CN106756070A - Process the method and system of vanadium-bearing slag of high calcium and high phosphor - Google Patents
Process the method and system of vanadium-bearing slag of high calcium and high phosphor Download PDFInfo
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- CN106756070A CN106756070A CN201710184730.5A CN201710184730A CN106756070A CN 106756070 A CN106756070 A CN 106756070A CN 201710184730 A CN201710184730 A CN 201710184730A CN 106756070 A CN106756070 A CN 106756070A
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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
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses the method and system for the treatment of vanadium-bearing slag of high calcium and high phosphor, wherein, the method for processing vanadium-bearing slag of high calcium and high phosphor includes：Vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent are carried out into mixed processing, to obtain mixed material；The mixed material is carried out into forming processes, to obtain mixing pelletizing；The mixing pelletizing is carried out into reduction roasting dephosphorization treatment, to obtain dephosphorization metallized pellet and phosphorous flue gas；The dephosphorization metallized pellet is carried out into mill ore magnetic selection treatment, to obtain iron powder and low-phosphorous vanadium slag；The low-phosphorous 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 product.By the method using present invention treatment vanadium-bearing slag of high calcium and high phosphor, the phosphorus in vanadium-bearing slag of high calcium and high phosphor can be effectively removed, and then significantly improve the rate of recovery and quality of iron and vanadium.
Description
Technical field
The invention belongs to metallurgical technology field, specifically, the present invention relates to processing the method for vanadium-bearing slag of high calcium and high phosphor and being
System.
Background technology
Vanadium slag refers to that vanadium-bearing hot metal is oxidized into a kind of slag rich in barium oxide and ferriferous oxide through bessemerizing,
Its main component has MFe, FeO, SiO2、V2O3、TiO2、CaO、Al2O3, MgO and Cr2O3.The vanadium that there are about 60% in the world is from vanadium
Extracted in slag, the extraction vanadium method of existing vanadium slag is to be put into carry out oxidation roasting in rotary kiln or multiple hearth furnace after being mixed with additive
Burn, obtain the vanadate of solubility, precipitation is carried out again after vanadium is transferred to liquid phase by wet-leaching means from solid phase, by precipitation
Product calcining obtains V2O5Product.Phosphorus is that, containing the harmful element in vanadium leachate precipitation, it can form steady with vanadium in acid medium
Fixed and complicated complex compound phosphorus vanadium system's heteropoly acid and their salt, additionally, can also be with the iron ion in solution and aluminium ion
Form FePO4、AlPO4Precipitation, these can all pollute ammonium vanadate precipitation, have a strong impact on the carrying out of acid ammonium salt precipitation.Conventional is de-
Phosphorus means are subsequently adding appropriate calcium salt or magnesium salts formation calcium phosphate precipitation, typically to adjust pH value of solution between 9.5-11.0
It is required that the leachate P concentration after dephosphorization<0.015g/L.
CaO mass fractions are generally less than 3%, P in common vanadium slag2O5Mass fraction is generally less than 0.2%.In order to mitigate half
The burden of steel dephosphorization, vanadium-bearing hot metal blowing vanadium slag can add the calcium salt to carry out pre- dephosphorization simultaneously, obtain low-phosphorous half steel and high calcium is high
The special vanadium slag of phosphorus.This vanadium-bearing slag of high calcium and high phosphor is high because of itself CaO content, CaO meetings and V during sodium roasting2O5Generation is water insoluble
Calcium vanadate CaOV2O5Or the vanadium green grass or young crops calcium CaV containing calcium12O30, the mass fraction of CaO often increases by 1% will bring 4.7-
9.0% V2O5Loss, therefore sodium roasting-water logging process for extracting vanadium should not be used；If using calcification baking-acid-leaching vanadium-extracted work
Skill, can be such that substantial amounts of calcium and phosphorus is together entered into leachate along with vanadium, due to the presence for having a large amount of calcium ions in solution, adjust
Section pH value of solution can re-form vanadic acid calcium precipitate between 9.5-11.0, so can not be using the dephosphorization under traditional alkalescence condition
Method, and the dephosphorization problem under acid system is not yet captured.
Therefore, the technology to vanadium-bearing slag of high calcium and high phosphor dephosphorization vanadium extraction need further development.
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 to propose a kind of method and system for processing vanadium-bearing slag of high calcium and high phosphor, wherein the method for the treatment of vanadium-bearing slag of high calcium and high phosphor is led to
The phosphorus crossed in removing vanadium-bearing slag of high calcium and high phosphor in advance, can effectively reclaim the iron and vanadium for obtaining high-quality, while can also further carry
The rate of recovery of high ferro and vanadium.
According to an aspect of the present invention, the present invention proposes a kind of method for processing vanadium-bearing slag of high calcium and high phosphor, including：By height
Calcium high phosphorus vanadium slag, silica, reduction coal and binding agent carry out mixed processing, to obtain mixed material；Mixed material is carried out into
Type treatment, to obtain mixing pelletizing；Mixing pelletizing is carried out into reduction roasting dephosphorization treatment, to obtain dephosphorization metallized pellet
With phosphorous flue gas；Dephosphorization metallized pellet is carried out into mill ore magnetic selection treatment, to obtain iron powder and low-phosphorous vanadium slag；By low-phosphorous vanadium slag
Oxidation roasting with calcium compounds treatment is carried out, to obtain acid-soluble vanadic acid calcium clinker；And acid-soluble vanadic acid calcium clinker is carried out into acidleach
Vanadium extraction is processed, to obtain vanadic anhydride product.Thus, the method for the treatment vanadium-bearing slag of high calcium and high phosphor of the embodiment of the present invention, no
Only can effectively remove the phosphorus in vanadium-bearing slag of high calcium and high phosphor, it is to avoid vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted enters containing in vanadium leachate
So as to have a strong impact on precipitation effect, recycling can also be carried out to the iron resource in vanadium-bearing slag of high calcium and high phosphor, finally be contained
Phosphorus amount low high-quality iron resource and vanadic anhydride product.
The method for the treatment of vanadium-bearing slag of high calcium and high phosphor according to the above embodiment of the present invention can also have following additional technology
Feature：
In some embodiments of the invention, the content of CaO is 3-25 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5Content
It is 0.2-1 weight %, V2O5Content for 5-20 weight %, Fe content be 20-35 weight %.Thus the embodiment of the present invention
The method for processing vanadium-bearing slag of high calcium and high phosphor can be processed effectively for high calcium Phosphorus vanadium slag high, and then improve being applicable for the method
Scope.
