CN106868311A - 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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- CN106868311A CN106868311A CN201710210095.3A CN201710210095A CN106868311A CN 106868311 A CN106868311 A CN 106868311A CN 201710210095 A CN201710210095 A CN 201710210095A CN 106868311 A CN106868311 A CN 106868311A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
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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, magnetic calcining entrance is connected with the outlet of magnetic calcining；Selective oxidation alkali bath unit, with except ferrovanadium chromium slag entrance, alkali liquor inlet, oxidant inlet, containing vanadium leachate outlet and chromium slag outlet, except ferrovanadium chromium slag entrance with except ferrovanadium chromium slag export be connected；Unit is calcined in precipitation, and with the outlet of entrance containing vanadium leachate, ammonium salt entrance, acidity regulator entrance and vanadic anhydride, entrance containing vanadium leachate is connected with the outlet containing vanadium leachate.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；
Selective oxidation alkali bath unit, the selective oxidation alkali bath unit have except ferrovanadium chromium slag entrance, alkali liquor inlet,
Oxidant inlet, containing vanadium leachate outlet and chromium slag outlet, it is described except ferrovanadium chromium slag entrance with it is described except ferrovanadium chromium slag export phase
Even；
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, and gained then is removed into ferrovanadium chromium slag selective oxidation
Alkali leaching is processed so that vanadium trioxide therein is dissolved in alkali lye, and chromium and is reclaimed in chromium slag form, realizes efficiently returning for chromium resource
Receive, gained is then carried out into precipitation and calcination processing again containing vanadium leachate, it is possible to achieve the high efficiente callback of vanadium resource.Thus, adopt
The high efficiente callback of iron, vanadium and chromium resource in vanadium chromium slag can be realized with the system, and the rate of recovery of iron is not less than 87%, vanadium
The rate of recovery is not less than 90%, and the rate of recovery of chromium is not less than 88%.
In some embodiments of the invention, the oxidation magnetizing roasting device is rotary hearth furnace, tunnel cave, rotary kiln or many
Layer roaster, preferably tunnel cave.
In another aspect of the invention, the present invention proposes the method that secondary said system processes converter vanadium chromium slag.Root
According to embodiments of the 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) oxygen is carried out into the selective oxidation alkali bath unit except ferrovanadium chromium slag, alkali lye and oxidant are supplied by described
Choline leaching is processed, to obtain containing vanadium leachate and chromium slag；
(4) 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, and gained then is removed into ferrovanadium chromium slag selective oxidation
Alkali leaching is processed so that vanadium trioxide therein is dissolved in alkali lye, and chromium and is reclaimed in chromium slag form, realizes efficiently returning for chromium resource
Receive, gained is then carried out into precipitation and calcination processing again containing vanadium leachate, it is possible to achieve the high efficiente callback of vanadium resource.Thus, adopt
The high efficiente callback of iron, vanadium and chromium resource in vanadium chromium slag can be realized with the method, and the rate of recovery of iron is not less than 87%, vanadium
The rate of recovery 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 concentration of the alkali lye is 2~4mol/L.Thus, may be used
Further to improve the rate of recovery of vanadium and chromium in subsequent process.
In some embodiments of the invention, in step (3), in alkali oxide leaching treatment the solid mass ratio of liquid for (3~
6)：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, the temperature of the alkali oxide leaching treatment is 85~95 degrees Celsius, and the time is 30
~90 minutes.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, selective oxidation alkali bath unit
300 and precipitation-calcining unit 400.
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 tunnel cave.
