CN206721308U - The system for handling vanadium-bearing slag of high calcium and high phosphor - Google Patents
The system for handling vanadium-bearing slag of high calcium and high phosphor Download PDFInfo
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Abstract
The utility model discloses the system of processing vanadium-bearing slag of high calcium and high phosphor, including：Mixing arrangement, high pressure para-roller ball pressing machine, reduction roasting dephosphorization apparatus, molten separating device, 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 mixed material outlet；High pressure para-roller ball pressing machine has mixed material entrance and the outlet of mixing pelletizing；Reduction roasting dephosphorization apparatus has mixing pelletizing entrance, the outlet of dephosphorization metallized pellet and phosphorous exhanst gas outlet；Molten separating device has dephosphorization metallized pellet entrance, molten iron outlet and the outlet of low-phosphorous vanadium slag；Oxidation roasting with calcium compounds device has low-phosphorous vanadium slag entrance, air intake and the outlet of acid-soluble vanadic acid calcium clinker；Acid-leaching vanadium-extracted device has acid-soluble vanadic acid calcium clinker entrance, vanadic anhydride outlet and tailings outlet.The phosphorus in vanadium-bearing slag of high calcium and high phosphor can be effectively removed using the system, and then significantly improves the rate of recovery and quality of iron and vanadium.
Description
Technical field
The utility model belongs to metallurgical technology field, specifically, the utility model is related to processing vanadium-bearing slag of high calcium and high phosphor
System.
Background technology
Vanadium slag refers to that vanadium-bearing hot metal is oxidized into a kind of clinker 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 rotary kiln or multiple hearth furnace to carry out oxidation roasting after mixing with additive
Burn, obtain the vanadate of solubility, precipitation is carried out again after vanadium is transferred into liquid phase from solid phase by wet-leaching means, by precipitation
Product is calcined to obtain V2O5Product.Phosphorus is the harmful element in being precipitated containing vanadium leachate, and it can be formed surely with vanadium in acid medium
Fixed and complicated complex compound phosphorus vanadium system's heteropoly acid and their salt, in addition, can also be with the iron ion and aluminium ion in solution
Form FePO4、AlPO4Precipitation, these can all pollute ammonium vanadate precipitation, have a strong impact on the progress of acid ammonium salt precipitation.Conventional is de-
Then phosphorus means add appropriate calcium salt or magnesium salts form 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 calcium salt and carry out pre- dephosphorization simultaneously, and it is high to obtain low-phosphorous half steel and high calcium
The special vanadium slag of phosphorus.This vanadium-bearing slag of high calcium and high phosphor is because itself CaO content is high, CaO meetings and V during sodium roasting2O5Generate not soluble in water
Calcium vanadate CaOV2O5Or the vanadium green grass or young crops calcium CaV containing calcium12O30, CaO mass fraction, which 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, substantial amounts of calcium and phosphorus can be made together to be entered along with vanadium in leachate, due to there is the presence of a large amount of calcium ions in solution, adjusted
Section pH value of solution can re-form vanadic acid calcium precipitate between 9.511.0, so the dephosphorization under traditional alkalescence condition can not be used
Method, and the dephosphorization problem under acid system is not yet captured.
Therefore, the technology of vanadium-bearing slag of high calcium and high phosphor dephosphorization vanadium extraction is need further to develop.
Utility model content
The utility model is intended to one of technical problem at least solving in correlation technique to a certain extent.Therefore, this reality
It is to propose a kind of system for handling vanadium-bearing slag of high calcium and high phosphor with a new purpose, the system can carry in vanadium-bearing slag of high calcium and high phosphor
Effective dephosphorization is carried out before vanadium, and can effectively reclaim the iron and vanadium for obtaining high-quality, while can also further improve iron and vanadium
The rate of recovery.
According to one side of the present utility model, the utility model proposes a kind of system for handling vanadium-bearing slag of high calcium and high phosphor,
Including：
Mixing arrangement, the mixing arrangement have vanadium-bearing slag of high calcium and high phosphor entrance, silica entrance, reduction coal entrance, binding agent
Entrance and mixed material outlet；
High pressure para-roller ball pressing machine, the high pressure para-roller ball pressing machine has mixed material entrance and the outlet of mixing pelletizing, described
Mixed material entrance is connected with mixed material outlet；
Reduction roasting dephosphorization apparatus, the reduction roasting dephosphorization apparatus have mixing pelletizing entrance, dephosphorization metallized pellet
Outlet and phosphorous exhanst gas outlet, the mixing pelletizing entrance are connected with the mixing pelletizing outlet；
Molten separating device, the molten separating device have dephosphorization metallized pellet entrance, molten iron outlet and the outlet of low-phosphorous vanadium slag, institute
Dephosphorization metallized pellet entrance is stated with dephosphorization metallized pellet outlet to be connected；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device have low-phosphorous vanadium slag entrance, air intake and acid molten
Property the outlet of vanadic acid calcium clinker, the low-phosphorous vanadium slag entrance exports with the low-phosphorous vanadium slag to be connected；
Acid-leaching vanadium-extracted device, the acid-leaching vanadium-extracted device have acid-soluble vanadic acid calcium clinker entrance, vanadic anhydride outlet
Exported with tailings, the acid-soluble vanadic acid calcium clinker entrance is connected with the acid-soluble vanadic acid calcium clinker outlet.
