CN104064795A - Preparation method of high-purity vanadyl sulfate electrolyte - Google Patents
Preparation method of high-purity vanadyl sulfate electrolyte Download PDFInfo
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- CN104064795A CN104064795A CN201410265280.9A CN201410265280A CN104064795A CN 104064795 A CN104064795 A CN 104064795A CN 201410265280 A CN201410265280 A CN 201410265280A CN 104064795 A CN104064795 A CN 104064795A
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- vanadic sulfate
- electrolyte
- vanadyl sulfate
- solution
- vanadium
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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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a preparation method of high-purity vanadyl sulfate electrolyte. The preparation method of the high-purity vanadyl sulfate electrolyte comprises the steps of extracting a vanadyl sulfate solution, inorganically reducing the vanadyl sulfate solution, preparing a mixed extracting agent, performing reverse extraction on vanadyl sulfate, organically reducing a vanadyl sulfate reverse extracting solution, concentrating a vanadyl sulfate electrolyte precursor and the like, so that the high-purity vanadyl sulfate electrolyte is prepared. The preparation method of the high-purity vanadyl sulfate electrolyte is simple in technology and low in cost, and is widely applied to large-scale production of the vanadyl sulfate electrolyte for an all-vanadium battery.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity sulfuric acid vanadyl electrolyte.
Background technology
Vanadium redox battery (VRB) is a kind of outstanding energy storage device.This battery capacity depends on amount and the vanadium ion concentration of electrolyte, and electrolyte can be separated with battery, and battery life is long, and reliability is high, can fast charging and discharging.At aspects such as photovoltaic generation, wind power generation, peak load shiftings, have great prospects for development.VRB battery does not have solid-state reaction, the not change of generating electrodes structure of matter form, and low price, and safety and environmental protection, operation and maintenance expense is low.VRB battery is comprised of two electrolysis liquid pools and battery unit from level to level.Electrolysis liquid pool is for holding two kinds of different electrolyte, and each electrolysis liquid pool is furnished with a pump, for the pipeline in sealing, is battery unit conveying electrolyte.Battery unit is comprised of two " half-cells ", holds respectively the electrolyte of the vanadium of different ions form in two " half-cell ", and there is barrier film centre and for the electrode of collected current.Vanadic sulfate electrolyte is the active material of vanadium cell electrochemical reaction and the carrier of electric energy, is the critical material of all-vanadium flow battery, and battery performance is had a direct impact.At present, the research of vanadium cell has entered practical stage, and its development is restricted by some key factors still, and the low cost preparation of the vanadic sulfate electrolyte of high concentration and good stability is one of main restricting factor.Under existing all-vanadium flow battery technical conditions, in order to ensure the combination property of battery, require vanadium concentration > 2mol/L in vanadic sulfate electrolyte, require sodium in vanadic sulfate, potassium or magnesium difference < 40ppm, calcium < 25ppm, iron, manganese, aluminium, copper, nickel, zinc, titanium, chromium, molybdenum, cobalt, silicon or arsenic philosophy < 10ppm, vanadic sulfate purity is answered more than 99.98%.China has abundant steel-making vanadium slag and Rock coal containing alum resource, leaching in vanadium extracting process, reextraction, resin are resolved the vanadium concentration < 0.8mol/L of gained vanadic sulfate solution, contain ferric iron and vanadic sulfate mass ratio in 0.008 ~ 0.05 scope, vanadic sulfate and metal total impurities quality (VOSO
4/ Σ Me < 80, pH < 1.0, this vanadic sulfate solution can not meet electrolyte of vanadium redox battery specification requirement.Current, the preparation method of the vanadic sulfate solution of all-vanadium flow battery is V
2o
5powder directly adds H
2sO
4solution, heating for dissolving, then add reducing agent that the valence state of vanadium is reduced to tetravalence.Vanadic sulfate solution concentration prepared by the method is low, and commercially available V
2o
5powder, before acid is dissolved, be purified through further removal of impurities, and its energy consumption and cost are high.Directly dissolve vanadic sulfate and be prepare vanadic sulfate electrolyte the most directly, the easiest method.But vanadic sulfate is expensive, adopt that to prepare in this way electrolyte of vanadium redox battery infeasible economically.Electrolysis barium oxide is also used to prepare vanadic sulfate electrolyte.Method is to adopt H
2sO
4for anode chamber's electrolyte, V
2o
5and H
2sO
4for cathode chamber electrolyte, use graphite electrode constant-current electrolysis.The vanadium utilance of the method is low, and electrolyte purity depends on the purity of raw material V2O5 equally.
Summary of the invention
The technical problem to be solved in the present invention is the above-mentioned defect that how to overcome prior art, and a kind of preparation method of high-purity sulfuric acid vanadyl electrolyte is provided.
