CN106978544A - The system and method for handling converter vanadium chromium slag - Google Patents
The system and method for handling converter vanadium chromium slag Download PDFInfo
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- CN106978544A CN106978544A CN201710210333.0A CN201710210333A CN106978544A CN 106978544 A CN106978544 A CN 106978544A CN 201710210333 A CN201710210333 A CN 201710210333A CN 106978544 A CN106978544 A CN 106978544A
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- vanadium
- chromium slag
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- calcium
- chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
Abstract
The invention discloses a kind of system and method for handling converter vanadium chromium slag, the system includes：Direct reduction unit, with the outlet of converter vanadium chromium slag entrance, reducing agent entrance and reduced calcine；Mill ore magnetic selection device, with reduced calcine entrance, iron powder outlet and except the outlet of ferrovanadium chromium slag；Oxidation roasting with calcium compounds device, with except the outlet of ferrovanadium chromium slag entrance, calcium salt entrance, air intake and high price vanadic acid calcium clinker；Carbonic acid leaching device, is exported with high price vanadic acid calcium clinker entrance, carbon acid solution entrance, chromium slag and containing vanadium leachate outlet；Precipitation calciner plant, with the outlet of entrance containing vanadium leachate, ammonium salt entrance, acidity regulator entrance and vanadic anhydride.The system can not only realize that vanadium in converter vanadium chromium slag, chromium are efficiently separated, and reclaim the ferro element in vanadium chromium slag, moreover it is possible to greatly improve and reclaim obtained vanadium, chromium, the grade of iron final products.
Description
Technical field
The invention belongs to METAL EXTRACTION field, specifically, the present invention relates to the system and method for processing converter vanadium chromium slag.
Background technology
China is a chromium depleted country, and 97% chrome ore all relies on import.It is worth noting that, the red lattice of Panzhihua
Chromium content is up to 9,000,000 tons in the high-chromic vanadium-titanium ferroferrite in area, and content of the chromium with vanadium in raw ore is suitable.The country is to this red
The processing method of lattice vanadium titano-magnetite is first passes around blast furnace process into containing vanadium and chromium molten iron, and then oxidation is blown out and turned in converter
Stove vanadium chromium slag (or abbreviation vanadium chromium slag).Converter vanadium chromium slag belongs to that vanadium chromium is suitable or chromium type high vanadium slag of low vanadium Gao Ge, its chromium content
(5%~13%) is nearly 10 times of common vanadium slag, with larger application value.Prior art carries out high temperature for the vanadium chromium slag
The high chromium solution of low vanadium that sodium oxide baking-water logging is obtained, contains the impurity such as more silicon, iron, aluminium, phosphorus, precipitation product purity
It is not high, and be difficult to remove containing a small amount of vanadium in obtained high chromium solution, qualified chromium product can not be obtained under present condition.
The extraction separation of vanadium chromium mainly precipitates the work of chromium using sodium roasting-water logging-ammonium salt precipitation-wastewater reduction at present
Skill, but the technique is only applicable to the relatively low low chromium type vanadium slag of chromium content at present.For the vanadium chromium separation of chromium type high vanadium slag, there is first calcium
Roasting vanadium-extracting, again sodium roasting put forward the step by step arithmetic technique of chromium, but this method economy is poor, and it is pure that vanadium, chromium product is made
Degree is not high.The vanadium titano-magnetite of separate sources, obtains the different slag containing chrome alum of vanadium chromium content, through different roasting-leaching methods
Different vanadium chromium solution systems are obtained again, the compositional difference of vanadium chromium solution is larger, this just increases separation and recovery vanadium, the difficulty of chromium
Degree.For traditional slag containing chrome alum, Chinese Academy of Sciences's process uses sub-molten salt method to separate and recover vanadium, chromium, and the leaching rate of vanadium and chromium can
Up to 95% and 90%, but high-alkali condition requires very high to equipment materials such as reactor, pipeline, valve, flanges, realizes industrialization
Using acquiring a certain degree of difficulty.
So far, vanadium, chromium are extracted in vanadium chromium slag and separation not yet has the technology of industrialized production, its main skill
Art difficult point is that vanadium, chromium are difficult to realize high efficiency extraction and separation is difficult, and efficient, the clean utilization of vanadium chromium resource are even more a disaster
Topic.Therefore, it is further improved at present for the treatment technology of vanadium chromium slag.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is to propose a kind of system and method for handling converter vanadium chromium slag.The system can be not only realized in converter vanadium chromium slag
Vanadium, chromium are efficiently separated, and reclaim the ferro element in vanadium chromium slag, moreover it is possible to greatly improve vanadium, chromium, the iron final products for reclaiming and obtaining
Grade.
In one aspect of the invention, the present invention proposes a kind of system for handling converter vanadium chromium slag, according to the present invention's
Embodiment, the system includes：
Direct reduction unit, the direct reduction unit has converter vanadium chromium slag entrance, reducing agent entrance and reduced calcine
Outlet；
Mill ore magnetic selection device, the mill ore magnetic selection device has reduced calcine entrance, iron powder outlet and except ferrovanadium chromium slag goes out
Mouthful, the reduced calcine entrance is connected with reduced calcine outlet；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device, which has, removes ferrovanadium chromium slag entrance, calcium salt entrance, air
Entrance and the outlet of high price vanadic acid calcium clinker, it is described except ferrovanadium chromium slag entrance is connected with described except ferrovanadium chromium slag is exported；
Carbonic acid leaching device, the carbonic acid leaching device has high price vanadic acid calcium clinker entrance, carbon acid solution entrance, chromium slag
Export and containing vanadium leachate outlet, the high price vanadic acid calcium clinker entrance is connected with high price vanadic acid calcium clinker outlet；
Precipitation-calciner plant, the precipitation-calciner plant has entrance containing vanadium leachate, ammonium salt entrance, acidity regulator
Entrance and vanadic anhydride outlet, the entrance containing vanadium leachate are connected with the outlet containing vanadium leachate.
The system of processing converter vanadium chromium slag according to embodiments of the present invention, because the main thing of converter vanadium chromium slag is mutually FeO
(Cr, V, Ti)2O3And 2FeOSiO2, i.e., vanadium, chromium and part iron are main exists in the form of vanadium iron and chromohercynite, also has
A part of iron exists in the form of fayalite, different according to the active degree of metal, in the presence of reducing agent, the preferential quilt of iron
Reduction, obtains iron powder and except ferrovanadium chromium slag after mill ore magnetic selection.By the way that oxidation roasting with calcium compounds will be carried out except ferrovanadium chromium slag, it may be such that
Except the vanadium in ferrovanadium chromium slag is oxidized to pentavalent vanadium as far as possible, in carbonic acid leaching process, pentavalent vanadium can be transferred in liquid phase, so that
Separated with chromium slag, obtain chromium slag and containing vanadium leachate, the chromium in chromium slag can be utilized separately as chromium resource is carried, in this way, realizing
The separation and recovery of vanadium and chromium, containing vanadium leachate again through precipitation-calcination processing, can obtain vanadic anhydride.Whole technique is real
Show efficiently separating for iron, vanadium and chromium, and the grade of vanadium and chromium is substantially improved, while so that the rate of recovery of iron is not less than 85%,
The rate of recovery of vanadium is not less than 88%, and the rate of recovery of chromium is not less than 86%, has reached the effect of iron, vanadium and chromium resource comprehensive reutilization
Really.
