CN206721320U - The system for handling vanadium chromium slag - Google Patents
The system for handling vanadium chromium slag Download PDFInfo
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- CN206721320U CN206721320U CN201720339842.9U CN201720339842U CN206721320U CN 206721320 U CN206721320 U CN 206721320U CN 201720339842 U CN201720339842 U CN 201720339842U CN 206721320 U CN206721320 U CN 206721320U
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Abstract
The utility model discloses the system of processing vanadium chromium slag, including：Mixing device, it has vanadium chromium slag entrance, reduction coal entrance, binding agent entrance, fluxing agent entrance and mixed material outlet；Shaped device, it has mixed material entrance and pelletizing outlet；Reduction apparatus, it has pelletizing entrance and metallized pellet outlet；Separator, it has metallized pellet entrance, ferrochrome outlet and the outlet of rich vanadium slag；Sodium oxide baking device, it has rich vanadium slag entrance, sodium salt entrance, air intake and the outlet of water-soluble sodium vanadate clinker；Water logging vanadium extraction device, it has water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and tailings outlet.The comprehensive reutilization of iron, chromium and v element in vanadium chromium slag can be realized using the system, obtains the ferrochrome and vanadic anhydride product of high-quality, and technological process is short, is adapted to industrialization promotion.
Description
Technical field
Metal smelt field is the utility model is related to, specifically, the system that the utility model is related to processing vanadium chromium slag.
Background technology
China is a chromium depleted country, and 97% chrome ore all relies on import.It is worth noting that, the red lattice of Panzhihua
Chromium content is up to 9,000,000 tons in the high-chromic vanadium-titanium ferroferrite in area, and content of the chromium with vanadium in raw ore is suitable.The country is to this red
The processing method of lattice vanadium titano-magnetite is first passes around blast furnace process into containing vanadium and chromium molten iron, and then oxidation is blown out and turned in converter
Stove vanadium chromium slag (abbreviation vanadium chromium slag).Converter vanadium chromium slag is vanadium, chromium content is suitable or low vanadium Gao Ge chromium type high vanadium slag, its chromium content
About 5~13%, it is nearly 10 times of common vanadium slag, there is larger application value.Prior art is directly carried out to the vanadium chromium slag
High-temperature oxydation sodium roasting-Soaking treatment, the low high chromium solution of vanadium is obtained, wherein containing impurity such as more silicon, iron, aluminium, phosphorus, after
The purity of continuous precipitation products obtained therefrom is not high, and a small amount of vanadium contained in obtained high chromium solution is difficult to remove, using prior art
Qualified chromium product can not be obtained.
Therefore, the means of existing processing vanadium chromium slag still have much room for improvement.
Utility model content
The utility model is intended to one of technical problem at least solving in correlation technique to a certain extent.Therefore, this reality
It is to propose the system for handling vanadium chromium slag with a new purpose.Iron, chromium and vanadium in vanadium chromium slag can be realized using the system
The comprehensive reutilization of element, the ferrochrome and vanadic anhydride product of high-quality are obtained, and technological process is short, is adapted to industry
Change and promote.
In one side of the present utility model, the utility model proposes a kind of system for handling vanadium chromium slag.According to this reality
With new embodiment, the system includes：Mixing device, the mixing device have vanadium chromium slag entrance, reduction coal entrance, bonding
Agent entrance, fluxing agent entrance and mixed material outlet；There is mixed material entrance and pelletizing to go out for shaped device, the shaped device
Mouthful, the mixed material entrance is connected with pelletizing outlet；Reduction apparatus, the reduction apparatus have pelletizing entrance and metal
Pellet exports, and the pelletizing entrance is connected with pelletizing outlet；Separator, the separator have metallized pellet
Entrance, ferrochrome outlet and the outlet of rich vanadium slag, the metallized pellet entrance are connected with metallized pellet outlet；Oxidation
Sodium roasting device, the sodium oxide baking device have rich vanadium slag entrance, sodium salt entrance, air intake and water-soluble vanadic acid
Sodium clinker exports, and the rich vanadium slag entrance is connected with the rich vanadium slag outlet；Water logging vanadium extraction device, the water logging vanadium extraction device tool
There are water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and tailings outlet, the water-soluble sodium vanadate clinker entrance and institute
Water-soluble sodium vanadate clinker outlet is stated to be connected.
Thus, according to the utility model embodiment processing vanadium chromium slag system by using shaped device by vanadium chromium slag,
Reduction coal, binding agent and fluxing agent mixing, and obtained mixed material is molded to obtain pelletizing, then pelletizing is supplied to also original-pack
Middle carry out reduction treatment is put, the iron in pelletizing, chromated oxide are reduced to simple substance using reduction coal, metallized pellet is obtained, enters
And metallized pellet is subjected to separating treatment using separator, respectively obtain ferrochrome product and rich vanadium slag；Further,
By rich vanadium slag is supplied with sodium salt carry out mixing into sodium oxide baking device and sodium oxide baking handle, obtain water-soluble
Property sodium vanadate clinker, then by water logging vanadium extraction device by water-soluble sodium vanadate clinker carry out water logging vanadium extraction processing, obtain five oxidations
Two vanadium products and tailings.Thus, the system of the processing vanadium chromium slag of the utility model embodiment is by the way that chromium, iron and vanadium substep are gone back
Original, ferrochrome product is obtained first, and further handle rich vanadium slag, vanadic anhydride product is obtained, so as to realize in vanadium chromium slag
The comprehensive reutilization of iron, chromium and v element, and technological process is short, is adapted to industrialization promotion.
