CN106868312A - The system and method for processing converter vanadium chromium slag - Google Patents
The system and method for processing converter vanadium chromium slag Download PDFInfo
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- CN106868312A CN106868312A CN201710210101.5A CN201710210101A CN106868312A CN 106868312 A CN106868312 A CN 106868312A CN 201710210101 A CN201710210101 A CN 201710210101A CN 106868312 A CN106868312 A CN 106868312A
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- Prior art keywords
- vanadium
- chromium slag
- calcium
- entrance
- oxidation
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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 the system and method for the treatment of converter vanadium chromium slag.System includes：Oxidation magnetizing roasting device, with the outlet of converter vanadium chromium slag entrance, air intake and magnetic calcining；Concentration equipment, with magnetic calcining entrance, iron ore concentrate 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, the carbonic acid leaching device has high price vanadic acid calcium clinker entrance, carbon acid solution entrance, the outlet of chromium slag and is exported containing vanadium leachate；Unit is calcined in precipitation, with the outlet of entrance containing vanadium leachate, ammonium salt entrance, acidity regulator entrance and vanadic anhydride.The high efficiente callback of iron, vanadium and chromium resource in vanadium chromium slag can be realized using the system, and the rate of recovery of iron is not less than 87%, and the rate of recovery of vanadium is not less than 90%, and the rate of recovery of chromium is not less than 88%.
Description
Technical field
The invention belongs to metallurgical technology field, specifically, the present invention relates to a kind of system for processing converter vanadium chromium slag and
Method.
Background technology
China is a chromium depleted country, and 97% chrome ore all relies on import.It is worth noting that, the red lattice ground of Panzhihua
Chromium content is up to 9,000,000 tons in the high-chromic vanadium-titanium ferroferrite in area, and content of the chromium with vanadium in raw ore is suitable.The country is to this red
The processing method of lattice vanadium titano-magnetite is aoxidized to blow out to first pass around blast furnace process into containing vanadium and chromium molten iron, then in converter and turned
Stove vanadium chromium slag (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 low vanadium chromium solution high 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 the chromium solution high for obtaining, qualified chromium product cannot be obtained under present condition.
So far, vanadium, chromium extract and separate the technology for not yet having industrialized production, its main skill in vanadium chromium slag
Art difficult point is vanadium, chromium is 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.
If the research to vanadium chromium slag is separated on vanadium and chromium with concentrating on economical and efficient at present, and have ignored iron in vanadium chromium slag
The synchronous extraction of resource.And vanadium and chromium in the vanadium chromium solution that obtains of existing oxidizing roasting-wet-leaching technical finesse vanadium chromium slag
Separating difficulty is big, does not have industrial prospect.
Therefore, the technology of existing treatment converter vanadium chromium slag is further improved.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, of the invention
One purpose is to propose a kind of system and method for processing converter vanadium chromium slag, using the system can realize iron in vanadium chromium slag,
The high efficiente callback of vanadium and chromium resource, and the rate of recovery of iron is not less than 87%, and the rate of recovery of vanadium is not less than 90%, the rate of recovery of chromium
It is not less than 88%.
In one aspect of the invention, the present invention proposes a kind of system for processing converter vanadium chromium slag.It is of the invention
Embodiment, the system includes：
Oxidation magnetizing roasting device, the oxidation magnetizing roasting device has converter vanadium chromium slag entrance, air intake and magnetic
Property calcining outlet；
Concentration equipment, the concentration equipment has magnetic calcining entrance, iron ore concentrate outlet and except ferrovanadium chromium slag is exported, described
Magnetic calcining entrance is connected with magnetic calcining outlet；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device has except ferrovanadium chromium slag entrance, calcium salt entrance, air
Entrance and high price vanadic acid calcium clinker are exported, 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-calcining unit, the precipitation-calcining unit has entrance containing vanadium leachate, ammonium salt entrance, acidity regulator
Entrance and vanadic anhydride are exported, and the entrance containing vanadium leachate is connected with the outlet containing vanadium leachate.
The system for the treatment of converter vanadium chromium slag according to embodiments of the present invention carries out oxidation magnetic successively by by converter vanadium chromium slag
Change roasting and magnetic separation treatment, so as to reclaim the iron resource in vanadium chromium slag, and can cause that gained is removed with isolated iron ore concentrate
The grade of vanadium and chromium is substantially improved in ferrovanadium chromium slag, so as to be conducive to follow-up vanadium extraction and carry chromium, while during iron is vanadium waste liqouor
Harmful element, except iron or is more beneficial for the recovery of vanadium and chromium in subsequent process, then by gained except ferrovanadium chromium slag passes sequentially through oxygen
Change calcification baking and carbonic acid leaching process, it is possible to achieve the high efficiente callback of chromium resource, then carry out gained again containing vanadium leachate
Precipitation and calcination processing, it is possible to achieve the high efficiente callback of vanadium resource.Thus, iron, vanadium in vanadium chromium slag can be realized using the system
87% is not less than with the rate of recovery of the high efficiente callback of chromium resource, and iron, the rate of recovery of vanadium is not less than 90%, and the rate of recovery of chromium is not
Less than 88%.
In addition, the system for the treatment of converter vanadium chromium slag according to the above embodiment of the present invention can also have following additional skill
Art feature：
In some embodiments of the invention, the oxidation magnetizing roasting device is rotary hearth furnace, tunnel cave, rotary kiln or many
Layer roaster, preferably rotary hearth furnace.
In some embodiments of the invention, the oxidation roasting with calcium compounds device is rotary hearth furnace, rotary kiln, tunnel cave or many
Layer roaster, preferably rotary kiln or multihearth roaster.
In another aspect of the invention, the present invention proposes the side that a kind of use said system processes converter vanadium chromium slag
Method.Embodiments in accordance with the present invention, methods described includes：
(1) supplying into the oxidation magnetizing roasting device converter vanadium chromium slag and air is carried out at oxidation magnetizing roast
Reason, to obtain magnetic calcining；
(2) will the magnetic calcining supply the concentration equipment in carry out magnetic separation treatment, to obtain iron ore concentrate and except iron
Vanadium chromium slag；
(3) calcium oxide is carried out into the oxidation roasting with calcium compounds device except ferrovanadium chromium slag, calcium salt and air are supplied by described
Change calcination process, to obtain high price vanadic acid calcium clinker；
(4) supplying into the carbonic acid leaching device high price vanadic acid calcium clinker and carbon acid solution is carried out at leaching
Reason, to obtain containing vanadium leachate and chromium slag；
(5) described supply into the precipitation-calcining unit containing vanadium leachate and ammonium salt and acidity regulator is located
Reason, to obtain vanadic anhydride.
