阅读说明：本技术 一种失效钒电解液的处理方法 (Treatment method of failure vanadium electrolyte ) 是由 张忠裕 刘建国 赵锋 刘磊 赵金玲 刘在波 吴晓亮 秦野 严川伟 于 2019-11-01 设计创作，主要内容包括：本发明涉及液流电池储能技术领域,且公开了一种失效钒电解液的处理方法,以失效钒电解液为原料,引入复合沉淀剂,并使用常规碱液调节溶液至中性,在常温下,充分搅拌,使溶液中的钒100％完全沉淀的方法。该失效钒电解液的处理方法,原料极易得到,处理过程方法比较简单,无需较为复杂的操作,易于推广使用,极大的降低了处理成本,提高了经济效益,同时将失效钒电解液中的钒进行沉淀后,溶液无需多余处理过程,减少了处理过程,进一步的节省了时间,提高回收钒的效率,缩短处理周期,使用起来更加环保,钒的沉淀率为100％,防止钒的排放污染周边环境,避免周边的环境遭到破坏,从而非常适合于工业大规模生产,可完全回收废液中的钒。(The invention relates to the technical field of energy storage of flow batteries, and discloses a treatment method of a failure vanadium electrolyte, which is a method for completely precipitating 100% of vanadium in a solution by taking the failure vanadium electrolyte as a raw material, introducing a composite precipitator, adjusting the solution to be neutral by using a conventional alkali liquor, and fully stirring at normal temperature. The processing method of the failure vanadium electrolyte has the advantages that raw materials are easy to obtain, the processing method is simple, complex operation is not needed, the method is easy to popularize and use, the processing cost is greatly reduced, the economic benefit is improved, after vanadium in the failure vanadium electrolyte is precipitated, the solution does not need redundant processing, the processing process is reduced, the time is further saved, the efficiency of recovering the vanadium is improved, the processing period is shortened, the use is more environment-friendly, the precipitation rate of the vanadium is 100%, the vanadium is prevented from being discharged to pollute the surrounding environment, the damage to the surrounding environment is avoided, the method is very suitable for industrial large-scale production, and the vanadium in waste liquid can be completely recovered.)

1. A treatment method of a failure vanadium electrolyte is characterized in that the failure vanadium electrolyte is used as a raw material, a composite precipitator is introduced, a conventional alkali liquor is used for regulating a solution to be neutral, and the solution is fully stirred at normal temperature to ensure that 100 percent of vanadium in the solution is completely precipitated.

2. The method for treating the failed vanadium electrolyte according to claim 1, wherein the vanadium concentration in the failed vanadium electrolyte is: 0.1-3.0 mol/L, and the temperature of the failure vanadium electrolyte is normal temperature.

3. The method for treating the spent vanadium electrolyte according to claim 1, wherein the main salt in the composite precipitator is an organic amine substance such as: one or more of ethylenediamine, triethylamine, polyacrylamide, triethanolamine, dmf, cyclohexylamine, morpholine, aniline, krafft acid, naphthalene diamine, and hydroxylamine.

4. The method for treating the spent vanadium electrolyte according to claim 1, wherein the composite precipitator is compounded with one or more of polyhydroxy compounds such as polyvinyl alcohol, polyethylene glycol, glucose and fructose.

5. The method for treating the spent vanadium electrolyte according to claim 1, wherein the composite precipitator is compounded with one or more of tween compounds such as tween-20, tween 40, tween-60 and tween-80.

6. The method for treating the spent vanadium electrolyte according to claim 1, wherein the solvent used in the composite precipitator is a high boiling point solvent, such as one of N-methyl pyrrolidone, glycerol, silicone oil and triethylene glycol.

7. The method for treating the spent vanadium electrolyte according to claim 1, wherein the conventional alkali liquor is used for adjusting the ph value, and the conventional alkali liquor is one of sodium hydroxide, potassium hydroxide and ammonia water.

8. The method for treating the spent vanadium electrolyte according to claim 1, wherein the acidity of the adjusted solution is neutral, and particularly has a pH of 6 to 8.

9. The method for treating the failed vanadium electrolyte according to claim 1, wherein the mass ratio of the vanadium to be treated to the vanadium precipitation agent is as follows: (1: 1) to (1: 2).

Technical Field

The invention relates to the technical field of energy storage of flow batteries, in particular to a method for treating a failure vanadium electrolyte.

Background

The all vanadium redox flow battery, vanadium battery for short, is a new kind of electrochemical energy storage system, compare with traditional storage battery, it has can be fast, high capacity charge and discharge, the self-discharge rate is low and the characteristic such as the simple battery structure, it is the ideal power supply form that satisfies the large-scale energy storage of new energy such as wind energy, solar energy, etc., as the electrolyte of the battery active material, the positive pole electrolyte is made up of mixed solution of tetravalent and pentavalent vanadium ion and sulfuric acid, the negative pole electrolyte is made up of mixed solution of divalent and trivalent vanadium ion and sulfuric acid; after the battery is charged, the positive electrode substance is a pentavalent vanadium ion sulfuric acid solution, and the negative electrode is a divalent vanadium ion sulfuric acid solution; after the battery is discharged, the positive electrode and the negative electrode are respectively tetravalent and trivalent vanadium ion sulfuric acid solutions, vanadium pentoxide is used as a main raw material for preparing a vanadium electrolyte, and the vanadium electrolyte is widely applied to the related field of vanadium batteries.

