CN116814989A - Vanadium-containing leaching solution mediated extraction separation method for vanadium and method for preparing vanadyl sulfate electrolyte - Google Patents
Vanadium-containing leaching solution mediated extraction separation method for vanadium and method for preparing vanadyl sulfate electrolyte Download PDFInfo
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- CN116814989A CN116814989A CN202310783295.3A CN202310783295A CN116814989A CN 116814989 A CN116814989 A CN 116814989A CN 202310783295 A CN202310783295 A CN 202310783295A CN 116814989 A CN116814989 A CN 116814989A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 177
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000000605 extraction Methods 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 80
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 title claims abstract description 65
- 229940041260 vanadyl sulfate Drugs 0.000 title claims abstract description 65
- 229910000352 vanadyl sulfate Inorganic materials 0.000 title claims abstract description 65
- 238000002386 leaching Methods 0.000 title claims abstract description 59
- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- 230000001404 mediated effect Effects 0.000 title claims abstract description 16
- 238000000926 separation method Methods 0.000 title abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012074 organic phase Substances 0.000 claims abstract description 45
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- -1 vanadyl peroxide anions Chemical class 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003350 kerosene Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001172 regenerating effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- XIOKYBMTLNJBFD-UHFFFAOYSA-N OO.[V]=O Chemical compound OO.[V]=O XIOKYBMTLNJBFD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for extracting and separating vanadium and preparing vanadyl sulfate electrolyte by a vanadium-containing leaching solution in a mediated manner, which comprises the following steps: (1) Carrying out reaction treatment on the vanadium-containing leaching solution by hydrogen peroxide to obtain a material containing peroxovanadate; the vanadium-containing leaching solution contains vanadium and metal impurities at the same time; (2) Extracting the material containing the peroxovanadate by an organic extraction system to obtain an organic phase containing the peroxovanadate; (3) And carrying out back extraction on the organic phase containing the peroxovanadate by inorganic acid to obtain a pure vanadium-containing solution. The method is simple and easy to implement, and the vanadyl peroxide anions are obtained through the adjustment of the vanadium occurrence form, so that the extraction and separation of vanadium/metal ion impurities in the solution are realized, and the 3.5-valent vanadyl sulfate electrolyte is directly prepared by taking the acidic vanadium-containing leaching solution as a raw material.
Description
Technical Field
The invention relates to the technical field of vanadium products, in particular to a method for extracting and separating vanadium and preparing vanadyl sulfate electrolyte by using a vanadium-containing leaching solution.
Background
All-vanadium redox flow batteries are one of the research hot spots in the current electrochemical energy storage field. The vanadium electrolyte of the 3.5-valent vanadyl sulfate is an important component of the all-vanadium redox flow battery.
The current preparation method of the 3.5-valent vanadyl sulfate electrolyte mainly comprises a chemical reduction method and an electrochemical reduction method. Both methods need high-purity vanadium pentoxide as raw materials, and the raw materials have high cost, so that the price of the 3.5-valent vanadium electrolyte is high.
In order to reduce the preparation cost of the vanadium electrolyte, researchers propose a solvent extraction method, wherein the method takes a vanadium-containing leaching solution as a raw material, and vanadyl sulfate solution is directly prepared through extraction-back extraction. However, at present, because the components of the vanadium-containing leaching solution are complex, the impurities are more, and particularly, the low-acid vanadium-containing leaching solution system, the impurities and vanadium in the solution are all in the form of cations, wherein the extraction priority of part of the cationic impurities (ferric iron) is higher than that of vanadium, so that great difficulty exists in extracting vanadium through extraction.
CN102683733a discloses a method for preparing vanadyl sulfate electrolyte of an all-vanadium redox flow battery. The method is characterized in that the vanadyl sulfate solution obtained through leaching vanadium slag and stone coal, back extraction and resin resolution is regulated to pH value by using alkali metal or alkaline earth metal oxide or hydroxide, and an inorganic reducing agent is added; p204 or P507, TBP and sulfonated kerosene are used as extractant, multistage countercurrent extraction is carried out, and after two phases are separated, vanadium-carrying organic phase is washed; 2-5-level multistage countercurrent back extraction of vanadium-carrying organic phase with sulfuric acid solution to obtain vanadyl sulfate back extraction liquid; adjusting vanadyl sulfate back-extraction liquid; adding an organic reducing agent to adjust the potential value of the solution, extracting by using the extracting agent, washing a vanadium-carrying organic phase by using a sulfuric acid solution after two-phase separation, and carrying out multistage countercurrent back extraction by using the sulfuric acid solution to obtain an vanadyl sulfate solution; distilling to the required concentration of the vanadium redox flow battery. The method adopts a reduction-extraction-back extraction method to obtain the vanadyl sulfate solution, but the process does not design an impurity separation process, and the purity of the obtained vanadyl sulfate electrolyte is difficult to ensure.
