CN104319412A - Method for preparing high-purity and high-concentration vanadium electrolyte - Google Patents
Method for preparing high-purity and high-concentration vanadium electrolyte Download PDFInfo
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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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- 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
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Abstract
The invention relates to the field of preparing full-vanadium liquid flow battery electrolytes, in particular to the field of preparing quadrivalent electrolytes of liquid flow batteries from qualified pentavalent vanadium liquid produced by a vanadium plant. The existing vanadyl sulfate electrolyte is prepared by vanadium pentoxide or vanadium trioxide, and is low in purity and high in price. The invention aims at producing a high-concentration and high-purity vanadyl sulfate electrolyte by taking the qualified pentavalent vanadium liquid produced by the vanadium plant as a raw material based on cost lowering. With the adoption of a preparation method, the high-purity and high-concentration quadrivalent vanadyl sulfate electrolyte can be prepared by fewer steps; the product performance is improved; and the production cost is lowered. Nowadays, with flourishing development of the full-vanadium liquid flow battery industry, the demand of a vanadium electrolyte is increasing, and if a technology is popularized, objective economic benefits can be brought.
Description
Technical field
The present invention relates to a kind of all-vanadium redox flow battery electrolyte preparation field, the qualified vanadium liquid of the pentavalent of particularly being produced by vanadium factory is to flow battery tetravalence electrolyte preparation field.
Background technology
Flow battery is developed by fuel cell, proposes to start from concept in 1974, the characteristic property many due to it and cause extensive concern.Be included in anode and negative electrode different from the solid active material of usual storage battery, high and low current potential two oxidationreduction electricity as active material in flow battery are right, two or one of them be dissolved in the solution be contained in fluid reservoir, make solution flow through battery by pump, oxidation and reduction reaction occur inert solid electrode.Flow battery is divided into three-decker: monomer (Cell), pile (Stack) and system (System).The core of flow battery system carries out the monocell that oxidation-reduction reaction realizes charge and discharge process.Monocell is made up of positive pole, negative pole, electrolyte and barrier film.Therefore, flow battery has capacity can separate the features such as independent design, the life-span is long, cost is low with power, from the viewpoint of fail safe, energy storage efficiency and property/valency ratio etc., flow battery should be the energy storage system being most suitable for extensive electric power storage, and its prospect for scale energy storage is boundless.
In existing flow battery system, all-vanadium flow battery is the battery that Commercial Prospect is had an optimistic view of the most.Wherein the V electrolyte of both positive and negative polarity is the important component part of all-vanadium flow battery.Concentration of electrolyte due to flow battery decides the specific energy of battery; the quality influence of electrolyte the cycle performance of battery; the cost of electrolyte governs the scale application of all-vanadium flow battery, and how preparing the electrolyte that concentration is high, performance good, cost is low is the important topic that researcher faces.On the basis of Primary Study, the understanding that we have had some preliminary on the performance of electrolyte and the relation of composition: the impurity in V electrolyte is the key factor affecting battery performance.For this reason, the impurity content how reduced in electrolyte is the key improving its performance.