In some embodiments of the invention, the content of CaO is 5-15 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5Content
It is 0.2-0.6 weight %, V2O5Content for 5-10 weight %, Fe content be 20-30 weight %.Thus the embodiment of the present invention
The method for the treatment of vanadium-bearing slag of high calcium and high phosphor effectively can be processed for high calcium Phosphorus vanadium slag high, and then improve the suitable of the method
Use scope.
In some embodiments of the invention, high calcium high phosphorus is in mass ratio except ferrovanadium slag, silica, reduction coal and binding agent
100:(5-15):(8-15)：(2-5) carries out mixed processing.Mixing pelletizing can be effectively prepared, and further after raising
Continuous reduced iron and dephosphorization under reducing atmosphere effect.
In some embodiments of the invention, the temperature of reduction roasting dephosphorization treatment is 1200-1400 DEG C.Thus, it is possible to
Further improve reduced iron and dephosphorization under reducing atmosphere effect.
In some embodiments of the invention, the degree of metalization of dephosphorization metallized pellet is not less than 75%.Thus, it is possible to enter
One step improves the rate of recovery of iron when follow-up mill ore magnetic selection is processed.
In some embodiments of the invention, P in low-phosphorous vanadium slag2O5Content be not more than 0.1 weight %.Thus, it is possible to carry
The quality of vanadium in follow-up acid-leaching vanadium-extracted treatment high.
In some embodiments of the invention, P in low-phosphorous vanadium slag2O5Content be not more than 0.05 weight %.Thus, it is possible to
Further improve the quality of vanadium in follow-up acid-leaching vanadium-extracted treatment.
In some embodiments of the invention, Fe contents are not more than 5 weight %, iron in vanadium-bearing slag of high calcium and high phosphor in low-phosphorous vanadium slag
The rate of recovery be not less than 80 weight %.Thus, it is possible to further improve the quality of vanadic anhydride product.
In some embodiments of the invention, the temperature of oxidation roasting with calcium compounds treatment is 900-1200 DEG C, and the time is 1-2h.
Thus, it is possible to further improve the yield of acid-soluble vanadic acid calcium clinker, and then improve the rate of recovery of vanadium.
In some embodiments of the invention, the calcium vanadate in acid-soluble vanadic acid calcium clinker be positive tetravalence calcium vanadate and/or
Positive pentavalent calcium vanadate, the calcium vanadate in acid-soluble vanadic acid calcium clinker be in positive calcium vanadate, pyrovanadic acid calcium and metavanadic acid calcium at least
It is a kind of.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted treatment vanadium the rate of recovery.
According to another aspect of the present invention, the invention allows for a kind for the treatment of high calcium high phosphorus for implementing above-described embodiment
The system of the method for vanadium slag, the system includes：Mixing arrangement, disc balling machine, reduction roasting dephosphorization apparatus, mill ore magnetic selection dress
Put, oxidation roasting with calcium compounds device and acid-leaching vanadium-extracted device.
Wherein, mixing arrangement has vanadium-bearing slag of high calcium and high phosphor entrance, silica entrance, reduction coal entrance, binding agent entrance and mixes
Material outlet is closed, mixing arrangement is suitable to for vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent to carry out mixed processing, so as to
To mixed material；There is disc balling machine mixed material entrance and mixing pelletizing to export, and mixed material entrance goes out with mixed material
Mouth is connected, and disc balling machine is suitable to for mixed material to carry out forming processes, to obtain mixing pelletizing；Reduction roasting dephosphorization apparatus
With mixing pelletizing entrance, the outlet of dephosphorization metallized pellet and phosphorous exhanst gas outlet, mixing pelletizing entrance is exported with pelletizing is mixed
It is connected, reduction roasting dephosphorization apparatus are suitable to for mixing pelletizing to carry out reduction roasting dephosphorization treatment, to obtain dephosphorization metallization ball
Group and phosphorous flue gas；There is mill ore magnetic selection device dephosphorization metallized pellet entrance, iron powder outlet and low-phosphorous vanadium slag to export, dephosphorization gold
Category pellet entrance is connected with the outlet of dephosphorization metallized pellet, and mill ore magnetic selection device is suitable to for dephosphorization metallized pellet to carry out ore grinding
Magnetic separation is processed, to obtain iron powder and low-phosphorous vanadium slag；Oxidation roasting with calcium compounds device, oxidation roasting with calcium compounds device has low-phosphorous vanadium slag
Entrance, air intake and acid-soluble vanadic acid calcium clinker outlet, low-phosphorous vanadium slag entrance are connected with the outlet of low-phosphorous vanadium slag, oxidation calcification roasting
Burn device to be suitable to for low-phosphorous vanadium slag to carry out oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；Acid-leaching vanadium-extracted dress
Put with acid-soluble vanadic acid calcium clinker entrance, vanadic anhydride outlet and tailings outlet, acid-soluble vanadic acid calcium clinker entrance and acid
The outlet of dissolubility vanadic acid calcium clinker is connected, and acid-leaching vanadium-extracted device is suitable to for acid-soluble vanadic acid calcium clinker to carry out acid-leaching vanadium-extracted treatment, with
Just vanadic anhydride and tailings are obtained.
Thus, by the system of the treatment vanadium-bearing slag of high calcium and high phosphor using the above embodiment of the present invention, not only can effectively take off
Except the phosphorus in vanadium-bearing slag of high calcium and high phosphor, it is to avoid vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted enter containing in vanadium leachate so as to have a strong impact on
Precipitation effect, can also carry out recycling to the iron resource in vanadium-bearing slag of high calcium and high phosphor, final to obtain the low high-quality of phosphorus content
Iron resource and vanadic anhydride product.
The system for the treatment of vanadium-bearing slag of high calcium and high phosphor according to the above embodiment of the present invention can also have following additional technology
Feature：
In some embodiments of the invention, reduction roasting dephosphorization apparatus are rotary hearth furnace, and mill ore magnetic selection device includes linkage
The ball mill and magnetic separator of setting, oxidation roasting with calcium compounds device are rotary kiln.Thus, it is possible to further improve treatment high calcium high phosphorus
Efficiency during vanadium slag.
