CN106834726A - 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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- CN106834726A CN106834726A CN201710209761.1A CN201710209761A CN106834726A CN 106834726 A CN106834726 A CN 106834726A CN 201710209761 A CN201710209761 A CN 201710209761A CN 106834726 A CN106834726 A CN 106834726A
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- chromium slag
- vanadium
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- chromium
- calcium
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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, the first air intake and acid-soluble vanadic acid calcium clinker；Acid-leaching vanadium-extracted device, with acid-soluble vanadic acid calcium clinker entrance, sour entrance, ammonium salt entrance, vanadic anhydride outlet and the outlet of chromium slag；Sodium oxide baking device, with chromium slag entrance, sodium salt entrance, second air intake and water-soluble sodium chromate chamotte outlet；Flooding chromium device, with the outlet of water-soluble sodium chromate chamotte entrance, water inlet, acidity regulator entrance and sodium dichromate.The high efficiente callback of iron, vanadium and chromium resource in vanadium chromium slag can be realized using the system.
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：
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, first
Air intake and acid-soluble vanadic acid calcium clinker are exported, described except ferrovanadium chromium slag entrance is connected with described except ferrovanadium chromium slag is exported；
There is acid-leaching vanadium-extracted device, the acid-leaching vanadium-extracted device acid-soluble vanadic acid calcium clinker entrance, sour entrance, ammonium salt to enter
Mouth, vanadic anhydride outlet and the outlet of chromium slag, the acid-soluble vanadic acid calcium clinker entrance go out with the acid-soluble vanadic acid calcium clinker
Mouth is connected；
There is sodium oxide baking device, the sodium oxide baking device chromium slag entrance, sodium salt entrance, the second air to enter
Mouth and water-soluble sodium chromate chamotte outlet, the chromium slag entrance are connected with chromium slag outlet；
Flooding chromium device, the flooding chromium device has water-soluble sodium chromate chamotte entrance, water inlet, acidity adjustment
Agent entrance and sodium dichromate are exported, and the water-soluble sodium chromate chamotte entrance is connected with the water-soluble sodium chromate chamotte outlet.
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 acid-leaching vanadium-extracted treatment, it is possible to achieve the high efficiente callback of vanadium resource, then enter acid-leaching vanadium-extracted obtained chromium residue again
Row sodium oxide baking and flooding chromium, it is possible to achieve the high efficiente callback of chromium resource.Thus, vanadium chromium can be realized using the system
The high efficiente callback of iron, vanadium and chromium resource in slag, and the rate of recovery of iron is not less than 87%, and the rate of recovery of vanadium is not less than 90%, chromium
The rate of recovery be 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, rotary kiln, tunnel cave or many
Layer roaster, preferably tunnel cave.
In some embodiments of the invention, the oxidation roasting with calcium compounds device is rotary hearth furnace, tunnel cave, rotary kiln or many
Layer roaster, preferably rotary kiln or multihearth roaster.
In some embodiments of the invention, the sodium oxide baking device is rotary hearth furnace, rotary kiln, tunnel cave or many
Layer roaster, preferably rotary hearth furnace.
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 acid-soluble vanadic acid calcium clinker；
(4) the acid-soluble vanadic acid calcium clinker is supplied into the acid-leaching vanadium-extracted device and is processed with acid and ammonium salt,
To obtain vanadic anhydride and chromium slag；
(5) supply the chromium slag, sodium salt and air carries out sodium oxide baking into the sodium oxide baking device
Treatment, to obtain water-soluble sodium chromate chamotte；
(6) the water-soluble sodium chromate and water and acidity regulator are supplied into the flooding chromium device and is located
Reason, to obtain sodium dichromate.