The patent that investigation V electrolyte prepares aspect is visible, and what the raw material that existing patented technology adopts mostly was the most frequently used is trivalent and pentavalent vanadium oxide.Patent ZL200710188392.9 adopts trivalent vanadium to prepare electrolyte of vanadium redox battery.Vanadium trioxide is mixed with sulfuric acid, puts into tube furnace, at the temperature lower calcination of 100 ~ 300 degree, utilize air that part trivalent vanadium is oxidized into tetravalence, obtain the mixture of each half of three tetravalences.Number of patent application 200910015369.9 adopts pentavalent vanadium to prepare electrolyte of vanadium redox battery.In vanadic oxide and sulfuric acid, add one or more aliphat organic substances as reducing agent, fully react under high temperature, obtain the tetravalence V electrolyte of vanadium concentration between 1 ~ 6M.Technology more conventional in patent is mixed dissolution in sulfuric acid solution by vanadic oxide and vanadium trioxide, carry out chemistry and electrochemical reduction, preparation becomes three ~ tetravalence vanadium solution, the vanadic oxide of 1: 1 ratio and vanadium trioxide mix by patent ZL02133808.6, react with after sulfuric acid dissolution, obtain the vanadic sulfate solution of tetravalence; Patent ZL03159533.2 is on the basis that vanadic oxide and vanadium trioxide 1: 1 mix, and adopt the method for electrolysis to be reduced by electrolyte, preparation becomes trivalent and tetravalence vanadium ratio is the mixture of 1: 1.Number of patent application 200610038914.2 by vanadium trioxide and vanadic oxide according to 1.5 ~ 2.5: 1 ratio mixing, high-temperature roasting, obtains many vfanadium compound, then sulfuric acid is added, preparation becomes three ~ tetravalence V electrolyte, and wherein, tetravalence vanadium is greater than the .50% of total vanadium.Number of patent application 200910171737.3 also by vanadic oxide and vanadium trioxide sulfuric acid dissolution, adds organic substance reducing agent simultaneously, obtains three ~ tetravalence vanadium solution.In above-mentioned various methods, adopt vanadic oxide, vanadium trioxide powder or the mixture of the two more, be dissolved in strong acid, by the reaction under hot conditions, prepare V electrolyte.The raw material of these class methods is barium oxide, and feed preparation process is complicated, expensive, should be not suitable for the large-scale production of electrolyte.
In the prerequisite reducing production cost, we see two patents by vanadium factory raw material direct production pentavalent vanadium: after the pentavalent qualified vanadium liquid sulfuric acid that vanadium factory produces by number of patent application 200510075608.1 is adjusted to acidity, with sulphur dioxide reduction, regulate acidity with sodium carbonate more subsequently, hydrolysis obtains tetravalence vanadium oxide precipitation.Tetravalence vanadium precipitation sulfuric acid dissolution, adopts the preparation of the method for electrolysis to become the V electrolyte that three tetravalences respectively account for 50%.Number of patent application 200710122837.3, by Rock coal containing alum ore deposit, through the roasting of strong basicity sodium calcium salt-mixture, obtains pentavalent vanadium solution after water logging, after removal of impurities after reduction, the hydrolysis of tetravalence vanadium is precipitated, and obtains high-purity sulphuric acid vanadyl by sulfuric acid dissolution.These two kinds of methods adopt the method for tetravalence vanadium hydrolysis, and from vanadium stoste, be separated vanadium, the vanadic acid of tetravalence is colloidal precipitation, is mingled with more, and the V electrolyte impurity content that thus these class methods obtain must be higher.
The qualified vanadium liquid that we have employed the production of vanadium factory is equally raw material, adopts the preparation of removal of impurities-precipitation-reduction-extraction-capable V electrolyte of oil removing five steps.Wherein, removal of impurities, precipitation, extraction three steps are effective impurity.In dedoping step, colloidal impurity is stayed in filter residue and is separated with vanadium liquid; In precipitation process, the metavanadic acid ammonia precipitation of lenticular, impurity is stayed in filtrate; This two steps process, eliminates most of impurity in vanadium liquid; A small amount of residual impurity and potassium, sodium, ammonium plasma are removed by extraction process; Effectively control the impurity content in electrolyte.Raw material in preparation process is common agents, and price is lower; Effectively control the cost of electrolyte.Application the method can obtain high-purity, at a low price, be applicable to the tetravalence V electrolyte of large-scale production.
Summary of the invention
Existing vanadic sulfate electrolyte, be prepared from by the product such as vanadic oxide or vanadium trioxide, purity is low and price is high.The object of the invention is, on the basis reduced costs, the qualified vanadium liquid of pentavalent adopting vanadium factory to produce is raw material, produces high concentration, highly purified vanadic sulfate electrolyte.
