CN106756120A - 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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- CN106756120A CN106756120A CN201710183971.8A CN201710183971A CN106756120A CN 106756120 A CN106756120 A CN 106756120A CN 201710183971 A CN201710183971 A CN 201710183971A CN 106756120 A CN106756120 A CN 106756120A
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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
- 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
- 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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- 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-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 molten office reason, to obtain molten iron 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 9.511.0, 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 molten office reason, to obtain molten iron and low-phosphorous vanadium slag；Low-phosphorous vanadium slag is carried out
Oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker；And carry out acid-soluble vanadic acid calcium clinker acid-leaching vanadium-extracted
Treatment, 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, not only may be used
Effectively to 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 enter containing in vanadium leachate so as to
Precipitation effect is had a strong impact on, recycling can also be carried out to the iron resource in vanadium-bearing slag of high calcium and high phosphor, finally obtain phosphorus content
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.Can be 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 molten office is managed.
In some embodiments of the invention, P in low-phosphorous vanadium slag2O5Content be not more than 0.1 weight %.Thus, it is possible to have
Effect improves the quality of vanadium in follow-up acid-leaching vanadium-extracted treatment.
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 the vanadic anhydride product for reclaiming.
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, high pressure para-roller ball pressing machine, reduction roasting dephosphorization apparatus, molten packing
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；High pressure para-roller ball pressing machine has mixed material entrance and mixing pelletizing outlet, mixed material entrance and mixture
Material outlet is connected, and high pressure para-roller ball pressing machine is suitable to for mixed material to carry out forming processes, to obtain mixing pelletizing；Reduction roasting
Dephosphorization apparatus have mixing pelletizing entrance, the outlet of dephosphorization metallized pellet and phosphorous exhanst gas outlet, mix pelletizing entrance and mix
Pelletizing outlet is connected, and reduction roasting dephosphorization apparatus are suitable to for mixing pelletizing to carry out reduction roasting dephosphorization treatment, to obtain dephosphorization
Metallized pellet and phosphorous flue gas；There is molten separating device dephosphorization metallized pellet entrance, molten iron outlet and low-phosphorous vanadium slag to export, and take off
Phosphorus metallized pellet entrance is connected with the outlet of dephosphorization metallized pellet, and molten separating device is suitable to for dephosphorization metallized pellet to carry out molten point
Treatment, to obtain molten iron and low-phosphorous vanadium slag；Oxidation roasting with calcium compounds device has low-phosphorous vanadium slag entrance, air intake and acid-soluble
Vanadic acid calcium clinker is exported, and low-phosphorous vanadium slag entrance is connected with the outlet of low-phosphorous vanadium slag, and oxidation roasting with calcium compounds device is suitable to low-phosphorous vanadium slag
Oxidation roasting with calcium compounds treatment is carried out, to obtain acid-soluble vanadic acid calcium clinker；Acid-leaching vanadium-extracted device has acid-soluble calcium vanadate ripe
Material entrance, vanadic anhydride outlet and tailings outlet, acid-soluble vanadic acid calcium clinker entrance export phase with acid-soluble vanadic acid calcium clinker
Even, acid-leaching vanadium-extracted device is suitable to for acid-soluble vanadic acid calcium clinker to carry out acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride and tail
Slag.
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 tunnel cave, and molten packing is set to electric furnace, calcium oxide
Change calciner is multihearth roaster.Thus, it is possible to efficiency when further improving treatment vanadium-bearing slag of high calcium and high phosphor.
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 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.
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；Dephosphorization metallized pellet is carried out molten point
Treatment, to obtain molten iron 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
, molten office reason is then carried out to dephosphorization metallized pellet, iron is isolated in the form of molten iron from dephosphorization metallized pellet
Come, obtain molten iron and low-phosphorous vanadium slag, then oxidation roasting with calcium compounds treatment is carried out to low-phosphorous vanadium slag, obtain acid-soluble vanadic acid calcium clinker,
Acid-leaching vanadium-extracted treatment finally is carried out to acid-soluble vanadic acid calcium clinker, vanadic anhydride product is finally given.Thus, the present invention is implemented
The method of the treatment vanadium-bearing slag of high calcium and high phosphor of example 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 exists
Phosphorus enters containing so as to have a strong impact on precipitation effect, can also being provided to the iron in vanadium-bearing slag of high calcium and high phosphor in vanadium leachate when acid-leaching vanadium-extracted
Source carries out recycling, final to obtain phosphorus content low high-quality iron resource and vanadic anhydride product.Additionally, the method also has
There is vanadium-bearing slag of high calcium and high phosphor dephosphorization rate high, 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.
