CN106834724A - 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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- CN106834724A CN106834724A CN201710208516.9A CN201710208516A CN106834724A CN 106834724 A CN106834724 A CN 106834724A CN 201710208516 A CN201710208516 A CN 201710208516A CN 106834724 A CN106834724 A CN 106834724A
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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, method includes：Vanadium chromium slag, reduction coal, binding agent and calcium salt 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 carried out into oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；And the acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted 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 that vanadium chromium content is suitable or 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.
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 calcium salt are mixed, to obtain mixed material；Will be described mixed
Compound material is molded, to obtain pelletizing；The pelletizing is carried out into reduction treatment, to obtain metallized pellet；Will be described
Metallized pellet carries out separating treatment, to obtain ferrochrome and rich vanadium slag；The rich vanadium slag is carried out into oxidation roasting with calcium compounds
Treatment, to obtain acid-soluble vanadic acid calcium clinker；And the acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment, so as 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 calcium
Salt 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
Iron, chromated oxide be reduced to simple substance, obtain metallized pellet, and then metallized pellet is carried out into separating treatment, respectively obtain
Ferrochrome product and rich vanadium slag；Further, oxidation roasting with calcium compounds treatment is carried out by by rich vanadium slag, obtains acid-soluble vanadic acid
Calcium clinker, then acid-leaching vanadium-extracted treatment is carried out by by acid-soluble vanadic acid calcium clinker, obtain vanadic anhydride product and tailings.By
This, 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, first ferrochrome product,
And rich vanadium slag is further processed, vanadic anhydride product is obtained, so as to realize the synthetical recovery of iron, chromium and v element in vanadium chromium slag
Utilize, 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, the vanadium chromium slag, the reduction coal, the binding agent and the calcium salt are pressed
According to mass ratio 100:(6~12):(2~5):(5~15) are mixed.Thus, it is possible to significantly improve sequential reduction treatment obtain
Metallized pellet degree of metalization, improve ferrochrome the rate of recovery.
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, the calcium salt include selected from calcium oxide, calcium carbonate and calcium hydroxide extremely
It is one of few.Thus, it is possible to further improve the degree of metalization of the metallized pellet that sequential reduction treatment is obtained, returning for ferrochrome is improved
Yield.And can further improve the quality of the vanadic anhydride product for preparing.
In some embodiments of the invention, the oxidation roasting with calcium compounds treatment is the temperature at 900~1200 degrees Celsius
Under carry out 1~2h completion.Thus, it is possible to further improve the quality of the vanadic anhydride product for preparing.
In some embodiments of the invention, the acid-leaching vanadium-extracted treatment is further included：By the acid-soluble calcium vanadate
Clinker carries out acidleach treatment, to obtain immersion liquid containing vanadic acid；The immersion liquid containing vanadic acid is carried out into precipitation treatment, to obtain poly
Ammonium vanadate is precipitated；Poly ammonium vanadate precipitation is carried out into calcination processing, to obtain vanadic anhydride.Thus, it is possible to enter one
Step improves the quality of the vanadic anhydride product for preparing.
In the second aspect of the present invention, the present invention proposes a kind of side of the treatment vanadium chromium slag implemented described in preceding embodiment
The system of method.Embodiments in accordance with the present invention, the system includes：Mixing device, the mixing device has vanadium chromium slag entrance, goes back
The outlet of raw coal entrance, binding agent entrance, calcium salt entrance and mixed material；Shaped device, the shaped device mixed material entrance
Exported with pelletizing, the mixed material entrance is connected with the mixture 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；Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device has rich vanadium slag entrance, air intake and acid-soluble vanadium
Sour calcium clinker outlet, the rich vanadium slag entrance is connected with the rich vanadium slag outlet；Acid-leaching vanadium-extracted device, the acid-leaching vanadium-extracted device
With acid-soluble vanadic acid calcium clinker entrance, vanadic anhydride outlet and tailings outlet, the acid-soluble vanadic acid calcium clinker entrance with
The acid-soluble vanadic acid calcium clinker outlet is connected.