This preparation method, through preliminary removal of impurities → precipitation → reduction → extraction → oil removing, is directly prepared as high-purity tetravalence vanadic sulfate solution by pentavalent vanadium acid sodium solution; Concrete steps are:
(1) removal of impurities: add cleaner in stoste, makes the impurity that in vanadium liquid, content is higher form precipitation, filters and remove; In the scope of pH=8 ~ 9, with silicate, chromate, phosphate radical impurity anions in aluminium salt, magnesium salts and calcium salt removing vanadium liquid; In the scope of pH=10 ~ 11, with the metal impurities cation in carbonate, sulphion removing vanadium liquid; Aluminium salt is 1: 1.1 with the ratio of the amount of substance of silicate, and magnesium salts is 1: 1.1 with the ratio of the amount of substance of chromate, and calcium salt is 1: 1 with the ratio of the amount of substance of phosphate radical;
(2) precipitation: the precipitation reagent adding vanadium after removal of impurities in stoste, forms vanadate crystal precipitation, with other magazins' layout in stoste; Adopt that faintly acid ammonia sinks, acidic ammonium sinks and alkaline ammonia sink in one or more with the use of; First use sulfuric acid regulation solution about pH=5, add a certain amount of ammonium chloride, carry out faintly acid ammonia and sink; Then use sulfuric acid regulation solution acidity to 2 ~ 2.5, be heated to 98 degree simultaneously, carry out acid ammonia and sink; The water-soluble solution of the ammonium metavanadate precipitate obtained, regulates pH=9 with ammoniacal liquor, carries out alkaline ammonia and sinks, finally obtain ammonium metavanadate precipitate; Faintly acid ammonia sinks in process, and ammonium chloride is 1: 2 with the ratio of the amount of substance of vanadium, and alkaline ammonia sinks in process, and ammoniacal liquor is 1.2: 1 with the ratio of the amount of substance of vanadium;
(3) reduce: in vanadate precipitation, add reducing agent, regulate acidity, make vanadate reduction become vanadic sulfate; Adopt inorganic matter as oxyammonia hydrazine, adopt organic substance if oxalic acid is as reducing agent, adopt inorganic acid as sulfuric acid, adopt organic acid as the pH < 1 of vinegar acid-conditioning solution, ammonium metavanadate reduction is become vanadic sulfate;
(4) extract: reduction is obtained vanadic sulfate acidic extractant and extract, the sulfuric acid of 3 ~ 4M carries out back extraction, is further purified vanadic sulfate solution; Adopt neutral containing oxygen ester type compound and acidic phosphorus containing compound as extractant; In extraction process, adopt the di (isooctyl) phosphate of 35% as extractant, adopt the tributyl phosphate of 7% as synergic reagent, adopt sulfonated kerosene as diluent; In stripping process, adopt the sulfuric acid of 3 ~ 4M as back washing agent; Extraction is in a ratio of 1: 1, and back extraction is in a ratio of 1: 1; After the extraction, extractant sulfuric acid back extraction, the pH value that raffinate ammoniacal liquor, NaOH, calcium carbonate or brium carbonate regulate is 2 ~ 3, then carries out next stage extraction with the extractant after back extraction; Extracting-back extraction like this 4 ~ 6 grades completes extraction process;
(5) oil removing: the organic phase adopting charcoal absorption vanadic sulfate solution surface remnants, preparation becomes high-purity vanadic sulfate solution; Active carbon, before application through overpickling, washing, high-temperature process, removes organic and inorganic impurity; Activated carbon powder after removal of impurities joins in strip liquor, through heating, cooling, filters oil removing.
Pentavalent vanadium acid sodium solution is the qualified pentavalent vanadium solution of national standard, and wherein v element concentration is between 0.3 ~ 0.6M.
In high-purity tetravalence vanadic sulfate solution, except v element and potassium, sodium, ammonium, other metal impurities ion concentrations in electrolyte are at below 10ppm.