Optional, the reduction apparatus is tunnel cave or rotary hearth furnace.
Optional, separator described in the separator is mill ore magnetic selection device or molten separating device.
Optional, the mill ore magnetic selection device is the linkage of ball mill and magnetic separator, and the molten packing is set to combustion gas
It is molten to divide stove.
Optional, the sodium oxide baking device is multihearth roaster.
Additional aspect and advantage of the present utility model will be set forth in part in the description, partly by from following description
In become obvious, or by it is of the present utility model practice recognize.
Brief description of the drawings
Of the present utility model above-mentioned and/or additional aspect and advantage will in the description from combination accompanying drawings below to embodiment
Become obvious and be readily appreciated that, wherein：
Fig. 1 is the system structure diagram according to the processing vanadium chromium slag of the utility model one embodiment；
Fig. 2 is shown using the method flow of the system processing vanadium chromium slag of the processing vanadium chromium slag of the utility model one embodiment
It is intended to；
Fig. 3 is the method flow using the system processing vanadium chromium slag of the processing vanadium chromium slag of the utility model further embodiment
Schematic diagram；
Embodiment
Embodiment of the present utility model is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning
Same or similar element is represented to same or similar label eventually or there is the element of same or like function.Below by ginseng
The embodiment for examining accompanying drawing description is exemplary, it is intended to for explaining the utility model, and it is not intended that to the utility model
Limitation.
In the utility model, unless otherwise clearly defined and limited, term " connected " should be interpreted broadly, for example,
Can be fixedly connected or be detachably connected, or integrally；Can be mechanical connection or electrical connection；Can be with
It is to be joined directly together, can also be indirectly connected by intermediary, can is connection or the phase of two elements of two element internals
Interaction relation, limited unless otherwise clear and definite.For the ordinary skill in the art, can manage as the case may be
Solve concrete meaning of the above-mentioned term in the utility model.
In one side of the present utility model, the utility model proposes a kind of system for handling vanadium chromium slag.According to this reality
With new embodiment, with reference to figure 1, the system includes：Mixing device 100, shaped device 200, reduction apparatus 300, separation dress
Put 400, sodium oxide baking device 500 and water logging vanadium extraction device 600.Wherein, mixing device 100 have vanadium chromium slag entrance 101,
Reduction coal entrance 102, binding agent entrance 103, fluxing agent entrance 104 and mixed material outlet 105；Shaped device 200 has mixed
Material inlet 201 and pelletizing outlet 202 are closed, mixed material entrance 201 is connected with mixed material outlet 105；Reduction apparatus 300 has
There are pelletizing entrance 301 and metallized pellet outlet 302, pelletizing entrance 301 is connected with pelletizing outlet 202；Separator 400 has
Metallized pellet entrance 401, ferrochrome outlet 402 and rich vanadium slag outlet 403, metallized pellet entrance 401 and metallization ball
Group outlet 302 is connected；Sodium oxide baking device 500 has rich vanadium slag entrance 501, sodium salt entrance 502, the and of air intake 503
Water-soluble sodium vanadate clinker outlet 504, rich vanadium slag entrance 501 are connected with rich vanadium slag outlet 403；Water logging vanadium extraction device 600 has
Water-soluble sodium vanadate clinker entrance 601, vanadic anhydride outlet 602 and tailings outlet 603, water-soluble sodium vanadate clinker entrance
601 are connected with water-soluble sodium vanadate clinker outlet 504.
The system of the processing vanadium chromium slag according to the utility model embodiment is described in detail below with reference to Fig. 1：
According to embodiment of the present utility model, mixing device 100 has vanadium chromium slag entrance 101, reduction coal entrance 102, glued
Agent entrance 103, fluxing agent entrance 104 and mixed material outlet 105 are tied, mixing device 100 is suitable to vanadium chromium slag, reduction coal, glued
Knot agent and fluxing agent are mixed, to obtain mixed material.Specifically, vanadium chromium slag is red lattice vanadium titano-magnetite through blast furnace process
With the mine tailing obtained after converter oxidation blowing, its main thing is mutually FeO (Cr, V, Ti)2O3And 2FeOSiO2, vanadium, chromium and portion
Iron is divided mainly to exist in the form of vanadium iron and chromohercynite, some iron exists in the form of fayalite.Converter vanadium
Chromium slag is vanadium, chromium content is suitable or low vanadium Gao Ge chromium type high vanadium slag, wherein Cr2O3Mass fraction is about 8~16%, Fe mass
Fraction is about 20~35%, V2O5Mass fraction be about 8~16%, there is larger recycling to be worth.According to different metal
Active degree it is different, using reduction coal as reducing agent, it is possible to achieve the step-by-step reduction of different metal, and carrying out reduction treatment
Before, in advance vanadium chromium slag, reduction coal, binding agent and fluxing agent are carried out being mixed to get mixed material, follow-up go back can be significantly improved
The efficiency of original place reason.
According to embodiment of the present utility model, the proportioning for the vanadium chromium slag of mixing, reduction coal, binding agent and fluxing agent is simultaneously
It is not particularly limited, those skilled in the art can be selected according to being actually needed, according to specific implementation of the present utility model
Example, can be by vanadium chromium slag, reduction coal, binding agent and fluxing agent according to mass ratio 100:(6~12):(2~5):(5~15) carry out
Mixing.Thus, it is possible to significantly improve the degree of metalization of metallized pellet that sequential reduction handles to obtain, the recovery of ferrochrome is improved
Rate.Inventor has found, if the amount of allocating of reduction coal is too high, by Cr in pelletizing2O3After being reduced to Cr, pair will further occur
React 3Cr+7C=Cr3C7, cause the Cr rate of recovery to reduce.In addition, by being incorporated fluxing agent, can also improve at sequential reduction
The reduction effect of chromium and iron in reason.