Thus, by using the system for handling vanadium-bearing slag of high calcium and high phosphor of the utility model above-described embodiment, can not only have
Phosphorus in effect removing vanadium-bearing slag of high calcium and high phosphor, avoid vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted from entering and contain in vanadium leachate so as to serious
Precipitation effect is influenceed, recycling can also be carried out to the iron resource in vanadium-bearing slag of high calcium and high phosphor, final acquisition phosphorus content is low
High-quality iron resource and vanadic anhydride product.
Can also have what is added as follows according to the system of the processing vanadium-bearing slag of high calcium and high phosphor of the utility model above-described embodiment
Technical characteristic：
In the utility model, the reduction roasting dephosphorization apparatus is tunnel cave.Thus, it is possible to further improve reduction roasting
Burn the efficiency of dephosphorization.
In the utility model, the molten packing is set to electric furnace.Thus, it is possible to further improve separation dephosphorization product of roasting
The efficiency of middle iron.
In the utility model, the oxidation roasting with calcium compounds device is multihearth roaster.Thus, it is possible to further improve oxygen
Change the efficiency of calcification baking.
Brief description of the drawings
Of the present utility model above-mentioned and/or additional aspect and advantage will in the description from combination accompanying drawings below to embodiment
Become obvious and be readily appreciated that, wherein：
Fig. 1 is the structural representation according to the system of the processing vanadium-bearing slag of high calcium and high phosphor of the utility model one embodiment；
Fig. 2 is the system processing vanadium-bearing slag of high calcium and high phosphor using the processing vanadium-bearing slag of high calcium and high phosphor of the utility model one embodiment
Method flow diagram.
Embodiment
Embodiment of the present utility model is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning
Same or similar element is represented to same or similar label eventually or there is the element of same or like function.Below by ginseng
The embodiment for examining accompanying drawing description is exemplary, it is intended to for explaining the utility model, and it is not intended that to the utility model
Limitation.
According to one side of the present utility model, the utility model proposes a kind of system for handling vanadium-bearing slag of high calcium and high phosphor,
With reference to figure 1, including：Mixing arrangement 100, high pressure para-roller ball pressing machine 200, reduction roasting dephosphorization apparatus 300, molten separating device 400, oxygen
Change calcification baking device 500 and acid-leaching vanadium-extracted device 600.
Using the system of above-mentioned processing 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, mixed material are obtained, then by mixed material in high pressure para-roller ball pressing machine 200
Middle carry out forming processes, obtain mixing pelletizing, mixing pelletizing is then subjected to reduction roasting in reduction roasting dephosphorization apparatus 300
Dephosphorization treatment, obtain dephosphorization metallized pellet and phosphorous flue gas, be 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 processing 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 processing is carried out to acid-soluble vanadic acid calcium clinker in putting 600, finally gives vanadic anhydride product.
Thus, the utility model, can be further by using the system of the processing vanadium-bearing slag of high calcium and high phosphor of above-described embodiment
The rate of recovery of the iron resource in vanadium-bearing slag of high calcium and high phosphor is improved, and effectively removes the phosphorus in vanadium-bearing slag of high calcium and high phosphor, avoids calcium vanadate ripe
Material phosphorus when acid-leaching vanadium-extracted, which enters, to be contained so as to have a strong impact on precipitation effect in vanadium leachate, and then further improves high calcium high phosphorus vanadium
The dephosphorization effect of slag, and improve the rate of recovery and quality of iron and vanadium.
Retouched in detail below with reference to the system of processing vanadium-bearing slag of high calcium and high phosphor of the Fig. 1 to the utility model above-described embodiment
State.
Mixing arrangement 100
According to embodiment of the present utility model, mixing arrangement 100 has vanadium-bearing slag of high calcium and high phosphor entrance 110, silica entrance
120th, reduction coal entrance 130, binding agent entrance 140 and mixed material outlet 150.
According to specific embodiment of the utility model, by mixing arrangement 100 to vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal
Mixed processing is carried out with binding agent, obtains mixed material.
