CN108531718A - A method of producing chrome green using tailings in vanadium extraction - Google Patents
A method of producing chrome green using tailings in vanadium extraction Download PDFInfo
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- CN108531718A CN108531718A CN201810367466.3A CN201810367466A CN108531718A CN 108531718 A CN108531718 A CN 108531718A CN 201810367466 A CN201810367466 A CN 201810367466A CN 108531718 A CN108531718 A CN 108531718A
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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
- C22B34/30—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
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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
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Abstract
The invention discloses a kind of methods producing chrome green using tailings in vanadium extraction, include the following steps：(1) tailings in vanadium extraction and sodium salt are carried out after being mixed to get mixed material, roasting clinker is obtained by being roasted at high temperature to the mixed material；(2) it after the roasting clinker that step (1) obtains being obtained turbid solution with water leaching process, is separated by solid-liquid separation by being filtered to the turbid solution, obtains leachate containing chromium and leached mud；(3) after carrying out precipitate reduction processing to the leachate containing chromium that step (2) obtains, high-purity chrome green product is obtained by roasting to precipitate.Tailings in vanadium extraction provided by the invention is raw material of the raw material as extraction chromium and production chrome green, on the one hand searches out a kind of new raw material for the extraction of chromium, on the other hand alleviates influence of this harmful trade waste of tailings in vanadium extraction to environment.
Description
Technical field
The invention belongs to chromium Chemical Engineering Technologies and resource circulation utilization field, and in particular to a kind of to produce three using tailings in vanadium extraction
The method for aoxidizing two chromium.
Background technology
Chromium and compound is important rare metal resources, is usually used in metallurgy, plating, and photography and leather process hides etc. are many
Field.But the compound of all chromium is all toxic in higher concentrations, especially Cr (VI) is by Environmental Protection Agency USA
(USEPA) it is included in and constitutes a threat in maximum 17 kinds of chemical substances to the mankind.In China, the primary raw material for extracting chromium is ferrochrome
Mine, by being water soluble hexavalent chromium by the trivalent chromium conversion not soluble in water in chromite, and chromium detached with other impurities from
And chromium is extracted.It will produce a large amount of chromium tailing and chromate waste water in this process, serious dirt caused to environment
Dye.On the other hand, chromite resources are reduced year by year at present, high-grade chromium resource can be used increasingly exhausted, are found other and are contained chromium resource
And therefrom chromium is effectively extracted and provides a new road for chromium chemical industry.
Currently, tailings in vanadium extraction, which is used as from vanadium slag or bone coal, extracts a kind of remaining industrial waste of vanadium, and in Chinese steel
Iron industry about produces 600,000 tons of tailings in vanadium extraction every year, and increases year by year.Wherein only have only a few tailings in vanadium extraction to be used to produce conjunction
Gold, function ceramics and coating etc., most tailings in vanadium extraction are directly to stack due to lacking economic and environmental-friendly processing method
Storage.Existing tailings in vanadium extraction is substantially the tailings by being obtained after vanadium slag sodium-salt calcination water logging vanadium extraction, and vanadium slag sodium-salt calcination
It can bring a series of problem, such as sodium chloride, the use of the sodium salts such as sodium sulphate that can generate Cl in roasting process2, SO2Deng harmful
Molten sintering material can occur in roasting process and make formation rings in a kiln simultaneously because sodium salt fusing point is relatively low for gas, damage equipment
Service life.However contain a large amount of chromium in tailings in vanadium extraction, if directly stockpiling is bound to cause more serious environmental problem.But
If this part chromium can be used, it on the one hand can alleviate the present situation of chromium resource shortage, industry on the other hand may be implemented
Waste efficiently uses.