The method for the treatment of converter vanadium chromium slag according to embodiments of the present invention carries out oxidation magnetic successively by by converter vanadium chromium slag
Change roasting and magnetic separation treatment, so as to reclaim the iron resource in vanadium chromium slag, and can cause that gained is removed with isolated iron ore concentrate
The grade of vanadium and chromium is substantially improved in ferrovanadium chromium slag, so as to be conducive to follow-up vanadium extraction and carry chromium, while during iron is vanadium waste liqouor
Harmful element, except iron or is more beneficial for the recovery of vanadium and chromium in subsequent process, then by gained except ferrovanadium chromium slag passes sequentially through oxygen
Change calcification baking and carbonic acid leaching process, it is possible to achieve the high efficiente callback of chromium resource, then carry out gained again containing vanadium leachate
Precipitation and calcination processing, it is possible to achieve the high efficiente callback of vanadium resource.Thus, iron, vanadium in vanadium chromium slag can be realized using the method
87% is not less than with the rate of recovery of the high efficiente callback of chromium resource, and iron, the rate of recovery of vanadium is not less than 90%, and the rate of recovery of chromium is not
Less than 88%.
In addition, the method for the treatment of converter vanadium chromium slag according to the above embodiment of the present invention can also have following additional skill
Art feature：
In some embodiments of the invention, in step (1), Cr in the converter vanadium chromium slag2O3Mass fraction be 8~
16%, V2O5Mass fraction is that 8~16%, Fe mass fractions are 20~35%.
In some embodiments of the invention, in step (1), the temperature of the oxidation magnetizing roast treatment for 300~
500 degrees Celsius, the time is 5~20min, and oxygen concentration is calculated as 0.5~2% by percent by volume in the air.Thus, it is possible to
Significantly improve the rate of recovery of iron in subsequent process.
In some embodiments of the invention, in step (2), weight of iron fraction is not more than in the chromium slag except ferrovanadium
8%.Thus, it is possible to significantly improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, in step (3), the temperature of oxidation roasting with calcium compounds treatment for 900~
1100 degrees Celsius.Thus, it is possible to further improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, it is described except ferrovanadium chromium slag and the mixing quality of the calcium salt in step (3)
Than 100:(5~15).Thus, it is possible to further improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, in step (3), the calcium salt is selected from calcium carbonate, calcium oxide, hydroxide
At least one in calcium, calcium sulfate and calcium chloride.Thus, it is possible to further improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, in step (4), the extraction temperature is 85~95 degrees Celsius, and the time is
30~120 minutes, liquid-solid ratio was (3~5):1.Thus, it is possible to further improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, in step (4), the carbon acid solution is selected from sodium carbonate liquor and carbonic acid
At least one in hydrogen sodium solution.Thus, it is possible to further improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, in step (4), the mass concentration of the carbon acid solution is 10~20%.
Thus, it is possible to further improve the rate of recovery of vanadium and chromium in subsequent process.
Additional aspect of the invention and advantage will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by practice of the invention.
Brief description of the drawings
Of the invention above-mentioned and/or additional aspect and advantage will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the system structure diagram for the treatment of converter vanadium chromium slag according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram for the treatment of converter vanadium chromium slag according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
It is exemplary to scheme the embodiment of description, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In the description of the invention, it is to be understood that term " " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", " on ", D score, "front", "rear", "left", "right", " vertical ", " level ", " top ", " bottom ", " interior ", " outward ", " up time
The orientation or position relationship of the instruction such as pin ", " counterclockwise ", " axial direction ", " radial direction ", " circumference " be based on orientation shown in the drawings or
Position relationship, is for only for ease of the description present invention and simplifies description, must rather than the device or element for indicating or imply meaning
With specific orientation, with specific azimuth configuration and operation, therefore must be not considered as limiting the invention.
Additionally, term " first ", " second " are only used for describing purpose, and it is not intended that indicating or implying relative importance
Or the implicit quantity for indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or
Implicitly include at least one this feature.In the description of the invention, " multiple " is meant that at least two, such as two, three
It is individual etc., unless otherwise expressly limited specifically.
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, it is also possible to be indirectly connected to by intermediary, can be in two elements
The connection in portion or two interaction relationships of element, unless otherwise clearly restriction.For one of ordinary skill in the art
For, can as the case may be understand above-mentioned term concrete meaning in the present invention.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score can be with
It is the first and second feature directly contacts, or the first and second features are by intermediary mediate contact.And, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature are directly over second feature or oblique upper, or be merely representative of
Fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " can be
One feature is immediately below second feature or obliquely downward, or is merely representative of fisrt feature level height less than second feature.
In one aspect of the invention, the present invention proposes a kind of system for processing converter vanadium chromium slag.It is of the invention
Embodiment, with reference to Fig. 1, the system includes：Oxidation magnetizing roasting device 100, concentration equipment 200, oxidation roasting with calcium compounds device
300th, carbonic acid leaching device 400 and precipitation-calcining unit 500.