According to specific embodiment of the utility model, CaO content is 3-25 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5's
Content is 0.2-1 weight %, V2O5Content be that 5-20 weight %, Fe content is 20-35 weight %.Thus, the utility model
The method of the processing vanadium-bearing slag of high calcium and high phosphor of embodiment effectively can be higher than 3 weight %, P for CaO content2O5Content is higher than 0.2 weight
Amount % vanadium-bearing slag of high calcium and high phosphor is handled, and can obtain the iron and vanadic anhydride product of high-quality.
According to specific embodiment of the utility model, CaO content is 5-15 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5's
Content is 0.2-0.6 weight %, V2O5Content be that 5-10 weight %, Fe content is 20-30 weight %.Thus, this practicality is new
The method of the processing vanadium-bearing slag of high calcium and high phosphor of type embodiment can be 5-15 weight %, P effectively for CaO content2O5Content is 0.2-
0.6 weight % vanadium-bearing slag of high calcium and high phosphor is handled, and can obtain the iron and vanadic anhydride product of high-quality.
According to specific embodiment of the utility model, high calcium high phosphorus iron removaling vanadium slag, silica, reduction coal and binding agent press quality
Than for 100:(5-15):(8-15)：(2-5) carries out mixed processing.Mixing pelletizing can effectively be prepared, and further carry
High sequential reduction iron and dephosphorization under reducing atmosphere effect.According to specific example of the present utility model, inventor has found, to high calcium high phosphorus iron removaling
The silica and reduction coal of aforementioned proportion are incorporated in vanadium slag, the percent reduction of calcium phosphate in high calcium high phosphorus iron removaling vanadium slag can be effectively improved
And the percent reduction of iron, and then improve the rate of recovery of dephosphorization effect and iron.
According to specific embodiment of the utility model, the type of binding agent is not particularly restricted, for example, according to this practicality
New binding agent can be the one or more in bentonite, waterglass, molasses, starch solution.Thus, it is possible to further carry
The quality of efficiency and mixing pelletizing during high subsequent forming processing.
High pressure para-roller ball pressing machine 200
According to embodiment of the present utility model, high pressure para-roller ball pressing machine 200 has mixed material entrance 210 and mixing pelletizing
Outlet 220, mixed material entrance 210 are connected with mixed material outlet 150.
According to specific embodiment of the utility model, mixed material is carried out at shaping in high pressure para-roller ball pressing machine 200
Reason, obtain mixing pelletizing.
According to specific embodiment of the utility model, the device of forming processes is not particularly restricted, for example, according to this reality
With new implementation example, forming processing equipment can be high pressure para-roller ball pressing machine 200.Thus, it is possible to further improve shaping
The efficiency of processing.
Reduction roasting dephosphorization apparatus 300
According to embodiment of the present utility model, reduction roasting dephosphorization apparatus 300 has mixing pelletizing entrance 310, dephosphorization gold
Belong to pellet outlet 320 and phosphorous exhanst gas outlet 330, mixing pelletizing entrance 310 is connected with mixing pelletizing outlet 220.
According to specific embodiment of the utility model, mixing pelletizing is reduced in reduction roasting dephosphorization apparatus 300
Dephosphorization treatment is calcined, obtains dephosphorization metallized pellet and phosphorous flue gas.Thus, carried out by mixing pelletizing at reduction roasting dephosphorization
Reason, the calcium phosphate in mixed material can be made to be reduced into phosphorus simple substance, and be entered in the form of steam in flue gas, hereby it is achieved that
The effect of dephosphorization；Simultaneously the iron in mixed material can also be reduced to obtain fe.
According to specific embodiment of the utility model, silica, reduction coal and binding agent are incorporated to high calcium high phosphorus iron removaling vanadium slag
And reduction roasting dephosphorization treatment is carried out after being molded to carry out dephosphorization and to carry iron.Specifically, dephosphorization and propose 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 specific embodiment of the utility model, the temperature of reduction roasting dephosphorization treatment can be 1200-1400 DEG C.Hair
A person of good sense has found, under the conditions of the reduction roasting dephosphorization treatment, can further improve phosphorus removal efficiency and iron percent reduction.
According to specific embodiment of the utility model, by using above-mentioned reduction roasting dephosphorization treatment condition, what is obtained is de-
The degree of metalization of phosphorus metallized 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 specific embodiment of the utility model, reduction roasting dephosphorization apparatus 300 is tunnel cave.Thus, it is possible to enter one
Step improves the efficiency of reduction roasting dephosphorization treatment.