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 acid-leaching vanadium-extracted treatment, it is possible to achieve the high efficiente callback of vanadium resource, then enter acid-leaching vanadium-extracted obtained chromium residue again
Row sodium oxide baking and flooding chromium, it is possible to achieve the high efficiente callback of chromium resource.Thus, vanadium chromium can be realized using the method
The high efficiente callback of iron, vanadium and chromium resource in slag, and the rate of recovery of iron is not less than 87%, and the rate of recovery of vanadium is not less than 90%, chromium
The rate of recovery be 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 compares 100 with the mixing quality of the calcium salt:(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, the calcium salt be selected from calcium carbonate, calcium oxide, calcium hydroxide, calcium sulfate and
At least one in 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 (5), the temperature of sodium oxide baking treatment for 1100~
1200 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, the chromium slag compares 100 with the mixing quality of the sodium salt:(10~25).By
This, can further improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, during the sodium salt is selected from sodium carbonate, sodium chloride and sodium sulphate at least one
Kind.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, the system includes：Oxidation magnetizing roasting device 100, concentration equipment 200, oxidation roasting with calcium compounds device 300, acidleach are carried
Vanadium device 400, sodium oxide baking device 500 and flooding chromium device 600.
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, rotary kiln, tunnel cave or
Multihearth roaster, preferably rotary kiln or multihearth roaster.
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, the first air intake 303 and acid-soluble vanadic acid calcium clinker outlet 304, except ferrovanadium chromium slag entrance 301 with go out except ferrovanadium chromium slag
Mouth 203 is connected, and is suitable to obtained above except ferrovanadium chromium slag and calcium salt and air contact carry out oxidation roasting with calcium compounds treatment, with
Just acid-soluble vanadic acid calcium clinker is obtained.Specifically, except the vanadium trioxide in ferrovanadium chromium slag and calcium salt and oxygen react
To 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 (4)~(9)：
CaO+V2O3+O2=CaV2O6 (4)
2CaO+V2O3+O2=Ca2V2O7 (5)
3CaO+V2O3+O2=Ca3V2O8 (6)
CaO+V2O3+0.5O2=CaV2O5 (7)
2CaO+V2O3+0.5O2=Ca2V2O6 (8)
3CaO+V2O3+0.5O2=Ca3V2O7 (9)
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；And oxidation roasting with calcium compounds temperature is too high, it is possible to reach calcium oxide and three
Aoxidize the reaction temperature of two chromium, calcium chromate Yi Dan formed will with calcium vanadate acidleach when together enter into solution, it is impossible to completely
Realize that vanadium chromium is separated.Thus, can to ensure that follow-up gained vanadium chromium is respectively provided with using the oxidation roasting with calcium compounds treatment temperature higher
The rate of recovery.
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 the loss of vanadium can be caused during acidleach；Calcium salt allocates the leaching rate that can not excessively improve vanadium into, conversely, excessive
Calcium oxide substantial amounts of acid can be also consumed in acidleach, cause waste.Inventor by lot of experiments find, except ferrovanadium chromium slag with
The mixing quality ratio of calcium salt can be 100:When (5~15), the generation of calcium vanadate and Leach reaction effect are 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, tunnel cave, rotary kiln or
Multihearth roaster, preferably rotary kiln or multihearth roaster.
Embodiments in accordance with the present invention, acid-leaching vanadium-extracted device 400 has acid-soluble vanadic acid calcium clinker entrance 401, sour entrance
402nd, ammonium salt entrance 403, vanadic anhydride outlet 404 and chromium slag outlet 405, acid-soluble vanadic acid calcium clinker entrance 401 is molten with acid
Property vanadic acid calcium clinker outlet 304 be connected, and be suitable to water-soluble sodium vanadate clinker obtained above and water, acidity regulator and ammonium
Salt mixing carries out acid-leaching vanadium-extracted treatment, to obtain vanadic anhydride and chromium slag.Specifically, vanadic acid calcium clinker is acid soluble,
Acid soluble vanadic acid calcium clinker is carried out into acidleach first and obtains immersion liquid containing vanadic acid, then carry out acid after vanadic acid immersion liquid purification and impurity removal will be contained
Property ammonium salt precipitation treatment obtain poly ammonium vanadate precipitation, poly ammonium vanadate is finally carried out into calcination processing and obtains vanadic anhydride.