In addition, the system of processing converter vanadium chromium slag according to the above embodiment of the present invention, can also have what is added as follows
Technical characteristic：
In some embodiments of the invention, the direct reduction unit is rotary hearth furnace or gas-based shaft kiln.Thus, be conducive to
The reduction efficiency of converter vanadium chromium slag is improved, so as to realize the high efficiente callback of iron.
In some embodiments of the invention, the oxidation roasting with calcium compounds device is rotary hearth furnace, rotary kiln or multilayer roasting
Stove, preferably rotary kiln or multihearth roaster.Thus, be conducive to improving the oxidation efficiency for removing vanadium in ferrovanadium chromium slag.
In some embodiments of the invention, the precipitation-calciner plant is the linkage dress of precipitation equipment and calciner
Put.Thus, the high efficiente callback of vanadium is advantageously implemented, while improving the rate of recovery of vanadium.
In another aspect of the invention, the present invention proposes a kind of system using above-mentioned processing converter vanadium chromium slag and handled
The method of converter vanadium chromium slag, embodiments in accordance with the present invention, this method includes：
(1) converter vanadium chromium slag and reducing agent are supplied into the direct reduction unit and carries out direct-reduction processing, so as to
Obtain reduced calcine；
(2) reduced calcine is supplied into the mill ore magnetic selection device and carries out ore grinding and magnetic separation processing, to obtain
Iron powder and except ferrovanadium chromium slag；
(3) by described except ferrovanadium chromium slag and calcium salt, air supply into the oxidation roasting with calcium compounds device and carry out aoxidizing-calcium
Change calcination process, to obtain high price vanadic acid calcium clinker；
(4) the high price vanadic acid calcium clinker and carbon acid solution are supplied into the carbonic acid leaching device and carries out carbonic acid leaching
Processing, to obtain chromium slag and containing vanadium leachate；
(5) supply containing vanadium leachate and ammonium salt, acidity regulator by described and carry out precipitation into the precipitation-calciner plant
And calcination processing, to obtain vanadic anhydride.
The method of processing converter vanadium chromium slag according to embodiments of the present invention, because the main thing of converter vanadium chromium slag is mutually FeO
(Cr, V, Ti)2O3And 2FeOSiO2, i.e., vanadium, chromium and part iron are main exists in the form of vanadium iron and chromohercynite, also has
A part of iron exists in the form of fayalite, different according to the active degree of metal, in the presence of reducing agent, the preferential quilt of iron
Reduction, obtains iron powder and except ferrovanadium chromium slag after mill ore magnetic selection.By the way that oxidation roasting with calcium compounds will be carried out except ferrovanadium chromium slag, it may be such that
Except the vanadium in ferrovanadium chromium slag is oxidized to pentavalent vanadium as far as possible, in carbonic acid leaching process, pentavalent vanadium can be transferred in liquid phase, so that
Separated with chromium slag, obtain chromium slag and containing vanadium leachate, the chromium in chromium slag can be utilized separately as chromium resource is carried, in this way, realizing
The separation and recovery of vanadium and chromium, containing vanadium leachate again through precipitation-calcination processing, can obtain vanadic anhydride.Whole technique is real
Show efficiently separating for iron, vanadium and chromium, and the grade of vanadium and chromium is substantially improved, while so that the rate of recovery of iron is not less than 85%,
The rate of recovery of vanadium is not less than 88%, and the rate of recovery of chromium is not less than 86%, has reached the effect of iron, vanadium and chromium resource comprehensive reutilization
Really.
In addition, the method for processing converter vanadium chromium slag according to the above embodiment of the present invention, can also have what is added as follows
Technical characteristic：
In some embodiments of the invention, in step (1), Cr in the converter vanadium chromium slag2O3Content be 8~16
Weight %, V2O5Content be 8~16 weight %, Fe content be 20~35 weight %.Thus, be conducive to improving iron, vanadium, chromium
The grade of final products.
In some embodiments of the invention, in step (1), the temperature of the direct-reduction processing is 1100-1280
Degree Celsius.Thus, be conducive to improving the rate of recovery of iron and the grade of iron powder.
In some embodiments of the invention, in step (2), it is described remove ferrovanadium chromium slag in weight of iron fraction be not more than
8%.Hereby it is achieved that the high efficiente callback of iron.
In some embodiments of the invention, it is described to remove ferrovanadium chromium slag with the calcium salt according to 100 in step (3):(5
~mass ratio 15) is mixed.Thus, it can further improve except the conversion ratio of the vanadium in ferrovanadium chromium slag.
In some embodiments of the invention, in step (3), the calcium salt is selected from calcium carbonate, calcium oxide, hydroxide
At least one of calcium, calcium sulfate and calcium chloride.Thus, it can further improve except the conversion ratio of the vanadium in ferrovanadium chromium slag.
In some embodiments of the invention, in step (3), pentavalent vanadium accounts for full vanadium in the high price vanadic acid calcium clinker
Ratio is not less than 95 weight %.Thus, it is advantageously implemented the recovery of vanadium.
In some embodiments of the invention, in step (4), the carbon acid solution and the high price vanadic acid calcium clinker
Liquid-solid ratio is (3~5):1.Thus, the high efficiente callback of vanadium can be further realized, while improving the rate of recovery of vanadium.
In some embodiments of the invention, in step (4), the carbon acid solution is sodium carbonate liquor or sodium acid carbonate
Solution, and the concentration of the carbon acid solution is 10~20 weight %.Thus, the high efficiente callback of vanadium can further be realized.
In some embodiments of the invention, in step (4), the temperature of the carbonic acid leaching process is Celsius for 85~95
Degree, the time is 30~120min.Thus, the high efficiente callback of vanadium can be further realized, while improving the rate of recovery of vanadium.
In some embodiments of the invention, in step (5), the precipitation-calcination processing is carried out according to the following steps：
(5-1) regulation it is described containing vanadium leachate to acid and add ammonium salt and precipitated, to obtain poly ammonium vanadate；(5-2) is by institute
State poly ammonium vanadate and carry out calcination processing, to obtain vanadic anhydride.Thus, the high efficiente callback of vanadium can be further realized, together
The rate of recovery of Shi Tigao vanadium.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the system structure diagram of processing converter vanadium chromium slag according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram of processing converter vanadium chromium slag according to an embodiment of the invention.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In the present invention, unless otherwise clearly defined and limited, term " installation ", " connected ", " connection ", " fixation " etc.