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 flow chart of the method for the treatment of vanadium-bearing slag of high calcium and high phosphor according to an embodiment of the invention；
Fig. 2 is the structural representation of the system for the treatment of vanadium-bearing slag of high calcium and high phosphor according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of embodiment is shown in the drawings, wherein identical from start to finish
Or similar label represents same or similar element or the element with same or like function.Retouched below with reference to accompanying drawing
The embodiment stated is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes a kind of method for processing vanadium-bearing slag of high calcium and high phosphor.According to this hair
The method of the treatment vanadium-bearing slag of high calcium and high phosphor of bright embodiment includes：Vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent are mixed
Conjunction is processed, to obtain mixed material；Mixed material is carried out into forming processes, to obtain mixing pelletizing；Mixing pelletizing is entered
Row reduction roasting dephosphorization treatment, to obtain dephosphorization metallized pellet and phosphorous flue gas；Mill ore magnetic selection treatment will be carried out, so as to
To iron powder and low-phosphorous vanadium slag；Low-phosphorous vanadium slag is carried out into oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；And
Acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride product.
It is according to the above embodiment of the present invention treatment vanadium-bearing slag of high calcium and high phosphor method, first by vanadium-bearing slag of high calcium and high phosphor, silica,
Reduction coal and binding agent carry out mixed processing and obtain mixed material, and mixed material is carried out forming processes obtain mix pelletizing,
Then mixing pelletizing is carried out into reduction roasting dephosphorization treatment, obtains dephosphorization metallized pellet and phosphorous flue gas, realize the mesh of dephosphorization
, mill ore magnetic selection treatment then is carried out to dephosphorization metallized pellet, by iron powder from dephosphorization metallized pellet separating treatment, obtain
Iron powder and low-phosphorous vanadium slag, then oxidation roasting with calcium compounds treatment is carried out to low-phosphorous vanadium slag, acid-soluble vanadic acid calcium clinker is obtained, finally to acid
Dissolubility vanadic acid calcium clinker carries out acid-leaching vanadium-extracted treatment, finally gives vanadic anhydride product.Thus, the treatment of the embodiment of the present invention
The method of vanadium-bearing slag of high calcium and high phosphor not only can effectively remove the phosphorus in vanadium-bearing slag of high calcium and high phosphor, it is to avoid vanadic acid calcium clinker is acid-leaching vanadium-extracted
When phosphorus enter containing so as to have a strong impact on precipitation effect, can also being returned to the iron resource in vanadium-bearing slag of high calcium and high phosphor in vanadium leachate
Receive and recycle, it is final to obtain phosphorus content low high-quality iron resource and vanadic anhydride product.Additionally, the method also has high calcium high
Phosphorus vanadium slag dephosphorization rate is high, and iron and vanadium recovery are high, the advantage of superior product quality.
The method of the treatment vanadium-bearing slag of high calcium and high phosphor of the above embodiment of the present invention is described in detail below with reference to Fig. 1.
S100：Mixed processing
Embodiments in accordance with the present invention, mixed processing is carried out by vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent, with
Just mixed material is obtained.
According to a particular embodiment of the invention, the content of CaO is 3-25 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5Content
It is 0.2-1 weight %, V2O5Content for 5-20 weight %, Fe content be 20-35 weight %.Thus, the embodiment of the present invention
The method for processing vanadium-bearing slag of high calcium and high phosphor can be higher than 3 weight %, P effectively for CaO content2O5Height of the content higher than 0.2 weight %
Calcium high phosphorus vanadium slag is processed, and can obtain the iron and vanadic anhydride product of high-quality.
According to a particular embodiment of the invention, the content of CaO is 5-15 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5Content
It is 0.2-0.6 weight %, V2O5Content for 5-10 weight %, Fe content be 20-30 weight %.Thus, the embodiment of the present invention
Treatment vanadium-bearing slag of high calcium and high phosphor method can effectively for CaO content be 5-15 weight %, P2O5Content is 0.2-0.6 weights
The vanadium-bearing slag of high calcium and high phosphor for measuring % is processed, and can obtain the iron and vanadic anhydride product of high-quality.
According to a particular embodiment of the invention, high calcium high phosphorus is in mass ratio except ferrovanadium slag, silica, reduction coal and binding agent
100:(5-15):(8-15)：(2-5) carries out mixed processing.Mixing pelletizing can be effectively prepared, and further after raising
Continuous reduced iron and dephosphorization under reducing atmosphere effect.Specific example of the invention, inventor has found, matches somebody with somebody in removing ferrovanadium slag to high calcium high phosphorus
Enter the silica and reduction coal of aforementioned proportion, high calcium high phosphorus can be effectively improved except the percent reduction of calcium phosphate in ferrovanadium slag and iron
Percent reduction, and then improve the rate of recovery of dephosphorization effect and iron.
According to a particular embodiment of the invention, the type of binding agent is not particularly restricted, for example, of the invention viscous
Knot agent can be one or more in bentonite, waterglass, molasses, starch solution.Thus, it is possible to further improve it is follow-up into
The quality of efficiency and mixing pelletizing during type treatment.
S200：Forming processes
Embodiments in accordance with the present invention, forming processes are carried out by mixed material, to obtain mixing pelletizing.
According to a particular embodiment of the invention, the device of forming processes is not particularly restricted, for example, of the invention
Implement example, forming processing equipment can be disc balling machine.Thus, it is possible to further improve the efficiency of forming processes.
S300：Reduction roasting dephosphorization treatment
Embodiments in accordance with the present invention, reduction roasting dephosphorization treatment is carried out by mixing pelletizing, to obtain dephosphorization metallization
Pelletizing and phosphorous flue gas.Thus, reduction roasting dephosphorization treatment is carried out by mixing pelletizing, the calcium phosphate in mixed material can be made
Phosphorus simple substance is reduced into, and is entered in flue gas in the form of steam, hereby it is achieved that the effect of dephosphorization；Simultaneously can also be to mixing
Iron in material reduce obtaining fe.
According to a particular embodiment of the invention, to high calcium high phosphorus except ferrovanadium slag allocate into silica, reduction coal and binding agent and into
Reduction roasting dephosphorization treatment is carried out after type to carry out dephosphorization and to carry iron.Specifically, dephosphorization and carry iron reaction can be according to following
Reaction equation is carried out：
Dephosphorisation reaction：Ca3PO4+5C+SiO2=P2↑+5CO↑+3CaSiO3
Propose iron reaction：FeO·V2O3+ C=V2O3+Fe+CO
FeO·V2O3+ CO=V2O3+Fe+CO2
According to a particular embodiment of the invention, the temperature of reduction roasting dephosphorization treatment can be 1200-1400 DEG C.Inventor
It was found that, under the conditions of the reduction roasting dephosphorization treatment, can further improve phosphorus removal efficiency and iron percent reduction.