Thus, the system for the treatment of vanadium chromium slag according to embodiments of the present invention is by using mixing device by vanadium chromium slag, reduction
Coal, binding agent and calcium salt mix, and the mixed material that will be obtained supplies into shaped device shaping and obtains pelletizing, then pelletizing is supplied
To reduction treatment is carried out in reduction apparatus, the iron in pelletizing, chromated oxide are reduced to simple substance using reduction coal, obtain metal
Pellet, and then metallized pellet is supplied separating treatment is carried out into mill ore magnetic selection device, respectively obtain ferrochrome product
With rich vanadium slag；Further, oxidation roasting with calcium compounds treatment is carried out into oxidation roasting with calcium compounds device by the way that rich vanadium slag is supplied, is obtained
To acid-soluble vanadic acid calcium clinker, then acid-soluble vanadic acid calcium clinker is carried out by acid-leaching vanadium-extracted treatment by acid-leaching vanadium-extracted device, obtained
Vanadic anhydride product and tailings.Thus, the system of the treatment vanadium chromium slag of the embodiment of the present invention is gone back by by chromium, iron and vanadium substep
Original, first ferrochrome product, and further process rich vanadium slag, vanadic anhydride product is obtained, so as in realizing vanadium chromium slag
The comprehensive reutilization of iron, chromium and v 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 shaped device is disc balling machine, and the reduction apparatus are rotary hearth furnace
Or tunnel cave.
In some embodiments of the invention, the separator is mill ore magnetic selection device or molten separating device；Preferably, institute
It is ball mill and the linkage of magnetic separator to state mill ore magnetic selection device, and the molten packing is set to electric furnace.
In some embodiments of the invention, the oxidation roasting with calcium compounds device is rotary kiln.
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 flow schematic 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 calcium salt are mixed, to obtain mixed material；By mixture
Material is molded, to obtain pelletizing；Pelletizing is carried out into reduction treatment, to obtain metallized pellet；Metallized pellet is entered
Row separating treatment, to obtain ferrochrome and rich vanadium slag；Rich vanadium slag is carried out into oxidation roasting with calcium compounds treatment, it is molten to obtain acid
Property vanadic acid calcium clinker；And acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride 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 calcium salt 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, is in advance entered vanadium chromium slag, reduction coal, binding agent and calcium salt
Row is mixed to get mixed material, can significantly improve the efficiency of sequential reduction treatment.
Embodiments in accordance with the present invention, the proportioning of vanadium chromium slag, reduction coal, binding agent and calcium salt for mixing does not receive spy
Do not limit, 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 calcium salt are according to mass ratio 100:(6~12):(2~5):(5~15) are mixed.Thus, may be used
To significantly improve the degree of metalization of the metallized pellet that sequential reduction treatment is obtained, the rate of recovery of ferrochrome is improved.Inventor's discovery,
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, calcium salt can play flux effect in reduction treatment, by allocating calcium salt into, also
The reduction effect of chromium and iron in sequential reduction treatment can be improved.
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+CaO=2Fe+CaO+SiO2+2CO；
2FeO·SiO2+ 2CO+CaO=2Fe+CaO+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.
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：Oxidation roasting with calcium compounds treatment
In the step, rich vanadium slag is carried out into oxidation roasting with calcium compounds treatment in atmosphere using the calcium salt in rich vanadium slag, so as to
Acid-soluble vanadic acid calcium clinker is obtained, wherein, during acid-soluble vanadic acid calcium clinker can be positive calcium vanadate, pyrovanadic acid calcium or metavanadic acid calcium
At least one of.Specifically, oxidation roasting with calcium compounds treatment is main includes following reaction：
CaO+V2O3+O2=CaV2O6Metavanadic acid calcium, (wherein vanadium is positive pentavalent)；
2CaO+V2O3+O2=Ca2V2O7Pyrovanadic acid calcium, (wherein vanadium is positive pentavalent)；
3CaO+V2O3+O2=Ca3V2O8Positive calcium vanadate, (wherein vanadium is positive pentavalent)；
CaO+V2O3+0.5O2=CaV2O5Metavanadic acid calcium, (wherein vanadium is positive tetravalence)；
2CaO+V2O3+0.5O2=Ca2V2O6Pyrovanadic acid calcium, (wherein vanadium is positive tetravalence)；
3CaO+V2O3+0.5O2=Ca3V2O7Positive calcium vanadate, (wherein vanadium is positive tetravalence)；
After testing, the ratio that positive pentavalent vanadium and positive tetravalence vanadium account for full vanadium in the acid-soluble vanadic acid calcium clinker of gained is not less than
90%.