CN113186395a discloses a method for preparing vanadyl sulfate from vanadium-containing solution, which comprises the steps of firstly reducing high-valence vanadium in the solution to obtain tetravalent vanadium solution, then extracting to obtain organic phase containing tetravalent vanadium and impurity ions, then back-extracting to obtain vanadyl sulfate solution, and finally removing iron-chromium impurities in the organic phase through secondary back-extraction. The method prepares and obtains vanadyl sulfate products, but impurities enter an organic phase in the extraction process, and a small amount of impurity ions are inevitably substituted when sulfuric acid is adopted for back extraction, so that the purity of the products is affected. In the process of regenerating the extractant, iron is difficult to remove, and the recycling performance of the extractant is affected.
In view of the foregoing, since the extraction priority of ferric iron in low-acid vanadium-containing leachate is much higher than that of vanadium, there is a need to develop new low-cost methods for separating vanadium from iron in leachate.
Disclosure of Invention
In view of the problems existing in the prior art, the invention establishes a vanadate ion occurrence form adjustment method for realizing effective extraction and separation of vanadium and metal impurities in the leaching solution, and provides theoretical reference for realizing efficient clean preparation of vanadyl sulfate electrolyte. The method comprises the steps of obtaining a solution containing vanadyl peroxide by adjusting the occurrence form of vanadyl peroxide in the solution, thereby realizing the effective separation of vanadium and metal ion impurities in the solution, and preparing the high-purity vanadyl sulfate electrolyte. Compared with the traditional extraction method, the method can directly extract and separate the ferrovanadium directly, and the iron does not enter an organic phase, so that the regeneration difficulty of the extractant is greatly reduced, and iron impurities are prevented from entering the product in the back extraction process.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for the separation of vanadium by vanadium-containing leachate mediated extraction, the method comprising the steps of:
(1) Carrying out reaction treatment on the vanadium-containing leaching solution by hydrogen peroxide to obtain a material containing peroxovanadate; the vanadium-containing leaching solution contains vanadium and metal impurities at the same time;
(2) Extracting the material containing the peroxovanadate by an organic extraction system to obtain an organic phase containing the peroxovanadate;
(3) And carrying out back extraction on the organic phase containing the peroxovanadate by inorganic acid to obtain a pure vanadium-containing solution.
According to the invention, through adding hydrogen peroxide, tetravalent vanadium cations in the solution are converted into pentavalent peroxyvanadate anions which can coexist with impurity cations such as aluminum, iron and the like, an organic extraction system is used for extraction, and inorganic acid is used as a back extraction reagent, so that the extraction separation of vanadium and cationic impurities such as ferric iron and the like in the low-acid vanadium-containing leaching solution can be directly realized, and a high-purity vanadyl sulfate solution product is obtained after back extraction.
Preferably, the mass concentration of the hydrogen peroxide in the step (1) is 5-30%. For example, 5%, 10%, 15%, 20%, 25% or 30% may be used. But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable. When the concentration of hydrogen peroxide is too low, vanadate ions in the solution cannot be effectively converted into peroxovanadate ions. When the concentration of the hydrogen peroxide is too high, the self-decomposition is serious, and the raw material waste is caused, so the concentration of the hydrogen peroxide is selected to be 5-30%.
Preferably, the volume ratio of the hydrogen peroxide to the vanadium-containing leaching solution is 1:300-1:1, for example, 1:300, 1:200, 1:50, 1:20, 1:5, and 1:1, but the hydrogen peroxide to the vanadium-containing leaching solution is not limited to the recited values, and other non-recited values in the numerical range are equally applicable. When the dosage of the hydrogen peroxide is too low, the invention is difficult to play a good oxidation effect.
Preferably, the reaction treatment is carried out with stirring.
The stirring temperature is preferably from room temperature to 80 ℃, and may be, for example, room temperature, 40 ℃, 60 ℃,70 ℃, or 80 ℃, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the stirring time is 0.1 to 6 hours, for example, 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours or 6 hours, but the stirring time is not limited to the listed values, and other non-listed values in the range are equally applicable.
Preferably, the vanadium-containing leaching solution in the step (1) includes any one or at least two of vanadium-containing shale, vanadium slag, vanadium titano-magnetite or vanadium-containing dead catalyst obtained after leaching in acid liquor, wherein typical but non-limiting combinations are combinations of vanadium-containing shale and vanadium titano-magnetite, combinations of vanadium-containing dead catalyst and vanadium slag, and the like, but not limited to the listed combinations, and other non-listed combinations are equally applicable within the scope.
Preferably, the acid solution comprises any one or a combination of at least two of sulfuric acid, hydrochloric acid or hydrofluoric acid, wherein typical but non-limiting combinations are combinations of sulfuric acid and hydrochloric acid, combinations of hydrofluoric acid and hydrochloric acid, combinations of sulfuric acid and hydrofluoric acid.
