to for pelletizing to carry out reduction treatment, to obtain the ball that metallizes
Group.Inventor has found that the active degree according to metal is different, using reduction coal as reducing agent, is preferentially reduced in reduction treatment
To be iron, followed by chromium is finally vanadium so that the condition by controlling reduction treatment, can be by iron, chromium and vanadium in pelletizing
Selective step-by-step reduction, realizes that iron, chromium are separated with vanadium.Specifically, the reduction to iron compound mainly includes following reaction：
2FeO·SiO2+ 2C=2Fe+SiO2+2CO；
2FeO·SiO2+ 2CO=2Fe+SiO2+2CO2；
FeO·(Cr,V,Ti)2O3+ C=(Cr, V, Ti)2O3+Fe+CO；
FeO·(Cr,V,Ti)2O3+ CO=(Cr, V, Ti)2O3+Fe+CO2。
Reduction to chromium compound mainly includes following reaction：
Cr2O3+ 3C=2Cr+3CO；
Cr2O3+ 3CO=2Cr+3CO2。
According to a particular embodiment of the invention, reduction treatment is completed at a temperature of 1300~1400 degrees Celsius.Hair
A person of good sense has found, if temperature is too high and reduction coal allocates excess into, side reaction may occur：V2O3+ 3C=2V+3CO and V2O3
+ 5C=2VC+3CO；So that vanadium is reduced in reduction treatment with chromium and iron simultaneously, vanadium is caused to be separated with chromium and iron.Together
When, the reduction of chromium needs uniform temperature, if temperature is too low, the reduction effect of chromium is bad.
According to a particular embodiment of the invention, reduction apparatus 300 can be tunnel cave or rotary hearth furnace, it is possible thereby to further
The effect of reduction treatment is improved, so as to further improve the rate of recovery of iron and chromium.
There is embodiments in accordance with the present invention, separator 400 metallized pellet entrance 401, ferrochrome to export 402 and
Rich vanadium slag outlet 403, metallized pellet entrance 401 is connected with metallized pellet outlet 302, and separator 400 is suitable to metal
Pellet carries out separating treatment, to obtain ferrochrome and rich vanadium slag, so as to realize that vanadium is separated with chromium, iron.After testing, obtain
To ferrochrome product in Cr mass fraction for 15~22%, Cr the rate of recovery up to more than 80%, Cr in rich vanadium slag2O3's
Mass fraction is not higher than 2%, V2O5Mass fraction be 12~22%.
Embodiments in accordance with the present invention, the condition of separating treatment is not particularly restricted, and those skilled in the art can be with root
Selected according to being actually needed, according to a particular embodiment of the invention, can be processed using mill ore magnetic selection or melt office reason to gold
Category pellet carries out separating treatment.
A specific embodiment of the invention, when separating treatment is carried out to metallized pellet using molten office reason,
Molten office reason can be carried out in non-reducing atmosphere at a temperature of 1500~1600 degrees Celsius, thus, it is possible to further improve
The grade of chromium and iron in isolated ferrochrome product.
A specific embodiment of the invention, contains O in the preferred atmosphere of non-reducing atmosphere2Volumetric concentration 3~
25%, it is possible thereby to ensure that metal is preferably separated during molten point.
According to a particular embodiment of the invention, separator can be mill ore magnetic selection device or molten separating device；Preferably, grind
Ore deposit concentration equipment can be the linkage of ball mill and magnetic separator, and molten separating device can be molten point of stove of combustion gas.It is possible thereby to aobvious
Write the efficiency for improving separating treatment.
The separator is molten separating device or mill ore magnetic selection device；Preferably, the mill ore magnetic selection device is ball milling
The linkage of machine and magnetic separator, the molten packing is set to molten point of stove of combustion gas.