Embodiments in accordance with the present invention, the condition of oxidation roasting with calcium compounds 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, oxidation roasting with calcium compounds treatment be 900~
1~2h completions are carried out under 1200 degrees Celsius.Thus, it is possible in ensureing to be calcined the acid-soluble vanadic acid calcium clinker for obtaining positive pentavalent and
The ratio that the vanadium of positive tetravalence accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
Embodiments in accordance with the present invention, the species of calcium 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, calcium salt can be selected from calcium oxide, calcium carbonate and calcium hydroxide
At least one.Thus, it is possible to further improve the rate of recovery of vanadium.
S600：Acid-leaching vanadium-extracted treatment
In the step, acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride and tailings.
Specifically, embodiments in accordance with the present invention, acid-leaching vanadium-extracted treatment specifically includes the following steps：
S610：Acidleach is processed
Embodiments in accordance with the present invention, acid-leaching vanadium-extracted treatment is carried out by by acid-soluble vanadic acid calcium clinker, and pickle liquor is body
The dilution heat of sulfuric acid of product concentration 5%~15%, extraction temperature is 60~80 degrees Celsius, and extraction time is 20~60min, leaches knot
Separation of solid and liquid after beam, can obtain immersion liquid containing vanadic acid
Wherein, the key reaction of generation is in above-mentioned acidleach treatment：
5Ca(VO3)2+6H+=H2V10O28 4-+2H2O+5Ca2+
S620：Precipitation is processed
Further, embodiments in accordance with the present invention, will contain vanadic acid immersion liquid purification and impurity removal, and immersion liquid containing vanadic acid is entered again after removal of impurities
The precipitation of row acid ammonium salt is processed, you can obtain poly ammonium vanadate precipitation.
Wherein, the key reaction of generation is in above-mentioned precipitation treatment：
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 calcium
Salt 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
Iron, chromated oxide be reduced to simple substance, obtain metallized pellet, and then metallized pellet is carried out into separating treatment, respectively obtain
Ferrochrome product and rich vanadium slag；Further, rich vanadium slag is carried out into oxidation roasting with calcium compounds by using the calcium salt in rich vanadium slag
Treatment, obtains acid-soluble vanadic acid calcium clinker, then acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment, obtains being soaked containing vanadic acid
Liquid, and will contain after vanadic acid immersion liquid carries out acid ammonium salt precipitation treatment, the poly ammonium vanadate precipitation to obtaining carries out calcination processing, with
Just vanadic anhydride product and tailings are obtained.It is computed, vanadium chromium slag is processed using the present processes, the rate of recovery of chromium is reachable
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 place of the embodiment of the present invention
The method of vanadium chromium slag is managed by by chromium, iron and vanadium step-by-step reduction, ferrochrome product being obtained first, and further processes rich vanadium slag,
Vanadic anhydride product is obtained, so as to realize the comprehensive reutilization of iron, chromium and v element in vanadium chromium slag, and technological process is short,
It is adapted to industrialization promotion.
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, oxidation roasting with calcium compounds device 500 and acid-leaching vanadium-extracted device 600.Wherein, mixing device 100 has vanadium chromium
Slag entrance 101, reduction coal entrance 102, binding agent entrance 103, calcium salt 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；Oxidation roasting with calcium compounds device 500 has rich vanadium slag entrance 501, air intake 502 and acid molten
Property vanadic acid calcium clinker outlet 503, rich vanadium slag entrance 501 exports 403 and is connected with rich vanadium slag；Acid-leaching vanadium-extracted device 600 has acid molten
Property vanadic acid calcium clinker entrance 601, vanadic anhydride outlet 602 and tailings outlet 603, acid-soluble vanadic acid calcium clinker entrance 601 with
Acid-soluble vanadic acid calcium clinker outlet 503 is connected.