The vanadium concentration in the vanadium-containing leaching solution is preferably 0.1 to 25g/L, and may be, for example, 0.1g/L, 0.5g/L, 1g/L, 2g/L, 5g/L, 15g/L, 25g/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The pH of the vanadium-containing leaching solution is preferably 0 to 4.0, and may be, for example, 0, 0.2, 0.5, 1.0, 2.0, 3.0 or 4.0, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the concentration of the metal impurities in the vanadium-containing leaching solution is 0.1-10 g/L, for example, but not limited to the listed values, other non-listed values within the range of values are equally applicable, and the concentration may be 0.1g/L, 0.2g/L, 0.5g/L, 1.0g/L, 1.2g/L, 1.5g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L, 5.0g/L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L, or 10g/L, etc.
Preferably, the metallic impurities include any one or a combination of at least two of iron element, aluminum element, calcium element, or nickel element, wherein typical but non-limiting combinations are combinations of iron element and aluminum element, combinations of calcium element and aluminum element, combinations of iron element and nickel element.
Preferably, the vanadium-containing leaching solution also contains sulfate and/or fluoride ions.
Preferably, the organic extraction system in step (2) comprises an extractant, an alcohol and an organic solvent.
Preferably, the organic extraction system comprises 10-20% extractant, 5-10% alcohol, 70-85% organic solvent by volume, for example, 15% extractant, 5% alcohol, 80% organic solvent, 10% extractant, 5% alcohol, 85% organic solvent, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The volume fraction of the extractant may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 18% or 20%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The volume fraction of the alcohol may be, for example, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The volume fraction of the organic solvent may be, for example, 70%, 72%, 75%, 78%, 80%, 82% or 85%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the extractant includes a quaternary ammonium salt type anionic extractant, preferably any one or a combination of at least two of an N263 extractant, an N235 extractant, or an N1923 extractant, wherein typical but non-limiting combinations are combinations of an N263 extractant and an N235 extractant, combinations of an N1923 extractant and an N235 extractant, and the like.
The organic extraction system is preferably adopted to separate cations such as vanadium and iron better, so that the high-purity vanadyl sulfate electrolyte is prepared.
Preferably, the alcohol comprises a long chain alcohol, preferably having a carbon number of C6 to C12, for example, C6, C7, C8, C9, C10, C11 or C12, etc., preferably butanol.
Preferably, the organic solvent comprises sulfonated kerosene.
Preferably, the extraction means in step (2) comprises countercurrent extraction.
The extraction stage number is preferably 1 to 10, and may be, for example, 1, 3, 4, 7 or 10, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the single stage ratio O/a ratio of the extraction is (1:1) - (1:10), for example, 1:1, 1:3, 1:5, 1:8, or 1:10, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the single stage reaction time of the extraction is 1min to 20min, for example, 1min, 5min, 10min, 12min, 15min or 20min, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The reaction temperature of the extraction is preferably from room temperature to 80 ℃, and may be, for example, room temperature, 30 ℃, 35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, or 80 ℃, but is not limited to the values recited, and other values not recited in the range are equally applicable. When the extraction temperature is too high, part of the peroxovanadate is decomposed, resulting in a decrease in extraction rate.
Preferably, the mineral acid in step (3) comprises sulfuric acid.
Preferably, the mass fraction of the sulfuric acid is 5 to 98%, for example, 5%, 10%, 20%, 40%, 80%, 90% or 98%, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The preferred stripping sulfuric acid mass fraction of the invention is in the above range, so that a better stripping effect can be achieved.
Preferably, the vanadium concentration in the organic phase containing peroxyvanadate is 1 to 60g/L, and may be, for example, 1g/L,5g/L,10g/L,20g/L,40g/L or 60g/L, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the back-extraction mode comprises counter-current back-extraction.
Preferably, the single stage ratio O/a of the stripping is (1:1) - (10:1), for example, it may be 1:1, 2:1, 3:1, 4:1, 7:1 or 10:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The temperature of the back extraction is preferably from room temperature to 80 ℃, and may be, for example, room temperature, 30 ℃, 45 ℃, 60 ℃, or 80 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the single stage time of the back extraction is 1 to 30min, for example, 1min, 5min, 8min, 12min, 13min, 15min, 18min, 20min, 22min, 23min, 25min, 28min or 30min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The number of stages of the stripping is preferably 1 to 10, and may be 1, 2, 4, 7 or 10, for example, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the method comprises the steps of:
(1) Mixing vanadium-containing leaching solution with the vanadium concentration of 0.1-25 g/L and the iron concentration of 0.1-10 g/L and the pH value of 0-4.0 with 5-30% hydrogen peroxide according to the volume ratio of 1:300-1:1, and stirring for 0.1-6 h at the temperature of normal temperature-80 ℃ to obtain a material containing peroxovanadate;
(2) Mixing the material containing the peroxovanadate with an organic extraction system which consists of 10-20% of quaternary ammonium salt anion extractant, 5-10% of alcohol and 70-85% of sulfonated kerosene according to the O/A ratio of (1:1) - (1:10), and carrying out single-stage reaction for 1-20 min at the temperature of room temperature to 80 ℃ in a multistage countercurrent extraction mode to obtain an organic phase containing the peroxovanadate, wherein the vanadium concentration of the organic phase is 1-60 g/L;
(3) And (3) carrying out back extraction on the organic phase containing the peroxovanadate with the mass fraction of 5-98% sulfuric acid solution under the conditions that the O/A ratio is (1:1) - (10:1), the temperature is between room temperature and 80 ℃ and the time is between 1 and 30 minutes, wherein the number of stages of the back extraction is between 1 and 10, and obtaining pure vanadium-containing solution after the back extraction.