According to embodiment of the present utility model, shaped device 200 has mixed material entrance 201 and pelletizing outlet 202, mixes
Close material inlet 201 with mixed material outlet 105 to be connected, shaped device 200 is suitable to the mixture that will be obtained in mixing device 100
Material is molded, to obtain pelletizing.
According to a specific embodiment of the present utility model, shaped device 200 can be disc balling machine.
According to embodiment of the present utility model, reduction apparatus 300 has pelletizing entrance 301 and metallized pellet outlet 302,
Pelletizing entrance 201 is connected with pelletizing outlet 202, and reduction apparatus 300 is suitable to pelletizing carrying out reduction treatment, to be metallized
Pelletizing.Inventor has found, different according to the active degree of metal, using reduction coal as reducing agent, is preferentially reduced in reduction treatment
What is obtained is iron, followed by chromium, is finally vanadium, can be by iron, chromium and vanadium in pelletizing so as to the condition by controlling reduction treatment
Selective step-by-step reduction, realize the separation of iron, chromium and vanadium.Specifically, the reduction to iron compound mainly includes following reaction：
2FeO·SiO2+ 2C=2Fe+SiO2+2CO；
2FeO·SiO2+ 2CO=2Fe+SiO2+2CO2；
FeO·(Cr,V,Ti)2O3+ C=(Cr, V, Ti)2O3+Fe+CO；
FeO·(Cr,V,Ti)2O3+ CO=(Cr, V, Ti)2O3+Fe+CO2。
Reduction to chromium compound mainly includes following reaction：
Cr2O3+ 3C=2Cr+3CO；
Cr2O3+ 3CO=2Cr+3CO2。
According to specific embodiment of the utility model, reduction treatment is completed at a temperature of 1300~1400 degrees Celsius
's.Inventor has found, if temperature is too high and reduction coal supplying is excessive, side reaction may occur：V2O3+ 3C=2V+3CO with
And V2O3+ 5C=2VC+3CO；So that vanadium is reduced in reduction treatment with chromium and iron simultaneously, cause vanadium can not be with chromium and iron point
From.Meanwhile the reduction of chromium needs certain temperature, if temperature is too low, the reduction effect of chromium is bad.
According to specific embodiment of the utility model, reduction apparatus 300 can be tunnel cave or rotary hearth furnace, it is possible thereby to enter
One step improves the effect of reduction treatment, so as to further improve the rate of recovery of iron and chromium.
According to embodiment of the present utility model, there is separator 400 metallized pellet entrance 401, ferrochrome to export
402 and rich vanadium slag outlet 403, metallized pellet entrance 401 and metallized pellet outlet 302 be connected, separator 400 is suitable for general
Metallized pellet carries out separating treatment, to obtain ferrochrome and rich vanadium slag, so as to realize the separation of vanadium and chromium, iron.Through inspection
Survey, the rate of recovery that Cr mass fraction is 15~22%, Cr in obtained ferrochrome product is up to more than 80%, in rich vanadium slag
Cr2O3Mass fraction be not higher than 2%, V2O5Mass fraction be 12~22%.
According to embodiment of the present utility model, the condition of separating treatment is not particularly restricted, and those skilled in the art can
It is actually needed and is selected with basis, according to specific embodiment of the utility model, mill ore magnetic selection can be used to handle or melt and divided
Processing carries out separating treatment to metallized pellet.
According to a specific embodiment of the present utility model, separating treatment is carried out to metallized pellet when being managed using molten office
When, molten office reason can be carried out in non-reducing atmosphere at a temperature of 1500~1600 degrees Celsius, thus, it is possible to further
Improve the grade of chromium and iron in isolated ferrochrome product.
According to a specific embodiment of the present utility model, contain O in the preferred atmosphere of non-reducing atmosphere2Volumetric concentration
3~25%, it is possible thereby to ensure that metal preferably separates during molten point.
According to a particular embodiment of the invention, separator can be mill ore magnetic selection device or molten separating device；Preferably, grind
Ore deposit concentration equipment can be the linkage of ball mill and magnetic separator, and molten separating device, which can be that combustion gas is molten, divides stove.It is it is possible thereby to aobvious
Write the efficiency for improving separating treatment.
According to embodiment of the present utility model, sodium oxide baking device 500 has rich vanadium slag entrance 501, sodium salt entrance
502nd, air intake 503 and water-soluble sodium vanadate clinker outlet 504, rich vanadium slag entrance 501 are connected with rich vanadium slag outlet 403, oxygen
Change sodium roasting device 500 to be suitable to rich vanadium slag carrying out sodium oxide baking processing in atmosphere, to obtain water-soluble vanadic acid
Sodium clinker, wherein, water-soluble sodium vanadate clinker can be at least one of sodium vanadate, sodium pyrovanadate or sodium metavanadate.Tool
Body, sodium oxide baking processing mainly includes following reaction：
Na2O+V2O3+O2=2NaVO3Sodium metavanadate；
2Na2O+V2O3+O2=Na4V2O7Sodium pyrovanadate；
3Na2O+V2O3+O2=Na3VO4Sodium vanadate.
After testing, positive pentavalent vanadium accounts for the ratio of full vanadium not less than 90% in gained water solubility sodium vanadate clinker.
