CN109292818A - Failure electrolyte prepares high-purity V2O5Method - Google Patents
Failure electrolyte prepares high-purity V2O5Method Download PDFInfo
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- CN109292818A CN109292818A CN201811260963.XA CN201811260963A CN109292818A CN 109292818 A CN109292818 A CN 109292818A CN 201811260963 A CN201811260963 A CN 201811260963A CN 109292818 A CN109292818 A CN 109292818A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/008—Disposal or recycling of fuel cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention relates to failure electrolyte to prepare high-purity V2O5Method, belong to vanadium battery field.Present invention solves the technical problem that be fail electrolyte recovery efficiency it is not high.The invention discloses failure electrolyte to prepare high-purity V2O5Method the vanadium ion of lower valency is oxidized to using the electrolyte of vanadium redox battery that fails as raw material by 5 valence vanadium ions using oxidant, then vanadium ion hydrolytic precipitation is made by heating, calcines sediment after filtering, high-purity V is prepared2O5.The present invention can effectively realize the recycling of vanadium in failure electrolyte, and vanadium recovery is high, recycle the V being prepared through the invention2O5Purity is high can be applied to prepare electrolyte of vanadium redox battery and catalyst material.
Description
Technical field
The invention belongs to vanadium battery fields, and in particular to failure electrolyte prepares high-purity V2O5Method.
Background technique
All-vanadium flow battery energy storage device due to the service life it is long, at low cost, high-efficient, easy to maintain the features such as, and support function
The extension of rate and stored energy capacitance.All-vanadium flow battery can be applied to the links of power supply, and renewable energy is supplied
Answer quotient, power grid enterprises and terminal user especially effective, main operating mode is fixed.In addition, all-vanadium flow battery energy storage system
It unites environmentally friendly, it is minimum to the influence of environment in all energy storage technologies.The main application fields of all-vanadium flow battery include:
(1) electric system guarantees the safety of operation of power networks and reliable, it may also be used for " peak load shifting "；(2) distributed generation system is made
For the energy storage device of electric energy, guarantee distributed power station stable power-supplying, improve the reliability of power generation, realizes distributed generation grid-connected；
(3) renewable energy (such as wind energy, solar energy) electrification energy storage system mentions for the stability of renewable energy power generation
For ensureing；(4) backup power source of important organ, department, uninterruptible power supply etc..
For the electrolyte of cell active materials, anode electrolyte by tetravalence and pentavalent vanadium ion and sulfuric acid mixing
Solution composition, electrolyte liquid are made of divalent and the mixed solution of trivalent vanadium ion and sulfuric acid；After battery charging, positive electrode material
For pentavalent vanadium ion sulfuric acid solution, cathode is divalent vanadium ion sulfuric acid solution；After battery discharge, positive and negative anodes are respectively tetravalence and three
Valence vanadium ion sulfuric acid solution.Vanadium cell, due to the presence of vanadium ion migration and water migration, causes positive and negative anodes in charge and discharge process
Electrolyte valence state mismatches and concentration mismatches, and leads to capacity attenuation, and energy efficiency reduces, and reduces the fortune of vanadium energy storage system
Line efficiency is unable to satisfy the demand of energy storage, it is therefore desirable to carry out recycling and reusing to electrolyte.Further, since vanadium cell is electrolysed
Liquid is strongly acidic solution, can will be miscellaneous in the pipeline being in contact with it, fluid reservoir, electrode etc. in vanadium cell During Process of Long-term Operation
Prime element dissolution, enrichment in the electrolytic solution, keep part of impurity elements exceeded, such as P, Si, Fe, K, Na, close to electrode, diaphragm etc.
Key material has negative impact, reduces the efficiency of vanadium energy storage system, it is therefore desirable to carry out recycling and reusing to electrolyte.
Patent document CN106395902A discloses a kind of five oxidation two of anode electrolyte of vanadium battery preparation using failure
The method of vanadium, by the anode electrolyte of vanadium battery of failure be passed through vanadium cell anode carry out charging pre-oxidation obtain pentavalent vanadium ion electricity
Liquid is solved, is concentrated by evaporation, filtered grinding and obtain V2O5Powder.Patent document CN102983379A discloses the vanadium electricity using failure
The method that vanadic anhydride is produced with electrolyte in pond, first energization pond is charged, and the vanadium ion of lower valency is oxidized to 5 valences, then adjust
The pH of solution can prepare the V of purity 98% using ammonium salt as precipitating reagent precipitation after calcining2O5.The recovery method of above-mentioned electrolyte
Be that anode is oxidized to 5 valences when charging by vanadium cell, to be recycled, for only failure anode electrolyte,
Partial electrolyte liquid can only thus be recycled, in addition, i.e. anode electrolyte reaches 5 valences when the state-of-charge that charges is high, 5 valence vanadium from
Irreversible hydrolysis can occur for son, can block pile.
Summary of the invention
Present invention solves the technical problem that being not high for the recovery efficiency for the electrolyte that fails in the prior art.