Embodiments in accordance with the present invention, oxidation magnetizing roasting device 100 has converter vanadium chromium slag entrance 101, air intake
102 and magnetic calcining outlet 103, and be suitable to for converter vanadium chromium slag and air contact to carry out oxidation magnetizing roast treatment, so as to
To magnetic calcining.Specifically, converter vanadium chromium slag is by blast furnace process into containing vanadium and chromium molten iron, then in converter by vanadium titano-magnetite
Middle to aoxidize the slag for blowing out and obtaining, iron is main with vanadium iron spinelle FeOV in converter vanadium chromium slag2O3, chromohercynite FeO
Cr2O3With fayalite FeOSiO2Form exist, and Cr in converter vanadium chromium slag2O3Mass fraction is 8~16%, V2O5
Mass fraction is that 8~16%, Fe mass fractions are 20~35%, and in the step, converter vanadium chromium slag carries out oxidation magnetizing roast and obtains
To magnetic calcining, the FeO in vanadium iron spinelle, vanadium picotite and fayalite is oxidized to Fe3O4, may during this
Understand some vanadium to be oxidized, the specific reaction for occurring is such as shown in (1)~(3)：
3(2FeO·SiO2)+O2=2Fe3O4+3SiO2 (1)
6(FeO·V2O3)+O2=2Fe3O4+6V2O3 (2)
6(FeO·Cr2O3)+O2=2Fe3O4+6Cr2O3 (3)
According to one embodiment of present invention, the condition of oxidation magnetizing roast treatment is not particularly restricted, this area skill
Art personnel can be selected according to actual needs, a specific embodiment of the invention, oxidation magnetizing roast treatment
Temperature can be 300~500 degrees Celsius, and the time is 5~20min.Inventor has found, if oxidation magnetizing roast treatment temperature is too low
Or the time is too short, FeO is oxidized to Fe in vanadium chromium slag3O4Reaction carry out it is insufficient, so as to influence the recovery of iron；And temperature
Too high or overlong time, FeO is easily excessively oxidated Fe in vanadium chromium slag2O3, due to Fe2O3Without magnetic, it is impossible to by magnetic separation
Reclaim, can also influence the recovery of iron.Thus, follow-up gained iron can be significantly improved using the oxidation magnetizing roast condition of the application
The rate of recovery.
According to still a further embodiment, in the step, oxygen content is not particularly restricted in air, this area skill
Art personnel can be selected according to actual needs, a specific embodiment of the invention, using oxygen concentration in air
0.5~2% is calculated as by percent by volume.Inventor has found, if oxygen concentration is too low in air so that FeO is by oxygen in vanadium chromium slag
Chemical conversion Fe3O4Reaction carry out it is insufficient, influence iron recovery；And if oxygen concentration is too high in air, FeO holds in vanadium chromium slag
Easily it is excessively oxidated Fe2O3, due to Fe2O3Without magnetic, it is impossible to by magnetic separation recovery, can also influence the recovery of iron.Thus
With the rate of recovery of follow-up gained iron can be significantly improved using the air concentration of the application.
According to still another embodiment of the invention, oxidation magnetizing roasting device can for rotary hearth furnace, tunnel cave, rotary kiln or
Multihearth roaster, preferably rotary hearth furnace.
Embodiments in accordance with the present invention, concentration equipment 200 has magnetic calcining entrance 201, iron ore concentrate outlet 202 and except iron
Vanadium chromium slag outlet 203, magnetic calcining entrance 201 is connected with magnetic calcining outlet 103, and is suitable to be calcined magnetic obtained above
Magnetic separation treatment is carried out, so as to isolated iron ore concentrate and except ferrovanadium chromium slag.Specifically, in the step, magnetic calcining is by magnetic separation
Afterwards by Fe3O4Reclaimed, by Fe after magnetic separation3O4Into the iron ore concentrate (iron in iron ore concentrate in ferroso-ferric oxide of magnetic part
Full iron ratio is accounted for be not less than 90%), and vanadium chromated oxide enter nonmagnetic part except ferrovanadium chromium slag.It should be noted that
Those skilled in the art can be selected the condition that magnetic separation is processed according to actual needs.
According to one embodiment of present invention, except in ferrovanadium chromium slag weight of iron fraction be not more than 8%.Inventor's discovery, iron
It is the harmful element in vanadium waste liqouor, the recovery of vanadium and chromium in subsequent process is conducive to except iron.Thus, by that will remove in the application
Vanadium chromium has the rate of recovery higher during weight of iron Fractional domination can ensure subsequent process at no more than 8% in ferrovanadium chromium slag.
Embodiments in accordance with the present invention, oxidation roasting with calcium compounds device 300 has except ferrovanadium chromium slag entrance 301, calcium salt entrance
302nd, air intake 303 and high price vanadic acid calcium clinker 304, except ferrovanadium chromium slag entrance 301 is connected with except ferrovanadium chromium slag exports 203,
And be suitable to obtained above except ferrovanadium chromium slag and calcium salt and air contact carry out oxidation roasting with calcium compounds treatment, to obtain high price
Vanadic acid calcium clinker (pentavalent vanadium accounts for full vanadium ratio and is not less than 95% in high price vanadic acid calcium clinker).Specifically, except in ferrovanadium chromium slag
Vanadium trioxide reacts and obtains high price calcium vanadate with calcium salt and oxygen.Specifically, calcium salt is by taking calcium oxide as an example, process tool
The reaction that body occurs is such as shown in (4)~(6)：
CaO+V2O3+O2=CaV2O6 (4)
2CaO+V2O3+O2=Ca2V2O7 (5)
3CaO+V2O3+O2=Ca3V2O8 (6)
According to one embodiment of present invention, in the step, the temperature of oxidation roasting with calcium compounds treatment is not particularly restricted,
Those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, oxidation calcification roasting
The temperature for burning treatment can be 900~1100 degrees Celsius.Inventor has found, if oxidation roasting with calcium compounds temperature is too low, the oxidation of vanadium
Calcification reaction can not be carried out or carry out inefficiency；Oxidation roasting with calcium compounds temperature is too high, can not improve the conversion ratio of calcium vanadate,
The generation of complex compound is also resulted in, is unfavorable for that follow-up carbonic acid is leached, cause vanadium to lose.Thus, roasted using the oxidation calcification
Burning treatment temperature can significantly improve the rate of recovery of follow-up vanadium chromium.
According to still a further embodiment, except ferrovanadium chromium slag is not particularly restricted with the mixed proportion of calcium salt, this
Art personnel can be selected according to actual needs, a specific embodiment of the invention, except ferrovanadium chromium slag with
The mixing quality ratio of calcium salt can be 100:(5~15).Inventor has found, if calcium salt allocates very few, the reaction of formation of calcium vanadate into
What is carried out is insufficient, and carbonic acid can cause the loss of vanadium when leaching；And if calcium salt is allocated into excessively, the leaching rate of vanadium can not be improved,
Conversely, the calcium oxide of excess can also consume substantial amounts of carbonate solvent when carbonic acid is leached, cause to waste.Inventor is by a large amount of examinations
Issue after examination and approval now, except the mixing quality ratio of ferrovanadium chromium slag and calcium salt can be 100:When (5~15), the generation of calcium vanadate and carbonic acid are leached
Reaction effect is best.