Embodiments in accordance with the present invention, the type of binding agent is not particularly restricted, for example, binding agent of the invention
Can be one or more in bentonite, waterglass, molasses, starch solution.Thus, it is possible to further improve at subsequent forming
The quality of efficiency and mixing pelletizing during reason.
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 high pressure para-roller ball pressing 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：Molten office reason
Embodiments in accordance with the present invention, carry out molten office reason, to obtain molten iron and low-phosphorous vanadium by dephosphorization metallized pellet
Slag.Thus, molten office reason is carried out to dephosphorization metallized pellet, iron can be divided in the form of molten iron from dephosphorization metallized pellet
Separate out and, obtain molten iron and low-phosphorous vanadium slag, realize the recovery to iron.According to a particular embodiment of the invention, it is isolated low
Fe contents are not more than 5 weight % in phosphorus vanadium slag, and the rate of recovery of iron is not less than 80 weight % in vanadium-bearing slag of high calcium and high phosphor.
According to a particular embodiment of the invention, P in the low-phosphorous vanadium slag that office reason is obtained is melted2O5Content 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 office reason is obtained is melted2O5Content be not more than 0.05 weight
Amount %.Thus, it is possible to further improve the quality of vanadium in follow-up acid-leaching vanadium-extracted treatment.Thus, it is possible to be prevented effectively from follow-up vanadic acid
Calcium clinker phosphorus when acid-leaching vanadium-extracted enters containing precipitation effect is had a strong impact in vanadium leachate, and the final high-quality vanadic anhydride that obtains is produced
Product.
According to a particular embodiment of the invention, it is 1500-1600 DEG C to melt the temperature divided.Thus, it is possible to further improve molten
Efficiency when office is managed.
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's discovery, oxidation roasting with calcium compounds treatment is carried out to low-phosphorous vanadium slag, and the vanadium in low-phosphorous vanadium slag can be made to be oxidized to just
Tetravalence or positive pentavalent, and exist in the form of acid-soluble calcium vanadate, especially under the oxidation roasting with calcium compounds treatment conditions, the oxygen of vanadium
Rate is higher.Thus, the present invention can further improve acid-soluble by the temperature and time for controlling oxidation roasting with calcium compounds to process
The yield of vanadic acid calcium clinker, and then improve 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.Wherein, in acid-soluble vanadic acid calcium clinker, the vanadium of positive pentavalent and positive tetravalence accounts for full vanadium
Ratio be not less than 90%.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted treatment calcium vanadate dissolving, and then significantly carry
The rate of recovery of vanadium high.
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, high pressure para-roller ball pressing machine 200, reduction roasting dephosphorization apparatus 300, molten point
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 by mixed material in high pressure para-roller ball pressing machine 200
In carry out forming processes, obtain mix pelletizing, then will mixing pelletizing reduction roasting is carried out in reduction roasting dephosphorization apparatus 300
Dephosphorization treatment, obtains dephosphorization metallized pellet and phosphorous flue gas, is achieved in the purpose of dephosphorization, then in molten separating device 400 it is right
Dephosphorization metallized pellet carries out molten office reason, obtains molten iron and low-phosphorous vanadium slag, realizes the recovery to iron, then in oxidation roasting with calcium compounds
Oxidation roasting with calcium compounds treatment is carried out to low-phosphorous vanadium slag in device 500, acid-soluble vanadic acid calcium clinker is obtained, finally in acid-leaching vanadium-extracted dress
Acid-leaching vanadium-extracted treatment is carried out to acid-soluble vanadic acid calcium clinker in putting 600, vanadic anhydride product is finally given.