According to embodiment of the present utility model, the proportioning of rich vanadium slag and sodium salt is not particularly restricted, people in the art
Member can be selected according to being actually needed, and according to specific embodiment of the utility model, the mass ratio of rich vanadium slag and sodium salt can
Think 100:(5~20), thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
According to embodiment of the present utility model, the species of sodium salt is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to specific embodiment of the utility model, sodium salt can include selected from sodium carbonate, sodium chloride and
At least one of sodium sulphate.Thus, it is possible to it is ripe effectively further to promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate
Material.
According to embodiment of the present utility model, the condition of sodium oxide baking processing is not particularly restricted, this area skill
Art personnel can be selected according to being actually needed, and according to specific embodiment of the utility model, sodium oxide baking processing is
Carry out what 1~2h was completed under 600~900 degrees Celsius.Thus, it is possible in ensureing the water-soluble sodium vanadate clinker that roasting obtains just
The ratio that the vanadium of pentavalent accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
According to specific embodiment of the utility model, sodium oxide baking device 500 can be multihearth roaster, thus may be used
Further to improve the effect of sodium oxide baking processing, so as to further improve the rate of recovery of vanadium.
According to embodiment of the present utility model, water logging vanadium extraction device 600 has water-soluble sodium vanadate clinker entrance 601, five
V 2 O outlet 602 and tailings outlet 603, water-soluble sodium vanadate clinker entrance 601 and water-soluble sodium vanadate clinker outlet 504
It is connected, water logging vanadium extraction device 600 is suitable to water-soluble sodium vanadate clinker carrying out water logging vanadium extraction processing, to obtain vanadic anhydride
And tailings.The water logging vanadium extraction device can be the linkage of water immersion, precipitation device and calciner plant, specifically, root
According to embodiment of the present utility model, water logging vanadium extraction processing may further include the following steps：
(1) Soaking treatment
According to embodiment of the present utility model, water-soluble sodium vanadate clinker is subjected to Soaking treatment, water logging condition：Leach temperature
80~95 degrees Celsius of degree, the solid mass ratio of liquid is (3~10):1, extraction time is 3~15min, and water logging terminates rear separation of solid and liquid, can
To obtain containing vanadium solution.
(2) precipitation is handled
According to embodiment of the present utility model, vanadium solution purification and impurity removal will be contained, acidic ammonium is carried out again containing vanadium solution after removal of impurities
Salt precipitation is handled, you can obtains poly ammonium vanadate precipitation.
Wherein, the key reaction occurred in above-mentioned precipitation processing is：
Acid adjustment degree：10VO3 -+6H+=H2V10O28 4-+2H2O
Ammonium salt precipitation：3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O。
(3) calcination processing
Further, according to embodiment of the present utility model, the poly ammonium vanadate precipitation that precipitation is handled to obtain is forged
Burning processing, control calcining heat reacts 2h under 550 degrees Celsius and carries out deamination, to obtain vanadic anhydride product.
Wherein, the key reaction occurred in above-mentioned calcination processing is：
(NH4)2V6O16=3V2O5+2NH3↑+H2O。
Thus, according to the utility model embodiment processing vanadium chromium slag system by mixing device by vanadium chromium slag, reduction
Coal, binding agent and fluxing agent mixing, and obtained mixed material is supplied into shaped device shaping and obtains pelletizing, then using also
Pelletizing is carried out reduction treatment by original device, and the iron in pelletizing, chromated oxide are reduced into simple substance using reduction coal, metallized
Pelletizing, and then metallized pellet is supplied into separator and carries out separating treatment, respectively obtain ferrochrome product and rich vanadium
Slag；Further, rich vanadium slag is mixed with sodium salt by using sodium oxide baking device and carries out sodium oxide baking processing,
Water-soluble sodium vanadate clinker is obtained, then water-soluble sodium vanadate clinker is supplied and carries out Soaking treatment into water logging vanadium extraction device, is obtained
It to containing vanadium solution, and will contain after vanadium solution carries out acid ammonium salt precipitation processing, obtained poly ammonium vanadate precipitation will be calcined
Processing, to obtain vanadic anhydride product and tailings.It is computed, vanadium chromium slag, the recovery of chromium is handled using the system of the application
Rate is up to more than 85%, and the rate of recovery of iron is up to more than 80%, and the rate of recovery of vanadium is up to more than 95%.Thus, the utility model
The system of the processing vanadium chromium slag of embodiment by by chromium, iron and vanadium step-by-step reduction, first ferrochrome product, and further locate
Rich vanadium slag is managed, obtains vanadic anhydride product, so as to realize the comprehensive reutilization of iron, chromium and v element in vanadium chromium slag, and work
Skill flow is short, is adapted to industrialization promotion.
In order to facilitate understanding, at system of Fig. 2~3 pair using the processing vanadium chromium slag of the utility model embodiment
The method of reason vanadium chromium slag is described in detail.According to embodiment of the present utility model, this method includes：
S100：Batch mixing
In the step, vanadium chromium slag, reduction coal, binding agent and fluxing agent are mixed, to obtain mixed material.Specifically
Ground, vanadium chromium slag are the mine tailings that red lattice vanadium titano-magnetite obtains after blast furnace process and converter oxidation blowing, and its main thing is mutually
FeO·(Cr,V,Ti)2O3And 2FeOSiO2, vanadium, chromium and part iron mainly exist in the form of vanadium iron and chromohercynite, gone back
Some iron exists in the form of fayalite.Converter vanadium chromium slag is vanadium, chromium content is suitable or low vanadium Gao Ge high-chromic vanadium
Slag, wherein Cr2O3Mass fraction is about that 8~16%, Fe mass fractions are about 20~35%, V2O5Mass fraction be about 8~
16%, there is larger recycling to be worth.It is different according to the active degree of different metal, can be with using reduction coal as reducing agent
The step-by-step reduction of different metal is realized, and before reduction treatment is carried out, in advance by vanadium chromium slag, reduction coal, binding agent and fluxing agent
Carry out being mixed to get mixed material, the efficiency of sequential reduction processing can be significantly improved.