Embodiments in accordance with the present invention, sodium oxide baking device 500 have rich vanadium slag entrance 501, sodium salt entrance 502,
Air intake 503 and water-soluble sodium vanadate clinker outlet 504, rich vanadium slag entrance 501 are connected with rich vanadium slag outlet 403, sodium oxide molybdena
Change calciner 500 to be suitable to for rich vanadium slag to carry out sodium oxide baking treatment in atmosphere, it is ripe to obtain water-soluble sodium vanadate
Material, wherein, water-soluble sodium vanadate clinker can be at least one of sodium vanadate, sodium pyrovanadate or sodium metavanadate.Specifically,
Sodium oxide baking treatment is main to include following reaction：
Na2O+V2O3+O2=2NaVO3Sodium metavanadate；
2Na2O+V2O3+O2=Na4V2O7Sodium pyrovanadate；
3Na2O+V2O3+O2=Na3VO4Sodium vanadate.
After testing, the ratio that positive pentavalent vanadium accounts for full vanadium in gained water solubility sodium vanadate clinker is not less than 90%.
Embodiments in accordance with the present invention, rich vanadium slag is not particularly restricted with the proportioning of sodium salt, and those skilled in the art can
To be selected according to actual needs, according to a particular embodiment of the invention, rich vanadium slag can be 100 with the mass ratio of sodium salt:
(5~20), thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the species of sodium salt is not particularly restricted, and those skilled in the art can be according to reality
Border needs to be selected, and according to a particular embodiment of the invention, sodium salt can be included selected from sodium carbonate, sodium chloride and sodium sulphate
At least one of.Thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the condition of sodium oxide baking treatment is not particularly restricted, people in the art
Member can be selected according to actual needs, according to a particular embodiment of the invention, sodium oxide baking treatment be 600~
1~2h completions are carried out under 900 degrees Celsius.Thus, it is possible to positive pentavalent in ensureing to be calcined the water-soluble sodium vanadate clinker for obtaining
The ratio that vanadium accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
According to a particular embodiment of the invention, sodium oxide baking device 500 can be multihearth roaster, it is possible thereby to enter
One step improves the effect of sodium oxide baking treatment, so as to further improve the rate of recovery of vanadium.
There is embodiments in accordance with the present invention, water logging vanadium extraction device 600 water-soluble sodium vanadate clinker entrance 601, five to aoxidize
Two vanadium outlet 602 and tailings outlet 603, water-soluble sodium vanadate clinker entrance 601 export 504 phases with water-soluble sodium vanadate clinker
Even, water logging vanadium extraction device 600 is suitable to for water-soluble sodium vanadate clinker to carry out water logging vanadium extraction treatment, so as to obtain vanadic anhydride and
Tailings.The water logging vanadium extraction device can be the linkage of water immersion, precipitation device and calciner plant, specifically, according to
Embodiments of the invention, water logging vanadium extraction treatment may further include the following steps：
(1) Soaking treatment
Embodiments in accordance with the present invention, Soaking treatment, water logging condition are carried out by water-soluble sodium vanadate clinker：Extraction temperature 80
~95 degrees Celsius, the solid mass ratio of liquid is (3~10):1, extraction time is 3~15min, and water logging terminates rear separation of solid and liquid, can obtain
To containing vanadium solution.
(2) precipitation treatment
Embodiments in accordance with the present invention, will contain vanadium solution purification and impurity removal, and carrying out acid ammonium salt again containing vanadium solution after removal of impurities sinks
Vanadium treatment, you can obtain poly ammonium vanadate precipitation.
Wherein, the key reaction of generation is in above-mentioned precipitation treatment：
Acid adjustment degree：10VO3 -+6H+=H2V10O28 4-+2H2O
Ammonium salt precipitation：3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O。
(3) calcination processing
Further, embodiments in accordance with the present invention, the poly ammonium vanadate precipitation that precipitation treatment is obtained is carried out at calcining
Reason, control calcining heat reacts 2h under 550 degrees Celsius carries out deamination, to obtain vanadic anhydride product.