According to still another embodiment of the invention, during being somebody's turn to do, the particular type of calcium salt is not particularly restricted, this area
Technical staff can be selected according to actual needs, a specific embodiment of the invention, calcium salt can for calcium carbonate,
At least one in calcium oxide, calcium hydroxide, calcium sulfate and calcium chloride.Inventor has found, using such calcium salt and except ferrovanadium chromium
Slag contact carries out oxidation roasting with calcium compounds treatment and can be substantially better than other types calcium salt raising V2O3Oxidation roasting with calcium compounds efficiency,
So as to improve the rate of recovery of vanadium in subsequent process.
According to still another embodiment of the invention, oxidation roasting with calcium compounds device can for rotary hearth furnace, rotary kiln, tunnel cave or
Multihearth roaster, preferably rotary kiln or multihearth roaster.
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 is suitable to contact high price vanadic acid calcium clinker with carbon acid solution, obtains chromium slag and containing vanadium leachate.Specifically,
High price vanadic acid calcium clinker is contacted with carbon acid solution, vanadic acid root can be cemented out and be entered solution, be i.e. high price vanadic acid calcium clinker
Leach to be transferred to vanadium in liquid phase by carbonic acid and separated with chromium slag, and the chromium in chromium slag obtains enrichment and can be provided separately as chromium is carried
Source is utilized, and acid ammonium salt precipitation generation poly ammonium vanadate is recycled containing vanadium leachate.Specifically, calcium salt is by taking calcium oxide as an example, should
The reaction that process specifically occurs is such as shown in (7)：
Ca(VO3)2+CO3 2-=CaCO3+2VO3 - (7)
According to one embodiment of present invention, the condition in leaching process is not particularly restricted, those skilled in the art
Can be selected according to actual needs, a specific embodiment of the invention, during being somebody's turn to do, extraction temperature can be 85
~95 degrees Celsius, the time can be 30~120 minutes, and liquid-solid ratio can be (3~5):1.Inventor's discovery, if extraction temperature,
Time and the too high too low leaching that can all influence vanadium of liquid-solid ratio, and inventor is had been surprisingly found that by lot of experiments, extraction temperature 85
~95 degrees Celsius, 30~120 minutes time, the solid mass ratio (3~5) of liquid：1, the carbonic acid leaching effect of vanadium is best.
According to still a further embodiment, the particular type of carbon acid solution is not particularly restricted, art technology
Personnel can be selected according to actual needs, a specific embodiment of the invention, and carbon acid solution can be selected from carbon
At least one in acid sodium solution and sodium bicarbonate solution.Inventor has found that such carbon acid solution can be significantly better than other classes
Type improves the conversion ratio of vanadic acid root, so as to improve the rate of recovery of vanadium in subsequent process.
According to still another embodiment of the invention, the concentration of carbon acid solution is not particularly limited, and those skilled in the art can
To be selected according to actual needs, a specific embodiment of the invention, the mass concentration of carbon acid solution can be 10
~20%.Inventor has found, if the too low leaching that can influence vanadium of the mass concentration of carbon acid solution, the mass concentration mistake of carbon acid solution
Height can not improve the leaching rate of vanadium, also result in chemical reagent waste, and inventor is had been surprisingly found that by lot of experiments, carbonic acid
The mass concentration of solution is 10~20%, and the carbonic acid leaching effect of vanadium is best.
Embodiments in accordance with the present invention, precipitation-calcining unit 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 exports 404 phases with containing vanadium leachate
Even, and be suitable to by it is obtained above mix with ammonium salt and acidity regulator containing vanadium leachate carry out precipitation and calcination processing, so as to
Obtain vanadic anhydride.Specifically, precipitation-calcining unit is the linkage of precipitation device and calciner plant, obtained above-mentioned
Supply and precipitation treatment carried out into precipitation device containing vanadium leachate and ammonium salt and acidity regulator so that containing vanadium in vanadium leachate
Generation poly ammonium vanadate is precipitated under acid ammonium salt environment, the poly ammonium vanadate that then will be obtained is supplied into calciner plant and carried out
Calcination processing, obtains vanadic anhydride.Specifically, the reaction that the process specifically occurs is such as shown in (8)~(10)：
10VO3 -+6H+=H2V10O28 4-+2H2O (8)
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (9)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (10)
The system for the treatment of converter vanadium chromium slag according to embodiments of the present invention carries out oxidation magnetic successively by by converter vanadium chromium slag
Change roasting and magnetic separation treatment, so as to reclaim the iron resource in vanadium chromium slag, and can cause that gained is removed with isolated iron ore concentrate
The grade of vanadium and chromium is substantially improved in ferrovanadium chromium slag, so as to be conducive to follow-up vanadium extraction and carry chromium, while during iron is vanadium waste liqouor
Harmful element, except iron or is more beneficial for the recovery of vanadium and chromium in subsequent process, then by gained except ferrovanadium chromium slag passes sequentially through oxygen
Change calcification baking and carbonic acid leaching process, it is possible to achieve the high efficiente callback of chromium resource, then carry out gained again containing vanadium leachate
Precipitation and calcination processing, it is possible to achieve the high efficiente callback of vanadium resource.Thus, iron, vanadium in vanadium chromium slag can be realized using the system
87% is not less than with the rate of recovery of the high efficiente callback of chromium resource, and iron, the rate of recovery of vanadium is not less than 90%, and the rate of recovery of chromium is not
Less than 88%.
As described above, the system for the treatment of converter vanadium chromium slag according to embodiments of the present invention can have the advantages that selected from following
At least one：
The system for the treatment of converter vanadium chromium slag according to embodiments of the present invention is carried out at magnetizing roast by converter vanadium chromium slag
Reason, reclaims iron resource after magnetic separation, vanadic anhydride and chromium slag are obtained except ferrovanadium chromium slag oxidation calcification baking-carbonic acid leaches vanadium extraction,
Chromium slag can finally realize the synthetical recovery of iron, vanadium, chromium resource as separately as Cr materials are carried.