According to a particular embodiment of the invention, by using above-mentioned reduction roasting dephosphorization treatment condition, the dephosphorization gold for obtaining
The degree of metalization for belonging to pellet is not less than 75%, and then effectively iron in vanadium-bearing slag of high calcium and high phosphor can be reclaimed.
S400：Mill ore magnetic selection treatment
Embodiments in accordance with the present invention, mill ore magnetic selection treatment is carried out by dephosphorization metallized pellet, to obtain iron powder and low
Phosphorus vanadium slag.Thus, magnetic separation treatment is being carried out after ore grinding treatment is carried out to dephosphorization metallized pellet, can be by dephosphorization metallized pellet
In iron powder and low-phosphorous vanadium slag efficiently separated, realize recovery to iron.Specific example of the invention, it is isolated
Low-phosphorous vanadium slag in Fe contents be not more than 5 weight %；The rate of recovery of iron is not less than 80 weight %.
According to a particular embodiment of the invention, P in the low-phosphorous vanadium slag that magnetic separation treatment is obtained2O5Content be not more than 0.1 weight
Amount %.Thus, it is possible to being prevented effectively from follow-up vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted enters heavy containing being had a strong impact in vanadium leachate
Vanadium effect, it is final to obtain high-quality vanadic anhydride product.
According to a particular embodiment of the invention, P in the low-phosphorous vanadium slag that magnetic separation treatment is obtained2O5Content be not more than 0.05 weight
Amount %.Thus, it is possible to being prevented effectively from follow-up vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted enters heavy containing being had a strong impact in vanadium leachate
Vanadium effect, it is final to obtain high-quality vanadic anhydride product.
S500：Oxidation roasting with calcium compounds treatment
Embodiments in accordance with the present invention, oxidation roasting with calcium compounds treatment is carried out by low-phosphorous vanadium slag, to obtain acid-soluble vanadic acid
Calcium clinker.
According to a particular embodiment of the invention, the temperature of oxidation roasting with calcium compounds treatment can be 900-1200 DEG C, and the time is
1-2h.Inventor has found, to dephosphorization after low-phosphorous vanadium slag carry out oxidation roasting with calcium compounds treatment again, in can making low-phosphorous vanadium slag
Vanadium is oxidized to positive tetravalence or positive pentavalent, and exists in the form of acid-soluble calcium vanadate, especially in oxidation roasting with calcium compounds treatment
Under the conditions of, the oxygenation efficiency of vanadium is higher.Thus, the present invention can enter one by the temperature and time for controlling oxidation roasting with calcium compounds to process
Step improves the yield of acid-soluble vanadic acid calcium clinker, and then improves the rate of recovery of vanadium.
According to a particular embodiment of the invention, in the oxidation roasting with calcium compounds processing procedure for carrying out under the above-described reaction conditions,
The specific reaction for occurring is as follows in dephosphorization agglomerates：
CaO+V2O3+O2=CaV2O6Metavanadic acid calcium (pentavalent, acid-soluble)
2CaO+V2O3+O2=Ca2V2O7Pyrovanadic acid calcium (pentavalent, acid-soluble)
3CaO+V2O3+O2=Ca3V2O8Positive calcium vanadate (pentavalent, acid-soluble)
CaO+V2O3+0.5O2=CaV2O5Metavanadic acid calcium (tetravalence, acid-soluble)
2CaO+V2O3+0.5O2=Ca2V2O6Pyrovanadic acid calcium (tetravalence, acid-soluble)
3CaO+V2O3+0.5O2=Ca3V2O7Positive calcium vanadate (tetravalence, acid-soluble)
Therefore, according to a particular embodiment of the invention, the acid-soluble calcium vanadate for obtaining is processed by oxidation roasting with calcium compounds ripe
Calcium vanadate in material can include at least one, or tetravalence vanadic acid in positive calcium vanadate, pyrovanadic acid calcium and metavanadic acid calcium
The arbitrary proportion mixing of calcium and pentavalent calcium vanadate.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted treatment calcium vanadate it is molten
Solution, and then significantly improve the rate of recovery of vanadium.
S600：Acid-leaching vanadium-extracted treatment
Embodiments in accordance with the present invention, acid-leaching vanadium-extracted treatment is carried out by acid-soluble vanadic acid calcium clinker, to obtain five oxidations
Two vanadium products
According to a particular embodiment of the invention, acid-leaching vanadium-extracted treatment can specifically be carried out according to the following steps：First by acid
The vanadic acid calcium clinker of dissolubility carries out acidleach and obtains containing vanadium solution and acid leaching residue, then will contain vanadium solution purification and impurity removal, then to purification
Afterwards containing vanadium solution carry out acid ammonium salt precipitation treatment obtain ammonium poly-vanadate precipitation, ammonium poly-vanadate is finally carried out into calcination processing and is obtained
To vanadic anhydride.Thus, five oxygen of acquisition can effectively be reclaimed by carrying out acid-leaching vanadium-extracted treatment to acid-soluble vanadic acid calcium clinker
Change two vanadium products.
According to another aspect of the present invention, the invention allows for a kind of side for implementing above-mentioned treatment vanadium-bearing slag of high calcium and high phosphor
The system of method, with reference to Fig. 2, including：Mixing arrangement 100, disc balling machine 200, reduction roasting dephosphorization apparatus 300, mill ore magnetic selection
Device 400, oxidation roasting with calcium compounds device 500 and acid-leaching vanadium-extracted device 600.
Using the system of above-mentioned treatment vanadium-bearing slag of high calcium and high phosphor, first by mixing arrangement 100 to vanadium-bearing slag of high calcium and high phosphor, silicon
Stone, reduction coal and binding agent carry out mixed processing, obtain mixed material, then enter mixed material in disc balling machine 200
Row forming processes, are obtained mixing pelletizing, and then mixing pelletizing is carried out at reduction roasting dephosphorization in reduction roasting dephosphorization apparatus 300
Reason, obtains dephosphorization metallized pellet and phosphorous flue gas, is achieved in the purpose of dephosphorization, then in mill ore magnetic selection device 400 to dephosphorization
Metallized pellet carries out mill ore magnetic selection treatment, by the iron powder separating treatment in dephosphorization metallized pellet, obtains iron powder and low-phosphorous vanadium
Slag, then oxidation roasting with calcium compounds treatment is carried out to low-phosphorous vanadium slag in oxidation roasting with calcium compounds device 500, obtain acid-soluble calcium vanadate ripe
Material, finally carries out acid-leaching vanadium-extracted treatment in acid-leaching vanadium-extracted device 600 to acid-soluble vanadic acid calcium clinker, finally gives five oxidations two
Vanadium product.