Wherein, the key reaction of generation is in above-mentioned calcination processing：
(NH4)2V6O16=3V2O5+2NH3↑+H2O。
Thus, the system for the treatment of vanadium chromium slag according to embodiments of the present invention by mixing device by vanadium chromium slag, reduction coal, viscous
Knot agent and flux mix, and the mixed material that will be obtained supplies into shaped device shaping and obtains pelletizing, then using also original-pack
Put carries out reduction treatment by pelletizing, and the iron in pelletizing, chromated oxide are reduced into simple substance using reduction coal, obtains the ball that metallizes
Group, and then metallized pellet is supplied into separator carry out separating treatment, respectively obtain ferrochrome product and rich vanadium slag；
Further, rich vanadium slag is mixed with sodium salt and sodium oxide baking treatment is carried out by using sodium oxide baking device, obtained
To water-soluble sodium vanadate clinker, then water-soluble sodium vanadate clinker is supplied carry out Soaking treatment into water logging vanadium extraction device, obtain
Containing vanadium solution, and will contain after vanadium solution carries out acid ammonium salt precipitation treatment, the poly ammonium vanadate precipitation to obtaining is carried out at calcining
Reason, to obtain vanadic anhydride product and tailings.It is computed, vanadium chromium slag, the rate of recovery of chromium is processed using the system of the application
Up to more than 85%, up to more than 80%, the rate of recovery of vanadium is up to more than 95% for the rate of recovery of iron.Thus, the embodiment of the present invention
Treatment vanadium chromium slag system by by chromium, iron and vanadium step-by-step reduction, first ferrochrome product, and further process rich vanadium
Slag, obtains vanadic anhydride product, so as to realize the comprehensive reutilization of iron, chromium and v element in vanadium chromium slag, and technological process
It is short, it is adapted to industrialization promotion.
Below with reference to specific embodiment, present invention is described, it is necessary to explanation, these embodiments are only description
Property, and the present invention is limited never in any form.
Embodiment 1
By domestic certain company converter vanadium chromium slag (Cr2O3Mass fraction is 8%, V2O5Mass fraction is 8%, Fe mass fractions
For 20%) with reduction coal, binding agent and flux in mass ratio 100:6:2:5 are mixed, and mixed material is passed through into disk
Pelletizer shaping obtains pelletizing.Pelletizing is supplied to tunnel cave carries out reduction roasting at 1300 DEG C, and reaction is obtained after terminating
Metallized pellet.Metallized pellet is carried out into mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome
(mass fraction containing Cr is 15%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Mass fraction
It is 1.5%, V2O5Mass fraction is 12%.By rich vanadium slag and sodium salt in mass ratio 100:After 5 mixing 600 in multihearth roaster
Sodium oxide baking 1h obtains water-soluble sodium vanadate clinker at DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 92%.Finally by water
Dissolubility sodium vanadate clinker carries out water logging vanadium extraction treatment and obtains vanadic anhydride (grade 98.8%) and tailings.The chromium of whole flow process is returned
Yield is 85%, and vanadium recovery is 95%, and iron recovery is 85%.
Embodiment 2
By domestic certain company converter vanadium chromium slag (Cr2O3Mass fraction is 10%, V2O5Mass fraction is 10%, Fe mass point
Number for 24%) with reduction coal, binding agent and flux in mass ratio 100:8:3:8 are mixed, and by mixed material by circle
The shaping of disk pelletizer obtains pelletizing.Pelletizing is supplied to tunnel cave carries out reduction roasting at 1350 DEG C, and reaction is obtained after terminating
To metallized pellet.Metallized pellet is carried out into mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome
(mass fraction containing Cr is 18%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Mass fraction
It is 1.7%, V2O5Mass fraction is 15%.By rich vanadium slag and sodium salt in mass ratio 100:After 10 mixing 900 in multihearth roaster
Sodium oxide baking 1.5h obtains water-soluble sodium vanadate clinker at DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 96%.Finally will
Water-soluble sodium vanadate clinker carries out water logging vanadium extraction treatment and obtains vanadic anhydride (grade 99.2%) and tailings.The chromium of whole flow process
The rate of recovery is 87%, and vanadium recovery is 97%, and iron recovery is 80%.
