CN109321931A - The method that failure electrolyte of vanadium redox battery prepares vanadic sulfate - Google Patents
The method that failure electrolyte of vanadium redox battery prepares vanadic sulfate Download PDFInfo
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- CN109321931A CN109321931A CN201811260931.XA CN201811260931A CN109321931A CN 109321931 A CN109321931 A CN 109321931A CN 201811260931 A CN201811260931 A CN 201811260931A CN 109321931 A CN109321931 A CN 109321931A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention relates to the methods that failure electrolyte of vanadium redox battery prepares vanadic sulfate, belong to vanadium battery field.Present invention solves the technical problem that being not high for the recovery efficiency for the electrolyte that fails in the prior art, but also the report of vanadic sulfate is not prepared about recycling.The present invention discloses the method that failure electrolyte of vanadium redox battery prepares vanadic sulfate, using the electrolyte of vanadium redox battery that fails as raw material, using vanadium cell electroreduction, prepares trivalent sulfuric acid vanadium solution, then stand by concentration, vanadic sulfate is prepared in filtration drying.The present invention can effectively realize the recycling of vanadium in failure electrolyte, and vanadium recovery is high, recycle the vanadic sulfate purity is high being prepared, 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 the method that failure electrolyte of vanadium redox battery prepares vanadic sulfate.
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.
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 passes through battery charging, the vanadium ion of lower valency is oxidized to 5 valences, then adjust
The pH of whole solution can prepare the V of purity 98% using ammonium salt as precipitating reagent precipitation after calcining2O5.The recycling side of above-mentioned electrolyte
Method is that anode is oxidized to 5 valences when charging by vanadium cell, to be recycled, for only failure anolyte
Liquid, thus partial electrolyte liquid can only be recycled.Patent document CN102983346A discloses a kind of vanadium cell use using failure
The method of electrolyte extracting sulfuric acid vanadyl makes the valence state of vanadium in electrolyte by battery charging using the V electrolyte that fails as raw material
Pentavalent is risen to, suitable precipitation agent is added, is settled out pentavalent vanadium therein, then adds organic reducing agent, room temperature culture is made
Oxygen vanadium sulfate crystals.V is mostly prepared with recycling for the recovery method of electrolyte at present2O5Based on, there are no prepare sulphur about recycling
The report of sour vanadium.
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, but also do not have
The report of vanadic sulfate is prepared about recycling.
Technical proposal that the invention solves the above-mentioned problems is to provide the method that failure electrolyte of vanadium redox battery prepares vanadic sulfate, with
Failure electrolyte of vanadium redox battery is raw material, using vanadium cell electroreduction, prepares trivalent sulfuric acid vanadium solution, then stand by concentration, mistake
Dry sediment is filtered, vanadic sulfate is prepared.
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, vanadium cell electrolysis is constant-current electrolysis, and current density is 60~140mA/cm2。
Wherein, vanadium ion concentration is 153~184g/L after concentration.Wherein, the mode of concentration is using vacuum distillation, vacuum degree
For -0.08~-0.09Mpa, temperature is 80~90 DEG C.
Wherein, it stands to place 24~40h at room temperature.
Wherein, vacuum drying temperature is 40~60 DEG C, and vacuum degree is -0.09~-0.095Mpa.
Beneficial effects of the present invention:
The mode that the present invention leads to vanadium cell electroreduction can effectively realize the recycling of vanadium in failure electrolyte, vanadium recovery
It is high；The vanadic sulfate purity is high being prepared is recycled through the invention, can be applied to prepare electrolyte of vanadium redox battery and catalyst material；
Preparation method of the present invention is simple, and process flow is simple, energy consumption is small, environmental pollution is small, realizes that industrialization possibility is larger.
Specific embodiment
It, can not since the feature of vanadium ion migration certainly will cause positive and negative anodes electrolyte to mismatch in vanadium cell operational process
It needs with avoiding to regularly replace a large amount of electrolyte, in addition, V electrolyte is strong acid solution, there is very strong mobility and corrosion
Property, transport difficulty is big, and transportation cost is high, this can undoubtedly greatly increase cost, to reduce the profit of product.