In a second aspect, the invention provides a method for preparing vanadyl sulfate electrolyte, comprising the method for extracting and separating vanadium from vanadium-containing leaching solution mediated by the first aspect.
Preferably, the method for preparing vanadyl sulfate electrolyte comprises the following steps: the pure vanadium-containing solution is subjected to electrochemical reduction to obtain the high-purity 3.5-valent vanadyl sulfate electrolyte.
Preferably, the concentration of vanadium in the pure vanadium-containing solution is 1 to 90g/L, for example, 1g/L,5g/L,10g/L,20g/L, 50g/L, 80g/L or 90g/L, but the concentration is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the electrochemical reduction is performed by cathodic electrolysis.
The electrochemical reduction temperature is preferably room temperature to 100 ℃, and may be, for example, room temperature, 30 ℃, 50 ℃, 80 ℃, or 100 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the electrochemical reduction time is 1 to 10 hours, for example, 1 hour, 3 hours, 5 hours, 7 hours, 9 hours or 10 hours, but the electrochemical reduction time is not limited to the recited values, and other non-recited values within the range are equally applicable.
The room temperature in the present invention is the ambient temperature without additional heating or cooling, and is generally 25 ℃, and may be changed according to latitude seasons, for example, may be-15 to 42 ℃.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the method for extracting and separating vanadium by the vanadium-containing leaching liquid in a mediated manner, vanadium cations in the solution can be adjusted to be peroxovanadate anions on the premise of not introducing other impurity ions by a clean regulation mode of the occurrence form of vanadium ions;
(2) The method for extracting and separating vanadium by the vanadium-containing leaching solution is a novel process of mediated extraction, can directly realize the direct extraction and separation of cationic impurities such as vanadium, ferric iron and the like from the low-acid vanadium-containing leaching solution, and obtains vanadyl sulfate solution products through back extraction, wherein the purity of the vanadyl sulfate solution is more than or equal to 99.9 percent and the yield is more than or equal to 98.3 percent under the preferable condition;
(3) The method for preparing the vanadyl sulfate electrolyte provided by the invention can prepare the high-purity vanadyl sulfate electrolyte with low cost by taking the vanadium-containing leaching solution as a raw material, and reduces the production cost of the vanadyl sulfate electrolyte.
Drawings
FIG. 1 is a flow chart of a method for preparing vanadyl sulfate electrolyte according to an embodiment of the invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
As a specific embodiment of the present invention, there is provided a method for preparing vanadyl sulfate electrolyte, as shown in fig. 1, comprising the steps of:
(1) Carrying out reaction treatment on the vanadium-containing leaching solution and hydrogen peroxide to obtain a material containing peroxovanadate;
(2) Mixing the material containing the peroxovanadate with an organic extraction system, and carrying out countercurrent extraction to obtain an organic phase containing the peroxovanadate and an extract;
(3) The organic phase containing the peroxovanadate is subjected to back extraction with sulfuric acid to obtain pure vanadium-containing solution and a back extraction organic phase, and the back extraction organic phase is regenerated to obtain an organic extraction system which is recycled to the step (2);
(4) The pure vanadium-containing solution is subjected to electrochemical reduction to obtain the high-purity 3.5-valent vanadyl sulfate electrolyte.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
It should be understood that the process provided by the embodiments of the present invention or the replacement or variation of conventional data is within the scope of the present invention and the disclosure.
Example 1
The embodiment provides a method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which specifically comprises the following steps:
(1) Mixing vanadium-containing leaching solution with vanadium concentration of 1.5g/L and iron concentration of 1.0g/L and pH=1.5 with 20% hydrogen peroxide in a volume ratio of 20:1, and stirring at 40 ℃ for 2h to perform reaction treatment to obtain yellow transparent clear solution (namely material containing peroxovanadate);
(2) Mixing the material containing the peroxovanadate with an organic extraction system (extractant N263: N-octanol: sulfonated kerosene=20:10:70), and carrying out 3-level countercurrent extraction at the O/A ratio of 1:3 and 50 ℃ for 10min to obtain an organic phase containing the peroxovanadate, wherein the concentration of vanadium element is 10.8 g/L;
(3) Mixing the organic phase containing the peroxovanadate with sulfuric acid with the mass fraction of 20%, carrying out 2-stage countercurrent stripping with the O/A ratio of 2:1 and the temperature of 40 ℃, wherein the single-stage stripping time is 20min, obtaining pure vanadium-containing solution with the vanadium concentration of 41.7g/L, and simultaneously, regenerating the obtained stripping organic phase and returning to the extraction process in the step (2).