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 calcium salt, to obtain mixed material.Specifically, vanadium chromium slag is red lattice vanadium titano-magnetite through blast furnace process and converter
The mine tailing obtained after oxidation blowing, its main thing is mutually FeO (Cr, V, Ti)2O3And 2FeOSiO2, vanadium, chromium and part iron master
To exist in the form of vanadium iron and chromohercynite, some iron exists in the form of fayalite.Converter vanadium chromium slag is
Vanadium, chromium content be suitable or chromium type high vanadium slag of low vanadium Gao Ge, wherein Cr2O3Mass fraction is about 8~16%, Fe mass fractions about
It is 20~35%, V2O5Mass fraction be about 8~16%, be worth with larger recycling.According to the active of different metal
Degree 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
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 calcium salt for mixing does not receive spy
Do not limit, 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 calcium salt are according to mass ratio 100:(6~12):(2~5):(5~15) are mixed.Thus, may be used
To significantly improve the degree of metalization of the metallized pellet that sequential reduction treatment is obtained, the rate of recovery of ferrochrome is improved.Inventor's discovery,
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, calcium salt can play flux effect in reduction treatment, by allocating calcium salt into, also
The reduction effect of chromium and iron in sequential reduction treatment can be improved.
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.
According to a particular 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 301 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, in reduction treatment preferentially also
What original was obtained is iron, followed by chromium, is finally vanadium so that the condition by controlling reduction treatment, can by iron in pelletizing, chromium and
The selective step-by-step reduction of vanadium, realizes that iron, chromium are separated with vanadium.Specifically, the reduction to iron compound is mainly included as follows instead
Should：
2FeO·SiO2+ 2C+CaO=2Fe+CaO+SiO2+2CO；
2FeO·SiO2+ 2CO+CaO=2Fe+CaO+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.
According to a particular embodiment of the invention, reduction apparatus 300 can be rotary hearth furnace or tunnel cave, 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 electric furnace.It is possible thereby to significantly improve
The efficiency of separating treatment.
Embodiments in accordance with the present invention, oxidation roasting with calcium compounds device 500 has the rich vanadium slag entrance 501, and of air intake 502
Acid-soluble vanadic acid calcium clinker outlet 503, rich vanadium slag entrance 501 is connected with rich vanadium slag outlet 403, oxidation roasting with calcium compounds device 500
It is suitable to rich vanadium slag is carried out into oxidation roasting with calcium compounds treatment in atmosphere using the calcium salt in rich vanadium slag, to obtain acid-soluble vanadic acid
Calcium clinker, wherein, acid-soluble vanadic acid calcium clinker can be at least one of positive calcium vanadate, pyrovanadic acid calcium or metavanadic acid calcium.Tool
Body ground, oxidation roasting with calcium compounds treatment is main to include following reaction：
CaO+V2O3+O2=CaV2O6Metavanadic acid calcium, (wherein vanadium is positive pentavalent)；
2CaO+V2O3+O2=Ca2V2O7Pyrovanadic acid calcium, (wherein vanadium is positive pentavalent)；
3CaO+V2O3+O2=Ca3V2O8Positive calcium vanadate, (wherein vanadium is positive pentavalent)；
CaO+V2O3+0.5O2=CaV2O5Metavanadic acid calcium, (wherein vanadium is positive tetravalence)；
2CaO+V2O3+0.5O2=Ca2V2O6Pyrovanadic acid calcium, (wherein vanadium is positive tetravalence)；
3CaO+V2O3+0.5O2=Ca3V2O7Positive calcium vanadate, (wherein vanadium is positive tetravalence)；
After testing, the ratio that positive pentavalent vanadium and positive tetravalence vanadium account for full vanadium in the acid-soluble vanadic acid calcium clinker of gained is not less than
90%.
Embodiments in accordance with the present invention, the condition of oxidation roasting with calcium compounds 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, oxidation roasting with calcium compounds treatment be 900~
1~2h completions are carried out under 1200 degrees Celsius.Thus, it is possible in ensureing to be calcined the acid-soluble vanadic acid calcium clinker for obtaining positive pentavalent and
The ratio that the vanadium of positive tetravalence accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
Embodiments in accordance with the present invention, the species of calcium 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, calcium salt can be selected from calcium oxide, calcium carbonate and calcium hydroxide
At least one.Thus, it is possible to further improve the rate of recovery of vanadium.
According to a particular embodiment of the invention, oxidation roasting with calcium compounds device 500 can be rotary kiln, it is possible thereby to further
The effect of oxidation roasting with calcium compounds treatment is improved, so as to further improve the rate of recovery of vanadium.