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, selective oxidation alkali bath unit 300 has except ferrovanadium chromium slag entrance 301, alkali lye enters
Mouthfuls 302, oxidant inlet 303, containing vanadium leachate outlet 304 and chromium slag outlet 305, except ferrovanadium chromium slag entrance 301 with remove ferrovanadium
Chromium slag outlet 203 is connected, and is suitable to except ferrovanadium chromium slag is selectively oxidized with alkali lye and oxidising agent, to be contained
Vanadium leachate and chromium slag.Specifically, due to vanadium and the difference of chromium electrode current potential, will be selected except ferrovanadium chromium slag and oxidising agent
Selecting property alkali oxide leaching treatment obtains water miscible sodium vanadate Na3VO4, wherein, the addition of oxidant is except ferrovanadium chromium slag amount
(2~4) %, makes vanadium be oxidized leaching and is transferred in liquid phase, and chromium is not leached, so as to realize that vanadium is separated with chromium.Specifically,
Alkali lye can be the aqueous solution of NaOH or potassium hydroxide, and oxidant can be hydrogen peroxide, turn leaching containing vanadium in vanadium leachate
Rate is not less than 85%, and the leaching rate that turns of chromium is not higher than 5%, and alkali lye is by taking NaOH as an example, and oxidant is specific to send out by taking hydrogen peroxide as an example
Raw reaction is such as shown in (4)：
6NaOH+V2O3+2H2O2=2Na3VO4+5H2O(4)
According to one embodiment of present invention, the concentration of alkali lye is not particularly restricted, and those skilled in the art can be with root
Selected according to being actually needed, a specific embodiment of the invention, the concentration of alkali lye can be 2~4mol/L.Invention
People had found, the excessive concentration of alkali lye or the too low leaching that can all influence vanadium, and inventor is had been surprisingly found that by lot of experiments, alkali lye
Concentration be 2~4mol/L, the leaching effect of vanadium is best.
According to still a further embodiment, the condition of alkali oxide leaching treatment is not particularly restricted, art technology
Personnel can be selected according to actual needs, a specific embodiment of the invention, and the temperature of alkali oxide leaching treatment can
Think 85~95 degrees Celsius, the time can be 30~90 minutes, the solid mass ratio of liquid is (3~6)：1.Inventor find, temperature, when
Between 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, alkali oxide leaching treatment
85~95 degrees Celsius of temperature, 30~90 minutes time, the solid mass ratio (3~6) of liquid：1, the leaching effect of vanadium is best.
Embodiments in accordance with the present invention, precipitation-calcining unit 400 have entrance containing vanadium leachate 401, ammonium salt entrance 402,
Acidity regulator entrance 403 and vanadic anhydride outlet 404, entrance containing vanadium leachate 401 exports 304 phases with containing vanadium leachate
Even, and it is suitable to mix with ammonium salt and acidity regulator containing vanadium leachate and carries out precipitation and calcination processing, to obtain five oxidations
Two vanadium.Specifically, precipitation-calcining unit is the linkage of precipitation device and calciner plant, in pH=1.0~2.5, temperature 85
Under the conditions of~95 DEG C, vanadium leachate will be contained and supplied into precipitation device, now V will be with H2V10O28 4-Form is present, then to containing vanadium
NH is added in leachate4Cl or (NH4)2SO4, NH4Cl or (NH4)2SO4Addition quality be containing V in vanadium leachate2O5Quality
0.5~1.0 times, 60~120min of reaction time, final vanadium is passed through precipitation in the form of poly ammonium vanadate, is separated by filtration out,
Poly ammonium vanadate is carried out into calcining deamination in supply to calciner plant again and obtains vanadic anhydride.The specific reaction for occurring is such as
(5) shown in~(8)：
VO4 3-+2H+=VO3 -+H2O(5)
10VO3 -+6H+=H2V10O28 4-+2H2O(6)
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O (7)
(NH4)2V6O16=3V2O5+2NH3↑+H2O (8)
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, and gained then is removed into ferrovanadium chromium slag selective oxidation
Alkali leaching is processed so that vanadium trioxide therein is dissolved in alkali lye, and chromium and is reclaimed in chromium slag form, realizes efficiently returning for chromium resource
Receive, gained is then carried out into precipitation and calcination processing again containing vanadium leachate, it is possible to achieve the high efficiente callback of vanadium resource.Thus, adopt
The high efficiente callback of iron, vanadium and chromium resource in vanadium chromium slag can be realized with the system, and the rate of recovery of iron is not less than 87%, vanadium
The rate of recovery 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, except ferrovanadium chromium slag separates vanadium chromium by the leaching of selective oxidation alkali, finally realize iron, vanadium, chromium money
The synthetical recovery in source.