The system for the treatment of converter vanadium chromium slag according to embodiments of the present invention is except the product of vanadium and chromium in the converter vanadium chromium slag after iron
Position is substantially improved, and is conducive to follow-up vanadium extraction and carries chromium.
Iron is the harmful element in vanadium, waste liqouor in the system for the treatment of converter vanadium chromium slag according to embodiments of the present invention, is removed
The recovery of vanadium and chromium in follow-up converter vanadium chromium slag is more beneficial for after iron.
In another aspect of the invention, the present invention proposes a kind of side that converter vanadium chromium slag is processed using above-mentioned system
Method.Embodiments in accordance with the present invention, with reference to Fig. 2, the method includes：
S100：Converter vanadium chromium slag and air are supplied into oxidation magnetizing roasting device carries out oxidation magnetizing roast treatment
In the step, converter vanadium chromium slag and air are supplied into oxidation magnetizing roasting device to be carried out at oxidation magnetizing roast
Reason, to obtain magnetic calcining.Specifically, converter vanadium chromium slag is by blast furnace process into containing vanadium and chromium molten iron by vanadium titano-magnetite,
Then the slag for blowing out and obtaining is aoxidized in converter, iron is main with vanadium iron spinelle FeOV in converter vanadium chromium slag2O3, ferrochrome
Spinelle FeOCr2O3With fayalite FeOSiO2Form exist, and Cr in converter vanadium chromium slag2O3Mass fraction is 8
~16%, V2O5Mass fraction is that 8~16%, Fe mass fractions are 20~35%, and in the step, converter vanadium chromium slag is aoxidized
Magnetizing roast obtains magnetic calcining, and the FeO in vanadium iron spinelle, vanadium picotite and fayalite is oxidized to Fe3O4, this
During might have a part of vanadium and be oxidized, the specific reaction for occurring is as shown in (a)~(c)：
3(2FeO·SiO2)+O2=2Fe3O4+3SiO2(a)
6(FeO·V2O3)+O2=2Fe3O4+6V2O3(b)
6(FeO·Cr2O3)+O2=2Fe3O4+6Cr2O3(c)
According to one embodiment of present invention, the condition of oxidation magnetizing roast treatment is not particularly restricted, this area skill
Art personnel can be selected according to actual needs, a specific embodiment of the invention, oxidation magnetizing roast treatment
Temperature can be 300~500 degrees Celsius, and the time is 5~20min.Inventor has found, if oxidation magnetizing roast treatment temperature is too low
Or the time is too short, FeO is oxidized to Fe in vanadium chromium slag3O4Reaction carry out it is insufficient, so as to influence the recovery of iron；And temperature
Too high or overlong time, FeO is easily excessively oxidated Fe in vanadium chromium slag2O3, due to Fe2O3Without magnetic, it is impossible to by magnetic separation
Reclaim, can also influence the recovery of iron.Thus, follow-up gained iron can be significantly improved using the oxidation magnetizing roast condition of the application
The rate of recovery.
According to still a further embodiment, in the step, oxygen content is not particularly restricted in air, this area skill
Art personnel can be selected according to actual needs, a specific embodiment of the invention, using oxygen concentration in air
0.5~2% is calculated as by percent by volume.Inventor has found, if oxygen concentration is too low in air so that FeO is by oxygen in vanadium chromium slag
Chemical conversion Fe3O4Reaction carry out it is insufficient, influence iron recovery；And if oxygen concentration is too high in air, FeO holds in vanadium chromium slag
Easily it is excessively oxidated Fe2O3, due to Fe2O3Without magnetic, it is impossible to by magnetic separation recovery, can also influence the recovery of iron.Thus
With the rate of recovery of follow-up gained iron can be significantly improved using the air concentration of the application.
According to still another embodiment of the invention, oxidation magnetizing roasting device can for rotary hearth furnace, tunnel cave, rotary kiln or
Multihearth roaster, preferably rotary hearth furnace.
S200：Magnetic separation treatment is carried out during magnetic calcining is supplied into concentration equipment
In the step, magnetic separation treatment is carried out during magnetic calcining obtained above is supplied into concentration equipment, so as to isolated
Iron ore concentrate and except ferrovanadium chromium slag.Specifically, in the step, magnetic calcining by after magnetic separation by Fe3O4Reclaimed, by magnetic separation
Fe afterwards3O4Into the iron ore concentrate (iron in iron ore concentrate in ferroso-ferric oxide accounts for full iron ratio and is not less than 90%) of magnetic part, and vanadium
Chromated oxide is into nonmagnetic part except ferrovanadium chromium slag.It should be noted that those skilled in the art can be according to reality
Need to select the condition of magnetic separation treatment.
According to one embodiment of present invention, except in ferrovanadium chromium slag weight of iron fraction be not more than 8%.Inventor's discovery, iron
It is the harmful element in vanadium waste liqouor, the recovery of vanadium and chromium in subsequent process is conducive to except iron.Thus, by that will remove in the application
Vanadium chromium has the rate of recovery higher during weight of iron Fractional domination can ensure subsequent process at no more than 8% in ferrovanadium chromium slag.
S300：Oxidation roasting with calcium compounds will be carried out into oxidation roasting with calcium compounds device except ferrovanadium chromium slag, calcium salt and air are supplied
Treatment
In the step, by obtained above except ferrovanadium chromium slag, calcium salt and air supply into oxidation roasting with calcium compounds device
The treatment of row oxidation roasting with calcium compounds, to obtain high price vanadic acid calcium clinker, (pentavalent vanadium accounts for full vanadium ratio not in high price vanadic acid calcium clinker
Less than 95%).Specifically, except the vanadium trioxide in ferrovanadium chromium slag and calcium salt and oxygen react and obtain high price calcium vanadate.