The present invention provides the failure method that electrolyte of vanadium redox battery prepares vanadic sulfate, using the electrolyte of vanadium redox battery that fails as raw material,
Using vanadium cell electroreduction, trivalent sulfuric acid vanadium solution is prepared, then is stood by concentration, filtration drying sediment, sulphur is prepared
Sour vanadium.
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) step (1) solution is respectively placed in the positive and negative anodes of vanadium cell pile, carries out constant-current electrolysis, is received in battery cathode
Collection obtains sulfuric acid vanadium solution；
(3) the sulfuric acid alum solution that step (2) obtains is subjected to vacuum distillation concentration, obtains vanadic sulfate concentrate；
(4) the vanadic sulfate concentrate of step (3) is stood into a period of time；
(5) step (4) sediment is filtered, vacuum drying obtains solid sulphuric acid vanadium.
Wherein, the reaction that step (2) is related to is VO2++e-+2H+→V3++H2O。
Wherein, vanadium ion concentration is 81.6~153g/L, V in failure electrolyte3+With V4+Concentration than be positive and negative anodes mix
Valence state ratio afterwards is 0.2~0.8, and sulfate concentration is 384~441g/L.
Wherein, vanadium cell electrolysis is constant-current electrolysis, and current density is 60~140mA/cm2。
Wherein, vanadium ion concentration is 153~184g/L after concentration.
Wherein, for the mode of concentration using vacuum distillation, vacuum degree is -0.08~-0.09Mpa, and temperature is 80~90 DEG C, is subtracted
Pressure distillation purpose is to prevent the oxidation of trivalent vanadium ion.
Wherein, it stands to place 24~40h at room temperature.
Wherein, vacuum drying temperature is 40~60 DEG C, and vacuum degree is -0.09~-0.095Mpa.
The following further explains the present invention by way of examples.
Embodiment 1
Taking 1L vanadium ion concentration is 81.6g/L, V3+/V4+=0.7 electrolyte, filtering remove solid suspension and insoluble
Object；It is placed in vanadium cell positive and negative anodes and carries out constant-current electrolysis, current density 60mA/cm2, cathode obtains 500mL sulfuric acid vanadium solution；?
Vacuum degree is that vacuum distillation to vanadium ion concentration is 163.2g/L under -0.08Mpa, is stood at room temperature for 24 hours；40 are deposited in after filtering
Dry 1h obtains vanadic sulfate product 183.6g at DEG C.Calculating vanadium yield is 72%, 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
Taking 1L vanadium ion concentration is 84.15g/L, V3+/V4+=0.5 electrolyte, filtering remove solid suspension and not
Molten object；It is placed in vanadium cell positive and negative anodes and carries out constant-current electrolysis, current density 60mA/cm2, cathode obtains 500mL sulfuric acid vanadium solution；
In the case where vacuum degree is -0.08Mpa, vacuum distillation is 173.4g/L to vanadium ion concentration, stands 30h at room temperature；It is deposited in after filtering
Dry 1h obtains vanadic sulfate product 205.12g at 40 DEG C.Calculating vanadium yield is 78%, 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
Taking 1L vanadium ion concentration is 86.7g/L, V3+/V4+=0.5 electrolyte, filtering remove solid suspension and insoluble
Object；It is placed in vanadium cell positive and negative anodes and carries out constant-current electrolysis, current density 60mA/cm2, cathode obtains 500mL sulfuric acid vanadium solution；?
Vacuum degree is that vacuum distillation to vanadium ion concentration is 183.6g/L under -0.08Mpa, stands 40h at room temperature；40 are deposited in after filtering
Dry 1h obtains vanadic sulfate product 216.75g at DEG C.Calculating vanadium yield is 80%, 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%.