According to embodiment of the present utility model, the proportioning for the vanadium chromium slag of mixing, reduction coal, binding agent and fluxing agent is simultaneously
It is not particularly limited, those skilled in the art can be selected according to being actually needed, according to specific implementation of the present utility model
Example, can be by vanadium chromium slag, reduction coal, binding agent and fluxing agent according to mass ratio 100:(6~12):(2~5):(5~15) carry out
Mixing.Thus, it is possible to significantly improve the degree of metalization of metallized pellet that sequential reduction handles to obtain, the recovery of ferrochrome is improved
Rate.Inventor has found, if the amount of allocating of reduction coal is too high, by Cr in pelletizing2O3After being reduced to Cr, pair will further occur
React 3Cr+7C=Cr3C7, cause the Cr rate of recovery to reduce.In addition, by being incorporated fluxing agent, can also improve at sequential reduction
The reduction effect of chromium and iron in reason.
S200：Shaping
In the step, the mixed material that S100 is obtained is molded, to obtain pelletizing.Specifically, circle can be used
Disk pelletizer enters to be about to mixed material to be molded.
S300：Reduction treatment
In the step, pelletizing is subjected to reduction treatment, to obtain metallized pellet.Inventor has found, according to metal
Active degree is different, and it is iron preferentially to reduce obtain using reduction coal as reducing agent, in reduction treatment, followed by chromium, is finally
Vanadium, so as to the condition by controlling reduction treatment, the selective step-by-step reduction of iron, chromium and vanadium in pelletizing can be realized iron, chromium
With the separation of vanadium.Specifically, the reduction to iron compound mainly includes following reaction：
2FeO·SiO2+ 2C=2Fe+SiO2+2CO；
2FeO·SiO2+ 2CO=2Fe+SiO2+2CO2；
FeO·(Cr,V,Ti)2O3+ C=(Cr, V, Ti)2O3+Fe+CO；
FeO·(Cr,V,Ti)2O3+ CO=(Cr, V, Ti)2O3+Fe+CO2。
Reduction to chromium compound mainly includes following reaction：
Cr2O3+ 3C=2Cr+3CO；
Cr2O3+ 3CO=2Cr+3CO2。
According to specific embodiment of the utility model, reduction treatment is completed at a temperature of 1300~1400 degrees Celsius
's.Inventor has found, if temperature is too high and reduction coal supplying is excessive, side reaction may occur：V2O3+ 3C=2V+3CO with
And V2O3+ 5C=2VC+3CO；So that vanadium is reduced in reduction treatment with chromium and iron simultaneously, cause vanadium can not be with chromium and iron point
From.Meanwhile the reduction of chromium needs certain temperature, if temperature is too low, the reduction effect of chromium is bad.
S400：Separating treatment
In the step, metallized pellet is subjected to separating treatment, to obtain ferrochrome and rich vanadium slag, so as to realize vanadium
With the separation of chromium, iron.After testing, Cr mass fraction is that 15~22%, the Cr rate of recovery reaches in the ferrochrome product obtained
More than 80%, Cr in rich vanadium slag2O3Mass fraction be not higher than 2%, V2O5Mass fraction be 12~22%.
According to embodiment of the present utility model, the condition of separating treatment is not particularly restricted, and those skilled in the art can
It is actually needed and is selected with basis, according to specific embodiment of the utility model, mill ore magnetic selection can be used to handle or melt and divided
Processing carries out separating treatment to metallized pellet.
According to a specific embodiment of the present utility model, separating treatment is carried out to metallized pellet when being managed using molten office
When, molten office reason can be carried out in non-reducing atmosphere at a temperature of 1500~1600 degrees Celsius, thus, it is possible to further
Improve the grade of chromium and iron in isolated ferrochrome product.
According to a specific embodiment of the present utility model, contain O in the preferred atmosphere of non-reducing atmosphere2Volumetric concentration
3~25%, it is possible thereby to ensure that metal preferably separates during molten point.
S500：Sodium oxide baking processing
In the step, rich vanadium slag is subjected to sodium oxide baking processing in atmosphere, it is ripe to obtain water-soluble sodium vanadate
Material, wherein, water-soluble sodium vanadate clinker can be at least one of sodium vanadate, sodium pyrovanadate or sodium metavanadate.Specifically,
Sodium oxide baking processing mainly includes following reaction：
Na2O+V2O3+O2=2NaVO3Sodium metavanadate；
2Na2O+V2O3+O2=Na4V2O7Sodium pyrovanadate；
3Na2O+V2O3+O2=Na3VO4Sodium vanadate.
After testing, positive pentavalent vanadium accounts for the ratio of full vanadium not less than 90% in gained water solubility sodium vanadate clinker.
According to embodiment of the present utility model, the proportioning of rich vanadium slag and sodium salt is not particularly restricted, people in the art
Member can be selected according to being actually needed, and according to specific embodiment of the utility model, the mass ratio of rich vanadium slag and sodium salt can
Think 100:(5~20), thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
According to embodiment of the present utility model, the species of sodium salt is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to specific embodiment of the utility model, sodium salt can include selected from sodium carbonate, sodium chloride and
At least one of sodium sulphate.Thus, it is possible to it is ripe effectively further to promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate
Material.