Term should be interpreted broadly, for example, it may be fixedly connected or be detachably connected, or integrally；Can be that machinery connects
Connect or electrically connect；Can be joined directly together, can also be indirectly connected to by intermediary, can be in two elements
The connection in portion or the interaction relationship of two elements, unless otherwise clear and definite restriction.For one of ordinary skill in the art
For, the concrete meaning of above-mentioned term in the present invention can be understood as the case may be.
In one aspect of the invention, the present invention proposes a kind of system for handling converter vanadium chromium slag, according to the present invention's
Embodiment, with reference to Fig. 1, the system includes：Direct reduction unit 100, mill ore magnetic selection device 200, oxidation roasting with calcium compounds device
300th, carbonic acid leaching device 400 and precipitation-calciner plant 500.
Embodiments in accordance with the present invention, direct reduction unit 100 has converter vanadium chromium slag entrance 101, reducing agent entrance 102
103 are exported with reduced calcine, and suitable for converter vanadium chromium slag and reducing agent are carried out into direct-reduction processing, to obtain reduction roasting
Sand.Inventor has found that the main thing of converter vanadium chromium slag is mutually FeOCr2O3、FeO·V2O3、FeO·Ti2O3And 2FeO
SiO2, i.e., vanadium, chromium and part iron are main exists in the form of vanadium iron and chromohercynite, and some iron is with fayalite
Form is present, thus, can preferentially be restored iron according to the difference of the active degree of metal.Converter vanadium chromium slag and reducing agent
The iron carried out in direct-reduction processing, converter vanadium chromium slag is reduced, and vanadium and chromium are not reduced, and are obtained ferrous metal rate and are not less than
80% reduced calcine.It should be noted that direct-reduction processing is not particularly restricted, those skilled in the art can basis
It is actually needed and is selected, for example, can is coal-based direct reduction or gas base directly reducing, accordingly, reducing agent can be reduction
Coal or also Primordial Qi.It is reduced directly in processing procedure, the chemical reaction of generation mainly has：
2FeO·SiO2+ 2C=2Fe+SiO2+2CO (1)
2FeO·SiO2+ 2CO=2Fe+SiO2+2CO2 (2)
FeO (Cr, V, Ti)2O3+ C=(Cr, V, Ti)2O3+Fe+CO (3)
FeO (Cr, V, Ti)2O3+ CO=(Cr, V, Ti)2O3+Fe+CO2 (4)
According to one embodiment of present invention, direct reduction unit is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, for example, can be rotary hearth furnace or gas-based shaft kiln.Thus, it is remarkably improved direct-reduction processing
Efficiency, improve reduced calcine ferrous metal rate.
According to still a further embodiment, the content of each component is not particularly restricted in converter vanadium chromium slag, ability
The technical staff in domain can be selected according to actual needs, according to the specific embodiment of the present invention, in converter vanadium chromium slag
Cr2O3Content can be 8~16 weight %, V2O5Content can be that 8~16 weight %, Fe content can be 20~35
Weight %.Specifically, converter vanadium chromium slag (abbreviation vanadium chromium slag) is red lattice vanadium titano-magnetite through blast furnace process into containing vanadium and chromium molten iron, so
Oxidation blows what is obtained in converter afterwards.
According to still another embodiment of the invention, the temperature of direct-reduction processing is not particularly restricted, the skill of this area
Art personnel can be selected according to actual needs, according to the specific embodiment of the present invention, be reduced directly the temperature of processing
It can be 1100~1280 degrees Celsius.Thus, it is possible to further improve the rate of recovery of iron.Inventor has found, if direct-reduction
The temperature of processing is too high, it will makes vanadium, chromium and iron in converter vanadium chromium slag while being reduced, causes vanadium, chromium can not be separated with iron；
And if the temperature of direct-reduction processing is too low, the reduction reaction of iron can not carry out or carry out inefficiency.Thus, using this hair
The direct-reduction treatment temperature of bright proposition is remarkably improved the reduction efficiency of iron while improving the grade of follow-up gained iron powder.
Embodiments in accordance with the present invention, mill ore magnetic selection device 200 has reduced calcine entrance 201, iron powder outlet 202 and removed
Ferrovanadium chromium slag outlet 203, reduced calcine entrance 201 is connected with reduced calcine outlet 103, and suitable for reduced calcine is carried out into ore grinding
With magnetic separation processing, to obtain iron powder and except ferrovanadium chromium slag.Inventor has found that reduced calcine is after ore grinding, iron and vanadium and chromium point
Leave, recycle iron different from the physical property of vanadium and chromium, iron powder can be respectively obtained and except ferrovanadium chromium slag by magnetic separation.Iron powder can conduct
The quality raw materials of steel-making, and the mass fraction of iron is not less than 85% in the iron powder of gained, the rate of recovery of iron is not less than 85%.
According to one embodiment of present invention, except the mass fraction of iron in ferrovanadium chromium slag is not more than 8%.Hereby it is achieved that
The separation of iron and vanadium chromium, namely realize the high efficiente callback of iron.
Embodiments in accordance with the present invention, oxidation roasting with calcium compounds device 300, which has, removes ferrovanadium chromium slag entrance 301, calcium salt entrance
302nd, air intake 303 and high price vanadic acid calcium clinker outlet 304, except ferrovanadium chromium slag entrance 301 is with removing 203 phases of ferrovanadium chromium slag outlet
Even, and suitable for ferrovanadium chromium slag and calcium salt, air will be removed carry out aoxidizing-calcification baking processing, to obtain high price vanadic acid calcium clinker.
Inventor has found, by that will carry out oxidation roasting with calcium compounds except ferrovanadium chromium slag, may be such that except the vanadium in ferrovanadium chromium slag is aoxidized as far as possible
For pentavalent vanadium, related chemical equation is：
CaO+V2O3+O2=2Ca (VO3)2 (5)
According to one embodiment of present invention, oxidation roasting with calcium compounds device is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, for example, can be rotary hearth furnace, rotary kiln or multihearth roaster, preferably rotary kiln or many
Layer roaster.Thus, it is remarkably improved except the oxidation roasting with calcium compounds treatment effeciency of ferrovanadium chromium slag so that except the vanadium in ferrovanadium chromium slag
It is as much as possible to be converted into pentavalent calcium vanadate.
According to still a further embodiment, the particular type of calcium salt is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, according to the specific embodiment of the present invention, and calcium salt can be selected from calcium carbonate, oxygen
Change at least one of calcium, calcium hydroxide, calcium sulfate and calcium chloride.Inventor has found, is compared using calcium salt proposed by the present invention
It is remarkably improved in other types except the oxidation roasting with calcium compounds efficiency of ferrovanadium chromium slag, improves the conversion ratio for removing vanadium in ferrovanadium chromium slag,
So that except the vanadium in ferrovanadium chromium slag is converted into pentavalent calcium vanadate as far as possible, so as to improve vanadium, the rate of recovery of chromium and its final products
Grade.