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 the side that a kind of use said system processes converter vanadium chromium slag
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 by vanadium titano-magnetite
Molten iron, then aoxidizes the slag for blowing out and obtaining in converter, and iron is main with vanadium iron spinelle FeOV in converter vanadium chromium slag2O3、
Chromohercynite FeOCr2O3With fayalite FeOSiO2Form exist, and Cr in converter vanadium chromium slag2O3Mass fraction
It is 8~16%, V2O5Mass fraction is that 8~16%, Fe mass fractions are 20~35%, and in the step, converter vanadium chromium slag carries out oxygen
Change magnetizing roast and obtain magnetic calcining, the FeO in vanadium iron spinelle, vanadium picotite and fayalite is oxidized to Fe3O4, this
Might have a part of vanadium during one to be oxidized, the specific reaction for occurring is such 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 tunnel cave.
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：Except ferrovanadium chromium slag, alkali lye and oxidant are supplied alkali oxide leaching will be carried out into selective oxidation alkali bath unit
Treatment
In the step, by obtained above except ferrovanadium chromium slag, alkali lye and oxidant are supplied to selective oxidation alkali bath unit
In carry out alkali oxide leaching treatment, to obtain containing vanadium leachate and chromium slag.Specifically, due to vanadium and the difference of chromium electrode current potential,
Water miscible sodium vanadate Na will be obtained except ferrovanadium chromium slag and oxidising agent are selectively oxidized alkali leaching treatment3VO4, wherein, oxygen
The addition of agent is, except (2~4) % of ferrovanadium chromium slag amount, vanadium is oxidized leaching and be transferred in liquid phase, and chromium is not immersed
Go out, so as to realize that vanadium is separated with chromium.Specifically, alkali lye can be the aqueous solution of NaOH or potassium hydroxide, oxidant can
Think hydrogen peroxide, the leaching rate that turns containing vanadium in vanadium leachate is not less than 85%, and the leaching rate that turns of chromium is not higher than 5%, and alkali lye is with hydroxide
As a example by sodium, by taking hydrogen peroxide as an example, the specific reaction for occurring is such as shown in (d) for oxidant：
6NaOH+V2O3+2H2O2=2Na3VO4+5H2O(d)
According to one embodiment of present invention, the concentration of alkali lye is not particularly restricted, and those skilled in the art can be with root
Selected according to being actually needed, a specific embodiment of the invention, the concentration of alkali lye can be 2~4mol/L.Invention
People had found, the excessive concentration of alkali lye or the too low leaching that can all influence vanadium, and inventor is had been surprisingly found that by lot of experiments, alkali lye
Concentration be 2~4mol/L, the leaching effect of vanadium is best.
According to still a further embodiment, the condition of alkali oxide leaching treatment is not particularly restricted, art technology
Personnel can be selected according to actual needs, a specific embodiment of the invention, and the temperature of alkali oxide leaching treatment can
Think 85~95 degrees Celsius, the time can be 30~90 minutes, the solid mass ratio of liquid is (3~6)：1.Inventor find, temperature, when
Between 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, alkali oxide leaching treatment
85~95 degrees Celsius of temperature, 30~90 minutes time, the solid mass ratio (3~6) of liquid：1, the leaching effect of vanadium is best.