Thus, the present invention can be improved further by the system of the treatment vanadium-bearing slag of high calcium and high phosphor using above-described embodiment
The rate of recovery of the iron resource in vanadium-bearing slag of high calcium and high phosphor, and the phosphorus effectively in removing vanadium-bearing slag of high calcium and high phosphor, it is to avoid vanadic acid calcium clinker exists
Phosphorus enters containing so as to have a strong impact on precipitation effect, and then further improving vanadium-bearing slag of high calcium and high phosphor in vanadium leachate when acid-leaching vanadium-extracted
Dephosphorization effect, and improve the rate of recovery and quality of iron and vanadium.
The system of the treatment vanadium-bearing slag of high calcium and high phosphor of the above embodiment of the present invention is described in detail below with reference to Fig. 2.
Mixing arrangement 100
Embodiments in accordance with the present invention, mixing arrangement 100 has vanadium-bearing slag of high calcium and high phosphor entrance 110, silica entrance 120, goes back
Raw coal entrance 130, binding agent entrance 140 and mixed material outlet 150, mixing arrangement 100 is suitable to vanadium-bearing slag of high calcium and high phosphor, silicon
Stone, reduction coal and binding agent carry out mixed processing, to obtain mixed material.
According to a particular embodiment of the invention, the content of CaO is 3-25 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5Content
It is 0.2-1 weight %, V2O5Content for 5-20 weight %, Fe content be 20-35 weight %.Thus, the embodiment of the present invention
The method for processing vanadium-bearing slag of high calcium and high phosphor can be higher than 3 weight %, P effectively for CaO content2O5Height of the content higher than 0.2 weight %
Calcium high phosphorus vanadium slag is processed, and can obtain the iron and vanadic anhydride product of high-quality.
According to a particular embodiment of the invention, the content of CaO is 5-15 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5Content
It is 0.2-0.6 weight %, V2O5Content for 5-10 weight %, Fe content be 20-30 weight %.Thus, the embodiment of the present invention
Treatment vanadium-bearing slag of high calcium and high phosphor method can effectively for CaO content be 5-15 weight %, P2O5Content is 0.2-0.6 weights
The vanadium-bearing slag of high calcium and high phosphor for measuring % is processed, and can obtain the iron and vanadic anhydride product of high-quality.
According to a particular embodiment of the invention, high calcium high phosphorus is in mass ratio except ferrovanadium slag, silica, reduction coal and binding agent
100:(5-15):(8-15)：(2-5) carries out mixed processing.Mixing pelletizing can be effectively prepared, and further after raising
Continuous reduced iron and dephosphorization under reducing atmosphere effect.Specific example of the invention, inventor has found, matches somebody with somebody in removing ferrovanadium slag to high calcium high phosphorus
Enter the silica and reduction coal of aforementioned proportion, high calcium high phosphorus can be effectively improved except the percent reduction of calcium phosphate in ferrovanadium slag and iron
Percent reduction, and then improve the rate of recovery of dephosphorization effect and iron.
According to a particular embodiment of the invention, the type of binding agent is not particularly restricted, for example, of the invention viscous
Knot agent can be one or more in bentonite, waterglass, molasses, starch solution.Thus, it is possible to further improve it is follow-up into
The quality of efficiency and mixing pelletizing during type treatment.
Disc balling machine 200
Embodiments in accordance with the present invention, disc balling machine 200 has mixed material entrance 210 and mixing pelletizing outlet 220,
Mixed material entrance 210 is connected with mixed material outlet 150, and disc balling machine 200 is suitable to for mixed material to carry out forming processes,
To obtain mixing pelletizing.
According to a particular embodiment of the invention, the device of forming processes is not particularly restricted, for example, of the invention
Implement example, forming processing equipment can be disc balling machine 200.Thus, it is possible to further improve the efficiency of forming processes.
Reduction roasting dephosphorization apparatus 300
Embodiments in accordance with the present invention, reduction roasting dephosphorization apparatus 300 have entrance 310, the dephosphorization metallization of mixing pelletizing
Pelletizing exports 320 and phosphorous exhanst gas outlet 330, and mixing pelletizing entrance 310 is connected with mixing pelletizing outlet 220, and reduction roasting takes off
Phosphorus device 300 is suitable to for mixing pelletizing to carry out reduction roasting dephosphorization treatment, to obtain dephosphorization metallized pellet and phosphorous flue gas.
According to a particular embodiment of the invention, mixing pelletizing is carried out into reduction roasting in reduction roasting dephosphorization apparatus 300
Dephosphorization treatment, obtains dephosphorization metallized pellet and phosphorous flue gas.Thus, reduction roasting dephosphorization treatment is carried out by mixing pelletizing,
The calcium phosphate in mixed material can be made to be reduced into phosphorus simple substance, and entered in flue gas in the form of steam, hereby it is achieved that dephosphorization
Effect；Can also the iron in mixed material reduce obtaining fe simultaneously.
According to a particular embodiment of the invention, to high calcium high phosphorus except ferrovanadium slag allocate into silica, reduction coal and binding agent and into
Reduction roasting dephosphorization treatment is carried out after type to carry out dephosphorization and to carry iron.Specifically, dephosphorization and carry iron reaction can be according to following
Reaction equation is carried out：
Dephosphorisation reaction：Ca3PO4+5C+SiO2=P2↑+5CO↑+3CaSiO3
Propose iron reaction：FeO·V2O3+ C=V2O3+Fe+CO
FeO·V2O3+ CO=V2O3+Fe+CO2
According to a particular embodiment of the invention, the temperature of reduction roasting dephosphorization treatment can be 1200-1400 DEG C.Inventor
It was found that, under the conditions of the reduction roasting dephosphorization treatment, can further improve phosphorus removal efficiency and iron percent reduction.
According to a particular embodiment of the invention, by using above-mentioned reduction roasting dephosphorization treatment condition, the dephosphorization gold for obtaining
The degree of metalization for belonging to pellet is not less than 75%, and then effectively iron in vanadium-bearing slag of high calcium and high phosphor can be reclaimed.