It can be ammonium chloride and ammonium sulfate to use ammonium salt during being somebody's turn to do.The reaction that the process specifically occurs is such as shown in (10)~(12)：
5CaV2O6+6H+=H2V10O28 4-+5Ca2++2H2O (10)
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (11)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (12)
Embodiments in accordance with the present invention, sodium oxide baking device 500 has chromium slag entrance 501, sodium salt entrance 502, the
Two air intakes 503 and water-soluble sodium chromate chamotte outlet 504, chromium slag entrance 501 export 405 and are connected with chromium slag, and be suitable to by
Chromium slag obtained above carries out sodium oxide baking treatment with sodium salt and air contact, to obtain water-soluble sodium vanadate clinker.
Specifically, the chrome green in chromium slag reacts and obtains sodium chromate with sodium salt and oxygen.Specifically, the process specifically occurs
Reaction such as shown in (13)：Wherein, sodium oxide molybdena is obtained for sodium salt through high-temperature process.
4Na2O+2Cr2O3+3O2=4Na2CrO4 (13)
According to one embodiment of present invention, in the step, the temperature of sodium oxide baking treatment is not particularly restricted,
Those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, oxidation sodium roasting
The temperature for burning treatment can be 1100~1200 degrees Celsius.Inventor has found, if sodium oxide baking temperature is too low, sodium chromate
Reaction of formation can not carry out or carry out it is insufficient；Sodium oxide baking temperature is too high, can cause material melting, influences the biography of oxygen
Pass, the dynamic conditions of reaction is deteriorated, and influences the reaction of formation of sodium chromate.Thus, the temperature for being processed using the sodium oxide baking
Degree can significantly improve the rate of recovery of chromium.
According to still a further embodiment, chromium slag is not particularly restricted with the mixed proportion of sodium salt, this area skill
Art personnel can be selected according to actual needs, a specific embodiment of the invention, the mixing matter of chromium slag and sodium salt
Amount ratio can be 100:(10~25).Inventor has found, if sodium salt addition is very few, cannot be according to life with chromium oxide and oxygen reaction
Stoichiometry into sodium chromate is carried out, and the sodium chromate of generation may not be water miscible, influence the recovery of chromium；And sodium salt is added
Too much, the rate of recovery of chromium can not be improved, conversely, the sodium of excess compound easily complicated with chromium generation, it is impossible to by follow-up
Water logging leach, influence chromium recovery.Thus, the rate of recovery of chromium can be significantly improved using the mixed proportion.
According to still another embodiment of the invention, during being somebody's turn to do, the particular type of sodium salt is not particularly restricted, this area
Technical staff can be selected according to actual needs, a specific embodiment of the invention, sodium salt can for sodium carbonate,
At least one in sodium chloride and sodium sulphate.Inventor has found that being contacted with chromium slag using such sodium salt carries out sodium oxide baking
Treatment can be substantially better than the sodium oxide baking efficiency that other types sodium salt improves chrome green, so as to improve subsequent process
The rate of recovery of middle chromium.
According to still another embodiment of the invention, sodium oxide baking device can for rotary hearth furnace, rotary kiln, tunnel cave or
Multihearth roaster, preferably rotary hearth furnace.