Molten separating device 400
According to embodiment of the present utility model, melting separating device 400, there is dephosphorization metallized pellet entrance 410, molten iron to export
420 and low-phosphorous vanadium slag outlet 430, dephosphorization metallized pellet entrance 410 and dephosphorization metallized pellet export 320 and be connected.
According to specific embodiment of the utility model, molten office is carried out to dephosphorization metallized pellet in molten separating device 400
Reason, obtains molten iron and low-phosphorous vanadium slag.Thus, molten office reason is carried out to dephosphorization metallized pellet, can be by iron in the form of molten iron
Separated from dephosphorization metallized pellet, obtain molten iron and low-phosphorous vanadium slag, realize the recovery to iron.According to of the present utility model
Specific embodiment, Fe contents are not more than 5 weight % in isolated low-phosphorous vanadium slag, and the rate of recovery of iron is not in vanadium-bearing slag of high calcium and high phosphor
Less than 80 weight %.
According to specific embodiment of the utility model, P in obtained low-phosphorous vanadium slag is managed in molten office2O5Content be not more than 0.1
Weight %.Thus, it is possible to follow-up vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted is effectively avoided to enter to contain and had a strong impact in vanadium leachate
Precipitation effect, finally obtain high-quality vanadic anhydride product.
According to specific embodiment of the utility model, P in obtained low-phosphorous vanadium slag is managed in molten office2O5Content 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 processing.Thus, it is possible to after effectively avoiding
Continuous vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted, which enters to contain in vanadium leachate, has a strong impact on precipitation effect, finally obtains high-quality five oxidation
Two vanadium products.
According to specific embodiment of the utility model, it is 1500-1600 DEG C to melt the temperature divided.Thus, it is possible to further carry
Efficiency when the molten office of height is managed.
According to specific embodiment of the utility model, it can be electric furnace to melt separating device 400.Thus, it is possible to further improve
The efficiency of molten office reason.
Oxidation roasting with calcium compounds device 500
According to embodiment of the present utility model, there is oxidation roasting with calcium compounds device 500 low-phosphorous vanadium slag entrance 510, air to enter
Mouth 520 and acid-soluble vanadic acid calcium clinker outlet 530, low-phosphorous vanadium slag entrance 510 are connected with low-phosphorous vanadium slag outlet 430.
According to specific embodiment of the utility model, low-phosphorous vanadium slag is aoxidized in oxidation roasting with calcium compounds device 500
Calcification baking processing, obtains acid-soluble vanadic acid calcium clinker.
According to specific embodiment of the utility model, the temperature of oxidation roasting with calcium compounds processing can be 900-1200 DEG C, when
Between be 1-2h.Inventor has found, carries out oxidation roasting with calcium compounds processing to low-phosphorous vanadium slag, can be oxidized the vanadium in low-phosphorous vanadium slag
For positive tetravalence or positive pentavalent, and exist in the form of acid-soluble calcium vanadate, especially under the oxidation roasting with calcium compounds treatment conditions, vanadium
Oxygenation efficiency it is higher.Thus, the utility model can be carried further by the temperature and time for controlling oxidation roasting with calcium compounds to handle
The yield of high acid-soluble calcium vanadate clinker, and then improve the rate of recovery of vanadium.
According to specific embodiment of the utility model, the oxidation roasting with calcium compounds processing procedure carried out under the above-described reaction conditions
In, the reaction specifically occurred in dephosphorization agglomerates is as follows：
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 specific embodiment of the utility model, the acid-soluble vanadic acid for handling to obtain by oxidation roasting with calcium compounds
Calcium vanadate in calcium clinker can include at least one of positive calcium vanadate, pyrovanadic acid calcium and metavanadic acid calcium or tetravalence
The arbitrary proportion of calcium vanadate and pentavalent calcium vanadate mixes.Wherein, in acid-soluble vanadic acid calcium clinker, the vanadium of positive pentavalent and positive tetravalence accounts for
The ratio of full vanadium is not less than 90%.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted processing calcium vanadate dissolving, Jin Erxian
Write the rate of recovery for improving vanadium.
According to specific embodiment of the utility model, oxidation roasting with calcium compounds device 500 can be multihearth roaster.Thus,
The efficiency of oxidation roasting with calcium compounds processing can further be improved.
Acid-leaching vanadium-extracted device 600
According to embodiment of the present utility model, acid-leaching vanadium-extracted device 600 has acid-soluble vanadic acid calcium clinker entrance 610, five
V 2 O outlet 620 and tailings outlet 630, acid-soluble vanadic acid calcium clinker entrance 610 and acid-soluble vanadic acid calcium clinker outlet 530
It is connected, acid-leaching vanadium-extracted device 600 is suitable to acid-soluble vanadic acid calcium clinker carrying out acid-leaching vanadium-extracted processing, to obtain vanadic anhydride
Product and tailings.