Embodiments in accordance with the present invention, acid-leaching vanadium-extracted device 500 is aoxidized with acid-soluble vanadic acid calcium clinker entrance 501, five
Two vanadium outlet 502 and tailings outlet 503, acid-soluble vanadic acid calcium clinker entrance 501 exports 403 phases with acid-soluble vanadic acid calcium clinker
Even, acid-leaching vanadium-extracted device 500 is suitable to for acid-soluble vanadic acid calcium clinker to carry out acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride
And tailings.Specifically, embodiments in accordance with the present invention,
Acid-leaching vanadium-extracted treatment specifically includes the following steps：
(1) acidleach treatment
Embodiments in accordance with the present invention, acid-leaching vanadium-extracted treatment is carried out by by acid-soluble vanadic acid calcium clinker, and pickle liquor is body
The dilution heat of sulfuric acid of product concentration 5%~15%, extraction temperature is 60~80 degrees Celsius, and extraction time is 20~60min, leaches knot
Separation of solid and liquid after beam, can obtain immersion liquid containing vanadic acid.
Wherein, the key reaction of generation is in above-mentioned acidleach treatment：
5Ca(VO3)2+6H+=H2V10O28 4-+2H2O+5Ca2+
(2) precipitation treatment
Embodiments in accordance with the present invention, will contain vanadic acid immersion liquid purification and impurity removal, and immersion liquid containing vanadic acid carries out acidic ammonium again after removal of impurities
Salt precipitation is processed, you can obtain poly ammonium vanadate precipitation.
Wherein, the key reaction of generation is in above-mentioned precipitation treatment：
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 calcium salt mix, and the mixed material that will be obtained supplies into shaped device shaping and obtains pelletizing, then using reduction apparatus
Pelletizing is carried out into reduction treatment, the iron in pelletizing, chromated oxide is reduced to simple substance using reduction coal, obtain metallized pellet,
And then metallized pellet is supplied separating treatment is carried out into mill ore magnetic selection device, respectively obtain ferrochrome product and rich vanadium
Slag；Further, rich vanadium slag is supplied into oxidation roasting with calcium compounds device, rich vanadium slag is carried out into oxygen using the calcium salt in rich vanadium slag
Change calcification baking treatment, obtain acid-soluble vanadic acid calcium clinker, then acid-soluble vanadic acid calcium clinker is supplied into acid-leaching vanadium-extracted device
Acid-leaching vanadium-extracted treatment is carried out, immersion liquid containing vanadic acid is obtained, and will be contained after vanadic acid immersion liquid carries out acid ammonium salt precipitation treatment, to what is obtained
Poly ammonium vanadate precipitation carries out calcination processing, to obtain vanadic anhydride product and tailings.It is computed, is using the application
System treatment vanadium chromium slag, up to more than 85%, up to more than 80%, the rate of recovery of vanadium is up to 95% for the rate of recovery of iron for the rate of recovery of chromium
More than.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 ferrochrome and closing first
Golden product, and further process rich vanadium slag, obtains vanadic anhydride product, so as to realize iron, chromium and v element in vanadium chromium slag
Comprehensive reutilization, and technological process is short, 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 calcium salt in mass ratio 100:6:2:5 are mixed, and mixed material is made by disk
Ball machine shaping obtains pelletizing.Pelletizing is supplied to rotary hearth furnace carries out reduction roasting at 1300 DEG C, and reaction obtains gold after terminating
Category pellet.In linkage of the ball mill with magnetic separator metallized pellet carried out into mill ore magnetic selection obtain ferrochrome (containing
15%) and rich vanadium slag Cr mass fractions are for, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Mass fraction is
1.5%, V2O5Mass fraction is 12%.By rich vanadium slag, oxidation roasting with calcium compounds 1h obtains acid-soluble vanadic acid at 900 DEG C in the rotary kiln
The ratio that calcium clinker, wherein pentavalent vanadium and tetravalence vanadium account for full vanadium is 92%.Acid-soluble vanadic acid calcium clinker finally is carried out into acidleach to carry
Vanadium treatment obtains vanadic anhydride (grade 98.8%) and tailings.The chromium recovery ratio of whole flow process is 85%, and vanadium recovery is
95%, iron recovery is 85%.