Specifically, calcium salt is by taking calcium oxide as an example, the reaction that the process specifically occurs is such as shown in (d)~(f)：
CaO+V2O3+O2=CaV2O6 (d)
2CaO+V2O3+O2=Ca2V2O7 (e)
3CaO+V2O3+O2=Ca3V2O8 (f)
According to one embodiment of present invention, in the step, the temperature of oxidation roasting with calcium compounds treatment is not particularly restricted,
Those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, oxidation calcification roasting
The temperature for burning treatment can be 900~1100 degrees Celsius.Inventor has found, if oxidation roasting with calcium compounds temperature is too low, the oxidation of vanadium
Calcification reaction can not be carried out or carry out inefficiency；Oxidation roasting with calcium compounds temperature is too high, can not improve the conversion ratio of calcium vanadate,
The generation of complex compound is also resulted in, is unfavorable for that follow-up carbonic acid is leached, cause vanadium to lose.Thus, roasted using the oxidation calcification
Burning treatment temperature can significantly improve the rate of recovery of follow-up vanadium chromium.
According to still a further embodiment, except ferrovanadium chromium slag is not particularly restricted with the mixed proportion of calcium salt, this
Art personnel can be selected according to actual needs, a specific embodiment of the invention, except ferrovanadium chromium slag with
The mixing quality ratio of calcium salt can be 100:(5~15).Inventor has found, if calcium salt allocates very few, the reaction of formation of calcium vanadate into
What is carried out is insufficient, and carbonic acid can cause the loss of vanadium when leaching；And if calcium salt is allocated into excessively, the leaching rate of vanadium can not be improved,
Conversely, the calcium oxide of excess can also consume substantial amounts of carbonate solvent when carbonic acid is leached, cause to waste.Inventor is by a large amount of examinations
Issue after examination and approval now, except the mixing quality ratio of ferrovanadium chromium slag and calcium salt can be 100:When (5~15), the generation of calcium vanadate and carbonic acid are leached
Reaction effect is best.
According to still another embodiment of the invention, during being somebody's turn to do, the particular type of calcium salt is not particularly restricted, this area
Technical staff can be selected according to actual needs, a specific embodiment of the invention, calcium salt can for calcium carbonate,
At least one in calcium oxide, calcium hydroxide, calcium sulfate and calcium chloride.Inventor has found, using such calcium salt and except ferrovanadium chromium
Slag contact carries out oxidation roasting with calcium compounds treatment and can be substantially better than other types calcium salt raising V2O3Oxidation roasting with calcium compounds efficiency,
So as to improve the rate of recovery of vanadium in subsequent process.
According to still another embodiment of the invention, oxidation roasting with calcium compounds device can for rotary hearth furnace, rotary kiln, tunnel cave or
Multihearth roaster, preferably rotary kiln or multihearth roaster.
S400：High price vanadic acid calcium clinker and carbon acid solution are supplied carries out leaching process into carbonic acid leaching device
In the step, high price vanadic acid calcium clinker obtained above is supplied with carbon acid solution to be carried out into carbonic acid leaching device
Leaching process, obtains chromium slag and containing vanadium leachate.Specifically, high price vanadic acid calcium clinker is contacted with carbon acid solution, can be by vanadium
Acid group is cemented out and enters solution, i.e., high price vanadic acid calcium clinker is leached to be transferred to vanadium in liquid phase and separated with chromium slag by carbonic acid,
And the chromium in chromium slag obtains enrichment and can be utilized separately as chromium resource is carried, acid ammonium salt precipitation generation is recycled containing vanadium leachate
Poly ammonium vanadate.Specifically, calcium salt is by taking calcium oxide as an example, the reaction that the process specifically occurs is such as shown in (g)：
Ca(VO3)2+CO3 2-=CaCO3+2VO3 - (g)
According to one embodiment of present invention, the condition in leaching process is not particularly restricted, those skilled in the art
Can be selected according to actual needs, a specific embodiment of the invention, during being somebody's turn to do, extraction temperature can be 85
~95 degrees Celsius, the time can be 30~120 minutes, and liquid-solid ratio can be (3~5):1.Inventor's discovery, if extraction temperature,
Time and the too high too low leaching that can all influence vanadium of liquid-solid ratio, and inventor is had been surprisingly found that by lot of experiments, extraction temperature 85
~95 degrees Celsius, 30~120 minutes time, the solid mass ratio (3~5) of liquid：1, the carbonic acid leaching effect of vanadium is best.
According to still a further embodiment, the particular type of carbon acid solution is not particularly restricted, art technology
Personnel can be selected according to actual needs, a specific embodiment of the invention, and carbon acid solution can be selected from carbon
At least one in acid sodium solution and sodium bicarbonate solution.Inventor has found that such carbon acid solution can be significantly better than other classes
Type improves the conversion ratio of vanadic acid root, so as to improve the rate of recovery of vanadium in subsequent process.
According to still another embodiment of the invention, the concentration of carbon acid solution is not particularly limited, and those skilled in the art can
To be selected according to actual needs, a specific embodiment of the invention, the mass concentration of carbon acid solution can be 10
~20%.Inventor has found, if the too low leaching that can influence vanadium of the mass concentration of carbon acid solution, the mass concentration mistake of carbon acid solution
Height can not improve the leaching rate of vanadium, also result in chemical reagent waste, and inventor is had been surprisingly found that by lot of experiments, carbonic acid
The mass concentration of solution is 10~20%, and the carbonic acid leaching effect of vanadium is best.
S500：Vanadium leachate will be contained supplied into precipitation-calcining unit with ammonium salt and acidity regulator and be processed
In the step, supplied obtained above to precipitation-calcining unit containing vanadium leachate and ammonium salt and acidity regulator
In processed, to obtain vanadic anhydride.Specifically, precipitation-calcining unit is the linkage of precipitation device and calciner plant
Device, supplies obtained above and precipitation treatment is carried out into precipitation device containing vanadium leachate and ammonium salt and acidity regulator, makes
Vanadium precipitates generation poly ammonium vanadate under acid ammonium salt environment during vanadium leachate must be contained, the poly ammonium vanadate supply that then will be obtained
Calcination processing is carried out into calciner plant, vanadic anhydride is obtained.Specifically, reaction such as (h)~(j) that the process specifically occurs
It is shown：
10VO3 -+6H+=H2V10O28 4-+2H2O (h)
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (i)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (j)
The method for the treatment of converter vanadium chromium slag according to embodiments of the present invention carries out oxidation magnetic successively by by converter vanadium chromium slag
Change roasting and magnetic separation treatment, so as to reclaim the iron resource in vanadium chromium slag, and can cause that gained is removed with isolated iron ore concentrate
The grade of vanadium and chromium is substantially improved in ferrovanadium chromium slag, so as to be conducive to follow-up vanadium extraction and carry chromium, while during iron is vanadium waste liqouor
Harmful element, except iron or is more beneficial for the recovery of vanadium and chromium in subsequent process, then by gained except ferrovanadium chromium slag passes sequentially through oxygen
Change calcification baking and carbonic acid leaching process, it is possible to achieve the high efficiente callback of chromium resource, then carry out gained again containing vanadium leachate
Precipitation and calcination processing, it is possible to achieve the high efficiente callback of vanadium resource.Thus, iron, vanadium in vanadium chromium slag can be realized using the method
87% is not less than with the rate of recovery of the high efficiente callback of chromium resource, and iron, the rate of recovery of vanadium is not less than 90%, and the rate of recovery of chromium is not
Less than 88%.