According to specific embodiment of the utility model, acid-leaching vanadium-extracted device 600 further comprises acidleach device, purification dress
Put, precipitation device and calciner plant.Wherein, acidleach device is suitable to acid-soluble vanadic acid calcium clinker carrying out acidleach processing, so as to
To containing vanadium solution and acid leaching residue；Purifier, which is suitable to that vanadium solution will be contained, carries out purification and impurity removal, so as to molten containing vanadium after being purified
Liquid；Precipitation device is suitable to carrying out acid ammonium salt precipitation processing containing vanadium solution after purification, to obtain ammonium poly-vanadate precipitation；Forge
Burn device to be suitable to carry out calcination processing to ammonium poly-vanadate, to obtain vanadic anhydride product.Thus, by acid-soluble vanadic acid
Calcium clinker, which carries out acid-leaching vanadium-extracted processing, can effectively reclaim acquisition vanadic anhydride product.
In order to facilitate the system for the processing vanadium-bearing slag of high calcium and high phosphor for understanding the utility model above-described embodiment, it is somebody's turn to do below to utilizing
The method of system processing vanadium-bearing slag of high calcium and high phosphor is described.
According to the utility model embodiment, the method for handling vanadium-bearing slag of high calcium and high phosphor using the system for handling vanadium-bearing slag of high calcium and high phosphor
Including：(1) vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent are subjected to mixed processing, to obtain mixed material；(2) will
Mixed material carries out forming processes, to obtain mixing pelletizing；(3) mixing pelletizing is subjected to reduction roasting dephosphorization treatment, so as to
Obtain dephosphorization metallized pellet and phosphorous flue gas；(4) dephosphorization metallized pellet is subjected to molten office reason, to obtain molten iron and low
Phosphorus vanadium slag；(5) low-phosphorous vanadium slag is subjected to oxidation roasting with calcium compounds processing, to obtain acid-soluble vanadic acid calcium clinker；(6) will be acid-soluble
Vanadic acid calcium clinker carries out acid-leaching vanadium-extracted processing, to obtain vanadic anhydride product.
According to the utility model above-described embodiment processing 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 carry out forming processes to mixed material and mixed
Pelletizing, mixing pelletizing is then subjected to reduction roasting dephosphorization treatment, dephosphorization metallized pellet and phosphorous flue gas is obtained, realizes dephosphorization
Purpose, molten office reason is then carried out to dephosphorization metallized pellet, by iron in the form of molten iron from dephosphorization metallized pellet point
Separate out and, obtain molten iron and low-phosphorous vanadium slag, then oxidation roasting with calcium compounds processing is carried out to low-phosphorous vanadium slag, it is ripe to obtain acid-soluble calcium vanadate
Material, acid-leaching vanadium-extracted processing finally is carried out to acid-soluble vanadic acid calcium clinker, finally gives vanadic anhydride product.Thus, this practicality
The method of the processing vanadium-bearing slag of high calcium and high phosphor of new embodiment not only can effectively remove the phosphorus in vanadium-bearing slag of high calcium and high phosphor, avoid vanadic acid
Calcium clinker phosphorus when acid-leaching vanadium-extracted, which enters, to be contained in vanadium leachate so as to have a strong impact on precipitation effect, can also be to vanadium-bearing slag of high calcium and high phosphor
In iron resource carry out recycling, it is final to obtain low high-quality iron resource and the vanadic anhydride product of phosphorus content.In addition, should
Method also has the advantages of vanadium-bearing slag of high calcium and high phosphor dephosphorization rate height, iron and vanadium recovery height, superior product quality.
Retouched in detail below with reference to the method for processing vanadium-bearing slag of high calcium and high phosphor of the Fig. 2 to the utility model above-described embodiment
State.
S100：Mixed processing
According to embodiment of the present utility model, by vanadium-bearing slag of high calcium and high phosphor, silica, reduction coal and binding agent in mixing arrangement
Mixed processing is carried out in 100, to obtain mixed material.
According to specific embodiment of the utility model, CaO content is 3-25 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5's
Content is 0.2-1 weight %, V2O5Content be that 5-20 weight %, Fe content is 20-35 weight %.Thus, the utility model
The method of the processing vanadium-bearing slag of high calcium and high phosphor of embodiment effectively can be higher than 3 weight %, P for CaO content2O5Content is higher than 0.2 weight
Amount % vanadium-bearing slag of high calcium and high phosphor is handled, and can obtain the iron and vanadic anhydride product of high-quality.