Technical proposal that the invention solves the above-mentioned problems is to provide failure electrolyte and prepares high-purity V2O5Method, with failure
Electrolyte of vanadium redox battery is raw material, and the vanadium ion of lower valency is oxidized to 5 valence vanadium ions using oxidant, then by heating make vanadium from
Sub- hydrolytic precipitation calcines sediment after filtering, and high-purity V is prepared2O5。
Wherein, vanadium ion concentration is 81.6~153g/L, V in failure electrolyte3+With V4+Concentration ratio be 0.2~0.8,
Sulfate concentration is 384~441g/L.
Wherein, oxidant is (NH4)2S2O8。
Wherein, (NH4)2S2O8Additional amount is measured according to chemical reaction than excessive by 10%~20%, and the reaction time is 1~2h.
Wherein, hydrolysis temperature is 90~100 DEG C, and the time is 0.5~2h.
Wherein, calcination temperature is 550~580 DEG C, 1~2h of time.
Beneficial effects of the present invention:
The present invention is logical to be added in enter the mode of oxidant in failure electrolyte and can effectively realize returning for vanadium in failure electrolyte
It receives, vanadium recovery is high；V is prepared in recycling through the invention2O5Purity is high can be applied to prepare electrolyte of vanadium redox battery and catalysis
Agent material；Present invention process is simple, and production procedure is short, is suitable for prepare with scale.
Specific embodiment
The present invention provides failure electrolyte and prepares high-purity V2O5Method, specially using the electrolyte of vanadium redox battery that fails as raw material,
The vanadium ion of lower valency is oxidized to by 5 valence vanadium ions using oxidant, then vanadium ion hydrolytic precipitation is made by heating, is forged after filtering
Sediment is burnt, high-purity V is prepared2O5。
Specifically, can follow the steps below:
(1) the vanadium cell positive and negative anodes electrolyte of failure is mixed, measures a certain amount of volume, filtered, removed solid and suspend
Object and insoluble matter；
(2) oxidant is added into step (1) solution under stirring condition, by the vanadium ion of lower valency be oxidized to pentavalent vanadium from
Son；
(3) the pentavalent vanadium solution heating of step (2) is boiled, makes vanadium ion hydrolytic precipitation；
(4) step (3) sediment is filtered, is calcined after sediment washing, drying, obtains high-purity V2O5；
Wherein, vanadium ion concentration is 81.6~153g/L, V in failure electrolyte3+With V4+Concentration ratio be 0.2~0.8,
Sulfate concentration is 384~441g/L.
Wherein, oxidant is (NH4)2S2O8.High-purity V is obtained since the present invention wishes to recycle2O5, so introducing oxidant
Shi Buneng introduces impurity element, so the present invention preferably (NH4)2S2O8As oxidant, wherein ammonium ion is in subsequent calcination
When can remove.
Wherein, (NH4)2S2O8Additional amount according to following chemical reaction measure ratio and it is excessive 10%~20% calculate, react
Time is 1~2h.(NH4)2S2O8As oxidant, react as follows with what failure electrolyte of vanadium redox battery occurred:
S2O8 2-+V3++2H2O→2SO4 2-+VO2 ++4H+
S2O8 2-+2VO2++2H2O→2SO4 2-+2VO2 ++4H+
Wherein, hydrolysis temperature is 90~100 DEG C, and the time is 0.5~2h.
Wherein, calcination temperature is 550~580 DEG C, 1~2h of time.
By the following examples to the present invention the present invention will be further explained explanation.
Embodiment 1
Measuring 2L vanadium ion concentration is 81.6g/L, V3+/V4+=0.5 electrolyte, filtering remove solid suspension and not
Molten object；534g (NH is added4)2S2O8, the vanadium ion of lower valency is oxidized to pentavalent vanadium ion, it is molten to obtain pentavalent vanadium by reaction time 1h
Liquid；Pentavalent vanadium solution is heated to 90 DEG C, time 1h makes vanadium ion hydrolytic precipitation；Sediment is washed, it is dry after, at 550 DEG C
Lower calcining 2h, obtains high-purity V2O5, vanadium yield 80.97%, high-purity V2O5Middle impurity content K=0.004%, Na=
0.003%, Ca=0.005%, Cr=0.002%, Fe=0.005%, Si=0.005%, other impurities constituent content≤
0.002%.
Embodiment 2
Measuring 2L vanadium ion concentration is 85g/L, V3+/V4+=0.4 electrolyte, filtering remove solid suspension and insoluble
Object；582g (NH is added4)2S2O8, the vanadium ion of lower valency is oxidized to pentavalent vanadium ion, it is molten to obtain pentavalent vanadium by reaction time 1h
Liquid；Pentavalent vanadium solution is heated to 95 DEG C, time 2h makes vanadium ion hydrolytic precipitation；Sediment is washed, it is dry after, at 550 DEG C
Lower calcining 2h, obtains high-purity V2O5, vanadium yield 82.15%, high-purity V2O5Middle impurity content K=0.005%, Na=
0.005%, Ca=0.005%, Cr=0.002%, Fe=0.005%, Si=0.005%, other impurities constituent content≤
0.002%.