Below with reference to specific embodiment, present invention is described, it is necessary to explanation, these embodiments are only description
Property, and the present invention is limited never in any form.
Embodiment 1
By converter vanadium chromium slag (Cr2O3Mass fraction is 8%, V2O5Mass fraction is 8%, Fe mass fractions 20%) to exist
Oxidation magnetic roasting is carried out in tunnel cave, 300 DEG C of temperature, oxygen concentration 0.5%, roasting time 5min obtains magnetic calcining, its
It is 92% that iron in middle magnetic calcining in ferroso-ferric oxide accounts for full iron ratio, and magnetic calcining is entered in concentration equipment (magnetic separator)
Row magnetic separation is processed, and obtains Armco magnetic iron concentrate and nonmagnetic except ferrovanadium chromium slag (weight of iron fraction 7.5%), and iron ore concentrate can be as
The quality raw materials of blast furnace ironmaking, then will be except ferrovanadium chromium slag and calcium oxide in mass ratio 100:After 5 mixing 900 DEG C in rotary kiln
Oxidation roasting with calcium compounds 1h obtains high price vanadic acid calcium clinker, and the ratio that pentavalent vanadium accounts for full vanadium in high price vanadic acid calcium clinker is 95%, will
High price vanadic acid calcium clinker carries out carbonic acid leaching, and the condition that carbonic acid is leached is sodium carbonate liquor, leaching agent mass concentration for leaching agent
It is 10%, extraction temperature is 85 DEG C, it is 5 to leach liquid-solid ratio:1, extraction time is 120min, and leaching obtains being leached containing vanadium after terminating
Liquid and chromium slag (Cr2O3Mass fraction is that 12%), vanadium turns leaching rate for 90%, then will contain vanadium leachate and carry out acid ammonium salt precipitation
Treatment obtains poly ammonium vanadate, and poly ammonium vanadate 500 DEG C of calcination processings in calcining furnace obtain vanadic anhydride.Whole technique iron
The rate of recovery 87%, vanadium recovery 90%, chromium recovery ratio 88%.
Embodiment 2
By converter vanadium chromium slag (Cr2O3Mass fraction is 10%, V2O5Mass fraction is 10%, Fe mass fractions for 24%)
Oxidation magnetic roasting is carried out in tunnel cave, 500 DEG C of temperature, oxygen concentration 1.5%, roasting time 15min obtains magnetic roasting
It is 94% that iron in sand, wherein magnetic calcining in ferroso-ferric oxide accounts for full iron ratio, to magnetic in concentration equipment (magnetic separator)
Calcining carries out magnetic separation treatment, obtains Armco magnetic iron concentrate and nonmagnetic except ferrovanadium chromium slag (weight of iron fraction 7.2%), then will remove
Ferrovanadium chromium slag and calcium hydroxide in mass ratio 100:1000 DEG C of sodium oxide baking 1.5h obtain height in rotary kiln after 10 mixing
Valency vanadic acid calcium clinker, the ratio that pentavalent vanadium accounts for full vanadium in high price vanadic acid calcium clinker is 96.5%, and high price vanadic acid calcium clinker is carried out
Carbonic acid is leached, and the condition that carbonic acid is leached is sodium bicarbonate solution for leaching agent, and leaching agent mass concentration is 15%, and extraction temperature is
90 DEG C, it is 4 to leach liquid-solid ratio:1, extraction time is 90min, and leaching is obtained containing vanadium leachate and chromium slag (Cr after terminating2O3Quality
Fraction is that 15%), vanadium turns leaching rate for 92%, then will contain vanadium leachate and carry out acid ammonium salt precipitation treatment and obtain poly vanadic acid
Ammonium, poly ammonium vanadate 500 DEG C of calcination processings in calcining furnace obtain vanadic anhydride.Whole technique iron recovery 89%, vanadium is returned
Yield 92%, chromium recovery ratio 89%.
Embodiment 3
By converter vanadium chromium slag (Cr2O3Mass fraction is 12%, V2O5Mass fraction is 12%, Fe mass fractions for 30%)
Oxidation magnetic roasting is carried out in tunnel cave, 450 DEG C of temperature, oxygen concentration 2%, roasting time 20min obtains magnetic calcining,
Iron wherein in magnetic calcining in ferroso-ferric oxide accounts for full iron ratio for 96% (weight of iron fraction 6.5%), in concentration equipment (magnetic
Select machine) in magnetic separation treatment is carried out to magnetic calcining, obtain Armco magnetic iron concentrate and nonmagnetic except ferrovanadium chromium slag, then will be except ferrovanadium
Chromium slag and calcium carbonate in mass ratio 100:1050 DEG C of sodium oxide baking 2h obtain high price vanadium in multihearth roaster after 12 mixing
Sour calcium clinker, the ratio that pentavalent vanadium accounts for full vanadium in 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 sodium carbonate liquor for leaching agent, leaching agent mass concentration is 20%, and extraction temperature is 95 DEG C, leaching
It is 3 to go out liquid-solid ratio:1, extraction time is 60min, and leaching is obtained containing vanadium leachate and chromium slag (Cr after terminating2O3Mass fraction is
18%), vanadium turns leaching rate for 94%, then will contain vanadium leachate and carry out acid ammonium salt precipitation treatment and obtain poly ammonium vanadate, poly
Ammonium vanadate 500 DEG C of calcination processings in calcining furnace obtain vanadic anhydride.Whole technique iron recovery 90%, vanadium recovery
94%, chromium recovery ratio 90%.