The invention with the application number of 201610994027.6 discloses a method for recycling failed vanadium electrolyte, which adopts chemical titration, potentiometric titration and ultraviolet spectrophotometry to determine the content of vanadium ions to regenerate the electrolyte, but vanadium ions in the electrolyte can not be fixed and precipitated at present, and the vanadium electrolyte can not be used due to the phenomena of precipitation, adhesion, valence state unbalance and the like caused by the serious standard exceeding of the vanadium concentration and the acid concentration after being used for a long time by a flow battery, and the existing method can not precipitate the vanadium ions in the failed vanadium electrolyte, is complex in treatment method, high in cost, not suitable for popularization and use and not suitable for industrial large-scale production, so that the problem can be solved by the treatment method of the failed vanadium electrolyte.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a treatment method of a failure vanadium electrolyte, which has the advantages of recovering vanadium in waste liquid and the like, and solves the problems that the vanadium ions in the electrolyte can not be fixed and precipitated at present, the vanadium concentration and the acid concentration of the vanadium electrolyte are seriously overproof after the vanadium electrolyte is used for a long time by a flow battery, the phenomena of precipitation, adhesion, valence state unbalance and the like are generated, the vanadium ions can not be used, the vanadium ions in the failure vanadium electrolyte can not be precipitated at present, the treatment method is complex, the cost is increased, the method is not suitable for popularization and use, and the method is not suitable for industrial large-scale production.

(II) technical scheme

In order to achieve the purpose of recovering vanadium in the waste liquid, the invention provides the following technical scheme: a treatment method of failure vanadium electrolyte is a method which takes failure vanadium electrolyte as raw material, introduces composite precipitator, uses conventional alkali liquor to adjust the solution to be neutral, and fully stirs at normal temperature to ensure that 100 percent of vanadium in the solution is completely precipitated.

Preferably, the vanadium concentration in the spent vanadium electrolyte is: 0.1-3.0 mol/L, and the temperature of the failure vanadium electrolyte is normal temperature.

Preferably, the main salt in the composite precipitator is an organic amine substance such as: one or more of ethylenediamine, triethylamine, polyacrylamide, triethanolamine, dmf, cyclohexylamine, morpholine, aniline, krafft acid, naphthalene diamine, and hydroxylamine.

Preferably, the composite precipitator is compounded with one or more than two of polyhydroxy compounds such as polyvinyl alcohol, polyethylene glycol, glucose and fructose.

Preferably, the composite precipitator is compounded with one or more than two of tween compounds such as tween-20, tween 40, tween-60 and tween-80.

Preferably, the solvent used in the composite precipitant is a high boiling point solvent, such as one of N-methyl pyrrolidone, glycerol, silicone oil, and triethylene glycol.

Preferably, the conventional alkali liquor is used for adjusting the ph value, and the conventional alkali liquor is one of sodium hydroxide, potassium hydroxide and ammonia water.

Preferably, the acidity of the adjusted solution is neutral, and in particular, pH 6-8.

Preferably, the mass ratio of the vanadium to be treated to the vanadium precipitation agent is as follows: (1: 1) to (1: 2).

(III) advantageous effects

Compared with the prior art, the invention provides a treatment method of a failure vanadium electrolyte, which has the following beneficial effects:

1. the processing method of the failure vanadium electrolyte is characterized in that a composite precipitator is introduced, the solution is adjusted to be neutral by using conventional alkali liquor, the required materials are all the existing materials on the market, the required cost is low, the raw materials are easily obtained, more time can be saved for proportioning, in the operation process, only the pH value of the solution needs to be measured, other more accurate measurement is not needed, the influence of measurement errors on the vanadium content in the recovered waste liquid can be well avoided, meanwhile, only stirring is carried out at normal temperature, the processing method is simple, complex operation is not needed, the required time is short, the crystalline vanadium compound is easily prepared, the efficiency of preparing the crystalline vanadium compound can be improved, the required reaction environment is also easily obtained at normal temperature, the crystalline vanadium compound can be prepared by reaction only, the reaction solution does not need to be heated, and the cost is saved more, the use is more environment-friendly and more efficient, and the popularization and the use are easy.

2. The treatment method of the failure vanadium electrolyte introduces the composite precipitator, the precipitation rate of vanadium in the waste liquid is 100 percent of precipitation, because only the PH value needs to be measured during the treatment, the reaction environment is easy to obtain, the raw materials are easy to obtain, the cost is low, the reaction time is short, thereby the period for recovering the vanadium in the waste liquid is shorter, the efficiency for recovering the vanadium is higher, the treatment cost is greatly reduced, the economic benefit is improved, meanwhile, after the vanadium in the failed vanadium electrolyte is precipitated, the solution does not need redundant treatment processes, the treatment processes are reduced, the time is further saved, the efficiency of recovering the vanadium is improved, the treatment period is shortened, the vanadium is more environment-friendly to use, the precipitation rate of the vanadium is 100%, the vanadium is prevented from being discharged to pollute the surrounding environment, the surrounding environment is prevented from being damaged, and therefore the vanadium recovery method is very suitable for industrial large-scale production, and the vanadium in the waste liquid can be completely recovered.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.