Recycle obtained vanadic sulfate V2(SO4)3It serves not only as in vanadium redox battery negative pole electrolyte, and in catalysis, medicine
Field also has a wide range of applications.Since the feature of vanadium ion migration certainly will cause positive and negative anodes to be electrolysed in vanadium cell operational process
Liquid mismatches, and inevitably needs to regularly replace a large amount of electrolyte, waste and old electrolyte is prepared into trivalent solid sulphuric acid vanadium,
Need to only be dissolved in sulfuric acid solution can be configured to V electrolyte recycling.Future with vanadium energy storage system flourishing hair
Exhibition, the demand of solid sulphuric acid vanadium will be doubled and redoubled.Therefore preparation trivalent vanadic sulfate electrolyte can bring very big economic effect
Should and social value.
Claims (7)
1. the method that failure electrolyte of vanadium redox battery prepares vanadic sulfate, it is characterised in that: using the electrolyte of vanadium redox battery that fails as raw material, adopt
With vanadium cell electroreduction, trivalent sulfuric acid vanadium solution is prepared, then is stood by concentration, filtration drying sediment, sulfuric acid is prepared
Vanadium.
2. the method that failure electrolyte of vanadium redox battery according to claim 1 prepares vanadic sulfate, it is characterised in that: the failure
Vanadium ion concentration is 81.6~153g/L, V in electrolyte3+With V4+Concentration ratio be 0.2~0.8, sulfate concentration be 384~
441g/L。
3. the method that failure electrolyte of vanadium redox battery according to claim 1 or 2 prepares vanadic sulfate, it is characterised in that: described
Vanadium cell electrolysis is constant-current electrolysis, and current density is 60~140mA/cm2。
4. the method that described in any item failure electrolyte of vanadium redox battery prepare vanadic sulfate, feature exist according to claim 1~3
In: vanadium ion concentration is 153~184g/L after the concentration.
5. the method that failure electrolyte of vanadium redox battery according to any one of claims 1 to 4 prepares vanadic sulfate, feature exist
In: for the mode of the concentration using vacuum distillation, vacuum degree is -0.08~-0.09Mpa, and temperature is 80~90 DEG C.
6. the method that described in any item failure electrolyte of vanadium redox battery prepare vanadic sulfate, feature exist according to claim 1~5
In: the time of repose is 24~40h.
7. the method that described in any item failure electrolyte of vanadium redox battery prepare vanadic sulfate, feature exist according to claim 1~6
In: the drying is vacuum drying, and temperature is 40~60 DEG C, and vacuum degree is -0.09~-0.095Mpa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1111949A (en) * | 1997-06-17 | 1999-01-19 | Shinko Kagaku Kogyo Kk | Production of vanadium (iii) sulfate and its sulfuric acid aqueous solution |
| CN102394308A (en) * | 2011-10-17 | 2012-03-28 | 上海裕豪机电有限公司 | Manufacturing process of electrolyte for oxidation reduction cell |
| CN105406098A (en) * | 2015-12-24 | 2016-03-16 | 湖南汇锋高新能源有限公司 | Method for preparing vanadyl sulfate by using failure vanadium cell electrolyte |
| CN106450371A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling failed vanadium electrolyte |
-
2018
- 2018-10-26 CN CN201811260931.XA patent/CN109321931A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1111949A (en) * | 1997-06-17 | 1999-01-19 | Shinko Kagaku Kogyo Kk | Production of vanadium (iii) sulfate and its sulfuric acid aqueous solution |
| CN102394308A (en) * | 2011-10-17 | 2012-03-28 | 上海裕豪机电有限公司 | Manufacturing process of electrolyte for oxidation reduction cell |
| CN105406098A (en) * | 2015-12-24 | 2016-03-16 | 湖南汇锋高新能源有限公司 | Method for preparing vanadyl sulfate by using failure vanadium cell electrolyte |
| CN106450371A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling failed vanadium electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| 冯秀丽等: "V(Ⅲ)一V(Ⅳ)电解液的电解合成", 《合成化学》 * |
| 杨明平等: "利用失效钒电解液回收钒制备偏钒酸铵工艺", 《化工进展》 * |
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Application publication date: 20190212 |