Adopt preparation method of the present invention, with less step, the tetravalence vanadic sulfate electrolyte of high-purity, high concentration can be prepared, both improve properties of product, and again reduced production cost.In today that all-vanadium flow battery industry is flourish, the demand of V electrolyte strengthens day by day, and this technology, as promoted, must bring objective economic benefit.
Embodiment
Embodiment 1:
In the accurate pentavalent vanadium stoste of 10 raising of indices, vanadium concentration is 0.4M, and other impurity have silicate, chromate, phosphate radical, and cation has iron ion, calcium ion, magnesium ion, manganese ion etc.
(1) removal of impurities: add cleaner in stoste, makes the impurity that in vanadium liquid, content is higher form precipitation, filters and remove; In the scope of pH=8 ~ 9, with silicate, chromate, phosphate radical impurity anions in aluminium salt, magnesium salts and calcium salt removing vanadium liquid; In the scope of pH=10 ~ 11, with the metal impurities cation in carbonate, sulphion removing vanadium liquid; Aluminium salt is 1: 1.1 with the ratio of the amount of substance of silicate, and magnesium salts is 1: 1.1 with the ratio of the amount of substance of chromate, and calcium salt is 1: 1 with the ratio of the amount of substance of phosphate radical;
(2) precipitation: the precipitation reagent adding vanadium after removal of impurities in stoste, forms vanadate crystal precipitation, with other magazins' layout in stoste; Adopt that faintly acid ammonia sinks, acidic ammonium sinks and alkaline ammonia sink in one or more with the use of; First use sulfuric acid regulation solution about pH=5, add a certain amount of ammonium chloride, carry out faintly acid ammonia and sink; Then use sulfuric acid regulation solution acidity to 2 ~ 2.5, be heated to 98 degree simultaneously, carry out acid ammonia and sink; The water-soluble solution of the ammonium metavanadate precipitate obtained, regulates pH=9 with ammoniacal liquor, carries out alkaline ammonia and sinks, finally obtain ammonium metavanadate precipitate; Faintly acid ammonia sinks in process, and ammonium chloride is 1: 2 with the ratio of the amount of substance of vanadium, and alkaline ammonia sinks in process, and ammoniacal liquor is 1.2: 1 with the ratio of the amount of substance of vanadium;
(3) reduce: in vanadate precipitation, add reducing agent, regulate acidity, make vanadate reduction become vanadic sulfate; Adopt inorganic matter as oxyammonia hydrazine, adopt organic substance if oxalic acid is as reducing agent, adopt inorganic acid as sulfuric acid, adopt organic acid as the pH < 1 of vinegar acid-conditioning solution, ammonium metavanadate reduction is become vanadic sulfate;
(4) extract: reduction is obtained vanadic sulfate acidic extractant and extract, the sulfuric acid of 3 ~ 4M carries out back extraction, is further purified vanadic sulfate solution; Adopt neutral containing oxygen ester type compound and acidic phosphorus containing compound as extractant; In extraction process, adopt the di (isooctyl) phosphate of 35% as extractant, adopt the tributyl phosphate of 7% as synergic reagent, adopt sulfonated kerosene as diluent; In stripping process, adopt the sulfuric acid of 3 ~ 4M as back washing agent; Extraction is in a ratio of 1: 1, and back extraction is in a ratio of 1: 1; After the extraction, extractant sulfuric acid back extraction, the pH value that raffinate ammoniacal liquor, NaOH, calcium carbonate or brium carbonate regulate is 2 ~ 3, then carries out next stage extraction with the extractant after back extraction; Extracting-back extraction like this 4 ~ 6 grades completes extraction process;
(5) oil removing: the organic phase adopting charcoal absorption vanadic sulfate solution surface remnants, preparation becomes high-purity vanadic sulfate solution; Active carbon, before application through overpickling, washing, high-temperature process, removes organic and inorganic impurity; Activated carbon powder after removal of impurities joins in strip liquor, through heating, cooling, filters oil removing.