According to still another embodiment of the invention, except the mixing quality ratio of ferrovanadium chromium slag and calcium salt is not particularly restricted,
Those skilled in the art can be selected according to actual needs, according to the specific embodiment of the present invention, except ferrovanadium chromium
Slag can be according to 100 with calcium salt:The mass ratio of (5~15) is mixed.Inventor is had found, ferrovanadium chromium slag is removed using the present invention
The oxidation roasting with calcium compounds efficiency of ferrovanadium chromium slag is removed than can further improve with the mixing quality of calcium salt, improves and removes vanadium in ferrovanadium chromium slag
Conversion ratio so that except the vanadium in ferrovanadium chromium slag is converted into pentavalent calcium vanadate as far as possible, thus improve vanadium, the rate of recovery of chromium and its
The grade of final products.
According to still another embodiment of the invention, pentavalent vanadium accounts for the ratio of full vanadium not by special in high price vanadic acid calcium clinker
Limitation, those skilled in the art can be selected according to actual needs, according to the specific embodiment of the present invention, high price
Pentavalent vanadium, which accounts for the ratio of full vanadium, in vanadic acid calcium clinker can be not less than 95 weight %.Thus, vanadium, chromium is can further improve finally to produce
The grade of product.
Embodiments in accordance with the present invention, carbonic acid leaching device 400 has high price vanadic acid calcium clinker entrance 401, carbon acid solution
Entrance 402, chromium slag export 403 and containing vanadium leachate outlet 404, high price vanadic acid calcium clinker entrance 401 and high price vanadic acid calcium clinker
Outlet 304 is connected, and suitable for high price vanadic acid calcium clinker and carbon acid solution are carried out into carbonic acid leaching process, to obtain chromium slag and to contain
Vanadium leachate.Inventor has found that because the concentration product of calcium carbonate is less than calcium vanadate, therefore the pentavalent calcium vanadate in high price calcium vanadate is in carbon
It can be leached in the presence of acid solution, vanadium is transferred in liquid phase to be separated with chromium slag, obtain containing vanadium leachate and chromium slag, wherein, chromium
Chromium in slag is enriched with, Cr in chromium slag2O3Mass fraction be not less than 12%, the rate of recovery of chromium is not less than 86%, can individually make
Utilized to carry chromium resource.Related chemical equation is：
Ca(VO3)2+CO3 2-=CaCO3+2VO3 - (6)
According to one embodiment of present invention, the particular type of carbon acid solution is not particularly restricted, the technology of this area
Personnel can be selected according to actual needs, and according to the specific embodiment of the present invention, carbon acid solution can be sodium carbonate
Solution or sodium bicarbonate solution.Inventor is had found, other types can be significantly better than using the type of above-mentioned carbon acid solution of the invention
Improve the leaching efficiency of high price vanadic acid calcium clinker so that the vanadium in high price vanadic acid calcium clinker is leached as far as possible, so as to improve vanadium
With the grade and the rate of recovery of the final products of chromium.
According to still a further embodiment, the concentration of carbon acid solution is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, according to the specific embodiment of the present invention, and the concentration of carbon acid solution can be 10
~20 weight %.Inventor invents, and the concentration of carbon acid solution is too low, and the leaching effect of vanadium is bad；And the concentration mistake of carbon acid solution
Height, can not significantly improve the leaching rate of vanadium, can also cause reagent waste.Thus, using carbon acid solution proposed by the present invention
Concentration can further improve the leaching rate of vanadium, while cost-effective.
According to still another embodiment of the invention, the liquid-solid ratio of carbon acid solution and high price vanadic acid calcium clinker is not limited especially
System, those skilled in the art can be selected according to actual needs, and according to the specific embodiment of the present invention, carbonic acid is molten
The liquid-solid ratio of liquid and high price vanadic acid calcium clinker can be (3~5):1.Inventor has found, if carbon acid solution and high price calcium vanadate are ripe
The liquid-solid ratio of material is too high can cause to obtain to contain vanadium concentration in vanadium leachate too low, be that follow-up precipitation brings adverse effect；And
If the liquid-solid ratio of carbon acid solution and high price vanadic acid calcium clinker is too low, pulp density is too high, can reduce the leaching rate of vanadium.Thus,
The leaching rate of vanadium can further improve using the liquid-solid ratio of carbon acid solution proposed by the present invention and high price vanadic acid calcium clinker, so as to carry
The grade of the grade of high chromium slag and follow-up gained vanadic anhydride.
According to still another embodiment of the invention, the condition of carbonic acid leaching process is not particularly restricted, the skill of this area
Art personnel can be selected according to actual needs, according to the specific embodiment of the present invention, the temperature of carbonic acid leaching process
It can be 85~95 degrees Celsius, the time can be 30~120min.Inventor has found, the temperature of carbonic acid leaching process is too low, when
Between too short can all reduce the leaching efficiency of vanadium；And the temperature of carbonic acid leaching process is too high, overlong time can not significantly improve vanadium
Leaching rate, can also cause energy dissipation.Thus, it can further improve using the condition of carbonic acid leaching process proposed by the present invention
The leaching efficiency of vanadium, while saving energy consumption.
Embodiments in accordance with the present invention, precipitation-calciner plant 500 have entrance containing vanadium leachate 501, ammonium salt entrance 502,
Acidity regulator entrance 503 and vanadic anhydride outlet 504, entrance containing vanadium leachate 501 containing vanadium leachate with exporting 404 phases
Even, and suitable for vanadium leachate and ammonium salt, acidity regulator will be contained precipitation and calcination processing are carried out, to obtain vanadic anhydride.
Thus, the recovery of vanadium can be achieved so that the rate of recovery of vanadium is not less than 88%.
According to one embodiment of present invention, precipitation-calciner plant is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, for example, can be precipitation equipment and the linkage of calciner.Thus, it is remarkably improved
Precipitation and calcination processing efficiency containing vanadium leachate, improve the rate of recovery of vanadium and the grade of vanadic anhydride.