According to embodiment of the present utility model, the condition of sodium oxide baking processing is not particularly restricted, this area skill
Art personnel can be selected according to being actually needed, and according to specific embodiment of the utility model, sodium oxide baking processing is
Carry out what 1~2h was completed under 600~900 degrees Celsius.Thus, it is possible in ensureing the water-soluble sodium vanadate clinker that roasting obtains just
The ratio that the vanadium of pentavalent accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
S600：Water logging vanadium extraction is handled
In the step, water-soluble sodium vanadate clinker is subjected to water logging vanadium extraction processing, to obtain vanadic anhydride and tailings.
Specifically, the following steps can further include according to embodiment of the present utility model, water logging vanadium extraction processing：
S610：Soaking treatment
According to embodiment of the present utility model, water-soluble sodium vanadate clinker is subjected to Soaking treatment, water logging condition：Leach temperature
80~95 degrees Celsius of degree, the solid mass ratio of liquid is (3~10):1, extraction time is 3~15min, and water logging terminates rear separation of solid and liquid, can
To obtain containing vanadium solution.
S620：Precipitation is handled
According to embodiment of the present utility model, vanadium solution purification and impurity removal will be contained, acidic ammonium is carried out again containing vanadium solution after removal of impurities
Salt precipitation is handled, you can obtains poly ammonium vanadate precipitation.
Wherein, the key reaction occurred in above-mentioned precipitation processing is：
Acid adjustment degree：10VO3 -+6H+=H2V10O28 4-+2H2O
Ammonium salt precipitation：3H2V10O28 4-+10NH4 ++2H+=5 (NH4)2V6O16↓+4H2O。
S630：Calcination processing
Further, according to embodiment of the present utility model, the poly ammonium vanadate precipitation that precipitation is handled to obtain is forged
Burning processing, control calcining heat reacts 2h under 550 degrees Celsius and carries out deamination, to obtain vanadic anhydride product.
Wherein, the key reaction occurred in above-mentioned calcination processing is：
(NH4)2V6O16=3V2O5+2NH3↑+H2O。
Thus, according to the method for the processing vanadium chromium slag of the utility model embodiment by by vanadium chromium slag, reduction coal, binding agent
Mixed with fluxing agent, and obtained mixed material is molded to obtain pelletizing, then pelletizing is subjected to reduction treatment, utilize reduction coal will
Iron, chromated oxide in pelletizing are reduced to simple substance, obtain metallized pellet, and then metallized pellet is carried out into separating treatment, point
Ferrochrome product and rich vanadium slag are not obtained；Further, by being mixed rich vanadium slag with sodium salt and carrying out sodium oxide baking
Processing, water-soluble sodium vanadate clinker is obtained, then water-soluble sodium vanadate clinker is subjected to water logging vanadium extraction processing, obtain containing vanadium solution,
And after vanadium solution progress acid ammonium salt precipitation processing will be contained, calcination processing is carried out to obtained poly ammonium vanadate precipitation, so as to
To vanadic anhydride product and tailings.Be computed, vanadium chromium slag handled using the present processes, the rate of recovery of chromium up to 85% with
On, the rate of recovery of iron is up to more than 80%, and the rate of recovery of vanadium is up to more than 95%.Thus, the processing of the utility model embodiment
The method of vanadium chromium slag by by chromium, iron and vanadium step-by-step reduction, first ferrochrome product, and further handle rich vanadium slag, obtain
To vanadic anhydride product, so as to realize the comprehensive reutilization of iron, chromium and v element in vanadium chromium slag, and technological process is short, fits
Close industrialization promotion.
Below with reference to specific embodiment, the utility model is described, it is necessary to which explanation is, these embodiments are only
Descriptive, without limiting the utility model in any way.
Embodiment 1
By the country certain company converter vanadium chromium slag (Cr2O3Mass fraction is 8%, V2O5Mass fraction is 8%, Fe mass fractions
For 20%) with reduction coal, binding agent and fluxing agent in mass ratio 100:6:2:5 are mixed, and mixed material is passed through into disk
Pelletizer is molded to obtain pelletizing.Pelletizing is supplied to reduction roasting is carried out in tunnel cave at 1300 DEG C, reaction obtains after terminating
Metallized pellet.Metallized pellet is subjected to mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome
(mass fraction containing Cr be 15%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Mass fraction
For 1.5%, V2O5Mass fraction is 12%.By rich vanadium slag and sodium salt in mass ratio 100:After 5 mixing 600 in multihearth roaster
Sodium oxide baking 1h obtains water-soluble sodium vanadate clinker at DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 92%.Finally by water
Dissolubility sodium vanadate clinker carries out water logging vanadium extraction and handles to obtain vanadic anhydride (grade 98.8%) and tailings.The chromium of whole flow process returns
Yield is 85%, vanadium recovery 95%, iron recovery 85%.
Embodiment 2
By the country certain company converter vanadium chromium slag (Cr2O3Mass fraction is 10%, V2O5Mass fraction is 10%, Fe mass point
Number for 24%) with reduction coal, binding agent and fluxing agent in mass ratio 100:8:3:8 are mixed, and mixed material is passed through into circle
Disk pelletizer is molded to obtain pelletizing.Pelletizing is supplied to carrying out reduction roasting in tunnel cave at 1350 DEG C, reaction terminate after
To metallized pellet.Metallized pellet is subjected to mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome
(mass fraction containing Cr be 18%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Mass fraction
For 1.7%, V2O5Mass fraction is 15%.By rich vanadium slag and sodium salt in mass ratio 100:After 10 mixing 900 in multihearth roaster
Sodium oxide baking 1.5h obtains water-soluble sodium vanadate clinker at DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 96%.Finally will
Water-soluble sodium vanadate clinker carries out water logging vanadium extraction and handles to obtain vanadic anhydride (grade 99.2%) and tailings.The chromium of whole flow process
The rate of recovery is 87%, vanadium recovery 97%, iron recovery 80%.