Invention content
Place in view of the deficiency of the prior art utilizing three oxidation of tailings in vanadium extraction production the present invention provides a kind of
The method of two chromium.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A method of producing chrome green using tailings in vanadium extraction, which is characterized in that include the following steps：
(1) tailings in vanadium extraction and sodium salt are carried out after being mixed to get mixed material, by the mixed material at high temperature
It is roasted to obtain roasting clinker；
(2) after the roasting clinker that step (1) obtains being obtained turbid solution with water leaching process, by the muddiness
Liquid filters to be separated by solid-liquid separation, and obtains leachate containing chromium and leached mud；
(3) after carrying out precipitate reduction processing to the leachate containing chromium that step (2) obtains, height is obtained by roasting to precipitate
Purity chrome green product.
Further, a kind of method producing chrome green using tailings in vanadium extraction according to claim 1, it is special
Sign is that the tailings in vanadium extraction in step (1) is that chromium type high vanadium slag obtains after calcium salt roasting-acid-leaching vanadium-extracted processing
Waste, processing step includes：After mixing by high chrome alum slag raw material and calcium salt, it is carried out at being 850~950 DEG C in temperature
60~180min is roasted, obtains just roasting clinker；The sulfuric acid that volume fraction is 5~30% is added into the just roasting clinker again
Solution, or by it is described just roasting clinker in add a small amount of sulfuric acid solution make the ph values of turbid solution be maintained at 2.5~2.7 it
Between, so that the liquid-solid ratio in turbid solution is maintained between 8~15, to its extraction temperature be 40~80 DEG C, extraction time be 20~
It carries out leaching vanadium extraction processing under conditions of 60min, obtains the tailings in vanadium extraction in step (1)；Wherein, the high chrome alum slag is former
Material and calcium salt are by the V in the high chrome alum slag raw material2O5It is 1 with calcium salt molar ratio:1~5 is mixed.
Further, the chromium type high vanadium slag is calcium oxide, calcium hydroxide, carbon by selected calcium salt in calcium salt roasting process
Sour calcium, the mixing of one or more of calcium sulfate.
Further, the V in the tailings in vanadium extraction raw material2O5Shared mass fraction is 10%~15%, Cr2O3It is shared
Mass fraction be 5~15%.
Further, the sodium salt in step (1) is one or more of sodium carbonate, sodium sulphate, sodium chloride
Mixing.
Further, the sodium salt in the mixed material in step (1) and Cr in the tailings in vanadium extraction2O3Molar ratio
It is 4~10：1, calcination temperature when being roasted to the mixed material is 700~1000 DEG C, roasting constant temperature time is 30~
180min。
Further, clinker water leaching process is roasted described in step (2), is included the following steps：By water and the roasting
Overburnt material is 2~20 in mass ratio：After 1 is mixed, under 25~100 DEG C of extraction temperature, 120~180min is leached.
It further, will after being neutrality with the ph values that deionized water is rinsed to washing lotion by the leached mud in step (2)
The leached mud after flushing returns after removing sodium is reacted in blast furnace.
Further, the method for precipitate reduction processing being carried out to the leachate containing chromium in step (3), including walk as follows
Suddenly：After reducing agent is added into the leachate containing chromium, then after adjusting the ph values of the leachate containing chromium between 8~9, make chromium
It is formed and is precipitated, after standing to be precipitated, after detaching solid-liquid and being rinsed with water solid phase, at 800~1200 DEG C after solid phase is dried
At a temperature of, it roasts after 30~300min to get to high-purity chrome green.
Further, the reducing agent is selected as vulcanized sodium, sodium sulfite, iron sulfite, sodium thiosulfate, sodium pyrosulfite
One or both of or more mixing.
The present invention provides a kind of methods producing chrome green using tailings in vanadium extraction, by sodium-salt calcination by vanadium extraction
Low price chromium sodium oxide molybdena not soluble in water turns to the chromate for being dissolved in water and is leached with water in tailings, then will by precipitate reduction
Chromium in leachate precipitates, and roasting sediment obtains chrome green.In short, tailings in vanadium extraction provided by the invention is raw material
As the raw material of extraction chromium and production chrome green, a kind of new raw material on the one hand is searched out for the extraction of chromium, on the other hand
Alleviate influence of this harmful trade waste of tailings in vanadium extraction to environment；Obtained chrome green purity exists simultaneously
80% or more, it on the one hand can continue the chrome green that purification prepares technical grade, on the other hand can be used as Additive Production ferrochrome
Alloy, leather, coating etc., to realize the comprehensive utilization of tailings in vanadium extraction.