Embodiment 3
By domestic certain company converter vanadium chromium slag (Cr2O3Mass fraction is 12%, V2O5Mass fraction is 12%, Fe mass point
Number for 30%) with reduction coal, binding agent and flux in mass ratio 100:10:4:10 are mixed, and mixed material is passed through
Disc balling machine shaping obtains pelletizing.Pelletizing is supplied to tunnel cave carries out reduction roasting at 1400 DEG C, after reaction terminates
Obtain metallized pellet.Metallized pellet is carried out into mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome conjunction
Gold (mass fraction containing Cr is 20%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Quality point
Number is 1.8%, V2O5Mass fraction is 18%.By rich vanadium slag and sodium salt in mass ratio 100:After 20 mixing in multihearth roaster
Sodium oxide baking 2h obtains water-soluble sodium vanadate clinker at 800 DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 95%.Finally will
Water-soluble sodium vanadate clinker carries out water logging vanadium extraction treatment and obtains vanadic anhydride (grade 99.0%) and tailings.The chromium of whole flow process
The rate of recovery is 88%, and vanadium recovery is 96%, and iron recovery is 87%.
Embodiment 4
By domestic certain company converter vanadium chromium slag (Cr2O3Mass fraction is 16%, V2O5Mass fraction is 16%, Fe mass point
Number for 35%) with reduction coal, binding agent and flux in mass ratio 100:12:5:15 are mixed, and mixed material is passed through
Disc balling machine shaping obtains pelletizing.Pelletizing is supplied to tunnel cave carries out reduction roasting at 1375 DEG C, after reaction terminates
Obtain metallized pellet.Metallized pellet is carried out into mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome conjunction
Gold (mass fraction containing Cr is 22%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Quality point
Number is 1.9%, V2O5Mass fraction is 22%.By rich vanadium slag and sodium salt in mass ratio 100:After 20 mixing in multihearth roaster
Sodium oxide baking 2h obtains water-soluble sodium vanadate clinker at 750 DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 98%.Finally will
Water-soluble sodium vanadate clinker carries out water logging vanadium extraction treatment and obtains vanadic anhydride (grade 99.4%) and tailings.The chromium of whole flow process
The rate of recovery is 90%, and vanadium recovery is 98%, and iron recovery is 90%.
Embodiment 5
By domestic certain company converter vanadium chromium slag (Cr2O3Mass fraction is 8%, V2O5Mass fraction is 8%, Fe mass fractions
For 20%) with reduction coal, binding agent and flux in mass ratio 100:6:2:5 mixed processings obtain mixed material, and will mixing
Material is molded by disc balling machine and obtains pelletizing, and pelletizing is carried out into reduction roasting, reaction knot in tunnel cave at 1300 DEG C
Reduction roasting product is obtained after beam.Reduction roasting product is carried out into molten getting for 1500 DEG C under neutral atmosphere in molten point of stove of combustion gas
Ferrochrome (mass fraction containing Cr is 15%) and rich vanadium slag, ferrochrome can send to smelting stainless steel, Cr in rich vanadium slag2O3
Mass fraction is 1.5%, V2O5Mass fraction is 12%.By rich vanadium slag and sodium salt in mass ratio 100:In multilayer roasting after 5 mixing
600 DEG C of sodium oxide baking 1h obtain water-soluble sodium vanadate clinker in stove, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 92%.Finally
Water-soluble sodium vanadate clinker is carried out into water logging vanadium extraction treatment and obtains vanadic anhydride (grade 98.8%) and tailings.Whole flow process
Chromium recovery ratio 91%, vanadium recovery 95%, iron recovery 85%.
Embodiment 6
By domestic certain company vanadium-bearing slag of high calcium and high phosphor (Cr2O3Mass fraction is 10%, V2O5Mass fraction is 10%, Fe mass
Fraction be 24%) with reduction coal, binding agent and flux in mass ratio 100:8:3:8 mixed processings obtain mixed material, and will
Mixed material is molded by disc balling machine and obtains pelletizing, pelletizing is carried out into reduction roasting at 1350 DEG C in tunnel cave, instead
Reduction roasting product is obtained after should terminating.Reduction roasting product is carried out for 1550 DEG C under weak oxide atmosphere in molten point of stove of combustion gas
Molten to get ferrochrome (mass fraction containing Cr is 18%) and rich vanadium slag, ferrochrome can send to smelting stainless steel, Fu Fan
Cr in slag2O3Mass fraction is 1.7%, V2O5Mass fraction is 15%.By rich vanadium slag and sodium salt in mass ratio 100:After 10 mixing
900 DEG C of sodium oxide baking 1.5h obtain water-soluble sodium vanadate clinker in multihearth roaster, and wherein pentavalent vanadium accounts for the ratio of full vanadium
Example is 96%.Water-soluble sodium vanadate clinker is finally carried out into water logging vanadium extraction treatment and obtains vanadic anhydride (grade 99.2%) and tail
Slag.The chromium recovery ratio 93% of whole flow process, vanadium recovery 97%, iron recovery 80%.