Embodiment 3
By the country certain company converter vanadium chromium slag (Cr2O3Mass fraction is 12%, V2O5Mass fraction is 12%, Fe mass point
Number for 30%) with reduction coal, binding agent and fluxing agent in mass ratio 100:10:4:10 are mixed, and mixed material is passed through
Disc balling machine is molded to obtain pelletizing.Pelletizing is supplied to carrying out reduction roasting in tunnel cave at 1400 DEG C, after reaction terminates
Obtain metallized pellet.Metallized pellet is subjected to mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome conjunction
Gold (mass fraction containing Cr be 20%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Quality point
Number is 1.8%, V2O5Mass fraction is 18%.By rich vanadium slag and sodium salt in mass ratio 100:After 20 mixing in multihearth roaster
Sodium oxide baking 2h obtains water-soluble sodium vanadate clinker at 800 DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 95%.Finally will
Water-soluble sodium vanadate clinker carries out water logging vanadium extraction and handles to obtain vanadic anhydride (grade 99.0%) and tailings.The chromium of whole flow process
The rate of recovery is 88%, vanadium recovery 96%, iron recovery 87%.
Embodiment 4
By the country certain company converter vanadium chromium slag (Cr2O3Mass fraction is 16%, V2O5Mass fraction is 16%, Fe mass point
Number for 35%) with reduction coal, binding agent and fluxing agent in mass ratio 100:12:5:15 are mixed, and mixed material is passed through
Disc balling machine is molded to obtain pelletizing.Pelletizing is supplied to carrying out reduction roasting in tunnel cave at 1375 DEG C, after reaction terminates
Obtain metallized pellet.Metallized pellet is subjected to mill ore magnetic selection in the linkage of ball mill and magnetic separator and obtains ferrochrome conjunction
Gold (mass fraction containing Cr be 22%) and rich vanadium slag, ferrochrome can be used for smelting stainless steel, Cr in rich vanadium slag2O3Quality point
Number is 1.9%, V2O5Mass fraction is 22%.By rich vanadium slag and sodium salt in mass ratio 100:After 20 mixing in multihearth roaster
Sodium oxide baking 2h obtains water-soluble sodium vanadate clinker at 750 DEG C, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 98%.Finally will
Water-soluble sodium vanadate clinker carries out water logging vanadium extraction and handles to obtain vanadic anhydride (grade 99.4%) and tailings.The chromium of whole flow process
The rate of recovery is 90%, vanadium recovery 98%, iron recovery 90%.
Embodiment 5
By the country certain company converter vanadium chromium slag (Cr2O3Mass fraction is 8%, V2O5Mass fraction is 8%, Fe mass fractions
For 20%) with reduction coal, binding agent and fluxing agent in mass ratio 100:6:2:5 mixed processings obtain mixed material, and will mixing
Material is molded to obtain pelletizing by disc balling machine, and pelletizing is carried out into reduction roasting, reaction knot in tunnel cave at 1300 DEG C
Reduction roasting product is obtained after beam.1500 DEG C are divided in stove under neutral atmosphere to carry out molten get combustion gas is molten reduction roasting product
Ferrochrome (mass fraction containing Cr be 15%) and rich vanadium slag, ferrochrome can send to smelting stainless steel, Cr in rich vanadium slag2O3
Mass fraction is 1.5%, V2O5Mass fraction is 12%.By rich vanadium slag and sodium salt in mass ratio 100:It is calcined after 5 mixing in multilayer
600 DEG C of sodium oxide baking 1h obtain water-soluble sodium vanadate clinker in stove, and the ratio that wherein pentavalent vanadium accounts for full vanadium is 92%.Finally
The progress water logging vanadium extraction of water-soluble sodium vanadate clinker is handled to obtain vanadic anhydride (grade 98.8%) and tailings.Whole flow process
Chromium recovery ratio 91%, vanadium recovery 95%, iron recovery 85%.
Embodiment 6
By the country certain company vanadium-bearing slag of high calcium and high phosphor (Cr2O3Mass fraction is 10%, V2O5Mass fraction is 10%, Fe mass
Fraction be 24%) with reduction coal, binding agent and fluxing agent in mass ratio 100:8:3:8 mixed processings obtain mixed material, and will
Mixed material is molded to obtain pelletizing by disc balling machine, pelletizing is carried out into reduction roasting in tunnel cave at 1350 DEG C, instead
Reduction roasting product is obtained after should terminating.Reduction roasting product is melted in combustion gas and divides 1550 DEG C of progress under weak oxide atmosphere in stove
The molten ferrochrome (mass fraction containing Cr is 18%) and rich vanadium slag, ferrochrome got can send to smelting stainless steel, Fu Fan
Cr in slag2O3Mass fraction is 1.7%, V2O5Mass fraction is 15%.By rich vanadium slag and sodium salt in mass ratio 100:After 10 mixing
900 DEG C of sodium oxide baking 1.5h obtain water-soluble sodium vanadate clinker in multihearth roaster, and wherein pentavalent vanadium accounts for the ratio of full vanadium
Example is 96%.Finally the progress water logging vanadium extraction of water-soluble sodium vanadate clinker is handled to obtain vanadic anhydride (grade 99.2%) and tail
Slag.The chromium recovery ratio 93% of whole flow process, vanadium recovery 97%, iron recovery 80%.