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, by the way that mixing arrangement 100 is to vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and glues
Knot agent carries out mixed processing, obtains 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.
High pressure para-roller ball pressing machine 200
Embodiments in accordance with the present invention, high pressure para-roller ball pressing machine 200 has mixed material entrance 210 and mixing pelletizing outlet
220, mixed material entrance 210 is connected with mixed material outlet 150, and high pressure para-roller ball pressing machine 200 is suitable to carry out mixed material
Forming processes, to obtain mixing pelletizing.
According to a particular embodiment of the invention, mixed material is carried out into forming processes in high pressure para-roller ball pressing machine 200, is obtained
To 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 high pressure para-roller ball pressing machine 200.Thus, it is possible to further improve the effect of forming processes
Rate.
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 are tunnel cave.Thus, it is possible to further carry
The efficiency of reduction roasting dephosphorization treatment high.
Molten separating device 400
Embodiments in accordance with the present invention, there is dephosphorization metallized pellet entrance 410, molten iron to export 420 and to melt separating device 400
Low-phosphorous vanadium slag outlet 430, dephosphorization metallized pellet entrance 410 is connected with dephosphorization metallized pellet outlet 320, melts separating device 400
It is suitable to for dephosphorization metallized pellet to carry out molten office reason, to obtain molten iron and low-phosphorous vanadium slag；
According to a particular embodiment of the invention, molten office reason is carried out to dephosphorization metallized pellet in molten separating device 400, is obtained
To molten iron and low-phosphorous vanadium slag.Thus, molten office reason is carried out to dephosphorization metallized pellet, can by iron in the form of molten iron from dephosphorization
Separated in metallized pellet, obtain molten iron and low-phosphorous vanadium slag, realize the recovery to iron.Specific implementation of the invention
Example, Fe contents are not more than 5 weight % in isolated low-phosphorous vanadium slag, and the rate of recovery of iron is not less than 80 weights in vanadium-bearing slag of high calcium and high phosphor
Amount %.
According to a particular embodiment of the invention, P in the low-phosphorous vanadium slag that office reason is obtained is melted2O5Content 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 office reason is obtained is melted2O5Content be not more than 0.05 weight
Amount %.Thus, it is possible to further improve the quality of vanadium in follow-up acid-leaching vanadium-extracted treatment.Thus, it is possible to be prevented effectively from follow-up vanadic acid
Calcium clinker phosphorus when acid-leaching vanadium-extracted enters containing precipitation effect is had a strong impact in vanadium leachate, and the final high-quality vanadic anhydride that obtains is produced
Product.
According to a particular embodiment of the invention, it is 1500-1600 DEG C to melt the temperature divided.Thus, it is possible to further improve molten
Efficiency when office is managed.
According to a particular embodiment of the invention, it can be electric furnace to melt separating device 400.Thus, it is possible to further improve molten point
The efficiency for the treatment of.
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 is connected with low-phosphorous vanadium slag outlet 430, oxidation roasting with calcium compounds dress
Put 500 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.
According to a particular embodiment of the invention, oxidation calcification is carried out to low-phosphorous vanadium slag in oxidation roasting with calcium compounds device 500
Calcination process, obtains 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's discovery, oxidation roasting with calcium compounds treatment is carried out to low-phosphorous vanadium slag, and the vanadium in low-phosphorous vanadium slag can be made to be oxidized to just
Tetravalence or positive pentavalent, and exist in the form of acid-soluble calcium vanadate, especially under the oxidation roasting with calcium compounds treatment conditions, the oxygen of vanadium
Rate is higher.Thus, the present invention can further improve acid-soluble by the temperature and time for controlling oxidation roasting with calcium compounds to process
The yield of vanadic acid calcium clinker, and then improve 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.Wherein, in acid-soluble vanadic acid calcium clinker, the vanadium of positive pentavalent and positive tetravalence accounts for full vanadium
Ratio be not less than 90%.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted treatment calcium vanadate dissolving, and then significantly carry
The rate of recovery of vanadium high.