According to still a further embodiment, precipitation-calcination processing is not particularly restricted, those skilled in the art
It can be selected according to actual needs, according to the specific embodiment of the present invention, precipitation-calcination processing can be according to following
Step is carried out：Regulation containing vanadium leachate to acid and add ammonium salt and precipitated, to obtain poly ammonium vanadate；By poly vanadic acid
Ammonium carries out calcination processing, to obtain vanadic anhydride.Related chemical equation is：
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (7)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (8)
The system of processing converter vanadium chromium slag according to embodiments of the present invention, because the main thing of converter vanadium chromium slag is mutually FeO
(Cr, V, Ti)2O3And 2FeOSiO2, i.e., vanadium, chromium and part iron are main exists in the form of vanadium iron and chromohercynite, also has
A part of iron exists in the form of fayalite, different according to the active degree of metal, in the presence of reducing agent, the preferential quilt of iron
Reduction, obtains iron powder and except ferrovanadium chromium slag after mill ore magnetic selection.By the way that oxidation roasting with calcium compounds will be carried out except ferrovanadium chromium slag, it may be such that
Except the vanadium in ferrovanadium chromium slag is oxidized to pentavalent vanadium as far as possible, in carbonic acid leaching process, pentavalent vanadium can be transferred in liquid phase, so that
Separated with chromium slag, obtain chromium slag and containing vanadium leachate, the chromium in chromium slag can be utilized separately as chromium resource is carried, in this way, realizing
The separation and recovery of vanadium and chromium, containing vanadium leachate again through precipitation-calcination processing, can obtain vanadic anhydride.Whole technique is real
Show efficiently separating for iron, vanadium and chromium, and the grade of vanadium and chromium is substantially improved, while so that the rate of recovery of iron is not less than 85%,
The rate of recovery of vanadium is not less than 88%, and the rate of recovery of chromium is not less than 86%, has reached the effect of iron, vanadium and chromium resource comprehensive reutilization
Really.
As described above, according to an embodiment of the invention processing converter vanadium chromium slag system at least have following advantages it
One：
The method of processing converter vanadium chromium slag according to embodiments of the present invention to converter vanadium chromium slag by being first reduced directly
Iron processing is proposed, recycles oxidation roasting with calcium compounds-carbonic acid to leach vanadium extraction, obtains iron powder, chromium slag and containing vanadium leachate, finally realize
The separation of iron, chromium and vanadium；
The method of processing converter vanadium chromium slag according to embodiments of the present invention except ferrovanadium chromium slag phase is for converter vanadium chromium slag, vanadium and
The grade of chromium is substantially improved, and is conducive to follow-up vanadium extraction and carries chromium；
The method of processing converter vanadium chromium slag according to embodiments of the present invention, compared with prior art, vanadium, the separative efficiency of chromium
Significantly improve, while also having reclaimed ferro element, reached the effect of comprehensive utilization of resources.
In another aspect of the invention, the present invention proposes a kind of system using above-mentioned processing converter vanadium chromium slag and handled
The method of converter vanadium chromium slag, embodiments in accordance with the present invention, with reference to Fig. 2, this method includes：
S100：Converter vanadium chromium slag and reducing agent are supplied into direct reduction unit and carry out direct-reduction processing
In the step, converter vanadium chromium slag and reducing agent are supplied into direct reduction unit and carry out direct-reduction processing, with
Just reduced calcine is obtained.It should be noted that direct reduction unit is not particularly restricted, those skilled in the art can basis
It is actually needed and is selected, for example, can is rotary hearth furnace or gas-based shaft kiln.Inventor has found that the main thing of converter vanadium chromium slag is mutually
FeO·Cr2O3、FeO·V2O3、FeO·Ti2O3And 2FeOSiO2, i.e., vanadium, chromium and part iron are mainly with vanadium iron and ferrochrome point crystalline substance
The form of stone is present, and some iron exists in the form of fayalite, thus, can be according to the active degree of metal not
Together, iron is preferentially restored.Converter vanadium chromium slag carries out the iron in direct-reduction processing, converter vanadium chromium slag with reducing agent and gone back
Original, and vanadium and chromium are not reduced, and obtain the reduced calcine that ferrous metal rate is not less than 80%.It should be noted that direct-reduction
Processing is not particularly restricted, and those skilled in the art can be selected according to actual needs, for example can be direct for coal base
Reduction or gas base directly reducing, accordingly, reducing agent can be reduction coal or go back Primordial Qi.It is reduced directly in processing procedure, occurs
Chemical reaction mainly have：
2FeO·SiO2+ 2C=2Fe+SiO2+2CO (1)
2FeO·SiO2+ 2CO=2Fe+SiO2+2CO2 (2)
FeO (Cr, V, Ti)2O3+ C=(Cr, V, Ti)2O3+Fe+CO (3)
FeO (Cr, V, Ti)2O3+ CO=(Cr, V, Ti)2O3+Fe+CO2 (4)
According to one embodiment of present invention, the content of each component is not particularly restricted in converter vanadium chromium slag, this area
Technical staff can be selected according to actual needs, according to the specific embodiment of the present invention, in converter vanadium chromium slag
Cr2O3Content can be 8~16 weight %, V2O5Content can be that 8~16 weight %, Fe content can be 20~35
Weight %.Specifically, converter vanadium chromium slag (abbreviation vanadium chromium slag) is red lattice vanadium titano-magnetite through blast furnace process into containing vanadium and chromium molten iron, so
Oxidation blows what is obtained in converter afterwards.
According to still a further embodiment, the temperature of direct-reduction processing is not particularly restricted, the skill of this area
Art personnel can be selected according to actual needs, according to the specific embodiment of the present invention, be reduced directly the temperature of processing
It can be 1100~1280 degrees Celsius.Thus, it is possible to further improve the rate of recovery of iron.Inventor has found, if direct-reduction
The temperature of processing is too high, it will makes vanadium, chromium and iron in converter vanadium chromium slag while being reduced, causes vanadium, chromium can not be separated with iron；
And if the temperature of direct-reduction processing is too low, the reduction reaction of iron can not carry out or carry out inefficiency.Thus, using this hair
The direct-reduction treatment temperature of bright proposition is remarkably improved the reduction efficiency of iron while improving the grade of follow-up gained iron powder.
S200：Reduced calcine is supplied into mill ore magnetic selection device and carries out ore grinding and magnetic separation processing
In the step, reduced calcine is supplied into mill ore magnetic selection device and carries out ore grinding and magnetic separation processing, to obtain iron
Powder and except ferrovanadium chromium slag.Inventor has found that reduced calcine is after ore grinding, and iron is separated with vanadium and chromium, recycles iron and vanadium and chromium
Physical property it is different, iron powder can be respectively obtained and except ferrovanadium chromium slag by magnetic separation.Iron powder can as steel-making quality raw materials, and gained
Iron powder in the mass fraction of iron be not less than 85%, the rate of recovery of iron is not less than 85%.
According to one embodiment of present invention, except the mass fraction of iron in ferrovanadium chromium slag is not more than 8%.Hereby it is achieved that
The separation of iron and vanadium chromium, namely realize the high efficiente callback of iron.