Description of the drawings
Fig. 1 is a kind of flow of method producing chrome green using tailings in vanadium extraction of exemplary embodiment of the present
Figure；
Fig. 2 is a kind of specific stream of method producing chrome green using tailings in vanadium extraction of exemplary embodiment of the present
Cheng Tu.
Specific implementation mode
To overcome deficiency in the prior art, the present invention to provide a kind of side producing chrome green using tailings in vanadium extraction
Method.To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached in the preferred embodiment of the present invention
Figure, technical solution in the embodiment of the present invention are further described in more detail.Described embodiment is a part of the invention
Embodiment, instead of all the embodiments.The embodiments described below with reference to the accompanying drawings are exemplary, it is intended to for explaining
The present invention, and be not considered as limiting the invention.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
There is the every other embodiment obtained under the premise of making creative work, shall fall within the protection scope of the present invention.With reference to
The embodiment of the present invention is described in detail in attached drawing.
As illustrated in fig. 1 and 2, an embodiment of the present invention provides it is a kind of using tailings in vanadium extraction produce chrome green method,
Include the following steps：
(1) tailings in vanadium extraction that granularity is 250~300 mesh is carried out with sodium salt after being mixed to get mixed material, by mixed
It closes material to be roasted at high temperature to obtain roasting clinker, and it is 250~300 mesh to roast the granularity of clinker after crushing；
(2) after the roasting clinker that step (1) obtains being obtained turbid solution with water leaching process, by turbid solution filter come
It is separated by solid-liquid separation, obtains leachate containing chromium and leached mud；
(3) after carrying out precipitate reduction processing to the leachate containing chromium that step (2) obtains, high-purity is obtained by roasting to precipitate
Chrome green product.
During extracting chromium using the acid-leaching vanadium-extracted tailings of calcification baking and preparing chrome green, one side of sodium salt is added
Face can destroy the structure of the phase of object containing chromium in tailings, on the other hand the chromium sodium oxide molybdena of low price be turned to the sodium chromate of high price, then
It leaching with water, reducing agent then, which is added, to the aqueous solution containing high valence chrome carries out precipitate reduction, obtains chromium hydroxide precipitation,
It is roasted, obtains the chrome green of high-purity；Wherein, the granularity of tailings in vanadium extraction can make to carry between 250~300 mesh
Vanadium tailing soil contacts well in roasting with air and sodium salt, is conducive to mass transfer；The granularity of clinker is roasted between 250~300 mesh,
It can be made more preferable with leaching media contact, be conducive to leaching process.
The tailings in vanadium extraction in step (1) is chromium type high vanadium slag by calcium salt roasting-as a preferred implementation manner,
The waste obtained after acid-leaching vanadium-extracted processing, processing step include：After mixing by high chrome alum slag raw material and calcium salt, in temperature
It is to carry out 60~180min of roasting at 850~950 DEG C, obtains just roasting clinker；Volume fraction is added into first roasting clinker again
For 5~30% sulfuric acid solution, or the ph values of turbid solution are made to be maintained at by adding a small amount of sulfuric acid solution into first roasting clinker
Between 2.5~2.7, the liquid-solid ratio in turbid solution is made to be maintained between 8~15, to its extraction temperature be 40~80 DEG C, leach
Time carries out leaching vanadium extraction processing under conditions of being 20~60min, obtains the tailings in vanadium extraction in step (1)；Wherein, tailings in vanadium extraction
Raw material and calcium salt are by the V in tailings in vanadium extraction raw material2O5It is 1 with calcium salt molar ratio:1~5 is mixed.In high chrome alum slag raw material
The vanadium calcium oxide of vanadium slag middle or low price, is turned to the vanadate of high price by middle addition calcium salt, and acid is used in combination to be leached, from high chrome alum slag original
After extracting vanadium in material, the chromium contained in the tailings in vanadium extraction that calcification baking acidleach obtains is higher than the tailings that sodium roasting water logging obtains.