Embodiment 2
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 calcium salt 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 rotary hearth furnace 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 in the rotary kiln at 1000 DEG C oxidation roasting with calcium compounds 1.5h to obtain acid molten
Property vanadic acid calcium clinker, wherein pentavalent vanadium and tetravalence vanadium account for full vanadium ratio be 96%.Finally acid-soluble vanadic acid calcium clinker is carried out
Acid-leaching vanadium-extracted treatment obtains vanadic anhydride (grade 99.2%) and tailings.The chromium recovery ratio of whole flow process is 87%, and vanadium is reclaimed
Rate is 97%, and iron recovery is 80%.
Embodiment 3
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 calcium salt in mass ratio 100:10:4:10 are mixed, and will be mixed
Compound material is molded by disc balling machine and obtains pelletizing.Pelletizing is supplied to rotary hearth furnace carries out reduction roasting at 1400 DEG C,
Reaction obtains metallized pellet after terminating.Metallized pellet is carried out into mill ore magnetic selection in the linkage of ball mill and magnetic separator
Ferrochrome (mass fraction containing Cr is 20%) and rich vanadium slag are obtained, ferrochrome can be used for smelting stainless steel, in rich vanadium slag
Cr2O3Mass fraction is 1.8%, V2O5Mass fraction is 18%.By rich vanadium slag in the rotary kiln oxidation roasting with calcium compounds at 1100 DEG C
2h obtains acid-soluble vanadic acid calcium clinker, and the ratio that wherein pentavalent vanadium and tetravalence vanadium account for full vanadium is 95%.Finally by acid-soluble vanadic acid
Calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 99.0%) and tailings.The chromium recovery ratio of whole flow process is
88%, vanadium recovery is 96%, and iron recovery is 87%.
Embodiment 4
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 calcium salt 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 rotary hearth furnace 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 in the rotary kiln at 1200 DEG C oxidation roasting with calcium compounds 2h to obtain acid molten
Property vanadic acid calcium clinker, wherein pentavalent vanadium and tetravalence vanadium account for full vanadium ratio be 98%.Finally acid-soluble vanadic acid calcium clinker is carried out
Acid-leaching vanadium-extracted treatment obtains vanadic anhydride (grade 99.4%) and tailings.The chromium recovery ratio of whole flow process is 90%, and vanadium is reclaimed
Rate 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 calcium salt in mass ratio 100:6:2:5 are mixed to get mixed material, and mixed material is led to
Cross disc balling machine shaping and obtain pelletizing, pelletizing is carried out into reduction roasting in tunnel cave at 1300 DEG C, reaction is obtained after terminating
To reduction roasting product.Reduction roasting product is carried out molten getting ferrochrome for 1550 DEG C under weak oxide atmosphere in electric furnace
(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, 900 DEG C of oxidation roasting with calcium compounds 1h obtain acid-soluble vanadic acid in rotary kiln
Calcium clinker, the ratio that the gross mass of wherein pentavalent vanadium and tetravalence vanadium accounts for full vanadium is 92%.Finally acid-soluble vanadic acid calcium clinker is entered
The acid-leaching vanadium-extracted treatment of row obtains vanadic anhydride (grade 98.8%) and tailings.The chromium recovery ratio 91% of whole flow process, vanadium is reclaimed
Rate 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 calcium salt in mass ratio 100:8:3:8 are mixed to get mixed material, and by mixture
Material is molded by disc balling machine and obtains pelletizing, and pelletizing is carried out into reduction roasting at 1350 DEG C in tunnel cave, and reaction terminates
After obtain reduction roasting product.Reduction roasting product is carried out molten getting ferrochrome for 1500 DEG C under weak oxide atmosphere in electric furnace
Alloy (mass fraction containing Cr is 18%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Quality
Fraction is 1.7%, V2O5Mass fraction is 15%.By rich vanadium slag, 1000 DEG C of oxidation roasting with calcium compounds 1.5h obtain acid in rotary kiln
The ratio that dissolubility vanadic acid calcium clinker, wherein pentavalent vanadium and tetravalence vanadium account for full vanadium is 96%.Finally acid-soluble vanadic acid calcium clinker is entered
The acid-leaching vanadium-extracted treatment of row obtains vanadic anhydride (grade 99.2%) and tailings.The chromium recovery ratio 93% of whole flow process, vanadium is reclaimed
Rate 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 calcium salt in mass ratio 100:10:4:10 are mixed to get mixture
Material, and mixed material is obtained into pelletizing by disc balling machine shaping, pelletizing is reduced in tunnel cave at 1400 DEG C
Roasting, reaction obtains reduction roasting product after terminating.Reduction roasting product is melted for 1600 DEG C under neutral atmosphere in electric furnace