Embodiment 7
By the country certain company vanadium-bearing slag of high calcium and high phosphor (Cr2O3Mass fraction is 8~16%, V2O5Mass fraction is 8~16%,
Fe mass fractions are 20~35%) and reduction coal, binding agent and fluxing agent in mass ratio 100:10:4:10 mixed processings are mixed
Compound material, and mixed material is molded by disc balling machine to obtain pelletizing, pelletizing is carried out at 1400 DEG C in tunnel cave
Reduction roasting, reaction obtain reduction roasting product after terminating.Reduction roasting product is melted in combustion gas and divided in stove under neutral atmosphere
1600 DEG C carry out the molten ferrochrome (mass fraction containing Cr is 20%) and rich vanadium slag, ferrochrome got and can send to smelting not
Become rusty steel, Cr in rich vanadium slag2O3Mass fraction is 1.8%, V2O5Mass fraction is 18%.By rich vanadium slag and sodium salt in mass ratio
100:800 DEG C of sodium oxide baking 2h obtain water-soluble sodium vanadate clinker, wherein pentavalent vanadium in multihearth roaster after 20 mixing
The ratio for accounting for full vanadium is 95%.Finally the progress water logging vanadium extraction of water-soluble sodium vanadate clinker is handled to obtain vanadic anhydride (grade
And tailings 99.0%).The chromium recovery ratio 95% of whole flow process, vanadium recovery 96%, iron recovery 87%.
Embodiment 8
By the country certain company vanadium-bearing slag of high calcium and high phosphor (Cr2O3Mass fraction is 16%, V2O5Mass fraction is 16%, Fe mass
Fraction be 35%) with reduction coal, binding agent and fluxing agent in mass ratio 100:12:5:15 mixed processings obtain mixed material, and
Mixed material is molded by disc balling machine to obtain pelletizing, pelletizing is subjected to reduction roasting in tunnel cave at 1375 DEG C,
Reaction obtains reduction roasting product after terminating.1575 DEG C are divided in stove under neutral atmosphere to be melted combustion gas is molten reduction roasting product
Smelting stainless steel, rich vanadium slag can be sent to by getting ferrochrome (mass fraction containing Cr is 25%) and rich vanadium slag, ferrochrome
Middle Cr2O3Mass fraction is 1.9%, V2O5Mass fraction is 22%.By rich vanadium slag and sodium salt in mass ratio 100:20 mixing after
750 DEG C of sodium oxide baking 2h obtain water-soluble sodium vanadate clinker in multihearth roaster, and the ratio that wherein pentavalent vanadium accounts for full vanadium is
98%.Finally the progress water logging vanadium extraction of water-soluble sodium vanadate clinker is handled to obtain vanadic anhydride (grade 99.4%) and tailings.
The chromium recovery ratio 97% of whole flow process, vanadium recovery 98%, iron recovery 90%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present utility model.In this manual, to the schematic table of above-mentioned term
State and be necessarily directed to identical embodiment or example.Moreover, specific features, structure, material or the feature of description can be with
Combined in an appropriate manner in any one or more embodiments or example.In addition, in the case of not conflicting, this area
Technical staff the different embodiments or example and the feature of different embodiments or example described in this specification can be entered
Row combines and combination.
Although embodiment of the present utility model has been shown and described above, it is to be understood that above-described embodiment is
Exemplary, it is impossible to it is interpreted as to limitation of the present utility model, one of ordinary skill in the art is in the scope of the utility model
It is interior above-described embodiment to be changed, changed, replaced and modification.
Claims (5)
- A kind of 1. system for handling vanadium chromium slag, it is characterised in that including：Mixing device, the mixing device have vanadium chromium slag entrance, reduction coal entrance, binding agent entrance, fluxing agent entrance and mixed Close material outlet；Shaped device, the shaped device have mixed material entrance and pelletizing outlet, and the mixed material entrance mixes with described Material outlet is closed to be connected；Reduction apparatus, the reduction apparatus have pelletizing entrance and metallized pellet outlet, the pelletizing entrance and the pelletizing Outlet is connected；Separator, the separator have metallized pellet entrance, ferrochrome outlet and the outlet of rich vanadium slag, the metal Pellet entrance is connected with metallized pellet outlet；Sodium oxide baking device, the sodium oxide baking device have rich vanadium slag entrance, sodium salt entrance, air intake and water Dissolubility sodium vanadate clinker exports, and the rich vanadium slag entrance is connected with the rich vanadium slag outlet；Water logging vanadium extraction device, the water logging vanadium extraction device have water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and tail Slag exports, and the water-soluble sodium vanadate clinker entrance is connected with the water-soluble sodium vanadate clinker outlet.
- 2. the system of vanadium chromium slag is handled according to claim 1, it is characterised in that the reduction apparatus is tunnel cave or turns bottom Stove.
- 3. the system of vanadium chromium slag is handled according to claim 1, it is characterised in that the separator is mill ore magnetic selection device Or molten separating device.
- 4. according to claim 3 handle vanadium chromium slag system, it is characterised in that the mill ore magnetic selection device be ball mill and The linkage of magnetic separator, the molten packing, which is set to combustion gas and melted, divides stove.
- 5. the system of vanadium chromium slag is handled according to claim 1, it is characterised in that the sodium oxide baking device is multilayer Roaster.
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