The embodiment also provides a method for preparing the vanadyl sulfate electrolyte, which is to prepare the vanadyl sulfate electrolyte product by performing cathode electrolytic reduction on the pure vanadyl sulfate solution at 40 ℃ for 6 hours.
Example 2
The embodiment provides a method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which specifically comprises the following steps:
(1) Mixing vanadium-containing leaching solution with the vanadium element concentration of 1.0g/L and the iron element concentration of 0.5g/L and the pH=2 with 30% of hydrogen peroxide in a volume ratio of 100:1, and stirring for 1h at 50 ℃ to perform reaction treatment to obtain yellow transparent clear solution (namely the material containing peroxovanadium acid radical);
(2) Mixing the material containing the peroxovanadate with an organic extraction system (extractant N263: N-octanol: sulfonated kerosene=15:5:80), and carrying out 2-level countercurrent extraction at the O/A ratio of 1:6 and 50 ℃ for 20min to obtain an organic phase containing the peroxovanadate, wherein the concentration of vanadium element is 11.8 g/L;
(3) Mixing the organic phase containing the peroxovanadate with sulfuric acid with the mass fraction of 30%, carrying out 6-level countercurrent stripping with the O/A ratio of 1:1 and the temperature of 40 ℃, wherein the single-level stripping time is 15min, obtaining pure vanadium-containing solution with the vanadium concentration of 69.7g/L, and simultaneously, regenerating the obtained stripping organic phase and returning to the extraction process in the step (2).
The embodiment also provides a method for preparing vanadyl sulfate electrolyte, which is to prepare a 3.5-valence vanadium electrolyte product by performing cathode electrolytic reduction on the pure vanadium-containing solution at 60 ℃ for 8 hours.
Example 3
The embodiment provides a method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which specifically comprises the following steps:
(1) Mixing low-acid vanadium-containing leaching solution with vanadium element concentration of 6.0g/L and iron element concentration of 8.0g/L and pH=3.4 with 30% of hydrogen peroxide in a volume ratio of 100:1, and stirring at 60 ℃ for 2 hours to obtain yellow transparent clear solution (namely the material containing peroxovanadate);
(2) Mixing the material containing the peroxovanadate with an organic extraction system (extractant N263: isooctanol: sulfonated kerosene=10:10:80), and carrying out 2-level countercurrent extraction at the O/A ratio of 1:1 and 40 ℃ for 20min to obtain an organic phase containing the peroxovanadate, wherein the concentration of vanadium element is 11.5 g/L;
(3) Mixing the organic phase containing the peroxovanadate with sulfuric acid with the mass fraction of 50%, carrying out 1-stage countercurrent stripping with the O/A ratio of 3:1 and the temperature of 60 ℃, wherein the single-stage stripping time is 10min, obtaining pure vanadium-containing solution with the vanadium concentration of 32.76g/L, and simultaneously, regenerating the obtained stripping organic phase and returning to the extraction process in the step (2).
The embodiment also provides a method for preparing vanadyl sulfate electrolyte, which is to prepare a 3.5-valence vanadium electrolyte product by performing cathodic electrolytic reduction on the pure vanadium-containing solution at 50 ℃ for 2 hours.
Example 4
The embodiment provides a method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which specifically comprises the following steps:
(1) Mixing vanadium-containing leaching solution with vanadium concentration of 20g/L and iron concentration of 0.1g/L and pH=2.1 with 5% mass fraction hydrogen peroxide according to a volume ratio of 1:1, stirring at 50 ℃ for 6 hours for reaction treatment to obtain yellow transparent clear solution (namely material containing peroxovanadate);
(2) Mixing the material containing the peroxovanadate with an organic extraction system (extractant N263: N-octanol: sulfonated kerosene=17:8:75), and carrying out 1-level countercurrent extraction at the O/A ratio of 1:1 and 50 ℃ for 10min to obtain an organic phase containing the peroxovanadate, wherein the concentration of vanadium element is 19.3 g/L;
(3) Mixing the organic phase containing the peroxovanadate with 70% of sulfuric acid by mass fraction, carrying out 1-stage countercurrent stripping at the temperature of 50 ℃ and the O/A ratio of 3:1, wherein the single-stage stripping time is 20min, obtaining pure vanadium-containing solution with the vanadium concentration of 57.7g/L, and simultaneously, regenerating the obtained stripping organic phase and returning to the extraction process in the step (2).