Get ferrochrome (mass fraction containing Cr is 20%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, rich vanadium slag
Middle Cr2O3Mass fraction is 1.8%, V2O5Mass fraction is 18%.By rich vanadium slag in rotary kiln 1100 DEG C of oxidation roasting with calcium compounds
2h obtains acid-soluble vanadic acid calcium clinker, and the ratio that wherein pentavalent vanadium and tetravalence vanadium account for full vanadium is 95%.Finally by acid-soluble vanadic acid
Calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 99.0%) and tailings.The chromium recovery ratio of whole flow process
95%, 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 calcium salt in mass ratio 100:12:5:15 are mixed to get 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 1375 DEG C
Reduction roasting product is obtained after beam.Reduction roasting product is carried out molten ferrochrome of getting and closed for 1575 DEG C under neutral atmosphere in electric furnace
Gold (mass fraction containing Cr is 25%) 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, 1200 DEG C of oxidation roasting with calcium compounds 2h obtain acid-soluble in rotary kiln
The ratio that vanadic acid calcium clinker, wherein pentavalent vanadium and tetravalence vanadium account for full vanadium is 98%.Acid-soluble vanadic acid calcium clinker is finally carried out into acid
Leaching and vanadium extraction treatment 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 calcium salt 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 carried out into oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；And
The acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted 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 calcium salt 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 the calcium salt includes being selected from calcium oxide, calcium carbonate and hydrogen-oxygen
Change at least one of calcium.
5. method according to claim 1, it is characterised in that the oxidation roasting with calcium compounds treatment is taken the photograph 900~1200
1~2h completions are carried out at a temperature of family name's degree.
6. method according to claim 1, it is characterised in that the acid-leaching vanadium-extracted treatment is further included：
The acid-soluble vanadic acid calcium clinker is carried out into acidleach treatment, to obtain immersion liquid containing vanadic acid；
The immersion liquid containing vanadic acid is carried out into precipitation treatment, to obtain poly ammonium vanadate precipitation；
Poly ammonium vanadate precipitation is carried out into calcination processing, to obtain vanadic anhydride.
7. it is a kind of implement any one of claim 1~6 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, calcium salt entrance and mixing
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；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device has rich vanadium slag entrance, air intake and acid-soluble vanadic acid
Calcium clinker is exported, and the rich vanadium slag entrance is connected with the rich vanadium slag outlet；
Acid-leaching vanadium-extracted device, the acid-leaching vanadium-extracted device has acid-soluble vanadic acid calcium clinker entrance, vanadic anhydride outlet and tail
Slag is exported, and the acid-soluble vanadic acid calcium clinker entrance is connected with the acid-soluble vanadic acid calcium clinker outlet.
8. system according to claim 7, it is characterised in that the shaped device is disc balling machine, described also original-pack
It is set to rotary hearth furnace or tunnel cave.
9. system according to claim 7, it is characterised in that the separator is mill ore magnetic selection device or molten packing
Put；Preferably, the mill ore magnetic selection device is the linkage of ball mill and magnetic separator, and the molten packing is set to electric furnace.
10. system according to claim 7, it is characterised in that the oxidation roasting with calcium compounds device is rotary kiln.
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| CN111519021A (en) * | 2020-06-09 | 2020-08-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Calcification roasting method for vanadium-containing material |
| CN112011693A (en) * | 2020-09-24 | 2020-12-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium-chromium alloy by roasting, acid leaching and vanadium extracting of vanadium-chromium slag |
| CN115466848A (en) * | 2022-09-19 | 2022-12-13 | 西安建筑科技大学 | Method for extracting multiple elements from vanadium-rich slag and application |
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| CN112011693A (en) * | 2020-09-24 | 2020-12-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium-chromium alloy by roasting, acid leaching and vanadium extracting of vanadium-chromium slag |
| CN115466848A (en) * | 2022-09-19 | 2022-12-13 | 西安建筑科技大学 | Method for extracting multiple elements from vanadium-rich slag and application |
| CN115466848B (en) * | 2022-09-19 | 2024-02-20 | 西安建筑科技大学 | Method for extracting multiple elements from vanadium-rich slag and application |
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