According to a particular embodiment of the invention, reduction roasting dephosphorization apparatus 300 can be rotary hearth furnace.Thus, it is possible to enter one
Step improves the efficiency of reduction roasting dephosphorization treatment.
Mill ore magnetic selection device 400
Embodiments in accordance with the present invention, mill ore magnetic selection device 400 is exported with dephosphorization metallized pellet entrance 410, iron powder
420 and low-phosphorous vanadium slag outlet 430, dephosphorization metallized pellet entrance 410 and dephosphorization metallized pellet export 320 and are connected, ore grinding magnetic
Screening device 400 is suitable to for dephosphorization metallized pellet to carry out mill ore magnetic selection treatment, to obtain iron powder and low-phosphorous vanadium slag.
According to a particular embodiment of the invention, mill ore magnetic selection is carried out to dephosphorization metallized pellet in mill ore magnetic selection device 400
Treatment, by the iron powder separating treatment in dephosphorization metallized pellet, obtains iron powder and low-phosphorous vanadium slag.Thus, metallize ball to dephosphorization
Group is carrying out magnetic separation treatment after carrying out ore grinding treatment, can carry out effectively the iron powder in dephosphorization metallized pellet and low-phosphorous vanadium slag
Ground is separated, and realizes the recovery to iron.Specific example of the invention, Fe contents are not more than 5 in isolated low-phosphorous vanadium slag
Weight %；The rate of recovery of iron is not less than 80 weight %.
According to a particular embodiment of the invention, P in the low-phosphorous vanadium slag that magnetic separation treatment is obtained2O5Content be not more than 0.1 weight
Amount %.Thus, it is possible to being prevented effectively from follow-up vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted enters heavy containing being had a strong impact in vanadium leachate
Vanadium effect, it is final to obtain high-quality vanadic anhydride product.
According to a particular embodiment of the invention, P in low-phosphorous vanadium slag2O5Content be not more than 0.05 weight %.Thus, it is possible to
Follow-up vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted is prevented effectively to enter containing precipitation effect is had a strong impact in vanadium leachate, it is final to obtain
High-quality vanadic anhydride product.
According to a particular embodiment of the invention, mill ore magnetic selection device can include ball mill and magnetic separator that linkage is set.
Thus, it is possible to further improve the efficiency of mill ore magnetic selection treatment.
Oxidation roasting with calcium compounds device 500
Embodiments in accordance with the present invention, oxidation roasting with calcium compounds device 500 has low-phosphorous vanadium slag entrance 510, air intake 520
530 are exported with acid-soluble vanadic acid calcium clinker, low-phosphorous vanadium slag entrance 510 exports be connected 430, oxidation roasting with calcium compounds dress with low-phosphorous vanadium slag
Put and be suitable to for low-phosphorous vanadium slag to carry out oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker.
According to a particular embodiment of the invention, the temperature of oxidation roasting with calcium compounds treatment can be 900-1200 DEG C, and the time is
1-2h.Inventor has found, to dephosphorization after low-phosphorous vanadium slag carry out oxidation roasting with calcium compounds treatment again, in can making low-phosphorous vanadium slag
Vanadium is oxidized to positive tetravalence or positive pentavalent, and exists in the form of acid-soluble calcium vanadate, especially in oxidation roasting with calcium compounds treatment
Under the conditions of, the oxygenation efficiency of vanadium is higher.Thus, the present invention can enter one by the temperature and time for controlling oxidation roasting with calcium compounds to process
Step improves the yield of acid-soluble vanadic acid calcium clinker, and then improves the rate of recovery of vanadium.
According to a particular embodiment of the invention, in the oxidation roasting with calcium compounds processing procedure for carrying out under the above-described reaction conditions,
The specific reaction for occurring is as follows in dephosphorization agglomerates：
CaO+V2O3+O2=CaV2O6Metavanadic acid calcium (pentavalent, acid-soluble)
2CaO+V2O3+O2=Ca2V2O7Pyrovanadic acid calcium (pentavalent, acid-soluble)
3CaO+V2O3+O2=Ca3V2O8Positive calcium vanadate (pentavalent, acid-soluble)
CaO+V2O3+0.5O2=CaV2O5Metavanadic acid calcium (tetravalence, acid-soluble)
2CaO+V2O3+0.5O2=Ca2V2O6Pyrovanadic acid calcium (tetravalence, acid-soluble)
3CaO+V2O3+0.5O2=Ca3V2O7Positive calcium vanadate (tetravalence, acid-soluble)
Therefore, according to a particular embodiment of the invention, the acid-soluble calcium vanadate for obtaining is processed by oxidation roasting with calcium compounds ripe
Calcium vanadate in material can include at least one, or tetravalence vanadic acid in positive calcium vanadate, pyrovanadic acid calcium and metavanadic acid calcium
The arbitrary proportion mixing of calcium and pentavalent calcium vanadate.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted treatment calcium vanadate it is molten
Solution, and then significantly 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.Thus, it is possible to enter one
Step improves the efficiency of oxidation roasting with calcium compounds treatment.
Acid-leaching vanadium-extracted device 600
Embodiments in accordance with the present invention, acid-leaching vanadium-extracted device 600 is aoxidized with acid-soluble vanadic acid calcium clinker entrance 610, five
Two vanadium outlet 620 and tailings outlet 630, acid-soluble vanadic acid calcium clinker entrance 610 exports 530 phases with acid-soluble vanadic acid calcium clinker
Even, acid-leaching vanadium-extracted device 600 is suitable to for acid-soluble vanadic acid calcium clinker to carry out acid-leaching vanadium-extracted treatment, so as to obtain vanadic anhydride and
Tailings,
According to a particular embodiment of the invention, acid-leaching vanadium-extracted device 600 further includes acidleach device, purifier, sinks
Vanadium device and calciner plant.Wherein, acidleach device is suitable to for acid-soluble vanadic acid calcium clinker to carry out acidleach treatment, to obtain containing vanadium
Solution and acid leaching residue；Purifier is suitable to that purification and impurity removal will be carried out containing vanadium solution, so as to after being purified containing vanadium solution；Precipitation
Device be suitable to purification after carry out acid ammonium salt precipitation treatment containing vanadium solution, so as to obtain ammonium poly-vanadate precipitation；Calciner plant
It is suitable to carry out calcination processing to ammonium poly-vanadate, to obtain vanadic anhydride product.Thus, by acid-soluble vanadic acid calcium clinker
Carrying out acid-leaching vanadium-extracted treatment can effectively reclaim acquisition vanadic anhydride product.