The embodiment also provides a method for preparing vanadyl sulfate electrolyte, which is to prepare a 3.5-valence vanadium electrolyte product by performing cathodic electrolytic reduction on the pure vanadium-containing solution at 90 ℃ for 2 hours.
Example 5
The embodiment provides a method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which specifically comprises the following steps:
(1) Mixing vanadium-containing leaching solution with vanadium concentration of 3.2g/L and iron concentration of 10.0g/L and pH=0 with 30% hydrogen peroxide in a volume ratio of 60:1, stirring at 80 ℃ for 10min for reaction treatment to obtain yellow transparent clear solution (namely material containing peroxovanadate);
(2) Mixing the material containing the peroxovanadate with an organic extraction system (extractant N263: isooctanol: sulfonated kerosene=16:8:76), and carrying out 2-level countercurrent extraction at the O/A ratio of 1:10 and 50 ℃ for 1min to obtain an organic phase containing the peroxovanadate, wherein the concentration of vanadium element is 42.8 g/L;
(3) Mixing the organic phase containing the peroxovanadate with sulfuric acid with the mass fraction of 9%, carrying out 1-stage countercurrent stripping with the O/A ratio of 3:1 and the temperature of 40 ℃, wherein the single-stage stripping time is 1min, obtaining pure vanadium-containing solution with the vanadium concentration of 69.7g/L, and simultaneously, regenerating the obtained stripping organic phase and returning to the extraction process in the step (2).
The embodiment also provides a method for preparing the vanadyl sulfate electrolyte, which is to prepare the vanadyl sulfate electrolyte product by performing cathodic electrolytic reduction on the pure vanadium-containing solution for 1h at room temperature.
Example 6
The embodiment provides a method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which specifically comprises the following steps:
(1) Mixing vanadium-containing leaching solution with vanadium element concentration of 6.3g/L and iron element concentration of 0.9g/L and pH=4.0 with 5% of hydrogen peroxide in a volume ratio of 300:1, and stirring at 60 ℃ for 3 hours to perform reaction treatment to obtain yellow transparent clear solution (namely the material containing peroxovanadate);
(2) Mixing the material containing the peroxovanadate with an organic extraction system (extractant N263: N-octanol: sulfonated kerosene=20:5:75), and carrying out 4-level countercurrent extraction under the condition of O/A ratio of 1:2 and room temperature, wherein the single-stage extraction reaction time is 20min, so as to obtain an organic phase containing the peroxovanadate, wherein the concentration of vanadium element is 46.8 g/L;
(3) Mixing the organic phase containing the peroxovanadate with 70% of sulfuric acid by mass fraction, carrying out 1-stage countercurrent stripping at the temperature of 80 ℃ and the O/A ratio of 1:1, wherein the single-stage stripping time is 15min, obtaining pure vanadium-containing solution with the vanadium concentration of 43.7g/L, and simultaneously, regenerating the obtained stripping organic phase and returning to the extraction process in the step (2).
The embodiment also provides a method for preparing the vanadyl sulfate electrolyte, which is to prepare the vanadyl sulfate electrolyte product by performing cathodic electrolytic reduction on the pure vanadium-containing solution at 60 ℃ for 2 hours.
Example 7
The same procedure as in example 1 was followed except that the concentration of hydrogen peroxide added was 3%.
Example 8
The same procedure as in example 1 was followed except that the concentration of hydrogen peroxide added was 40%.
Example 9
The same procedure as in example 1 was followed except that the volume ratio of hydrogen peroxide to the leachate was 2:1.
Example 10
The same procedure as in example 1 was followed except that the volume ratio of hydrogen peroxide to the leachate was 1:400.
Example 11
The same procedure as in example 1 was followed except that the extractant composition was 5% N263 extractant, 10% n-octanol, 85% sulfonated kerosene.
Example 12
The same procedure as in example 1 was followed except that the extractant composition was 25% N263, 10% n-octanol, 65% sulfonated kerosene.
Example 13
The same procedure as in example 1 was followed except that the extractant composition was 20% n263,2% n-octanol, 78% sulfonated kerosene.
Example 14
The same procedure as in example 1 was followed except that the extractant composition was 20% n263, 12% n-octanol, 68% sulfonated kerosene.
Example 15
The same procedure as in example 1 was followed except that the sulfuric acid mass fraction in the stripping was 3%.
Example 16
The same procedure as in example 1 was followed except that the temperature of the stripping was 90 ℃.
Example 17
The same procedure as in example 1 was followed except that the extractant N263 was replaced with P204.
Example 18
The same procedure as in example 1 was followed except that the extractant N263 was replaced with TBP.
Comparative example 1
The same procedure as in example 1 was followed except that step (1) was not performed, and the vanadium-containing leachate was directly subjected to mixed extraction with an organic extraction system.
In the comparative example, vanadium in the solution is cationic, and the quaternary ammonium salt anion extractant cannot be used for extraction at all, so that the effect of separating and preparing the high-purity vanadyl sulfate electrolyte cannot be achieved.