According to specific embodiment of the utility model, CaO content is 5-15 weight %, P in vanadium-bearing slag of high calcium and high phosphor2O5's
Content is 0.2-0.6 weight %, V2O5Content be that 5-10 weight %, Fe content is 20-30 weight %.Thus, this practicality is new
The method of the processing vanadium-bearing slag of high calcium and high phosphor of type embodiment can be 5-15 weight %, P effectively for CaO content2O5Content is 0.2-
0.6 weight % vanadium-bearing slag of high calcium and high phosphor is handled, and can obtain the iron and vanadic anhydride product of high-quality.
According to specific embodiment of the utility model, high calcium high phosphorus iron removaling vanadium slag, silica, reduction coal and binding agent press quality
Than for 100:(5-15):(8-15)：(2-5) carries out mixed processing.Mixing pelletizing can effectively be prepared, and further carry
High sequential reduction iron and dephosphorization under reducing atmosphere effect.According to specific example of the present utility model, inventor has found, to high calcium high phosphorus iron removaling
The silica and reduction coal of aforementioned proportion are incorporated in vanadium slag, the percent reduction of calcium phosphate in high calcium high phosphorus iron removaling vanadium slag can be effectively improved
And the percent reduction of iron, and then improve the rate of recovery of dephosphorization effect and iron.
According to embodiment of the present utility model, the type of binding agent is not particularly restricted, for example, according to the utility model
Binding agent can be bentonite, waterglass, molasses, the one or more in starch solution.Thus, it is possible to after further improving
The quality of efficiency and mixing pelletizing during continuous forming processes.
S200：Forming processes
According to embodiment of the present utility model, mixed material is subjected to forming processes in high pressure para-roller ball pressing machine 200, with
Just obtain mixing pelletizing.
According to specific embodiment of the utility model, the device of forming processes is not particularly restricted, for example, according to this reality
With new implementation example, forming processing equipment can be high pressure para-roller ball pressing machine.Thus, it is possible to further improve forming processes
Efficiency.
S300：Reduction roasting dephosphorization treatment
According to embodiment of the present utility model, mixing pelletizing is subjected to reduction roasting in reduction roasting dephosphorization apparatus 300
Dephosphorization treatment, to obtain dephosphorization metallized pellet and phosphorous flue gas.Thus, carried out by mixing pelletizing at reduction roasting dephosphorization
Reason, the calcium phosphate in mixed material can be made to be reduced into phosphorus simple substance, and be entered in the form of steam in flue gas, hereby it is achieved that
The effect of dephosphorization；Simultaneously the iron in mixed material can also be reduced to obtain fe.
According to specific embodiment of the utility model, silica, reduction coal and binding agent are incorporated to high calcium high phosphorus iron removaling vanadium slag
And reduction roasting dephosphorization treatment is carried out after being molded to carry out dephosphorization and to carry iron.Specifically, dephosphorization and propose 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 specific embodiment of the utility model, the temperature of reduction roasting dephosphorization treatment can be 1200-1400 DEG C.Hair
A person of good sense has found, under the conditions of the reduction roasting dephosphorization treatment, can further improve phosphorus removal efficiency and iron percent reduction.
According to specific embodiment of the utility model, by using above-mentioned reduction roasting dephosphorization treatment condition, what is obtained is de-
The degree of metalization of phosphorus metallized 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
According to embodiment of the present utility model, dephosphorization metallized pellet is carried out to molten office reason in molten separating device 400, with
Just molten iron and low-phosphorous vanadium slag are obtained.Thus, molten office reason is carried out to dephosphorization metallized pellet, can by iron in the form of molten iron from
Separated in dephosphorization metallized pellet, obtain molten iron and low-phosphorous vanadium slag, realize the recovery to iron.According to tool of the present utility model
Body embodiment, Fe contents are not more than 5 weight % in isolated low-phosphorous vanadium slag, and the rate of recovery of iron is not low in vanadium-bearing slag of high calcium and high phosphor
In 80 weight %.
According to specific embodiment of the utility model, P in obtained low-phosphorous vanadium slag is managed in molten office2O5Content be not more than 0.1
Weight %.Thus, it is possible to follow-up vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted is effectively avoided to enter to contain and had a strong impact in vanadium leachate
Precipitation effect, finally obtain high-quality vanadic anhydride product.
According to specific embodiment of the utility model, P in obtained low-phosphorous vanadium slag is managed in molten office2O5Content 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 processing.Thus, it is possible to after effectively avoiding
Continuous vanadic acid calcium clinker phosphorus when acid-leaching vanadium-extracted, which enters to contain in vanadium leachate, has a strong impact on precipitation effect, finally obtains high-quality five oxidation
Two vanadium products.