Embodiment 1
By domestic certain company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 3 weight %, P2O5Content is 0.2 weight %, V2O5Content
For 20 weight %, Fe contents are 35 weight %), silica, reduction coal and bentonite in mass ratio 100:5:15:2 be mixed to get it is mixed
Compound material, mixed material on disc balling machine be molded obtains mixing pelletizing.Will mixing pelletizing in rotary hearth furnace
Reduction roasting is carried out at 1200 DEG C, phosphorus is mainly entered in flue gas in the form of phosphorous vapor, and reaction obtains dephosphorization metallization after terminating
Pelletizing, the degree of metalization of dephosphorization metallized pellet is 80%.Linkage by dephosphorization metallized pellet in ball mill and magnetic separator is filled
Put carry out mill ore magnetic selection treatment obtain iron powder and low-phosphorous vanadium slag, iron powder can send to steel-making, P in low-phosphorous vanadium slag2O5Content is
0.09 weight %, Fe content is 5 weight %.By low-phosphorous vanadium slag, 900 DEG C of oxidation roasting with calcium compounds 1h obtain acid-soluble in rotary kiln
Vanadic acid calcium clinker, wherein the ratio that the gross mass of positive pentavalent vanadium and positive tetravalence vanadium accounts for full vanadium is 92%.Finally by acid-soluble vanadic acid
Calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 98.7%) and tailings.The vanadium recovery of whole flow process
95.2%, iron recovery 85.4%.
Embodiment 2
By domestic certain company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 25 weight %, P2O5Content is 1 weight %, V2O5Content
For 5 weight %, Fe contents are 20 weight %), silica, reduction coal and starch solution in mass ratio 100:15:8:3 be mixed to get it is mixed
Compound material.Mixed material on disc balling machine be molded and obtains mixing pelletizing.Will mixing pelletizing in rotary hearth furnace
Reduction roasting is carried out at 1400 DEG C, phosphorus is mainly entered in flue gas in the form of phosphorous vapor, and reaction obtains dephosphorization metallization after terminating
Pelletizing, the degree of metalization of dephosphorization metallized pellet is 75%.Linkage by dephosphorization metallized pellet in ball mill and magnetic separator is filled
Put carry out mill ore magnetic selection treatment obtain iron powder and low-phosphorous vanadium slag, iron powder can send to steel-making, P in low-phosphorous vanadium slag2O5Content is
0.05 weight %, Fe content is 3 weight %.By low-phosphorous vanadium slag, 1000 DEG C of oxidation roasting with calcium compounds 1.5h obtain sour molten in rotary kiln
Property vanadic acid calcium clinker, wherein the gross mass of positive pentavalent vanadium and positive tetravalence vanadium account for full vanadium ratio be 96%.Finally by acid-soluble vanadium
Sour calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 99.3%) and tailings.The vanadium recovery of whole flow process
97.3%, iron recovery 80.7%.
Embodiment 3
By domestic certain company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 15 weight %, P2O5Content is 0.6 weight %, V2O5Contain
Measure as 7 weight %, Fe contents are 30 weight %), silica, reduction coal and waterglass in mass ratio 100:10:10:4 are mixed to get
Mixed material.Mixed material on disc balling machine be molded and obtains mixing pelletizing.Will mixing pelletizing in rotary hearth furnace
Reduction roasting is carried out at 1300 DEG C, phosphorus is mainly entered in flue gas in the form of phosphorous vapor, and reaction obtains dephosphorization metallization after terminating
Pelletizing, the degree of metalization of dephosphorization metallized pellet is 82%.Linkage by dephosphorization metallized pellet in ball mill and magnetic separator is filled
Put carry out mill ore magnetic selection treatment obtain iron powder and low-phosphorous vanadium slag, iron powder can send to steel-making, P in low-phosphorous vanadium slag2O5Content is
0.04 weight %, Fe content is 4 weight %.By low-phosphorous vanadium slag, 1100 DEG C of oxidation roasting with calcium compounds 2h obtain acid-soluble in rotary kiln
Vanadic acid calcium clinker, wherein the ratio that the gross mass of positive pentavalent vanadium and positive tetravalence vanadium accounts 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 99.2%) and tailings.The vanadium recovery of whole flow process
96.8%, iron recovery 87.3%.
Embodiment 4
By domestic certain company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 5 weight %, P2O5Content is 0.2 weight %, V2O5Content
For 10 weight %, Fe contents are 30 weight %), silica, reduction coal and molasses in mass ratio 100:8:9:5 are mixed to get mixture
Material.Mixed material on disc balling machine be molded and obtains mixing pelletizing.Pelletizing will be mixed in rotary hearth furnace at 1350 DEG C
Under carry out reduction roasting, phosphorus is mainly entered in flue gas in the form of phosphorous vapor, and reaction obtains dephosphorization metallized pellet after terminating, and takes off
The degree of metalization of phosphorus metallized pellet is 85%.Dephosphorization metallized pellet is carried out on the linkage of ball mill and magnetic separator
Mill ore magnetic selection treatment obtains iron powder and low-phosphorous vanadium slag, and iron powder can send to steel-making, P in low-phosphorous vanadium slag2O5Content is 0.03 weight
Amount %, Fe contents are 2 weight %.By low-phosphorous vanadium slag, 1200 DEG C of oxidation roasting with calcium compounds 2h obtain acid-soluble calcium vanadate in rotary kiln
Clinker, wherein the ratio that the gross mass of positive pentavalent vanadium and positive tetravalence vanadium accounts for full vanadium is 98%.Finally by acid-soluble vanadic acid calcium clinker
Carry out acid-leaching vanadium-extracted treatment and obtain vanadic anhydride (grade 99.6%) and tailings.The vanadium recovery 98.2% of whole flow process, iron
The rate of recovery 90.7%.