S400：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, under the conditions of pH=1.0~2.5,85~95 DEG C of temperature, will contain vanadium leachate and supply into precipitation device, now V with
H2V10O28 4-Form is present, then to containing adding NH in vanadium leachate4Cl or (NH4)2SO4, NH4Cl or (NH4)2SO4Addition matter
Amount is containing V in vanadium leachate2O50.5~1.0 times of quality, in 60~120min of the reaction time, final vanadium is with the shape of poly ammonium vanadate
Formula by precipitation, be separated by filtration out, then poly ammonium vanadate is obtained into five oxygen in supply to calcining deamination is carried out in calciner plant
Change two vanadium.The specific reaction for occurring is such as shown in (e)~(h)：
VO4 3-+2H+=VO3 -+H2O(e)
10VO3 -+6H+=H2V10O28 4-+2H2O(f)
3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O(g)
(NH4)2V6O16=3V2O5+2NH3↑+H2O(h)
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, and gained then is removed into ferrovanadium chromium slag selective oxidation
Alkali leaching is processed so that vanadium trioxide therein is dissolved in alkali lye, and chromium and is reclaimed in chromium slag form, realizes efficiently returning for chromium resource
Receive, gained is then carried out into precipitation and calcination processing again containing vanadium leachate, it is possible to achieve the high efficiente callback of vanadium resource.Thus, adopt
The high efficiente callback of iron, vanadium and chromium resource in vanadium chromium slag can be realized with the method, and the rate of recovery of iron is not less than 87%, vanadium
The rate of recovery 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 rotary hearth furnace, 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 (iron content mass fraction 7.5%), then will be except ferrovanadium
Chromium slag is selectively oxidized alkaline leaching, and leaching condition is：The NaOH solution of 2mol/L, the solid mass ratio 6 of liquid:1, extraction temperature
85 DEG C, extraction time 60min, hydrogen peroxide addition is 2% except ferrovanadium chromium slag amount, after leaching terminates, obtains being soaked containing vanadium
Go out liquid and chromium slag, the leaching rate that turns of vanadium is 92%, and the leaching rate that turns of chromium is 3.5%, and chromium slag can be as the raw material for carrying chromium.Vanadium leaching will be contained
Go out liquid under the conditions of pH=1.0,85 DEG C of temperature, add containing V in vanadium leachate2O5The NH of 0.5 times of quality4Cl, reaction time
60min, final vanadium is passed through precipitation in the form of poly ammonium vanadate, is separated by filtration out, then by poly ammonium vanadate in calcining furnace
500 DEG C of calcination processings obtain vanadic anhydride.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 rotary hearth furnace, 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 (iron content mass fraction 7.0%), then will
Except ferrovanadium chromium slag is selectively oxidized alkaline leaching, leaching condition is：The NaOH solution of 3mol/L, the solid mass ratio 5 of liquid:1, leaching
Go out 90 DEG C of temperature, extraction time 90min, hydrogen peroxide addition is 3% except ferrovanadium chromium slag amount, after leaching terminates, obtain
Containing vanadium leachate and chromium slag, the leaching rate that turns of vanadium is 94%, and the leaching rate that turns of chromium is 2.5%, and chromium slag can be as the raw material for carrying chromium, will
Containing vanadium leachate under the conditions of pH=2.0,90 DEG C of temperature, add containing V in vanadium leachate2O5The NH of 0.7 times of quality4Cl, reaction
Time 90min, final vanadium is passed through precipitation in the form of poly ammonium vanadate, is separated by filtration out, then by poly ammonium vanadate in calcining
500 DEG C of calcination processings obtain vanadic anhydride in stove.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 rotary hearth furnace, 450 DEG C of temperature, oxygen concentration 2%, roasting time 20min obtains magnetic calcining,
It is 96% that iron wherein in magnetic calcining in ferroso-ferric oxide accounts for full iron ratio, to magnetic calcining in concentration equipment (magnetic separator)
Magnetic separation treatment is carried out, Armco magnetic iron concentrate is obtained and nonmagnetic except ferrovanadium chromium slag (iron content mass fraction 6.8%), then will be except iron
Vanadium chromium slag is selectively oxidized alkaline leaching, and leaching condition is：The NaOH solution of 4mol/L, the solid mass ratio 4 of liquid:1, leach temperature
95 DEG C of degree, extraction time 90min, hydrogen peroxide addition is 4% except ferrovanadium chromium slag amount, after leaching terminates, is obtained containing vanadium
Leachate and chromium slag, the leaching rate that turns of vanadium is 94%, and the leaching rate that turns of chromium is 2%, and chromium slag can will contain vanadium leaching as the raw material for carrying chromium