According to a particular embodiment of the invention, oxidation roasting with calcium compounds device 500 can be multihearth roaster.Thus, it is possible to
Further improve 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, acidleach is carried out to acid-soluble vanadic acid calcium clinker in acid-leaching vanadium-extracted device 600
Vanadium extraction is processed, and finally gives vanadic anhydride product.
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 high pressure para-roller ball pressing machine be molded obtains mixing pelletizing.By mixing pelletizing in tunnel cave
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 metal after terminating
Pellet, the degree of metalization of dephosphorization metallized pellet is 80%.By dephosphorization metallized pellet on electric furnace and in 1500 DEG C of temperature
Molten office reason is carried out under the conditions of degree and obtains molten iron and low-phosphorous vanadium slag, molten iron can send to steel-making, P in low-phosphorous vanadium slag2O5Content is
0.09 weight %, Fe content is 5 weight %.Low-phosphorous vanadium slag is carried out oxidation calcification roasting in multihearth roaster and at 900 DEG C
Burn 1h and obtain acid-soluble 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%.Most
Acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment afterwards and obtains vanadic anhydride (grade 98.7%) and tailings.Whole flow process
Vanadium recovery 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 high pressure para-roller ball pressing machine be molded and obtains mixing pelletizing.By mixing pelletizing in tunnel cave
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 metal after terminating
Pellet, the degree of metalization of dephosphorization metallized pellet is 75%.By dephosphorization metallized pellet on electric furnace and in 1550 DEG C of temperature
Molten office reason is carried out under the conditions of degree and obtains molten iron and low-phosphorous vanadium slag, molten iron can send to steel-making, P in low-phosphorous vanadium slag2O5Content is
0.05 weight %, Fe content is 3 weight %.Low-phosphorous vanadium slag is carried out oxidation calcification roasting in multihearth roaster and at 1000 DEG C
Burn 1.5h and obtain acid-soluble vanadic acid calcium clinker, wherein the ratio that the gross mass of positive pentavalent vanadium and positive tetravalence vanadium accounts for full vanadium is 96%.
Acid-soluble vanadic acid calcium clinker is finally carried out into acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 99.3%) and tailings.Whole stream
The vanadium recovery 97.3% of journey, 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 high pressure para-roller ball pressing machine be molded and obtains mixing pelletizing.Pelletizing will be mixed in tunnel cave
Interior that 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 gold after terminating
Category pellet, the degree of metalization of dephosphorization metallized pellet is 82%.By dephosphorization metallized pellet on electric furnace and at 1600 DEG C
Molten office reason is carried out under temperature conditionss and obtains molten iron and low-phosphorous vanadium slag, molten iron can send to steel-making, P in low-phosphorous vanadium slag2O5Content is
0.04 weight %, Fe content is 4 weight %.Low-phosphorous vanadium slag is carried out oxidation calcification roasting in multihearth roaster and at 1100 DEG C
Burn 2h and obtain acid-soluble 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%.Most
Acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment afterwards and obtains vanadic anhydride (grade 99.2%) and tailings.Whole flow process
Vanadium recovery 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 high pressure para-roller ball pressing machine be molded and obtains mixing pelletizing.Will mixing pelletizing in tunnel cave
Reduction roasting is carried out at 1350 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 85%.By dephosphorization metallized pellet on electric furnace and in 1600 DEG C of temperature
Under the conditions of carry out molten office reason and obtain molten iron and low-phosphorous vanadium slag, molten iron can send to steel-making, P in low-phosphorous vanadium slag2O5Content is 0.03
Weight %, Fe content are 2 weight %.Low-phosphorous vanadium slag is carried out oxidation roasting with calcium compounds 2h in multihearth roaster and at 1200 DEG C
Acid-soluble vanadic acid calcium clinker is obtained, wherein the ratio that the gross mass of positive pentavalent vanadium and positive tetravalence vanadium accounts for full vanadium is 98%.Finally will
Acid-soluble vanadic acid calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 99.6%) and tailings.The vanadium of whole flow process
The rate of recovery 98.2%, iron 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 high pressure para-roller ball pressing machine and obtains mixing pelletizing.Pelletizing will be mixed in tunnel
Reduction roasting is carried out in road kiln at 1250 DEG C, phosphorus is mainly entered in flue gas in the form of phosphorous vapor, and reaction is taken off after terminating
Phosphorus metallized pellet, the degree of metalization of dephosphorization metallized pellet is 77%.By dephosphorization metallized pellet on electric furnace and 1500
DEG C temperature conditionss under carry out molten office reason and obtain molten iron and low-phosphorous vanadium slag, molten iron can send to steel-making, P in low-phosphorous vanadium slag2O5Contain
Measure as 0.01 weight %, Fe content is 3 weight %.Low-phosphorous vanadium slag is aoxidized with multihearth roaster and at 1150 DEG C
Calcification baking 2h obtains acid-soluble 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%.Acid-soluble vanadic acid calcium clinker is finally carried out into acid-leaching vanadium-extracted treatment and obtains vanadic anhydride (grade 98.7%) and tailings.