S300：Ferrovanadium chromium slag will be removed and calcium salt, air supply and carry out aoxidizing-calcification baking into oxidation roasting with calcium compounds device
Processing
In the step, ferrovanadium chromium slag will be removed and calcium salt, air supply and carry out aoxidizing-calcification into oxidation roasting with calcium compounds device
Calcination process, to obtain high price vanadic acid calcium clinker.It should be noted that oxidation roasting with calcium compounds device is not particularly restricted,
Those skilled in the art can be selected according to actual needs, for example can be rotary hearth furnace, rotary kiln or multihearth roaster, it is excellent
Select rotary kiln or multihearth roaster.Inventor has found, by that will carry out oxidation roasting with calcium compounds except ferrovanadium chromium slag, may be such that except ferrovanadium
Vanadium in chromium slag is oxidized to pentavalent vanadium as far as possible, and related chemical equation is：
CaO+V2O3+O2=2Ca (VO3)2 (5)
According to one embodiment of present invention, the particular type of calcium salt is not particularly restricted, those skilled in the art
It can be selected according to actual needs, according to the specific embodiment of the present invention, calcium salt can be selected from calcium carbonate, oxidation
At least one of calcium, calcium hydroxide, calcium sulfate and calcium chloride.Inventor find, using calcium salt proposed by the present invention compared to
Other types are remarkably improved except the oxidation roasting with calcium compounds efficiency of ferrovanadium chromium slag, are improved the conversion ratio for removing vanadium in ferrovanadium chromium slag, are made
The vanadium that must be removed in ferrovanadium chromium slag is converted into pentavalent calcium vanadate as far as possible, so as to improve vanadium, the rate of recovery of chromium and its final products
Grade.
According to still a further embodiment, except the mixing quality ratio of ferrovanadium chromium slag and calcium salt is not particularly restricted,
Those skilled in the art can be selected according to actual needs, according to the specific embodiment of the present invention, except ferrovanadium chromium
Slag can be according to 100 with calcium salt:The mass ratio of (5~15) is mixed.Inventor is had found, ferrovanadium chromium slag is removed using the present invention
The oxidation roasting with calcium compounds efficiency of ferrovanadium chromium slag is removed than can further improve with the mixing quality of calcium salt, improves and removes vanadium in ferrovanadium chromium slag
Conversion ratio so that except the vanadium in ferrovanadium chromium slag is converted into pentavalent calcium vanadate as far as possible, thus improve vanadium, the rate of recovery of chromium and its
The grade of final products.
According to still another embodiment of the invention, pentavalent vanadium accounts for the ratio of full vanadium not by special in high price vanadic acid calcium clinker
Limitation, those skilled in the art can be selected according to actual needs, according to the specific embodiment of the present invention, high price
Pentavalent vanadium, which accounts for the ratio of full vanadium, in vanadic acid calcium clinker can be not less than 95 weight %.Thus, vanadium, chromium is can further improve finally to produce
The grade of product.
S400：High price vanadic acid calcium clinker and carbon acid solution are supplied into carbonic acid leaching device and carry out carbonic acid leaching process
In the step, high price vanadic acid calcium clinker and carbon acid solution are supplied into carbonic acid leaching device and carried out at carbonic acid leaching
Reason, to obtain chromium slag and containing vanadium leachate.Inventor has found, is accumulated because of the concentration of calcium carbonate and is less than calcium vanadate, therefore high price vanadic acid
Pentavalent calcium vanadate in calcium can be leached in the presence of carbon acid solution, and vanadium is transferred in liquid phase to be separated with chromium slag, obtain containing vanadium
Leachate and chromium slag, wherein, the chromium in chromium slag is enriched with, Cr in chromium slag2O3Mass fraction be not less than 12%, the recovery of chromium
Rate is not less than 86%, can be utilized separately as chromium resource is carried.Related chemical equation is：
Ca(VO3)2+CO3 2-=CaCO3+2VO3 - (6)
According to one embodiment of present invention, the particular type of carbon acid solution is not particularly restricted, the technology of this area
Personnel can be selected according to actual needs, and according to the specific embodiment of the present invention, carbon acid solution can be sodium carbonate
Solution or sodium bicarbonate solution.Inventor is had found, other types can be significantly better than using the type of above-mentioned carbon acid solution of the invention
Improve the leaching efficiency of high price vanadic acid calcium clinker so that the vanadium in high price vanadic acid calcium clinker is leached as far as possible, so as to improve vanadium
With the grade and the rate of recovery of the final products of chromium.
According to still a further embodiment, the concentration of carbon acid solution is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, according to the specific embodiment of the present invention, and the concentration of carbon acid solution can be 10
~20 weight %.Inventor invents, and the concentration of carbon acid solution is too low, and the leaching effect of vanadium is bad；And the concentration mistake of carbon acid solution
Height, can not significantly improve the leaching rate of vanadium, can also cause reagent waste.Thus, using carbon acid solution proposed by the present invention
Concentration can further improve the leaching rate of vanadium, while cost-effective.
According to still another embodiment of the invention, the liquid-solid ratio of carbon acid solution and high price vanadic acid calcium clinker is not limited especially
System, those skilled in the art can be selected according to actual needs, and according to the specific embodiment of the present invention, carbonic acid is molten
The liquid-solid ratio of liquid and high price vanadic acid calcium clinker can be (3~5):1.Inventor has found, if carbon acid solution and high price calcium vanadate are ripe
The liquid-solid ratio of material is too high can cause to obtain to contain vanadium concentration in vanadium leachate too low, be that follow-up precipitation brings adverse effect；And
If the liquid-solid ratio of carbon acid solution and high price vanadic acid calcium clinker is too low, pulp density is too high, can reduce the leaching rate of vanadium.Thus,
The leaching rate of vanadium can further improve using the liquid-solid ratio of carbon acid solution proposed by the present invention and high price vanadic acid calcium clinker, so as to carry
The grade of the grade of high chromium slag and follow-up gained vanadic anhydride.
According to still another embodiment of the invention, the condition of carbonic acid leaching process is not particularly restricted, the skill of this area
Art personnel can be selected according to actual needs, according to the specific embodiment of the present invention, the temperature of carbonic acid leaching process
It can be 85~95 degrees Celsius, the time can be 30~120min.Inventor has found, the temperature of carbonic acid leaching process is too low, when
Between too short can all reduce the leaching efficiency of vanadium；And the temperature of carbonic acid leaching process is too high, overlong time can not significantly improve vanadium
Leaching rate, can also cause energy dissipation.Thus, it can further improve using the condition of carbonic acid leaching process proposed by the present invention
The leaching efficiency of vanadium, while saving energy consumption.
S500：Vanadium leachate will be contained and ammonium salt, acidity regulator supply into precipitation-calciner plant and carry out precipitation and calcining
Processing
In the step, will contain vanadium leachate and ammonium salt, acidity regulator supply into precipitation-calciner plant carry out precipitation and
Calcination processing, to obtain vanadic anhydride.Thus, the recovery of vanadium can be achieved so that the rate of recovery of vanadium is not less than 88%.Need
Illustrate, precipitation-calciner plant is not particularly restricted, those skilled in the art can be selected according to actual needs,
Can be for example precipitation equipment and the linkage of calciner.