Further, chromium type high vanadium slag is calcium oxide, calcium hydroxide, calcium carbonate, sulphur by calcium salt in calcium salt roasting process
The mixing of one or more of sour calcium.
Further, the V in high chrome alum slag raw material2O5Shared mass fraction is 10%~15%, Cr2O3Shared matter
It is 5~15% to measure score.
As a preferred implementation manner, the sodium salt in step (1) be sodium carbonate, sodium sulphate, one kind in sodium chloride or
Two or more mixing.
Cr in sodium salt and tailings in vanadium extraction in mixed material in step (1) as a preferred implementation manner,2O3Rub
You are than being 4~10：1, calcination temperature when being roasted to mixed material is 700~1000 DEG C, roasting constant temperature time is 30~
180min, wherein be that mixed material is put into stove when being roasted to mixed material, then by furnace temperature from room temperature with 2~30
DEG C/min is warming up to calcination temperature, mixed material can be made to be carried out during gradual heating by this heating mode pre-
Heat keeps the effect of sodium salt and the roasting clinker of tailings in vanadium extraction mixed material roasted out more preferable, and makes the leaching process of next step
The chromium content higher of the leachate containing chromium obtained.
Clinker water leaching process is roasted in step (2) as a preferred implementation manner, is included the following steps：By water
It is 2~20 in mass ratio with roasting clinker：After 1 is mixed, under 25~100 DEG C of extraction temperature, leaching 120~
180min。
It is with the ph values that deionized water is rinsed to washing lotion by the leached mud in step (2) as a preferred implementation manner,
After neutrality, the leached mud after flushing is returned after removing sodium is reacted in blast furnace.
The method that precipitate reduction processing is carried out to the leachate containing chromium in step (3) as a preferred implementation manner, packet
Include following steps：To after being added reducing agent in leachate containing chromium, then after adjusting the ph values of the leachate containing chromium between 8~9, make chromium
It is formed and is precipitated, after standing to be precipitated, after detaching solid-liquid and being rinsed with water solid phase, at 800~1200 DEG C after solid phase is dried
At a temperature of, it roasts after 30~300min to get to high-purity chrome green.In this step, it is straight in containing leachate
It connects after reducing agent is added, and is handled without any removal of impurities to prepare high-purity chrome green, reduced to being removed containing leachate
Live together reason, and then the preparation time and manufacturing cost for preparing chrome green saved.
Reducing agent is selected as vulcanized sodium, sodium sulfite, iron sulfite, sodium thiosulfate, coke as a preferred implementation manner,
The mixing of one or both of sodium sulfite or more.
Embodiment 1
A method of chrome green being produced using tailings in vanadium extraction, is included the following steps：
(1) tailings in vanadium extraction that granularity is 250~300 mesh is carried out with sodium carbonate after being mixed to get mixed material, by right
Mixed material carries out roasting 100min to obtain roasting clinker at a temperature of 700 DEG C；Wherein, in sodium carbonate and tailings in vanadium extraction
Cr2O3Molar ratio be 10：1, the granularity of roasting clinker after crushing is 250~300 mesh；
(2) the roasting clinker for obtaining water and step (1) is 15 in mass ratio：After 1 is mixed, in 100 DEG C of temperature
Under, turbid solution is obtained after carrying out leaching process 120min, is separated by solid-liquid separation by being filtered to turbid solution, obtains leaching containing chromium
After being neutrality with the ph values that deionized water is rinsed to washing lotion by leached mud, leached mud is returned after removing sodium is reacted for liquid and leached mud
It returns in blast furnace, it is 70.37% to analyze Steep cencentration containing chromium and measure chromium recovery rate；Wherein, when being roasted to mixed material,
It is that mixed material is put into stove, furnace temperature is then warming up to calcination temperature from room temperature with 2 DEG C/min；
(3) after vulcanized sodium being added in the leachate containing chromium obtained to step (2), then the ph values of the leachate containing chromium are adjusted 9
Afterwards, make chromium be formed to precipitate, after standing to be precipitated, after detaching solid-liquid and being rinsed with water solid phase, 1200 after solid phase is dried
At a temperature of DEG C, roast 300min after to get to purity be 85.44% chrome green.