Claims (3)
1. prepare a method for high-purity high-concentration V electrolyte, it is characterized in that: this preparation method, through preliminary removal of impurities → precipitation → reduction → extraction → oil removing, is directly prepared by pentavalent vanadium acid sodium solution and becomes high-purity tetravalence vanadic sulfate solution; Concrete steps are:
(1) removal of impurities: add cleaner in stoste, makes the impurity that in vanadium liquid, content is higher form precipitation, filters and remove; In the scope of pH=8 ~ 9, with silicate, chromate, phosphate radical impurity anions in aluminium salt, magnesium salts and calcium salt removing vanadium liquid; In the scope of pH=10 ~ 11, with the metal impurities cation in carbonate, sulphion removing vanadium liquid; Aluminium salt is 1: 1.1 with the ratio of the amount of substance of silicate, and magnesium salts is 1: 1.1 with the ratio of the amount of substance of chromate, and calcium salt is 1: 1 with the ratio of the amount of substance of phosphate radical;
(2) precipitation: the precipitation reagent adding vanadium after removal of impurities in stoste, forms vanadate crystal precipitation, with other magazins' layout in stoste; Adopt that faintly acid ammonia sinks, acidic ammonium sinks and alkaline ammonia sink in one or more with the use of; First use sulfuric acid regulation solution about pH=5, add a certain amount of ammonium chloride, carry out faintly acid ammonia and sink; Then use sulfuric acid regulation solution acidity to 2 ~ 2.5, be heated to 98 degree simultaneously, carry out acid ammonia and sink; The water-soluble solution of the ammonium metavanadate precipitate obtained, regulates pH=9 with ammoniacal liquor, carries out alkaline ammonia and sinks, finally obtain ammonium metavanadate precipitate; Faintly acid ammonia sinks in process, and ammonium chloride is 1: 2 with the ratio of the amount of substance of vanadium, and alkaline ammonia sinks in process, and ammoniacal liquor is 1.2: 1 with the ratio of the amount of substance of vanadium;
(3) reduce: in vanadate precipitation, add reducing agent, regulate acidity, make vanadate reduction become vanadic sulfate; Adopt inorganic matter as oxyammonia hydrazine, adopt organic substance if oxalic acid is as reducing agent, adopt inorganic acid as sulfuric acid, adopt organic acid as the pH < 1 of vinegar acid-conditioning solution, ammonium metavanadate reduction is become vanadic sulfate;
(4) extract: reduction is obtained vanadic sulfate acidic extractant and extract, the sulfuric acid of 3 ~ 4M carries out back extraction, is further purified vanadic sulfate solution; Adopt neutral containing oxygen ester type compound and acidic phosphorus containing compound as extractant; In extraction process, adopt the di (isooctyl) phosphate of 35% as extractant, adopt the tributyl phosphate of 7% as synergic reagent, adopt sulfonated kerosene as diluent; In stripping process, adopt the sulfuric acid of 3 ~ 4M as back washing agent; Extraction is in a ratio of 1: 1, and back extraction is in a ratio of 1: 1; After the extraction, extractant sulfuric acid back extraction, the pH value that raffinate ammoniacal liquor, NaOH, calcium carbonate or brium carbonate regulate is 2 ~ 3, then carries out next stage extraction with the extractant after back extraction; Extracting-back extraction like this 4 ~ 6 grades completes extraction process;
(5) oil removing: the organic phase adopting charcoal absorption vanadic sulfate solution surface remnants, preparation becomes high-purity vanadic sulfate solution; Active carbon, before application through overpickling, washing, high-temperature process, removes organic and inorganic impurity; Activated carbon powder after removal of impurities joins in strip liquor, through heating, cooling, filters oil removing.
2. preparation method according to claim 1, is characterized in that: pentavalent vanadium acid sodium solution is the qualified pentavalent vanadium solution of national standard, and wherein v element concentration is between 0.3 ~ 0.6M.