Comparative example 2
The same method as that for preparing vanadyl sulfate electrolyte in example 1 is different in that hydrogen peroxide is replaced with ozone for reaction treatment in step (1).
In the comparative example, vanadium-iron separation cannot be realized because the pentavalent vanadium anions generated after oxidation and iron in the solution form precipitates.
Comparative example 3
The same procedure as in example 1 was followed except that the extraction was not carried out in step (2) but the separation was carried out by chemical precipitation.
This comparative example is difficult to separate by chemical precipitation due to the extremely poor stability of the peroxovanadate anion itself.
Comparative example 4
The same method as in example 1 for preparing vanadyl sulfate electrolyte is different in that step (1) is not performed, and sodium hydroxide is added to adjust the pH of the vanadium-containing leaching solution to be alkaline to convert vanadium cations into vanadate, and the specific steps are as follows: mixing the vanadium-containing leaching solution and 20% sodium hydroxide by mass, mixing according to a volume ratio of 20:1, stirring at 40 ℃ for 2 hours to perform reaction treatment, and performing the subsequent step (2).
In the comparative example, when the pH of the solution is adjusted to be alkaline, after vanadate is converted into precipitate, cationic impurities such as iron and the like are also converted into precipitate and mixed with vanadium precipitate, so that separation cannot be achieved.
The concentration of each element in the solution is quantitatively determined and analyzed by ICP-OES, and the purity calculating method comprises the following steps: target element purity in solution = target element concentration/total concentration of all metallic elements. The product yield calculation method comprises the following steps: product yield = target element concentration in strip liquor/target element concentration in stock liquor.
Purity and yield were obtained according to the above test methods and calculation formulas, and the yield and purity of vanadyl sulfate solution products prepared in the above examples are shown in table 1.
TABLE 1
In table 1 "-" indicates that the detection limit is not exceeded.
From the data in table 1 we can see:
(1) According to the results of examples 1-6, the invention adjusts the occurrence form of vanadium in the solution by adopting hydrogen peroxide to obtain the vanadyl sulfate anion solution, then adopts the anion extractant to extract-sulfuric acid to carry out back extraction to obtain the vanadyl sulfate solution, and finally obtains the high-purity 3.5-valent vanadyl sulfate electrolyte product through cathodic reduction, thereby realizing the high-efficiency separation of vanadium and impurity ions in the leaching solution and the high-efficiency clean preparation of the vanadyl sulfate electrolyte.
(2) As can be seen from the combination of examples 1 and 7 to 10, when the amount of hydrogen peroxide is insufficient, VO in the solution cannot be dissolved 2+ The ions are fully converted into peroxovanadate, so that the concentration of vanadium in an organic phase obtained by extraction is reduced, and the concentration of vanadium in a vanadyl sulfate electrolyte product is reduced, but the valence state of the product and impurities are not influenced. When the concentration of the added hydrogen peroxide is excessive, the method has no influence on the vanadyl sulfate electrolyte product, but the material waste is more.
(3) It can be seen from the combination of examples 1 and 11 to 14 that when the volume ratio of N263 is too low and the volume content of alcohol is too high, sufficient extraction of vanadium in the aqueous phase cannot be achieved, resulting in a decrease in the vanadium concentration in the product. When the volume content is too low, the aqueous phase is emulsified, and effective phase separation extraction cannot be achieved. (4) It can be seen from the comprehensive examples 1 and 15-16 that the too low mass fraction of sulfuric acid during back extraction can affect the back extraction effect, resulting in the decrease of the vanadium concentration in the vanadyl sulfate electrolyte product. When the back extraction temperature is too high, part of the generated precipitate is mixed with an organic phase and is difficult to separate, so that the concentration of vanadium in the vanadyl sulfate electrolyte in the product is reduced. (5) As can be seen from the combination of examples 1 and examples 17 to 18, the present invention preferably uses N263 as the extractant, and has a better extraction effect.
In summary, the invention provides a method for preparing high-purity vanadyl sulfate electrolyte by low-acid vanadyl sulfate-containing leaching solution mediated extraction, which is used for realizing the extraction and separation of vanadium/metal ion impurities (including aluminum, calcium, ferric iron and the like) in solution by adjusting the vanadium occurrence form, and directly preparing 3.5-valent vanadyl sulfate electrolyte by taking acid vanadyl sulfate-containing leaching solution as a raw material, so that the purposes of clean production and recycling are achieved in the whole process, and the method is suitable for industrial production.
The foregoing is merely a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed herein fall within the protection scope and the disclosure scope of the present invention.