Embodiments in accordance with the present invention, flooding chromium device 600 has water-soluble sodium chromate chamotte entrance 601, water inlet
602nd, acidity regulator entrance 603 and sodium dichromate outlet 604, water-soluble sodium chromate chamotte entrance 601 and water-soluble sodium chromate
Clinker outlet 504 is connected, and is suitable to for water-soluble sodium chromate chamotte obtained above and water and acidity regulator to be mixed into water-filling
Extraction chromium treatment, to obtain sodium dichromate.Specifically, sodium chromate chamotte is water miscible, first by water miscible sodium chromate
Clinker carries out water logging and obtains chromium-containing solution, then chromium-containing solution is acidified using neutralization, sulfuric acid, evaporated at sulfuric acid sodium, crystallisation by cooling
Reason obtains sodium dichromate.The acidity regulator used during this can be sulfuric acid, hydrochloric acid and nitric acid.What the process specifically occurred
Reaction is as shown in (14)：
2Na2CrO4+H2SO4=Na2Cr2O7+Na2SO4+H2O (14)
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 acid-leaching vanadium-extracted treatment, it is possible to achieve the high efficiente callback of vanadium resource, then enter acid-leaching vanadium-extracted obtained chromium residue again
Row sodium oxide baking and flooding chromium, it is possible to achieve the high efficiente callback of chromium resource.Thus, vanadium chromium can be realized using the system
The high efficiente callback of iron, vanadium and chromium resource in slag, and the rate of recovery of iron is not less than 87%, and the rate of recovery of vanadium is not less than 90%, chromium
The rate of recovery be 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, vanadium is reclaimed in acid ammonium salt precipitation, and chromium is reclaimed in chrome liquor reduction-precipitation-calcining, finally realize iron,
The synthetical recovery of vanadium, chromium resource.
Except vanadium in the converter vanadium chromium slag after iron and chromium in the system for the treatment of converter vanadium chromium slag according to embodiments of the present invention
Grade 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 method that use system processes converter vanadium chromium slag.Root
According to embodiments of the 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 be the roasting of rotary hearth furnace, rotary kiln or multilayer
Burn stove, preferably rotary hearth furnace.
S200：Magnetic calcining is supplied into concentration equipment carries out magnetic separation treatment
In the step, magnetic calcining obtained above is supplied into concentration equipment carries out magnetic separation treatment, to separate
To iron ore concentrate and except ferrovanadium chromium slag.Specifically, in the step, magnetic calcining by after magnetic separation by Fe3O4Reclaimed, by magnetic
Fe after choosing3O4Into 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
Border needs 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
Row oxidation roasting with calcium compounds treatment, to obtain acid-soluble vanadic acid calcium clinker.Specifically, except the vanadium trioxide in ferrovanadium chromium slag with
Calcium salt and oxygen react and obtain 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)~(i)：
CaO+V2O3+O2=CaV2O6 (d)
2CaO+V2O3+O2=Ca2V2O7 (e)
3CaO+V2O3+O2=Ca3V2O8 (f)
CaO+V2O3+0.5O2=CaV2O5 (g)
2CaO+V2O3+0.5O2=Ca2V2O6 (h)
3CaO+V2O3+0.5O2=Ca3V2O7 (i)
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；And oxidation roasting with calcium compounds temperature is too high, it is possible to reach calcium oxide and three
Aoxidize the reaction temperature of two chromium, calcium chromate Yi Dan formed will with calcium vanadate acidleach when together enter into solution, it is impossible to completely
Realize that vanadium chromium is separated.Thus, can to ensure that follow-up gained vanadium chromium is respectively provided with using the oxidation roasting with calcium compounds treatment temperature higher
The rate of recovery.
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 the loss of vanadium can be caused during acidleach；Calcium salt allocates the leaching rate that can not excessively improve vanadium into, conversely, excessive
Calcium oxide substantial amounts of acid can be also consumed in acidleach, cause waste.Inventor by lot of experiments find, except ferrovanadium chromium slag with
The mixing quality ratio of calcium salt can be 100:When (5~15), the generation of calcium vanadate and Leach reaction effect are 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, tunnel cave, rotary kiln or
Multihearth roaster, preferably rotary kiln or multihearth roaster.