Embodiment 3
Measuring 2L vanadium ion concentration is 86.7g/L, V3+/V4+=0.2 electrolyte, filtering remove solid suspension and not
Molten object；558g (NH is added4)2S2O8, the vanadium ion of lower valency is oxidized to pentavalent vanadium ion, it is molten to obtain pentavalent vanadium by reaction time 1h
Liquid；Pentavalent vanadium solution is heated to 95 DEG C, time 2h makes vanadium ion hydrolytic precipitation；Sediment is washed, it is dry after, at 580 DEG C
Lower calcining 2h, obtains high-purity V2O5, vanadium yield 83.65%, high-purity V2O5Middle impurity content K=0.005%, Na=
0.005%, Ca=0.005%, Cr=0.002%, Fe=0.005%, Si=0.005%, other impurities constituent content≤
0.002%.
Claims (6)
1. failure electrolyte prepares high-purity V2O5Method, it is characterised in that: using the electrolyte of vanadium redox battery that fails as raw material, using oxygen
The vanadium ion of lower valency is oxidized to 5 valence vanadium ions by agent, then makes vanadium ion hydrolytic precipitation by heating, and precipitating is calcined after filtering
High-purity V is prepared in object2O5。
2. failure electrolyte according to claim 1 prepares high-purity V2O5Method, it is characterised in that: failure electrolysis
Vanadium ion concentration is 81.6~153g/L, V in liquid3+With V4+Concentration ratio be 0.2~0.8, sulfate concentration be 384~441g/
L。
3. failure electrolyte according to claim 1 or 2 prepares high-purity V2O5Method, it is characterised in that: the oxidant
For (NH4)2S2O8。
4. failure electrolyte according to claim 3 prepares high-purity V2O5Method, it is characterised in that: (the NH4)2S2O8
Additional amount according to chemical reaction metering ratio and it is excessive by 10%~20%, the reaction time be 1~2h.
5. failure electrolyte according to any one of claims 1 to 4 prepares high-purity V2O5Method, it is characterised in that: it is described
Hydrolysis temperature is 90~100 DEG C, and the time is 0.5~2h.
6. described in any item failure electrolyte prepare high-purity V according to claim 1~52O5Method, it is characterised in that: it is described
Calcination temperature is 550~580 DEG C, and the time is 1~2h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811260963.XA CN109292818A (en) | 2018-10-26 | 2018-10-26 | Failure electrolyte prepares high-purity V2O5Method |
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|---|---|---|---|
| CN201811260963.XA CN109292818A (en) | 2018-10-26 | 2018-10-26 | Failure electrolyte prepares high-purity V2O5Method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110994061A (en) * | 2019-10-29 | 2020-04-10 | 大连博融新材料有限公司 | Method for recovering vanadium electrolyte |
| CN111020231A (en) * | 2019-12-04 | 2020-04-17 | 杨秋良 | Method for precipitating vanadium from sodium vanadium-rich liquid without ammonia |
| CN111484076A (en) * | 2020-04-22 | 2020-08-04 | 承德新新钒钛储能科技有限公司 | Method for recovering high-purity vanadium from failure vanadium electrolyte |
| CN112551581A (en) * | 2020-11-30 | 2021-03-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium pentoxide by recovering electrolyte of failed vanadium battery |
| FR3138739A1 (en) * | 2022-08-08 | 2024-02-09 | Kemiwatt | Process for recycling aqueous electrolyte based on quinone compounds from flow redox batteries |
| FR3138740A1 (en) * | 2022-08-08 | 2024-02-09 | Kemiwatt | Process for recycling aqueous posolyte from flow redox battery |
-
2018
- 2018-10-26 CN CN201811260963.XA patent/CN109292818A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110994061A (en) * | 2019-10-29 | 2020-04-10 | 大连博融新材料有限公司 | Method for recovering vanadium electrolyte |
| CN111020231A (en) * | 2019-12-04 | 2020-04-17 | 杨秋良 | Method for precipitating vanadium from sodium vanadium-rich liquid without ammonia |
| CN111484076A (en) * | 2020-04-22 | 2020-08-04 | 承德新新钒钛储能科技有限公司 | Method for recovering high-purity vanadium from failure vanadium electrolyte |
| CN112551581A (en) * | 2020-11-30 | 2021-03-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium pentoxide by recovering electrolyte of failed vanadium battery |
| FR3138739A1 (en) * | 2022-08-08 | 2024-02-09 | Kemiwatt | Process for recycling aqueous electrolyte based on quinone compounds from flow redox batteries |
| FR3138740A1 (en) * | 2022-08-08 | 2024-02-09 | Kemiwatt | Process for recycling aqueous posolyte from flow redox battery |
| WO2024033305A1 (en) * | 2022-08-08 | 2024-02-15 | Kemiwatt | Method for recycling aqueous posolyte of a redox flow battery |
| WO2024033328A1 (en) * | 2022-08-08 | 2024-02-15 | Kemiwatt | Method for recycling aqueous electrolyte based on quinone compounds of a redox flow battery |
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Application publication date: 20190201 |
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