Embodiment 5
By domestic certain company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 10 weight %, P2O5Content is 0.4 weight %, V2O5Contain
Measure as 8 weight %, Fe contents are 25 weight %), silica, reduction coal and bentonite in mass ratio 100:11:12:3.5 mix
To mixed material.Just mixed material carries out being molded on disc balling machine and obtains mixing pelletizing.Pelletizing will be mixed in rotary hearth furnace
Interior that reduction roasting is carried out at 1250 DEG C, phosphorus is mainly entered in flue gas in the form of phosphorous vapor, and reaction obtains dephosphorization gold after terminating
Category pellet, the degree of metalization of dephosphorization metallized pellet is 77%.By dephosphorization metallized pellet in ball mill and the connection of magnetic separator
Mill ore magnetic selection treatment is carried out on dynamic device and obtains iron powder and low-phosphorous vanadium slag, iron powder can send to steel-making, P in low-phosphorous vanadium slag2O5Content
For 0.01 weight %, Fe content is 3 weight %.Low-phosphorous vanadium slag is obtained into acid with 1150 DEG C of oxidation roasting with calcium compounds 2h in rotary kiln
Dissolubility vanadic acid calcium clinker, wherein the ratio that the gross mass of positive pentavalent vanadium and positive tetravalence vanadium accounts for full vanadium is 91%.Finally will be acid-soluble
Vanadic acid calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 98.7%) and tailings.The vanadium recovery of whole flow process
94.2%, iron recovery 82.2%.
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 any
Combined in an appropriate manner in individual or multiple embodiments or example.Additionally, in the case of not conflicting, the technology of this area
Can be combined for the feature of the different embodiments or example described in this specification and different embodiments or example by personnel
And combination.
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-bearing slag of high calcium and high phosphor method, it is characterised in that including：
(1) vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent are carried out into mixed processing, to obtain mixed material；
(2) mixed material is carried out into forming processes, to obtain mixing pelletizing；
(3) the mixing pelletizing is carried out into reduction roasting dephosphorization treatment, to obtain dephosphorization metallized pellet and phosphorous flue gas；
(4) the dephosphorization metallized pellet is carried out into mill ore magnetic selection treatment, to obtain iron powder and low-phosphorous vanadium slag；
(5) the low-phosphorous vanadium slag is carried out into oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；And
(6) the acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride product.
2. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (1), the high calcium is high
The content of CaO is 3-25 weight %, P in phosphorus vanadium slag2O5Content be 0.2-1 weight %, V2O5Content be 5-20 weight %,
The content of Fe is 20-35 weight %；
Preferably, the content of CaO is 5-15 weight %, P in the vanadium-bearing slag of high calcium and high phosphor2O5Content be 0.2-0.6 weight %,
V2O5Content for 5-10 weight %, Fe content be 20-30 weight %.
3. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (1), by the high calcium
High phosphorus is 100 except ferrovanadium slag, the silica, the reduction coal and the binding agent in mass ratio:(5-15):(8-15)：(2-5)
Carry out the mixed processing.
4. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (3), the reduction roasting
The temperature for burning dephosphorization treatment is 1200-1400 DEG C.
5. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (3), the dephosphorization gold
The degree of metalization for belonging to pellet is not less than 75%.
6. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (4), the low-phosphorous vanadium
P in slag2O5Content be not more than 0.1 weight %；
Preferably, P in the low-phosphorous vanadium slag2O5Content be not more than 0.05 weight %.
7. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (4), the low-phosphorous vanadium
Fe contents are not more than 5 weight % in slag, and the rate of recovery of iron is not less than 80 weight % in the vanadium-bearing slag of high calcium and high phosphor.
8. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that in step (5), the calcium oxide
The temperature for changing calcination process is 900-1200 DEG C, and the time is 1-2h.
9. the method for processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that described acid-soluble in step (5)
Calcium vanadate in vanadic acid calcium clinker is positive tetravalence calcium vanadate and/or positive pentavalent calcium vanadate, in the acid-soluble vanadic acid calcium clinker
Calcium vanadate is at least one in positive calcium vanadate, pyrovanadic acid calcium and metavanadic acid calcium.
10. the system that the method for vanadium-bearing slag of high calcium and high phosphor is processed described in a kind of implementation claim any one of 1-9, it is characterised in that
Including：
Mixing arrangement, the mixing arrangement has vanadium-bearing slag of high calcium and high phosphor entrance, silica entrance, reduction coal entrance, binding agent entrance
Exported with mixed material, the mixing arrangement is suitable to carry out vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent at mixing
Reason, to obtain mixed material；
There is disc balling machine, the disc balling machine mixed material entrance and mixing pelletizing to export, the mixed material entrance
It is connected with mixed material outlet, the disc balling machine is suitable to for the mixed material to carry out forming processes, to obtain
Mixing pelletizing；
Reduction roasting dephosphorization apparatus, the reduction roasting dephosphorization apparatus have mixing pelletizing entrance, the outlet of dephosphorization metallized pellet
With phosphorous exhanst gas outlet, the mixing pelletizing entrance is connected with the mixing pelletizing outlet, and the reduction roasting dephosphorization apparatus are suitable
In the mixing pelletizing is carried out into reduction roasting dephosphorization treatment, to obtain dephosphorization metallized pellet and phosphorous flue gas；
There is mill ore magnetic selection device, the mill ore magnetic selection device dephosphorization metallized pellet entrance, iron powder outlet and low-phosphorous vanadium slag to go out
Mouthful, the outlet of the dephosphorization metallized pellet entrance and the dephosphorization metallized pellet is connected, the mill ore magnetic selection device be suitable to by
The dephosphorization metallized pellet carries out mill ore magnetic selection treatment, to obtain iron powder and low-phosphorous vanadium slag；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device has low-phosphorous vanadium slag entrance, air intake and acid-soluble vanadium
Sour calcium clinker outlet, the low-phosphorous vanadium slag entrance is connected with the low-phosphorous vanadium slag outlet, and the oxidation roasting with calcium compounds device is suitable to
The low-phosphorous vanadium slag is carried out into oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；
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, the acid-leaching vanadium-extracted dress
Put and be suitable to for the acid-soluble vanadic acid calcium clinker to carry out acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride and tailings,
Preferably, the reduction roasting dephosphorization apparatus are rotary hearth furnace, and the mill ore magnetic selection device includes the ball mill that linkage is set
And magnetic separator, the oxidation roasting with calcium compounds device is rotary kiln.
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| CN114807595A (en) * | 2022-04-11 | 2022-07-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Pretreatment method of high-phosphorus high-sulfur vanadium extraction tailings |
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| CN114807595A (en) * | 2022-04-11 | 2022-07-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Pretreatment method of high-phosphorus high-sulfur vanadium extraction tailings |
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