For solving the problems of the technologies described above, the preparation method of this high-purity sulfuric acid vanadyl electrolyte comprises the following steps,
Step (1): NaOH is extracted with vanadium slag and bone coal, obtain pH and be 3.0 ~ 4.0 vanadic sulfate solution;
Step (2): will add step (1) to extract the vanadic sulfate solution obtaining by the anhydrous sodium sulfite of 3 ~ 5 times of the required reduction dosage of oxides, divalent;
Step (3): according to weight ratio meter, by P507: TBP: sulfonated kerosene is 20 ~ 30: 10 ~ 20: 40 ~ 50 are mixed and made into extractant, comparing O/A=4:1, extraction time 30min, the vanadic sulfate solution under the condition of settling time 10min, step (2) being made carries out multi-stage counter current extraction, and progression is 3 ~ 6 grades;
Step (4): the extract that step (3) is obtained carries out two and is separated, carries vanadium organic phase with deionized water washing, is comparing O/A=10:1, under the condition of washing time 5min; Use the sulfuric acid solution of 100g/L to carry out 3 ~ 6 grades of multi-stage countercurrents and strip and carry vanadium organic phases, compare O/A=10 ~ 5: 1, extraction time 10min, settling time 5min, two make vanadic sulfate anti-stripping agent after being separated;
Step (5): add ammoniacal liquor in the vanadic sulfate anti-stripping agent making to step (4), to vanadic sulfate anti-stripping agent pH be 2, add citric acid to adjust solution potential value < 100mV, the extractant making by step (3) extraction, progression is 3 ~ 6 grades, compare O/A=5 ~ 1:1, extraction time is 20min, two be separated after, with the sulfuric acid solution washing of 3g/L, carry a vanadium organic phase, compare O/A=3:1, washing time 5min; With the sulfuric acid solution multi-stage countercurrent of 50g/L, strip, progression is 3 ~ 6 grades, compares O/A=10 ~ 5:1, and back-extraction time 20min obtains vanadic sulfate electrolyte precursor;
Step (6): the vanadic sulfate electrolyte precursor that step (5) is made to 70% of complete its quality, obtains this vanadic sulfate electrolyte by distillation concentration.
Preparation method's technique of a kind of high-purity sulfuric acid vanadyl of the present invention electrolyte is simple, with low cost, is widely used in vanadic sulfate electrolyte large-scale production for full vanadium cell.
Embodiment
The preparation method of this high-purity sulfuric acid vanadyl electrolyte comprises the following steps,
Step (1): NaOH is extracted with vanadium slag and bone coal, obtain pH and be 3.0 ~ 4.0 vanadic sulfate solution;
Step (2): will add step (1) to extract the vanadic sulfate solution obtaining by the anhydrous sodium sulfite sodium of 3 ~ 5 times of the required reduction dosage of oxides, divalent;
Step (3): according to weight ratio meter, by P507: TBP: sulfonated kerosene is 20 ~ 30: 10 ~ 20: 40 ~ 50 are mixed and made into extractant, comparing O/A=4:1, extraction time 30min, the vanadic sulfate solution under the condition of settling time 10min, step (2) being made carries out multi-stage counter current extraction, and progression is 3 ~ 6 grades;
Step (4): the extract that step (3) is obtained carries out two and is separated, carries vanadium organic phase with deionized water washing, is comparing O/A=10:1, under the condition of washing time 5min; Use the sulfuric acid solution of 100g/L to carry out 3 ~ 6 grades of multi-stage countercurrents and strip and carry vanadium organic phases, compare O/A=10 ~ 5: 1, extraction time 10min, settling time 5min, two make vanadic sulfate anti-stripping agent after being separated;
Step (5): add ammoniacal liquor in the vanadic sulfate anti-stripping agent making to step (4), to vanadic sulfate anti-stripping agent pH be 2, add citric acid to adjust solution potential value < 100mV, the extractant making by step (3) extraction, progression is 3 ~ 6 grades, compare O/A=5 ~ 1:1, extraction time is 20min, two be separated after, with the sulfuric acid solution washing of 3g/L, carry a vanadium organic phase, compare O/A=3:1, washing time 5min; With the sulfuric acid solution multi-stage countercurrent of 50g/L, strip, progression is 3 ~ 6 grades, compares O/A=10 ~ 5:1, and back-extraction time 20min obtains vanadic sulfate electrolyte precursor;
Step (6): the vanadic sulfate electrolyte precursor that step (5) is made to 70% of complete its quality, obtains this vanadic sulfate electrolyte by distillation concentration.