Embodiment 4
By converter vanadium chromium slag (Cr2O3Mass fraction is 16%, V2O5Mass fraction is 16%, Fe mass fractions for 35%)
Oxidation magnetic roasting is carried out in tunnel cave, 350 DEG C of temperature, oxygen concentration 1.5%, roasting time 15min obtains magnetic roasting
It is 91% that iron in sand, wherein magnetic calcining in ferroso-ferric oxide accounts for full iron ratio, to magnetic in concentration equipment (magnetic separator)
Calcining carries out magnetic separation treatment, obtains Armco magnetic iron concentrate and nonmagnetic except ferrovanadium chromium slag (weight of iron fraction 5.9%), then will remove
Ferrovanadium chromium slag and calcium chloride in mass ratio 100:1100 DEG C of sodium oxide baking 1.5h are obtained in multihearth roaster after 15 mixing
High price vanadic acid calcium clinker, the ratio that pentavalent vanadium accounts for full vanadium in high price vanadic acid calcium clinker is 98%, and high price vanadic acid calcium clinker is carried out
Carbonic acid is leached, and the condition that carbonic acid is leached is sodium bicarbonate solution for leaching agent, and leaching agent mass concentration is 20%, and extraction temperature is
95 DEG C, it is 3 to leach liquid-solid ratio:1, extraction time is 30min, and leaching is obtained containing vanadium leachate and chromium slag (Cr after terminating2O3Quality
Fraction is that 20%), vanadium turns leaching rate for 97%, then will contain vanadium leachate and carry out acid ammonium salt precipitation treatment and obtain poly vanadic acid
Ammonium, poly ammonium vanadate 500 DEG C of calcination processings in calcining furnace obtain vanadic anhydride.Whole technique iron recovery 88%, vanadium is returned
Yield 95%, chromium recovery ratio 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 spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (8)
1. it is a kind of process converter vanadium chromium slag system, it is characterised in that including：
There is oxidation magnetizing roasting device, the oxidation magnetizing roasting device converter vanadium chromium slag entrance, air intake and magnetic to roast
Sand is exported；
Concentration equipment, the concentration equipment has magnetic calcining entrance, iron ore concentrate outlet and except ferrovanadium chromium slag is exported, the magnetic
Calcining entrance is connected with magnetic calcining outlet；
Oxidation roasting with calcium compounds device, the oxidation roasting with calcium compounds device has except ferrovanadium chromium slag entrance, calcium salt entrance, air intake
Exported with high price vanadic acid calcium clinker, it is described except ferrovanadium chromium slag entrance is connected with described except ferrovanadium chromium slag is exported；
There is carbonic acid leaching device, the carbonic acid leaching device high price vanadic acid calcium clinker entrance, carbon acid solution entrance, chromium slag to export
Exported with containing vanadium leachate, the high price vanadic acid calcium clinker entrance is connected with high price vanadic acid calcium clinker outlet；
Precipitation-calcining unit, the precipitation-calcining unit has entrance containing vanadium leachate, ammonium salt entrance, acidity regulator entrance
Exported with vanadic anhydride, 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 oxidation magnetizing roasting device be rotary hearth furnace, tunnel cave,
Rotary kiln or multihearth roaster, preferably rotary hearth furnace.
3. system according to claim 1, it is characterised in that the oxidation roasting with calcium compounds device be rotary hearth furnace, rotary kiln,
Tunnel cave or multihearth roaster, preferably rotary kiln or multihearth roaster.
4. the method that the system any one of a kind of use claim 1-3 processes converter vanadium chromium slag, it is characterised in that bag
Include：
(1) supplying into the oxidation magnetizing roasting device converter vanadium chromium slag and air carries out oxidation magnetizing roast treatment, with
Just magnetic calcining is obtained；
(2) will the magnetic calcining supply the concentration equipment in carry out magnetic separation treatment, to obtain iron ore concentrate and except ferrovanadium chromium
Slag；
(3) oxidation calcification roasting is carried out except ferrovanadium chromium slag, calcium salt and air are supplied into the oxidation roasting with calcium compounds device by described
Burning treatment, to obtain high price vanadic acid calcium clinker；
(4) supply the high price vanadic acid calcium clinker and carbon acid solution carries out leaching process into the carbonic acid leaching device, with
Just obtain containing vanadium leachate and chromium slag；
(5) described supply into the precipitation-calcining unit containing vanadium leachate and ammonium salt and acidity regulator is processed, with
Just vanadic anhydride is obtained.
5. method according to claim 4, it is characterised in that in step (1), Cr in the converter vanadium chromium slag2O3Quality
Fraction is 8~16%, V2O5Mass fraction is that 8~16%, Fe mass fractions are 20~35%；
Optional, the temperature of the oxidation magnetizing roast treatment is 300~500 degrees Celsius, and the time is 5~20min, the air
Middle oxygen concentration is calculated as 0.5~2% by percent by volume.
6. the method according to claim 4 or 5, it is characterised in that in step (2), irony in the chromium slag except ferrovanadium
Amount fraction is not more than 8%.
7. method according to claim 4, it is characterised in that in step (3), the temperature of the oxidation roasting with calcium compounds treatment
Spend is 900~1100 degrees Celsius；
Optional, it is described except ferrovanadium chromium slag compares 100 with the mixing quality of the calcium salt:(5~15)；
Optional, the calcium salt is selected from least one in calcium carbonate, calcium oxide, calcium hydroxide, calcium sulfate and calcium chloride.
8. method according to claim 4, it is characterised in that in step (4), the extraction temperature is 85~95 Celsius
Degree, the time is 30~120 minutes, and liquid-solid ratio is (3~5):1；
Optional, the carbon acid solution is selected from least one in sodium carbonate liquor and sodium bicarbonate solution；
Optional, the mass concentration of the carbon acid solution is 10~20%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113430398A (en) * | 2021-05-17 | 2021-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | JCr 98-grade chromium metal containing vanadium element and preparation method thereof |
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Application publication date: 20170620 |