Wherein, the tailings in vanadium extraction in step (1) is that chromium type high vanadium slag obtains after calcium salt roasting-acid-leaching vanadium-extracted processing
The waste arrived, processing step include：After mixing by high chrome alum slag raw material and calcium oxide, it is carried out at being 900 DEG C in temperature
120min is roasted, obtains just roasting clinker；The sulfuric acid solution that volume fraction is 5% is added into first roasting clinker again, makes muddiness
Liquid-solid ratio in liquid is maintained at 8, to its extraction temperature be 60 DEG C, extraction time be 60min under conditions of carry out leaching vanadium extraction
Processing, obtains the tailings in vanadium extraction in step (1)；Wherein, high chrome alum slag raw material and calcium salt are by the V improved in chrome alum slag raw material2O5
It is 1 with calcium oxide molar ratio:1 is mixed；V in high chrome alum slag raw material2O5Shared mass fraction is 12%, Cr2O3It is shared
Mass fraction be 5%, the granularity of the tailings is 300 mesh.
Embodiment 2
A method of chrome green being produced using tailings in vanadium extraction, is included the following steps：
(1) tailings in vanadium extraction that granularity is 250~300 mesh is carried out with sodium carbonate after being mixed to get mixed material, by right
Mixed material carries out roasting 30min to obtain roasting clinker at a temperature of 900 DEG C；Wherein, in sodium carbonate and tailings in vanadium extraction
Cr2O3Molar ratio be 4：1, the granularity of roasting clinker after crushing is 250~300 mesh；
(2) the roasting clinker for obtaining water and step (1) is 2 in mass ratio：After 1 is mixed, at a temperature of 25 DEG C,
Turbid solution is obtained after carrying out leaching process 160min, is separated by solid-liquid separation by being filtered to turbid solution, obtains leachate containing chromium
And leached mud, after being neutrality with the ph values that deionized water is rinsed to washing lotion by leached mud, leached mud is returned after removing sodium is reacted
In blast furnace, it is 80.23% to analyze Steep cencentration containing chromium and measure chromium recovery rate；Wherein, when being roasted to mixed material, it is
Mixed material is put into stove, furnace temperature is then warming up to calcination temperature from room temperature with 15 DEG C/min；
(3) after vulcanized sodium being added in the leachate containing chromium obtained to step (2), then the ph values of the leachate containing chromium is adjusted and are existed
After 8.5, chromium is made to form precipitation, after standing to be precipitated, after detaching solid-liquid and being rinsed with water solid phase, after solid phase is dried
At a temperature of 1000 DEG C, roast 200min after to get to purity be 87.53% chrome green.
Wherein, the tailings in vanadium extraction in step (1) is that chromium type high vanadium slag obtains after calcium salt roasting-acid-leaching vanadium-extracted processing
The waste arrived, processing step include：After mixing by high chrome alum slag raw material and calcium oxide, it is carried out at being 850 DEG C in temperature
60min is roasted, obtains just roasting clinker；The ph values of turbid solution are made to keep by adding a small amount of sulfuric acid solution into first roasting clinker
Between 2.5~2.7, the liquid-solid ratio in turbid solution is made to be maintained at 10, in extraction temperature is 40 DEG C to it, extraction time is
It carries out leaching vanadium extraction processing under conditions of 40min, obtains the tailings in vanadium extraction in step (1)；Wherein, high chrome alum slag raw material and calcium salt
It is by the V in high chrome alum slag raw material2O5It is 1 with calcium oxide molar ratio:3 are mixed；V in high chrome alum slag raw material2O5Shared
Mass fraction is 10%, Cr2O3Shared mass fraction is 12%, and the granularity of the tailings is 300 mesh.