According to one embodiment of present invention, precipitation-calcination processing is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, according to the specific embodiment of the present invention, precipitation-calcination processing can be according to following step
It is rapid to carry out：Regulation containing vanadium leachate to acid and add ammonium salt and precipitated, to obtain poly ammonium vanadate；By poly ammonium vanadate
Calcination processing is carried out, to obtain vanadic anhydride.Related chemical equation is：
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (7)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (8)
The method of processing converter vanadium chromium slag according to embodiments of the present invention, because the main thing of converter vanadium chromium slag is mutually FeO
(Cr, V, Ti)2O3And 2FeOSiO2, i.e., vanadium, chromium and part iron are main exists in the form of vanadium iron and chromohercynite, also has
A part of iron exists in the form of fayalite, different according to the active degree of metal, in the presence of reducing agent, the preferential quilt of iron
Reduction, obtains iron powder and except ferrovanadium chromium slag after mill ore magnetic selection.By the way that oxidation roasting with calcium compounds will be carried out except ferrovanadium chromium slag, it may be such that
Except the vanadium in ferrovanadium chromium slag is oxidized to pentavalent vanadium as far as possible, in carbonic acid leaching process, pentavalent vanadium can be transferred in liquid phase, so that
Separated with chromium slag, obtain chromium slag and containing vanadium leachate, the chromium in chromium slag can be utilized separately as chromium resource is carried, in this way, realizing
The separation and recovery of vanadium and chromium, containing vanadium leachate again through precipitation-calcination processing, can obtain vanadic anhydride.Whole technique is real
Show efficiently separating for iron, vanadium and chromium, and the grade of vanadium and chromium is substantially improved, while so that the rate of recovery of iron is not less than 85%,
The rate of recovery of vanadium is not less than 88%, and the rate of recovery of chromium is not less than 86%, has reached the effect of iron, vanadium and chromium resource comprehensive reutilization
Really.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only description
Property, without limiting the present invention in any way.
Embodiment 1
By the converter vanadium chromium slag (Cr of certain domestic company2O3Mass fraction be 8%, V2O5Mass fraction for 8%, Fe
Mass fraction is 20%) to carry out coal-based direct reduction processing at a temperature of 1100 degrees Celsius in rotary hearth furnace, obtains reduced calcine,
Ferrous metal rate is 80%.Reduced calcine is subjected to mill ore magnetic selection processing and obtains except ferrovanadium chromium slag that (Fe mass fraction is
7.9%) with iron powder (Fe mass fraction is 88%), iron powder can be used as the quality raw materials of steel-making.Ferrovanadium chromium slag and oxygen will be removed
Change calcium in mass ratio 100：After 5 mixing in rotary kiln oxidation roasting with calcium compounds 1h at a temperature of 900 degrees Celsius, obtain high price vanadic acid
The ratio that pentavalent vanadium accounts for full vanadium in calcium clinker, high price vanadic acid calcium clinker is 96%, and high price vanadic acid calcium clinker is carried out into carbonic acid leaching,
The condition that carbonic acid is leached is that leaching agent is sodium carbonate liquor, and leaching agent mass concentration is 10%, and extraction temperature is 85 degrees Celsius, leaching
It is 5 to go out liquid-solid ratio：1, extraction time is 120min.Leaching obtains containing vanadium leachate and chromium slag (Cr after terminating2O3Mass fraction
For 12%), the leaching rate of vanadium is 90%, then will contain vanadium leachate and carry out acid ammonium salt precipitation processing and obtain poly ammonium vanadate, many
Poly- ammonium vanadate carries out calcination processing in calcining furnace at a temperature of 500 degrees Celsius, obtain vanadic anhydride.Whole technique iron is reclaimed
Rate is 85%, and vanadium recovery is 88%, and chromium recovery ratio is 86%.
Embodiment 2
By the converter vanadium chromium slag (Cr of certain domestic company2O3Mass fraction be 10%, V2O5Mass fraction be 10%, Fe
Mass fraction for 24%) in gas-based shaft kiln at a temperature of 1150 degrees Celsius carry out gas base directly reducing processing, reduced
Calcining, ferrous metal rate is 83%.Reduced calcine is subjected to mill ore magnetic selection processing and obtains except ferrovanadium chromium slag that (Fe mass fraction is
7.5%) with iron powder (Fe mass fraction is 89%), iron powder can be used as the quality raw materials of steel-making.Ferrovanadium chromium slag and oxygen will be removed
Change calcium in mass ratio 100：After 10 mixing in rotary kiln oxidation roasting with calcium compounds 1.5h at a temperature of 1000 degrees Celsius, obtain high price
The ratio that pentavalent vanadium accounts for full vanadium in vanadic acid calcium clinker, high price vanadic acid calcium clinker is 96.5%, and high price vanadic acid calcium clinker is carried out into carbon
Ore Leaching, the condition that carbonic acid is leached is that leaching agent is sodium bicarbonate solution, and leaching agent mass concentration is 15%, and extraction temperature is 90
Degree Celsius, it is 4 to leach liquid-solid ratio：1, extraction time is 90min.Leaching obtains containing vanadium leachate and chromium slag (Cr after terminating2O3's
Mass fraction is that 15%), the leaching rate of vanadium is 92%, then will contain vanadium leachate and carry out acid ammonium salt precipitation processing and obtain poly vanadium
Sour ammonium, poly ammonium vanadate carries out calcination processing in calcining furnace at a temperature of 500 degrees Celsius, obtain vanadic anhydride.Whole work
Skill iron recovery is 87%, and vanadium recovery is 90%, and chromium recovery ratio is 87%.
Embodiment 3
By the converter vanadium chromium slag (Cr of certain domestic company2O3Mass fraction be 12%, V2O5Mass fraction be 12%, Fe
Mass fraction for 30%) in rotary hearth furnace at a temperature of 1200 degrees Celsius carry out coal-based direct reduction processing, obtain reduction roasting
Sand, ferrous metal rate is 85%.Reduced calcine is subjected to mill ore magnetic selection processing and obtains except ferrovanadium chromium slag that (Fe mass fraction is
6.9%) with iron powder (Fe mass fraction is 91%), iron powder can be used as the quality raw materials of steel-making.Ferrovanadium chromium slag and oxygen will be removed
Change calcium in mass ratio 100：After 12 mixing in rotary kiln oxidation roasting with calcium compounds 2h at a temperature of 1050 degrees Celsius, obtain high price vanadium
The ratio that pentavalent vanadium accounts for full vanadium in sour calcium clinker, high price vanadic acid calcium clinker is 97%, and high price vanadic acid calcium clinker is carried out into carbonic acid leaching
Go out, the condition that carbonic acid is leached is that leaching agent is sodium carbonate liquor, and leaching agent mass concentration is 20%, and extraction temperature is 95 Celsius
Degree, it is 3 to leach liquid-solid ratio：1, extraction time is 60min.Leaching obtains containing vanadium leachate and chromium slag (Cr after terminating2O3Quality
Fraction is that 18%), the leaching rate of vanadium is 94%, then will contain vanadium leachate and carry out acid ammonium salt precipitation processing and obtain poly vanadic acid
Ammonium, poly ammonium vanadate carries out calcination processing in calcining furnace at a temperature of 500 degrees Celsius, obtain vanadic anhydride.Whole technique
Iron recovery is 88%, and vanadium recovery is 94%, and chromium recovery ratio is 90%.