S400：Acid-soluble vanadic acid calcium clinker is supplied into acid-leaching vanadium-extracted device and processed with acid and ammonium salt
In the step, acid-soluble vanadic acid calcium clinker obtained above is supplied into acid-leaching vanadium-extracted device with acid and ammonium salt
Row treatment, to obtain vanadic anhydride and chromium slag.Specifically, vanadic acid calcium clinker is acid soluble, first by acid soluble vanadium
Sour calcium clinker carries out acidleach and obtains immersion liquid containing vanadic acid, then will contain and carry out acid ammonium salt precipitation after vanadic acid immersion liquid purification and impurity removal and process
To poly ammonium vanadate precipitation, poly ammonium vanadate is finally carried out into calcination processing and obtains vanadic anhydride.Ammonium salt is used during being somebody's turn to do
Can be ammonium chloride and ammonium sulfate.The reaction that the process specifically occurs is such as shown in (j)~(l)：
5CaV2O6+6H+=H2V10O28 4-+5Ca2++2H2O (j)
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (k)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (l)
S500：Chromium slag, sodium salt and air are supplied carries out sodium oxide baking treatment into sodium oxide baking device
In the step, above-mentioned isolated chromium slag, sodium salt and air are supplied and carried out into sodium oxide baking device
Sodium oxide baking treatment, to obtain water-soluble sodium vanadate clinker.Specifically, chrome green and sodium salt and oxygen in chromium slag
Gas reacts and obtains sodium chromate.Specifically, the reaction that the process specifically occurs is such as shown in (m)：Wherein, sodium oxide molybdena is sodium salt warp
High-temperature process is obtained.
4Na2O+2Cr2O3+3O2=4Na2CrO4 (m)
According to one embodiment of present invention, in the step, the temperature of sodium oxide baking treatment is not particularly restricted,
Those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, oxidation sodium roasting
The temperature for burning treatment can be 1100~1200 degrees Celsius.Inventor has found, if sodium oxide baking temperature is too low, sodium chromate
Reaction of formation can not carry out or carry out it is insufficient；Sodium oxide baking temperature is too high, can cause material melting, influences the biography of oxygen
Pass, the dynamic conditions of reaction is deteriorated, and influences the reaction of formation of sodium chromate.Thus, the temperature for being processed using the sodium oxide baking
Degree can significantly improve the rate of recovery of chromium.
According to still a further embodiment, chromium slag is not particularly restricted with the mixed proportion of sodium salt, this area skill
Art personnel can be selected according to actual needs, a specific embodiment of the invention, the mixing matter of chromium slag and sodium salt
Amount ratio can be 100:(10~25).Inventor has found, if sodium salt addition is very few, cannot be according to life with chromium oxide and oxygen reaction
Stoichiometry into sodium chromate is carried out, and the sodium chromate of generation may not be water miscible, influence the recovery of chromium；And sodium salt is added
Too much, the rate of recovery of chromium can not be improved, conversely, the sodium of excess compound easily complicated with chromium generation, it is impossible to by follow-up
Water logging leach, influence chromium recovery.Thus, the rate of recovery of chromium can be significantly improved using the mixed proportion.
According to still another embodiment of the invention, during being somebody's turn to do, the particular type of sodium salt is not particularly restricted, this area
Technical staff can be selected according to actual needs, a specific embodiment of the invention, sodium salt can for sodium carbonate,
At least one in sodium chloride and sodium sulphate.Inventor has found that being contacted with chromium slag using such sodium salt carries out sodium oxide baking
Treatment can be substantially better than the sodium oxide baking efficiency that other types sodium salt improves chrome green, so as to improve subsequent process
The rate of recovery of middle chromium.
According to still another embodiment of the invention, sodium oxide baking device can for rotary hearth furnace, rotary kiln, tunnel cave or
Multihearth roaster, preferably rotary hearth furnace.