Embodiment 3
A method of chrome green being produced using tailings in vanadium extraction, is included the following steps：
(1) tailings in vanadium extraction that granularity is 250~300 mesh is carried out with sodium carbonate after being mixed to get mixed material, by right
Mixed material carries out roasting 180min to obtain roasting clinker at a temperature of 1000 DEG C；Wherein, in sodium carbonate and tailings in vanadium extraction
Cr2O3Molar ratio be 8：1, the granularity of roasting clinker after crushing is 250~300 mesh；
(2) the roasting clinker for obtaining water and step (1) is 20 in mass ratio：After 1 is mixed, in 65 DEG C of temperature
Under, turbid solution is obtained after carrying out leaching process 180min, is separated by solid-liquid separation by being filtered to turbid solution, obtains leaching containing chromium
After being neutrality with the ph values that deionized water is rinsed to washing lotion by leached mud, leached mud is returned after removing sodium is reacted for liquid and leached mud
It returns in blast furnace, it is 91.51% to analyze Steep cencentration containing chromium and measure chromium recovery rate；Wherein, when being roasted to mixed material,
It is that mixed material is put into stove, furnace temperature is then warming up to calcination temperature from room temperature with 30 DEG C/min；
(3) after vulcanized sodium being added in the leachate containing chromium obtained to step (2), then the ph values of the leachate containing chromium are adjusted 8
Afterwards, make chromium be formed to precipitate, after standing to be precipitated, after detaching solid-liquid and being rinsed with water solid phase, at 800 DEG C after solid phase is dried
At a temperature of, roast 30min after to get to purity be 83.40% chrome green.
Wherein, the tailings in vanadium extraction in step (1) is that chromium type high vanadium slag obtains after calcium salt roasting-acid-leaching vanadium-extracted processing
The waste arrived, processing step include：After mixing by high chrome alum slag raw material and calcium oxide, it is carried out at being 950 DEG C in temperature
180min is roasted, obtains just roasting clinker；Volume fraction is added into first roasting clinker again and is 30% sulfuric acid solution, or passes through
Between adding a small amount of sulfuric acid solution into first roasting clinker the ph values of turbid solution being made to be maintained at 2.5~2.7, make the liquid in turbid solution
Gu ratio is maintained at 15, to its extraction temperature be 80 DEG C, extraction time be 20min under conditions of carry out leach vanadium extraction processing, obtain
To the tailings in vanadium extraction in step (1)；Wherein, high chrome alum slag raw material and calcium salt are by the V in high chrome alum slag raw material2O5With calcium oxide
Molar ratio is 1:5 are mixed；V in high chrome alum slag raw material2O5Shared mass fraction is 15%, Cr2O3Shared quality point
Number is 15%, and the granularity of the tailings is 300 mesh.
It should be noted last that the above specific implementation mode is merely illustrative of the technical solution of the present invention and unrestricted,
Although being described the invention in detail with reference to example, it will be understood by those of ordinary skill in the art that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit of the technical scheme of the invention and range, should all cover
In the scope of the claims of the present invention.
Claims (10)
1. a kind of method producing chrome green using tailings in vanadium extraction, which is characterized in that include the following steps：
(1) tailings in vanadium extraction and sodium salt are carried out after being mixed to get mixed material, by being carried out at high temperature to the mixed material
It roasts to obtain roasting clinker；
(2) after the roasting clinker that step (1) obtains being obtained turbid solution with water leaching process, by the turbid solution mistake
It filters to be separated by solid-liquid separation, obtains leachate containing chromium and leached mud；
(3) after carrying out precipitate reduction processing to the leachate containing chromium that step (2) obtains, three oxygen of high-purity is precipitated by roasting
Change two chromium products.