3. preparation method according to claim 1, is characterized in that: in high-purity tetravalence vanadic sulfate solution, and except vanadium unit and potassium, sodium, except ammonium, other metal impurities ion concentrations in electrolyte are at below 10ppm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017128966A1 (en) * | 2016-01-28 | 2017-08-03 | 中国科学院过程工程研究所 | System and method for preparing high purity vanadium electrolyte |
| WO2017128968A1 (en) * | 2016-01-28 | 2017-08-03 | 中国科学院过程工程研究所 | System and method for preparing vanadium battery high-purity electrolyte |
| CN108336426A (en) * | 2018-02-07 | 2018-07-27 | 四川星明能源环保科技有限公司 | The preparation method and its oxygen vanadium sulfate crystals obtained of a kind of vanadic sulfate |
| CN108423712A (en) * | 2018-04-12 | 2018-08-21 | 四川星明能源环保科技有限公司 | Vanadium trioxide and preparation method thereof |
| CN112542603A (en) * | 2021-01-04 | 2021-03-23 | 贵州义信矿业有限公司 | Method for preparing energy storage vanadium electrolyte by using low-purity vanadium pentoxide |
| CN112551576A (en) * | 2019-09-25 | 2021-03-26 | 攀钢集团钒钛资源股份有限公司 | Preparation method of vanadyl sulfate solution for vanadium electrolyte |
| CN112607774A (en) * | 2020-11-26 | 2021-04-06 | 核工业北京化工冶金研究院 | Method for preparing vanadyl sulfate crystal |
| CN114772642A (en) * | 2022-04-22 | 2022-07-22 | 中国科学院过程工程研究所 | Preparation method of high-purity vanadyl sulfate solution |
| CN117673426A (en) * | 2024-01-26 | 2024-03-08 | 液流储能科技有限公司 | Electrolyte preparation method for flow battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017128966A1 (en) * | 2016-01-28 | 2017-08-03 | 中国科学院过程工程研究所 | System and method for preparing high purity vanadium electrolyte |
| WO2017128968A1 (en) * | 2016-01-28 | 2017-08-03 | 中国科学院过程工程研究所 | System and method for preparing vanadium battery high-purity electrolyte |
| US10868325B2 (en) | 2016-01-28 | 2020-12-15 | Institute Of Process Engineering, Chinese Academy Of Sciences | System and method for preparing vanadium battery high-purity electrolyte |
| CN108336426A (en) * | 2018-02-07 | 2018-07-27 | 四川星明能源环保科技有限公司 | The preparation method and its oxygen vanadium sulfate crystals obtained of a kind of vanadic sulfate |
| CN108423712A (en) * | 2018-04-12 | 2018-08-21 | 四川星明能源环保科技有限公司 | Vanadium trioxide and preparation method thereof |
| CN112551576A (en) * | 2019-09-25 | 2021-03-26 | 攀钢集团钒钛资源股份有限公司 | Preparation method of vanadyl sulfate solution for vanadium electrolyte |
| CN112607774A (en) * | 2020-11-26 | 2021-04-06 | 核工业北京化工冶金研究院 | Method for preparing vanadyl sulfate crystal |
| CN112542603A (en) * | 2021-01-04 | 2021-03-23 | 贵州义信矿业有限公司 | Method for preparing energy storage vanadium electrolyte by using low-purity vanadium pentoxide |
| CN114772642A (en) * | 2022-04-22 | 2022-07-22 | 中国科学院过程工程研究所 | Preparation method of high-purity vanadyl sulfate solution |
| CN114772642B (en) * | 2022-04-22 | 2024-03-01 | 中国科学院过程工程研究所 | Preparation method of high-purity vanadyl sulfate solution |
| CN117673426A (en) * | 2024-01-26 | 2024-03-08 | 液流储能科技有限公司 | Electrolyte preparation method for flow battery |
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Application publication date: 20150128 |