Above-mentioned execution mode is intended to illustrate the present invention and can be professional and technical personnel in the field's realization or use; it will be apparent for those skilled in the art that above-mentioned execution mode is modified; therefore the present invention includes but be not limited to above-mentioned execution mode; any these claims or specification of meeting described; meet and principle disclosed herein and novelty, the method for inventive features, technique, product, within all falling into protection scope of the present invention.
Claims (1)
1. a preparation method for high-purity sulfuric acid vanadyl electrolyte, is characterized in that: described preparation method comprises the following steps,
Step (1): NaOH is extracted with vanadium slag and bone coal, obtain pH and be 3.0 ~ 4.0 vanadic sulfate solution;
Step (2): will add step (1) to extract the vanadic sulfate solution obtaining by the anhydrous sodium sulfite of 3 ~ 5 times of the required reduction dosage of oxides, divalent;
Step (3): according to weight ratio meter, by P507: TBP: sulfonated kerosene is 20 ~ 30: 10 ~ 20: 40 ~ 50 are mixed and made into extractant, comparing O/A=4:1, extraction time 30min, the vanadic sulfate solution under the condition of settling time 10min, step (2) being made carries out multi-stage counter current extraction, and progression is 3 ~ 6 grades;
Step (4): the extract that step (3) is obtained carries out two and is separated, carries vanadium organic phase with deionized water washing, is comparing O/A=10:1, under the condition of washing time 5min; Use the sulfuric acid solution of 100g/L to carry out 3 ~ 6 grades of multi-stage countercurrents and strip and carry vanadium organic phases, compare O/A=10 ~ 5: 1, extraction time 10min, settling time 5min, two make vanadic sulfate anti-stripping agent after being separated;
Step (5): add ammoniacal liquor in the vanadic sulfate anti-stripping agent making to step (4), to vanadic sulfate anti-stripping agent pH be 2, add citric acid to adjust solution potential value < 100mV, the extractant making by step (3) extraction, progression is 3 ~ 6 grades, compare O/A=5 ~ 1:1, extraction time is 20min, two be separated after, with the sulfuric acid solution washing of 3g/L, carry a vanadium organic phase, compare O/A=3:1, washing time 5min; With the sulfuric acid solution multi-stage countercurrent of 50g/L, strip, progression is 3 ~ 6 grades, compares O/A=10 ~ 5:1, and back-extraction time 20min obtains vanadic sulfate electrolyte precursor;
Step (6): the vanadic sulfate electrolyte precursor that step (5) is made to 70% of complete its quality, obtains this vanadic sulfate electrolyte by distillation concentration.
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| CN201410265280.9A CN104064795A (en) | 2014-06-16 | 2014-06-16 | Preparation method of high-purity vanadyl sulfate electrolyte |
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| CN201410265280.9A CN104064795A (en) | 2014-06-16 | 2014-06-16 | Preparation method of high-purity vanadyl sulfate electrolyte |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745248A (en) * | 2017-01-17 | 2017-05-31 | 深圳力合通科技有限公司 | High-purity sulphuric acid vanadyl solution manufacturing method |
| CN107557598A (en) * | 2017-05-25 | 2018-01-09 | 中国科学院过程工程研究所 | The method for preparing V electrolyte |
| CN111200152A (en) * | 2018-11-19 | 2020-05-26 | 大连融科储能技术发展有限公司 | Formula and process of all-vanadium redox flow battery electrolyte |
| CN111200151A (en) * | 2018-11-19 | 2020-05-26 | 大连融科储能技术发展有限公司 | All-vanadium redox flow battery electrolyte for reducing battery material deposition and preparation method thereof |
-
2014
- 2014-06-16 CN CN201410265280.9A patent/CN104064795A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745248A (en) * | 2017-01-17 | 2017-05-31 | 深圳力合通科技有限公司 | High-purity sulphuric acid vanadyl solution manufacturing method |
| CN106745248B (en) * | 2017-01-17 | 2017-12-29 | 深圳力合通科技有限公司 | High-purity sulphuric acid vanadyl solution manufacturing method |
| CN107557598A (en) * | 2017-05-25 | 2018-01-09 | 中国科学院过程工程研究所 | The method for preparing V electrolyte |
| CN107557598B (en) * | 2017-05-25 | 2019-04-30 | 中国科学院过程工程研究所 | The method for preparing V electrolyte |
| CN111200152A (en) * | 2018-11-19 | 2020-05-26 | 大连融科储能技术发展有限公司 | Formula and process of all-vanadium redox flow battery electrolyte |
| CN111200151A (en) * | 2018-11-19 | 2020-05-26 | 大连融科储能技术发展有限公司 | All-vanadium redox flow battery electrolyte for reducing battery material deposition and preparation method thereof |
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Application publication date: 20140924 |