According to specific embodiment of the utility model, it is 1500-1600 DEG C to melt the temperature divided.Thus, it is possible to further carry
Efficiency when the molten office of height is managed.
S500：Oxidation roasting with calcium compounds processing
According to embodiment of the present utility model, low-phosphorous vanadium slag is subjected to oxidation calcification in oxidation roasting with calcium compounds device 500
Calcination process, to obtain acid-soluble vanadic acid calcium clinker.
According to specific embodiment of the utility model, the temperature of oxidation roasting with calcium compounds processing can be 900-1200 DEG C, when
Between be 1-2h.Inventor has found, carries out oxidation roasting with calcium compounds processing to low-phosphorous vanadium slag, can be oxidized the vanadium in low-phosphorous vanadium slag
For positive tetravalence or positive pentavalent, and exist in the form of acid-soluble calcium vanadate, especially under the oxidation roasting with calcium compounds treatment conditions, vanadium
Oxygenation efficiency it is higher.Thus, the utility model can be carried further by the temperature and time for controlling oxidation roasting with calcium compounds to handle
The yield of high acid-soluble calcium vanadate clinker, and then improve the rate of recovery of vanadium.
According to specific embodiment of the utility model, the oxidation roasting with calcium compounds processing procedure carried out under the above-described reaction conditions
In, the reaction specifically occurred in dephosphorization agglomerates is as follows：
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 specific embodiment of the utility model, the acid-soluble vanadic acid for handling to obtain by oxidation roasting with calcium compounds
Calcium vanadate in calcium clinker can include at least one of positive calcium vanadate, pyrovanadic acid calcium and metavanadic acid calcium or tetravalence
The arbitrary proportion of calcium vanadate and pentavalent calcium vanadate mixes.Wherein, in acid-soluble vanadic acid calcium clinker, the vanadium of positive pentavalent and positive tetravalence accounts for
The ratio of full vanadium is not less than 90%.Thus, it is possible to when further improving follow-up acid-leaching vanadium-extracted processing calcium vanadate dissolving, Jin Erxian
Write the rate of recovery for improving vanadium.
S600：Acid-leaching vanadium-extracted processing
According to embodiment of the present utility model, acid-soluble vanadic acid calcium clinker is subjected to acidleach in acid-leaching vanadium-extracted device 600
Vanadium extraction is handled, to obtain vanadic anhydride product.
According to specific embodiment of the utility model, acid-leaching vanadium-extracted processing can specifically be carried out according to the following steps：First
The progress acidleach of acid soluble vanadic acid calcium clinker is obtained containing vanadium solution and acid leaching residue, then will contain vanadium solution purification and impurity removal, then it is right
The progress acid ammonium salt precipitation containing vanadium solution after purification handles to obtain ammonium poly-vanadate precipitation, finally carries out ammonium poly-vanadate at calcining
Reason obtains vanadic anhydride.Thus, acquisition can effectively be reclaimed by carrying out acid-leaching vanadium-extracted processing to acid-soluble vanadic acid calcium clinker
Vanadic anhydride product.
Embodiment 1
By certain domestic company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 3 weight %, P2O5Content is 0.2 weight %, V2O5Content
Be 35 weight % for 20 weight %, Fe contents), silica, reduction coal and bentonite in mass ratio 100:5:15:2 be mixed to get it is mixed
Compound material, mixed material is molded on high pressure para-roller ball pressing machine to obtain mixing pelletizing.Pelletizing will be mixed 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 is carried out under the conditions of degree and manages to obtain 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 to 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 positive pentavalent vanadium and the gross mass of positive tetravalence vanadium account for full vanadium is 92%.Most
Acid-soluble vanadic acid calcium clinker is subjected to acid-leaching vanadium-extracted processing afterwards and obtains vanadic anhydride (grade 98.7%) and tailings.Whole flow process
Vanadium recovery 95.2%, iron recovery 85.4%.
Embodiment 2
By certain domestic company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 25 weight %, P2O5Content is 1 weight %, V2O5Content
Be 20 weight % for 5 weight %, Fe contents), silica, reduction coal and starch solution in mass ratio 100:15:8:3 be mixed to get it is mixed
Compound material.Mixed material is molded to obtain on high pressure para-roller ball pressing machine and mixes pelletizing.Pelletizing will be mixed 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 is carried out under the conditions of degree and manages to obtain 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 to 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 positive pentavalent vanadium and the gross mass of positive tetravalence vanadium account for full vanadium is 96%.