Go out liquid under the conditions of pH=2.5,95 DEG C of temperature, add containing V in vanadium leachate2O5(the NH of 0.8 times of quality4)2SO4, during reaction
Between 120min, final vanadium in the form of poly ammonium vanadate by precipitation, be separated by filtration out, then by poly ammonium vanadate in calcining furnace
Interior 500 DEG C of calcination processings obtain vanadic anhydride.Whole technique iron recovery 88%, vanadium recovery 92%, 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 rotary hearth furnace, 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 (iron content mass fraction 6.5%), then will
Except ferrovanadium chromium slag is selectively oxidized alkaline leaching, leaching condition is：The NaOH solution of 4mol/L, the solid mass ratio 3 of liquid:1, leaching
Go out 90 DEG C of temperature, extraction time 45min, hydrogen peroxide addition is 3% except ferrovanadium chromium slag amount, after leaching terminates, obtain
Containing vanadium leachate and chromium slag, the leaching rate that turns of vanadium is 97%, and the leaching rate that turns of chromium is 1.5%, and chromium slag can be as the raw material for carrying chromium, will
Containing vanadium leachate under the conditions of pH=1.8,90 DEG C of temperature, add containing V in vanadium leachate2O5(the NH of 1.0 times of quality4)2SO4,
Reaction time 100min, final vanadium is passed through precipitation in the form of poly ammonium vanadate, is separated by filtration out, then poly ammonium vanadate is existed
500 DEG C of calcination processings obtain vanadic anhydride in calcining furnace.Whole technique iron recovery 88%, vanadium recovery 95%, waste liqouor
Rate 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；
Selective oxidation alkali bath unit, the selective oxidation alkali bath unit has except ferrovanadium chromium slag entrance, alkali liquor inlet, oxidation
Agent entrance, containing vanadium leachate outlet and chromium slag outlet, it is described except ferrovanadium chromium slag entrance with it is described except ferrovanadium chromium slag outlet be connected；
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 tunnel cave.
3. the method that the system described in a kind of use claim 1 or 2 processes converter vanadium chromium slag, it is characterised in that including：
(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) alkali oxide is carried out into the selective oxidation alkali bath unit except ferrovanadium chromium slag, alkali lye and oxidant are supplied by described
Leaching is processed, to obtain containing vanadium leachate and chromium slag；
(4) described supply into the precipitation-calcining unit containing vanadium leachate and ammonium salt and acidity regulator is processed, with
Just vanadic anhydride is obtained.
4. method according to claim 3, 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%.
5. method according to claim 4, it is characterised in that in step (1), the temperature of the oxidation magnetizing roast treatment
It is 300~500 degrees Celsius to spend, and the time is 5~20min, and oxygen concentration is calculated as 0.5~2% by percent by volume in the air.
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 3, it is characterised in that in step (3), the concentration of the alkali lye is 2~4mol/
L。
8. method according to claim 7, it is characterised in that in step (3), liquid stereoplasm in the alkali oxide leaching treatment
Amount is than being (3~6)：1.
9. method according to claim 8, it is characterised in that in step (3), the temperature of the alkali oxide leaching treatment is
85~95 degrees Celsius, the time is 30~90 minutes.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329964A (en) * | 2011-09-08 | 2012-01-25 | 中国科学院过程工程研究所 | Method for separating and recovering vanadium and chromium from vanadium-chromium reduced waste residue |
| CN103194611A (en) * | 2013-04-01 | 2013-07-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing vanadium oxide |
| 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 |
| CN104532009A (en) * | 2014-12-19 | 2015-04-22 | 北京科技大学 | Vanadium extraction method of high-calcium and high-phosphor vanadium slag clinker |
| 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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2017
- 2017-03-31 CN CN201710210095.3A patent/CN106868311A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329964A (en) * | 2011-09-08 | 2012-01-25 | 中国科学院过程工程研究所 | Method for separating and recovering vanadium and chromium from vanadium-chromium reduced waste residue |
| CN103194611A (en) * | 2013-04-01 | 2013-07-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing vanadium oxide |
| 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 |
| CN104532009A (en) * | 2014-12-19 | 2015-04-22 | 北京科技大学 | Vanadium extraction method of high-calcium and high-phosphor vanadium slag clinker |
| 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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Application publication date: 20170620 |