Claims (10)
1. A method for extracting and separating vanadium from vanadium-containing leaching liquid in a mediated manner, which is characterized by comprising the following steps:
(1) Carrying out reaction treatment on the vanadium-containing leaching solution by hydrogen peroxide to obtain a material containing peroxovanadate; the vanadium-containing leaching solution contains vanadium and metal impurities at the same time;
(2) Extracting the material containing the peroxovanadate by an organic extraction system to obtain an organic phase containing the peroxovanadate;
(3) And carrying out back extraction on the organic phase containing the peroxovanadate by inorganic acid to obtain a pure vanadium-containing solution.
2. The method according to claim 1, wherein the mass concentration of the hydrogen peroxide in the step (1) is 5-30%.
Preferably, the volume ratio of the hydrogen peroxide to the vanadium-containing leaching solution is 1:300-1:1.
3. The method according to claim 1 or 2, wherein the vanadium-containing leaching solution in step (1) comprises any one or a combination of at least two of vanadium-containing shale, vanadium slag, vanadium titano-magnetite or vanadium-containing spent catalyst obtained after leaching in acid liquor;
preferably, the acid solution comprises any one or a combination of at least two of sulfuric acid, hydrochloric acid or hydrofluoric acid;
preferably, the concentration of vanadium in the vanadium-containing leaching solution is 0.1-25 g/L;
preferably, the pH of the vanadium-containing leaching solution is 0-4.0;
preferably, the concentration of metal impurities in the vanadium-containing leaching solution is 0.1-10 g/L;
preferably, the metal impurities include any one or a combination of at least two of iron element, aluminum element, calcium element, or nickel element;
preferably, the vanadium-containing leaching solution also contains sulfate and/or fluoride ions.
4. A process according to any one of claims 1 to 3, wherein the organic extraction system in step (2) comprises an extractant, an alcohol and an organic solvent;
preferably, the organic extraction system comprises 10-20% of extractant, 5-10% of alcohol and 70-85% of organic solvent by volume;
preferably, the extractant comprises a quaternary ammonium salt type anionic extractant, preferably any one or a combination of at least two of an N263 extractant, an N235 extractant, or an N1923 extractant;
preferably, the alcohol comprises a long chain alcohol, preferably having a carbon number of from C6 to C12, preferably butanol;
preferably, the organic solvent comprises sulfonated kerosene.
5. The process according to any one of claims 1 to 4, wherein the extraction means in step (2) comprises countercurrent extraction;
preferably, the extraction stage number is 1-10;
preferably, the single stage ratio O/a ratio of the extraction is (1:1) - (1:10).
6. The method of claim 1, wherein the mineral acid in step (3) comprises sulfuric acid;
preferably, the mass fraction of the sulfuric acid is 5-98%;
preferably, the vanadium concentration in the organic phase containing the peroxyvanadate is 1-60 g/L;
preferably, the single stage ratio O/A of the back extraction is (1:1) - (10:1).
7. The method according to claim 1, characterized in that it comprises the steps of:
(1) Mixing vanadium-containing leaching solution with the vanadium concentration of 0.1-25 g/L and the iron concentration of 0.1-10 g/L and the pH value of 0-4.0 with 5-30% hydrogen peroxide according to the volume ratio of 1:300-1:1, and stirring for 0.1-6 h at the temperature of normal temperature-80 ℃ to obtain a material containing peroxovanadate;
(2) Mixing the material containing the peroxovanadate with an organic extraction system which consists of 10-20% of quaternary ammonium salt anion extractant, 5-10% of alcohol and 70-85% of sulfonated kerosene according to the O/A ratio of (1:1) - (1:10), and carrying out single-stage reaction for 1-20 min at the temperature of room temperature to 80 ℃ in a multistage countercurrent extraction mode to obtain an organic phase containing the peroxovanadate, wherein the vanadium concentration of the organic phase is 1-60 g/L;
(3) And (3) carrying out back extraction on the organic phase containing the peroxovanadate with the mass fraction of 5-98% sulfuric acid solution under the conditions that the O/A ratio is (1:1) - (10:1), the temperature is between room temperature and 80 ℃ and the time is between 1 and 30 minutes, wherein the number of stages of the back extraction is between 1 and 10, and obtaining pure vanadium-containing solution after the back extraction.
8. A method for preparing vanadyl sulfate electrolyte, characterized in that the method for preparing vanadyl sulfate electrolyte comprises the method for extracting and separating vanadium by the vanadium-containing leaching solution mediated extraction according to any one of claims 1 to 7.
9. The method for preparing vanadyl sulfate electrolyte of claim, wherein the method for preparing vanadyl sulfate electrolyte comprises: the pure vanadium-containing solution is subjected to electrochemical reduction to obtain the high-purity 3.5-valent vanadyl sulfate electrolyte.
10. The method for preparing vanadyl sulfate electrolyte according to claim 8, wherein the concentration of vanadium in the pure vanadium-containing solution is 1-90 g/L;
preferably, the electrochemical reduction is cathodic electrolytic reduction;
preferably, the temperature of the electrochemical reduction is room temperature to 100 ℃;
preferably, the electrochemical reduction time is 1 to 10 hours.
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