Acid-soluble vanadic acid calcium clinker is finally subjected to acid-leaching vanadium-extracted processing 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 certain domestic company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 15 weight %, P2O5Content is 0.6 weight %, V2O5Contain
It is 30 weight % to measure as 7 weight %, Fe contents), silica, reduction coal and waterglass in mass ratio 100:10:10:4 are mixed to get
Mixed material.Mixed material is molded to obtain on high pressure para-roller ball pressing machine and mixes 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
Belong to 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 is carried out under temperature conditionss and manages to obtain 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 to 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 positive pentavalent vanadium and the gross mass of positive tetravalence vanadium account for full vanadium is 95%.Most
Acid-soluble vanadic acid calcium clinker is subjected to acid-leaching vanadium-extracted processing afterwards and obtains vanadic anhydride (grade 99.2%) and tailings.Whole flow process
Vanadium recovery 96.8%, iron recovery 87.3%.
Embodiment 4
By certain domestic company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 5 weight %, P2O5Content is 0.2 weight %, V2O5Content
Be 30 weight % for 10 weight %, Fe contents), silica, reduction coal and molasses in mass ratio 100:8:9:5 are mixed to get mixture
Material.Mixed material is molded to obtain on high pressure para-roller ball pressing machine and mixes 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 and manage to 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 to 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 positive pentavalent vanadium and the gross mass of positive tetravalence vanadium account for full vanadium is 98%.Finally will
Acid-soluble vanadic acid calcium clinker carries out acid-leaching vanadium-extracted processing 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 certain domestic company's vanadium-bearing slag of high calcium and high phosphor, (CaO content is 10 weight %, P2O5Content is 0.4 weight %, V2O5Contain
It is 25 weight % to measure as 8 weight %, Fe contents), silica, reduction coal and bentonite in mass ratio 100:11:12:3.5 mix
To mixed material.Mixed material will be molded to obtain on high pressure para-roller ball pressing machine and mix 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 and manage to obtain molten iron and low-phosphorous vanadium slag, molten iron can send to steel-making, P in low-phosphorous vanadium slag2O5Contain
It is 3 weight % to measure as 0.01 weight %, Fe content.By low-phosphorous vanadium slag with being aoxidized in multihearth roaster and at 1150 DEG C
Calcification baking 2h obtains acid-soluble vanadic acid calcium clinker, wherein the ratio that positive pentavalent vanadium and the gross mass of positive tetravalence vanadium account for full vanadium is
91%.Acid-soluble vanadic acid calcium clinker is finally subjected to acid-leaching vanadium-extracted processing 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 specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present utility model.In this manual, to the schematic table of above-mentioned term
Identical embodiment or example need not be directed to by stating.Moreover, specific features, structure, material or the feature of description can be
Combined in an appropriate manner in any one or more embodiments or example.In addition, in the case of not conflicting, this area
Technical staff can be carried out the different embodiments or example and the feature of different embodiments or example described in this specification
With reference to and combination.
Although embodiment of the present utility model has been shown and described above, it is to be understood that above-described embodiment is
Exemplary, it is impossible to it is interpreted as to limitation of the present utility model, one of ordinary skill in the art is in the scope of the utility model
It is interior above-described embodiment to be changed, changed, replaced and modification.
Claims (4)
- A kind of 1. system for handling vanadium-bearing slag of high calcium and high phosphor, it is characterised in that including：Mixing arrangement, the mixing arrangement have vanadium-bearing slag of high calcium and high phosphor entrance, silica entrance, reduction coal entrance, binding agent entrance Exported with mixed material；High pressure para-roller ball pressing machine, the high pressure para-roller ball pressing machine have mixed material entrance and the outlet of mixing pelletizing, the mixing Material inlet is connected with mixed material outlet；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；Molten separating device, the molten separating device has dephosphorization metallized pellet entrance, molten iron outlet and the outlet of low-phosphorous vanadium slag, described de- Phosphorus metallized pellet entrance is connected with dephosphorization metallized pellet outlet；Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device have low-phosphorous vanadium slag entrance, air intake and acid-soluble vanadium Sour calcium clinker outlet, the low-phosphorous vanadium slag entrance are connected with the low-phosphorous vanadium slag outlet；Acid-leaching vanadium-extracted device, the acid-leaching vanadium-extracted device have acid-soluble vanadic acid calcium clinker entrance, vanadic anhydride outlet and tail Slag exports, and the acid-soluble vanadic acid calcium clinker entrance is connected with the acid-soluble vanadic acid calcium clinker outlet.
- 2. the system of processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that the reduction roasting dephosphorization dress It is set to tunnel cave.
- 3. the system of processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that the molten packing is set to electricity Stove.
- 4. the system of processing vanadium-bearing slag of high calcium and high phosphor according to claim 1, it is characterised in that the oxidation roasting with calcium compounds dress It is set to multihearth roaster.
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