2. a kind of method producing chrome green using tailings in vanadium extraction according to claim 1, which is characterized in that in step
Suddenly the tailings in vanadium extraction in (1) is the waste that chromium type high vanadium slag obtains after calcium salt roasting-acid-leaching vanadium-extracted processing, place
Managing step includes：After mixing by high chrome alum slag raw material and calcium salt, carried out at being 850~950 DEG C in temperature roasting 60~
180min obtains just roasting clinker；The sulfuric acid solution that volume fraction is 5~30% is added into the just roasting clinker again, or
By being added into the just roasting clinker between a small amount of sulfuric acid solution makes the ph values of turbid solution be maintained at 2.5~2.7, make muddiness
Liquid-solid ratio in liquid is maintained between 8~15, to its extraction temperature be 40~80 DEG C, extraction time be 20~60min item
It carries out leaching vanadium extraction processing under part, obtains the tailings in vanadium extraction in step (1)；Wherein, the high chrome alum slag raw material and calcium salt
It is by the V in the high chrome alum slag raw material2O5It is 1 with calcium salt molar ratio:1~5 is mixed.
3. a kind of method producing chrome green using tailings in vanadium extraction according to claim 2, which is characterized in that described
It is calcium oxide that chromium type high vanadium slag, which passes through selected calcium salt in calcium salt roasting process, calcium hydroxide, calcium carbonate, one kind in calcium sulfate or
Two or more mixing.
4. a kind of method producing chrome green using tailings in vanadium extraction according to claim 2, which is characterized in that described
V in high chrome alum slag raw material2O5Shared mass fraction is 10%~15%, Cr2O3Shared mass fraction is 5~15%.
5. a kind of method producing chrome green using tailings in vanadium extraction according to claim 1, which is characterized in that step
(1) sodium salt in is the mixing of one or more of sodium carbonate, sodium sulphate, sodium chloride.
6. a kind of method producing chrome green using tailings in vanadium extraction according to claim 1, which is characterized in that step
(1) sodium salt in the mixed material in and Cr in the tailings in vanadium extraction2O3Molar ratio be 4~10：1, to the mixture
Calcination temperature when material is roasted is 700~1000 DEG C, and roasting constant temperature time is 30~180min.
7. a kind of method producing chrome green using tailings in vanadium extraction according to claim 1, which is characterized in that step
(2) clinker water leaching process is roasted described in, is included the following steps：It is 2~20 in mass ratio by water and the roasting clinker：
After 1 is mixed, under 25~100 DEG C of extraction temperature, 120~180min is leached.
8. a kind of method producing chrome green using tailings in vanadium extraction according to claim 1, which is characterized in that will walk
Suddenly after the leached mud in (2) is neutrality with the ph values that deionized water is rinsed to washing lotion, the leached mud after flushing is passed through
It is returned in blast furnace after removing sodium reaction.
9. according to a kind of method producing chrome green using tailings in vanadium extraction of claim 1 to 8 any one of them, feature
It is, to the method that the leachate containing chromium in step (3) carries out precipitate reduction processing, includes the following steps：Contain to described
After reducing agent is added in chromium leachate, then after adjusting the ph values of the leachate containing chromium between 8~9, so that chromium is formed precipitation, wait for
After precipitation is stood, after detaching solid-liquid and being rinsed with water solid phase, after solid phase is dried at a temperature of 800~1200 DEG C, roasting
It burns after 30~300min to get to high-purity chrome green.
10. a kind of method producing chrome green using tailings in vanadium extraction according to claim 9, which is characterized in that institute
State reducing agent be selected as one or both of vulcanized sodium, sodium sulfite, iron sulfite, sodium thiosulfate, sodium pyrosulfite and with
On mixing.
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