S600：Water-soluble sodium chromate and water and acidity regulator are supplied into flooding chromium device and is processed
In the step, water-soluble sodium chromate obtained above and water and acidity regulator are supplied into flooding chromium device
Processed, to obtain sodium dichromate.Specifically, sodium chromate chamotte is water miscible, it is first that water miscible sodium chromate is ripe
Material carries out water logging and obtains chromium-containing solution, then chromium-containing solution using neutralization, sulfuric acid acidifying, evaporation sulfuric acid sodium, crystallisation by cooling treatment
Obtain sodium dichromate.The acidity regulator used during this can be sulfuric acid, hydrochloric acid and nitric acid.It is anti-that the process specifically occurs
Should be as Suo Shi (n)：
2Na2CrO4+H2SO4=Na2Cr2O7+Na2SO4+H2O (n)
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 acid-leaching vanadium-extracted treatment, it is possible to achieve the high efficiente callback of vanadium resource, then enter acid-leaching vanadium-extracted obtained chromium residue again
Row sodium oxide baking and flooding chromium, it is possible to achieve the high efficiente callback of chromium resource.Thus, vanadium chromium can be realized using the method
The high efficiente callback of iron, vanadium and chromium resource in slag, and the rate of recovery of iron is not less than 87%, and the rate of recovery of vanadium is not less than 90%, chromium
The rate of recovery be 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.Will be except ferrovanadium chromium slag and calcium oxide in mass ratio 100:900 DEG C of oxidations in rotary kiln after 5 mixing
Sodium roasting 1h obtains acid-soluble vanadic acid calcium clinker, and tetravalence vanadium and pentavalent vanadium sum account for the ratio of full vanadium in acid-soluble vanadic acid calcium clinker
Example is 92%, and acid-soluble vanadic acid calcium clinker is carried out into acid-leaching vanadium-extracted treatment obtains vanadic anhydride and chromium slag.By chromium slag and carbonic acid
Sodium in mass ratio 100:1100 DEG C of sodium oxide baking 1h obtain water-soluble sodium chromate chamotte in rotary hearth furnace after 10 mixing, by water
Dissolubility sodium chromate chamotte carries out the treatment of flooding chromium and obtains sodium dichromate.Whole technique iron 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%).Will be except ferrovanadium
Chromium slag and calcium hydroxide in mass ratio 100:1000 DEG C of sodium oxide baking 1.5h obtain acid-soluble in rotary kiln after 10 mixing
Vanadic acid calcium clinker, the ratio that tetravalence vanadium and pentavalent vanadium sum account for full vanadium in acid-soluble vanadic acid calcium clinker is 93%, by acid-soluble vanadium
Sour calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride and chromium slag.By chromium slag and sodium chloride in mass ratio 100:15 mixing
1150 DEG C of sodium oxide baking 1.5h obtain water-soluble sodium chromate chamotte in rotary hearth furnace afterwards, and water-soluble sodium chromate chamotte is carried out
The treatment of flooding chromium obtains sodium dichromate.Whole technique iron recovery 89%, vanadium recovery 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.Will be except ferrovanadium chromium slag
With calcium carbonate in mass ratio 100:1050 DEG C of sodium oxide baking 2h obtain acid-soluble vanadic acid in multihearth roaster after 12 mixing
Calcium clinker, the ratio that tetravalence vanadium and pentavalent vanadium sum account for full vanadium in acid-soluble vanadic acid calcium clinker is 94%, by acid-soluble calcium vanadate
Clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride and chromium slag.By chromium slag and sodium sulphate in mass ratio 100:20 mixing after
1175 DEG C of sodium oxide baking 2h obtain water-soluble sodium chromate chamotte in rotary hearth furnace, and water-soluble sodium chromate chamotte is carried out into flooding
Chromium treatment obtains sodium dichromate.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%).Will be except ferrovanadium
Chromium slag and calcium chloride in mass ratio 100:1100 DEG C of sodium oxide baking 1.5h obtain sour molten in multihearth roaster after 15 mixing
Property vanadic acid calcium clinker, it is 95% that tetravalence vanadium and pentavalent vanadium sum account for the ratio of full vanadium in acid-soluble vanadic acid calcium clinker, will be acid-soluble