Embodiment 7
By domestic certain company vanadium-bearing slag of high calcium and high phosphor (Cr2O3Mass fraction is 8~16%, V2O5Mass fraction is 8~16%,
Fe mass fractions be 20~35%) with reduction coal, binding agent and flux in mass ratio 100:10:4:10 mixed processings are mixed
Compound material, and mixed material is obtained into pelletizing by disc balling machine shaping, pelletizing is carried out in tunnel cave at 1400 DEG C
Reduction roasting, reaction obtains reduction roasting product after terminating.By reduction roasting product under neutral atmosphere in molten point of stove of combustion gas
1600 DEG C carry out it is molten get ferrochrome (mass fraction containing Cr is 20%) and richness vanadium slag, ferrochrome can be sent to be smelted not
Rust steel, Cr in rich vanadium slag2O3Mass fraction is 1.8%, V2O5Mass fraction is 18%.By rich vanadium slag and sodium salt in mass ratio
100:800 DEG C of sodium oxide baking 2h obtain water-soluble sodium vanadate clinker, wherein pentavalent vanadium in multihearth roaster after 20 mixing
The ratio for accounting for full vanadium is 95%.Water-soluble sodium vanadate clinker is finally carried out into water logging vanadium extraction treatment and obtains vanadic anhydride (grade
And tailings 99.0%).The chromium recovery ratio 95% of whole flow process, vanadium recovery 96%, iron recovery 87%.
Embodiment 8
By domestic certain company vanadium-bearing slag of high calcium and high phosphor (Cr2O3Mass fraction is 16%, V2O5Mass fraction is 16%, Fe mass
Fraction be 35%) with reduction coal, binding agent and flux in mass ratio 100:12:5:15 mixed processings obtain mixed material, and
Mixed material is molded by disc balling machine and obtains pelletizing, pelletizing is carried out into reduction roasting in tunnel cave at 1375 DEG C,
Reaction obtains reduction roasting product after terminating.Reduction roasting product is melted for 1575 DEG C under neutral atmosphere in molten point of stove of combustion gas
Get ferrochrome (mass fraction containing Cr is 25%) and rich vanadium slag, ferrochrome can send to smelting stainless steel, rich vanadium slag
Middle Cr2O3Mass fraction is 1.9%, V2O5Mass fraction is 22%.By rich vanadium slag and sodium salt in mass ratio 100:20 mixing after
750 DEG C of sodium oxide baking 2h obtain water-soluble sodium vanadate clinker in multihearth roaster, and the ratio that wherein pentavalent vanadium accounts for full vanadium is
98%.Water-soluble sodium vanadate clinker is finally carried out into water logging vanadium extraction treatment and obtains vanadic anhydride (grade 99.4%) and tailings.
The chromium recovery ratio 97% of whole flow process, vanadium recovery 98%, iron recovery 90%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. it is a kind of process vanadium chromium slag method, it is characterised in that including：
Vanadium chromium slag, reduction coal, binding agent and flux are mixed, to obtain mixed material；
The mixed material is molded, to obtain pelletizing；
The pelletizing is carried out into reduction treatment, to obtain metallized pellet；
The metallized pellet is carried out into separating treatment, to obtain ferrochrome and rich vanadium slag；
The rich vanadium slag is mixed with sodium salt and sodium oxide baking treatment is carried out, to obtain water-soluble sodium vanadate clinker；
The water-soluble sodium vanadate clinker is carried out into water logging vanadium extraction treatment, to obtain vanadic anhydride and tailings.
2. method according to claim 1, it is characterised in that by the vanadium chromium slag, the reduction coal, the binding agent and
The flux is according to mass ratio 100:(6~12):(2~5):(5~15) are mixed.