Embodiment 4
By the converter vanadium chromium slag (Cr of certain domestic company2O3Mass fraction be 16%, V2O5Mass fraction be 16%, Fe
Mass fraction for 35%) in gas-based shaft kiln at a temperature of 1280 degrees Celsius carry out gas base directly reducing processing, reduced
Calcining, ferrous metal rate is 87%.Reduced calcine is subjected to mill ore magnetic selection processing and obtains except ferrovanadium chromium slag that (Fe mass fraction is
6.5%) with iron powder (Fe mass fraction is 93%), iron powder can be used as the quality raw materials of steel-making.Ferrovanadium chromium slag and oxygen will be removed
Change calcium in mass ratio 100：After 15 mixing in rotary kiln oxidation roasting with calcium compounds 1.5h at a temperature of 1100 degrees Celsius, obtain high price
The ratio that pentavalent vanadium accounts for full vanadium in vanadic acid calcium clinker, high price vanadic acid calcium clinker is 98%, and high price vanadic acid calcium clinker is carried out into carbonic acid
Leach, the condition that carbonic acid is leached is that leaching agent is sodium bicarbonate solution, and leaching agent mass concentration is 20%, and extraction temperature is taken the photograph for 95
Family name's degree, it is 3 to leach liquid-solid ratio：1, extraction time is 30min.Leaching obtains containing vanadium leachate and chromium slag (Cr after terminating2O3Matter
Fraction is measured for 20%), the leaching rate of vanadium is 97%, then vanadium leachate progress acid ammonium salt precipitation processing will be contained and obtains poly vanadic acid
Ammonium, poly ammonium vanadate carries out calcination processing in calcining furnace at a temperature of 500 degrees Celsius, obtain vanadic anhydride.Whole technique
Iron recovery is 86%, and vanadium recovery is 95%, and chromium recovery ratio is 92%.
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 the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. a kind of system for handling converter vanadium chromium slag, it is characterised in that including：
Direct reduction unit, the direct reduction unit has converter vanadium chromium slag entrance, reducing agent entrance and reduced calcine outlet；
Mill ore magnetic selection device, the mill ore magnetic selection device has reduced calcine entrance, iron powder outlet and except the outlet of ferrovanadium chromium slag, institute
Reduced calcine entrance is stated with reduced calcine outlet to be connected；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device, which has, removes ferrovanadium chromium slag entrance, calcium salt entrance, air intake
With the outlet of high price vanadic acid calcium clinker, the ferrovanadium chromium slag entrance that removes is connected with described except ferrovanadium chromium slag is exported；
Carbonic acid leaching device, the carbonic acid leaching device has high price vanadic acid calcium clinker entrance, carbon acid solution entrance, the outlet of chromium slag
Exported with containing vanadium leachate, the high price vanadic acid calcium clinker entrance is connected with high price vanadic acid calcium clinker outlet；
Precipitation-calciner plant, the precipitation-calciner plant has entrance containing vanadium leachate, ammonium salt entrance, acidity regulator entrance
With vanadic anhydride outlet, the entrance containing vanadium leachate is connected with the outlet containing vanadium leachate.
2. system according to claim 1, it is characterised in that the direct reduction unit is rotary hearth furnace or gas-based shaft kiln.
3. system according to claim 1, it is characterised in that the oxidation roasting with calcium compounds device is rotary hearth furnace, rotary kiln
Or multihearth roaster, preferably rotary kiln or multihearth roaster.
4. system according to claim 1, it is characterised in that the precipitation-calciner plant is that precipitation equipment and calcining are set
Standby linkage.
5. a kind of system of the processing converter vanadium chromium slag any one of use claim 1-4 handles the side of converter vanadium chromium slag
Method, it is characterised in that including：
(1) converter vanadium chromium slag and reducing agent are supplied into the direct reduction unit and carries out direct-reduction processing, to obtain
Reduced calcine；
(2) reduced calcine is supplied into the mill ore magnetic selection device and carries out ore grinding and magnetic separation processing, to obtain iron powder
With except ferrovanadium chromium slag；
(3) carries out aoxidizing-calcification roasting except ferrovanadium chromium slag and calcium salt, air are supplied into the oxidation roasting with calcium compounds device by described
Burning processing, to obtain high price vanadic acid calcium clinker；
(4) the high price vanadic acid calcium clinker and carbon acid solution are supplied into the carbonic acid leaching device and carried out at carbonic acid leaching
Reason, to obtain chromium slag and containing vanadium leachate；
(5) described supplied containing vanadium leachate and ammonium salt, acidity regulator into the precipitation-calciner plant is carried out precipitation and forged
Burning processing, to obtain vanadic anhydride.
6. Cr in method according to claim 5, it is characterised in that in step (1), the converter vanadium chromium slag2O3Contain
Measure as 8~16 weight %, V2O5Content be 8~16 weight %, Fe content be 20~35 weight %；
Optional, the temperature of the direct-reduction processing is 1100-1280 degrees Celsius.
7. method according to claim 5, it is characterised in that in step (2), described to remove weight of iron point in ferrovanadium chromium slag
Number is not more than 8%.
8. method according to claim 5, it is characterised in that in step (3), described to remove ferrovanadium chromium slag and the calcium salt
According to 100:The mass ratio of (5~15) is mixed；
Optional, the calcium salt is selected from least one of calcium carbonate, calcium oxide, calcium hydroxide, calcium sulfate and calcium chloride；
Optional, pentavalent vanadium accounts for the ratio of full vanadium and is not less than 95 weight % in the high price vanadic acid calcium clinker.
9. method according to claim 5, it is characterised in that in step (4), the carbon acid solution and the high price vanadium
The liquid-solid ratio of sour calcium clinker is (3~5):1；
Optional, the carbon acid solution is sodium carbonate liquor or sodium bicarbonate solution, and the concentration of the carbon acid solution is 10
~20 weight %；
Optional, the temperature of the carbonic acid leaching process is 85~95 degrees Celsius, and the time is 30~120min.
10. method according to claim 5, it is characterised in that in step (5), the precipitation and calcination processing according to
The following steps are carried out：
Regulation it is described containing vanadium leachate to acid and add ammonium salt and precipitated, to obtain poly ammonium vanadate；
The poly ammonium vanadate is subjected to calcination processing, to obtain vanadic anhydride.
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| CN110343866A (en) * | 2019-08-15 | 2019-10-18 | 攀钢集团钒钛资源股份有限公司 | The method of vanadium chromium is separated from vanadium chromium reducing slag |
| CN115491506A (en) * | 2022-09-16 | 2022-12-20 | 四川顺应动力电池材料有限公司 | Method for efficiently separating vanadium, chromium and iron from vanadium slag |
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