Vanadic acid calcium clinker carries out acid-leaching vanadium-extracted treatment and obtains vanadic anhydride and chromium slag.By chromium slag and sodium chloride in mass ratio 100:25 mix
1200 DEG C of sodium oxide baking 2h obtain water-soluble sodium chromate chamotte in rotary hearth furnace after conjunction, and water-soluble sodium chromate chamotte is carried out
The treatment of flooding chromium obtains sodium dichromate.Whole technique iron recovery 88%, vanadium recovery 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 (9)
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, the first air
Entrance and acid-soluble vanadic acid calcium clinker are exported, described except ferrovanadium chromium slag entrance is connected with described except ferrovanadium chromium slag is exported；
Acid-leaching vanadium-extracted device, the acid-leaching vanadium-extracted device has acid-soluble vanadic acid calcium clinker entrance, sour entrance, ammonium salt entrance, five
V 2 O is exported and the outlet of chromium slag, and the acid-soluble vanadic acid calcium clinker entrance and the acid-soluble vanadic acid calcium clinker export phase
Even；
Sodium oxide baking device, the sodium oxide baking device have chromium slag entrance, sodium salt entrance, second air intake and
Water-soluble sodium chromate chamotte outlet, the chromium slag entrance is connected with chromium slag outlet；
There is flooding chromium device, the flooding chromium device water-soluble sodium chromate chamotte entrance, water inlet, acidity regulator to enter
Mouth and sodium dichromate outlet, the water-soluble sodium chromate chamotte entrance are connected with the water-soluble sodium chromate chamotte outlet.
2. system according to claim 1, it is characterised in that the oxidation magnetizing roasting device be rotary hearth furnace, rotary kiln,
Tunnel cave or multihearth roaster, preferably tunnel cave.
3. system according to claim 1, it is characterised in that the oxidation roasting with calcium compounds device be rotary hearth furnace, tunnel cave,
Rotary kiln or multihearth roaster, preferably rotary kiln or multihearth roaster.
4. system according to claim 1, it is characterised in that the sodium oxide baking device be rotary hearth furnace, rotary kiln,
Tunnel cave or multihearth roaster, preferably rotary hearth furnace.
5. the method that the system any one of a kind of use claim 1-4 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 acid-soluble vanadic acid calcium clinker；
(4) the acid-soluble vanadic acid calcium clinker is supplied into the acid-leaching vanadium-extracted device and is processed with acid and ammonium salt, so as to
Obtain vanadic anhydride and chromium slag；
(5) supply the chromium slag, sodium salt and air carries out sodium oxide baking treatment into the sodium oxide baking device,
To obtain water-soluble sodium chromate chamotte；
(6) the water-soluble sodium chromate and water and acidity regulator are supplied into the flooding chromium device and is processed, with
Just sodium dichromate is obtained.
6. method according to claim 5, 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.
7. the method according to claim 5 or 6, it is characterised in that in step (2), irony in the chromium slag except ferrovanadium
Amount fraction is not more than 8%.
8. method according to claim 5, 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.
9. method according to claim 5, it is characterised in that in step (5), the temperature of the sodium oxide baking treatment
Spend is 1100~1200 degrees Celsius；
Optional, the chromium slag compares 100 with the mixing quality of the sodium salt:(10~25)；
Optional, the sodium salt is selected from least one in sodium carbonate, sodium chloride and sodium sulphate.
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| CN103614566A (en) * | 2013-12-13 | 2014-03-05 | 重庆大学 | Method for extracting vanadium and chromium from converter vanadium chromium slag |
| CN104357652A (en) * | 2014-11-20 | 2015-02-18 | 重庆大学 | Method for directly extracting vanadium from high-calcium vanadium slag by roasting-alkali leaching |
| CN206052110U (en) * | 2016-07-18 | 2017-03-29 | 江苏省冶金设计院有限公司 | A kind of system for processing vanadium slag |
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| CN114381602A (en) * | 2022-01-14 | 2022-04-22 | 中南大学 | Method for selectively separating heavy metals in chromium-containing sludge |
| CN114381602B (en) * | 2022-01-14 | 2023-03-14 | 中南大学 | Method for selectively separating heavy metals in chromium-containing sludge |
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