3. method according to claim 1, it is characterised in that the reduction treatment is the temperature at 1300~1400 degrees Celsius
The lower completion of degree.
4. method according to claim 1, it is characterised in that by the rich vanadium slag with the sodium salt according to mass ratio 100:
(5~20) are mixed.
5. method according to claim 4, it is characterised in that the sodium salt includes being selected from sodium carbonate, sodium chloride and sulfuric acid
At least one of sodium.
6. method according to claim 1, it is characterised in that the sodium oxide baking treatment is Celsius 600~900
1~2h completions are carried out at a temperature of degree.
7. method according to claim 1, it is characterised in that the water logging vanadium extraction treatment is further included：
The water-soluble sodium vanadate clinker is carried out into Soaking treatment, to obtain containing vanadium solution；
Precipitation treatment is carried out containing vanadium solution by described, to obtain poly ammonium vanadate precipitation；
Poly ammonium vanadate precipitation is carried out into calcination processing, to obtain vanadic anhydride.
8. it is a kind of implement any one of claim 1~7 described in treatment vanadium chromium slag method system, it is characterised in that including：
Mixing device, the mixing device has vanadium chromium slag entrance, reduction coal entrance, binding agent entrance, flux entrance and mixes
Close material outlet；
There is shaped device, the shaped device mixed material entrance and pelletizing to export, and the mixed material entrance is mixed with described
Material outlet is closed to be connected；
Reduction apparatus, the reduction apparatus have pelletizing entrance and metallized pellet outlet, the pelletizing entrance and the pelletizing
Outlet is connected；
There is separator, the separator metallized pellet entrance, ferrochrome outlet and rich vanadium slag to export, the metal
Pellet entrance is connected with metallized pellet outlet；
Sodium oxide baking device, the sodium oxide baking device has rich vanadium slag entrance, sodium salt entrance, air intake and water
Dissolubility sodium vanadate clinker is exported, and the rich vanadium slag entrance is connected with the rich vanadium slag outlet；
Water logging vanadium extraction device, the water logging vanadium extraction device has water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and tail
Slag is exported, and the water-soluble sodium vanadate clinker entrance is connected with the water-soluble sodium vanadate clinker outlet.
9. system according to claim 8, it is characterised in that the reduction apparatus are tunnel cave or rotary hearth furnace, described point
It is mill ore magnetic selection device or molten separating device from device；Preferably, the mill ore magnetic selection device is the linkage of ball mill and magnetic separator
Device, the molten packing is set to molten point of stove of combustion gas.
10. system according to claim 8, it is characterised in that the sodium oxide baking device is multihearth roaster.
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| CN110616291A (en) * | 2019-09-29 | 2019-12-27 | 中冶赛迪工程技术股份有限公司 | Method for separating iron and vanadium by melting in electric furnace |
| CN112481488A (en) * | 2020-11-26 | 2021-03-12 | 攀枝花学院 | Method for preparing Fe-V-Cr alloy and titanium slag from high-chromium vanadium titano-magnetite through coal-based prereduction-electric furnace deep reduction melting separation |
| CN114164346A (en) * | 2021-12-10 | 2022-03-11 | 中南大学 | Method for synergistically recovering valuable metals in chromium-containing waste residues and carbon-containing waste materials |
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| CN108358246B (en) * | 2018-01-09 | 2019-12-10 | 中南大学 | Preparation method and application of sodium ferrochrome material |
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| CN110616291B (en) * | 2019-09-29 | 2021-12-07 | 中冶赛迪工程技术股份有限公司 | Method for separating iron and vanadium by melting in electric furnace |
| CN112481488A (en) * | 2020-11-26 | 2021-03-12 | 攀枝花学院 | Method for preparing Fe-V-Cr alloy and titanium slag from high-chromium vanadium titano-magnetite through coal-based prereduction-electric furnace deep reduction melting separation |
| CN114164346A (en) * | 2021-12-10 | 2022-03-11 | 中南大学 | Method for synergistically recovering valuable metals in chromium-containing waste residues and carbon-containing waste materials |
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