The vanadium recovery 94.2% of whole flow process, 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. a kind of method for processing vanadium-bearing slag of high calcium and high phosphor, comprises the following steps：
(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 molten office reason, to obtain molten iron 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 high pressure para-roller ball pressing machine, the high pressure para-roller ball pressing machine mixed material entrance and mixing pelletizing to export, the mixing
Material inlet is connected with mixed material outlet, and the high pressure para-roller ball pressing machine is suitable to carry out the mixed material at shaping
Reason, 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 molten separating device, the molten separating device dephosphorization metallized pellet entrance, molten iron outlet and low-phosphorous vanadium slag to export, described de-
Phosphorus metallized pellet entrance is connected with dephosphorization metallized pellet outlet, and the molten separating device is suitable to metallize the dephosphorization
Pelletizing carries out molten office reason, to obtain molten iron 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 tunnel cave, and the molten packing is set to electric furnace, the oxidation roasting with calcium compounds dress
It is set to multihearth roaster.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534397A (en) * | 2019-01-14 | 2019-03-29 | 河钢股份有限公司承德分公司 | A kind of preparation method of metavanadic acid magnesium |
| CN111057843A (en) * | 2019-12-31 | 2020-04-24 | 攀枝花市恒豪铸造有限公司 | Method for producing vanadium-containing pig iron by using vanadium-containing steel slag |
| CN114959310A (en) * | 2022-06-24 | 2022-08-30 | 岳庆丰 | Method for preparing rock wool and vanadium-containing pig iron by smelting stone coal vanadium ore through reduction roasting-electric furnace melting method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109534397A (en) * | 2019-01-14 | 2019-03-29 | 河钢股份有限公司承德分公司 | A kind of preparation method of metavanadic acid magnesium |
| CN109534397B (en) * | 2019-01-14 | 2021-04-02 | 河钢股份有限公司承德分公司 | Preparation method of magnesium metavanadate |
| CN111057843A (en) * | 2019-12-31 | 2020-04-24 | 攀枝花市恒豪铸造有限公司 | Method for producing vanadium-containing pig iron by using vanadium-containing steel slag |
| CN111057843B (en) * | 2019-12-31 | 2021-04-27 | 攀枝花市恒豪铸造有限公司 | Method for producing vanadium-containing pig iron by using vanadium-containing steel slag |
| CN114959310A (en) * | 2022-06-24 | 2022-08-30 | 岳庆丰 | Method for preparing rock wool and vanadium-containing pig iron by smelting stone coal vanadium ore through reduction roasting-electric furnace melting method |
| CN117230306A (en) * | 2023-11-14 | 2023-12-15 | 北京蒂本斯工程技术有限公司 | Method and system for treating vanadium extraction waste slag by adopting side-blown furnace melting separation method |
| CN117230306B (en) * | 2023-11-14 | 2024-02-09 | 北京蒂本斯工程技术有限公司 | Method and system for treating vanadium extraction waste slag by adopting side-blown furnace melting separation method |
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