CN108773847A - A method of the waste and old phosphoric acid vanadium lithium of recycling - Google Patents
A method of the waste and old phosphoric acid vanadium lithium of recycling Download PDFInfo
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- CN108773847A CN108773847A CN201810942090.4A CN201810942090A CN108773847A CN 108773847 A CN108773847 A CN 108773847A CN 201810942090 A CN201810942090 A CN 201810942090A CN 108773847 A CN108773847 A CN 108773847A
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- phosphoric acid
- waste
- lithium
- acid vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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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
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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
Abstract
A method of the waste and old phosphoric acid vanadium lithium of recycling includes the following steps：Step 1: waste and old phosphoric acid vanadium lithium is aoxidized 0.5-3h in 300-600 DEG C under the conditions of in the stove for being passed through air, according to 1 after oxidation:10-1:Water is added in 3 solid-to-liquid ratio, obtains the first slurry；Step 2: calcium salt is added into the first slurry obtained by step 1, solution, the filter residue containing vanadium and calcium phosphate that lithium-containing compound is then obtained by filtration；Step 3: into the filter residue containing vanadium and calcium phosphate according to solid-to-liquid ratio be 1:7-1:The second slurry is made in 2 addition water；Step 4: sodium carbonate or sodium hydroxide are added into the second slurry obtained by step 3, the pH value of solution is made to rise to 12.6-14.0, then filters up to sodium vanadate solution and calcium phosphate filter residue, sodium vanadate solution condensing crystallizing is obtained into sodium vanadate crystal.The recovery method is relatively simple, the phosphoric acid vanadium lithium Powder Recovery in phosphoric acid vanadium lithium cell positive material can be obtained to the solution and the higher sodium vanadate crystal of purity of lithium-containing compound, it is therefore prevented that waste and old phosphoric acid vanadium lithium powder pollutes the environment.
Description
Technical field
The present invention relates to old and useless battery recycling fields, are related specifically to a kind of method of the waste and old phosphoric acid vanadium lithium of recycling.
Background technology
It is more and more widely used with its excellent properties in fields, the lithium ion battery such as communication and digital product,
Yield constantly increases.Compared with LiFePO4, phosphoric acid vanadium lithium is because it is high, higher than energy with specific capacity, the good spy of heavy-current discharge
It is not the good advantage of low temperature performance, becomes the new hope of power lithium-ion battery positive electrode.Although phosphoric acid vanadium lithium battery
The big heavy metal element of the murders by poisoning such as not mercurous, cadmium, lead is compared with conventional batteries, positive and negative pole material and electrolyte can endanger environment
And health, it should be recycled.
Application No. is the Chinese patents of " 2011102223937 " to disclose one kind from phosphoric acid vanadium lithium power electric for electric vehicle
The method that vanadium is recycled in pond, this approach includes the following steps：1）Dismantling vanadium lithium phosphate power battery obtain positive electrode and crush,
Screening, obtains powder；2）The ionic compound of sodium is added in powder, is roasted after being sufficiently mixed；3）Material after roasting is used
Leachate and filter residue is obtained by filtration in extraction；4）In leachate plus the ionic compound of calcium, the pH values for adjusting leachate are 9
~11, it is stirred, filtrate and filter residue is obtained by filtration in Precipitation calcium vanadate；5）Washing step 4）In obtained filter residue, then
It is added in sodium salt solution, stirs and is passed through carbon dioxide into solution, filtrate and solid insoluble is obtained by filtration；6）Toward step
5）In soluble villiaumite is added in obtained filtrate, filtrate is obtained by filtration in precipitation；7）To step 6）Ammonium is added in obtained filtrate
Salt, it is 8~9 to adjust pH values, obtains ammonium metavanadate precipitate；8）Calcining step 7）In obtained ammonium metavanadate obtain five oxidations
Two vanadium.The patent can finally recycle to obtain vanadic anhydride, and in order to improve purity, production technology is sufficiently complex, need to control
Parameter is more harsh, and cost is higher, and the control of waste recovery field production cost is particularly significant, thus above scheme it is more difficult into
Row practical application.
For sodium vanadate in shallow white clear is needle-shaped or hexagonal prismatic crystal, easy-weathering, white after dehydration in air, can
It is more for the desulfurization and decarburization of industrial gasses, corrosion inhibiter, pharmaceuticals industry, photography, the manufacture printing and dyeing of ink and the inoculation of plant etc.
Kind purposes, consumption is very huge, as can the phosphoric acid vanadium lithium in waste and old phosphoric acid vanadium lithium cell positive material is recovered as positive vanadic acid
Sodium not only reduces the wasting of resources, but also protects environment, and is also found no about by waste and old phosphoric acid vanadium lithium before deadline
Recycling obtains the report of sodium vanadate.
Invention content
The technical problem to be solved in the present invention is to provide a kind of method of the waste and old phosphoric acid vanadium lithium of recycling, be returned by this method
Receipts obtain the solution and the higher sodium vanadate crystal of purity of lithium-containing compound, effectively realize the recycling of waste and old resource.
To solve the above-mentioned problems, using following technical scheme：A method of the waste and old phosphoric acid vanadium lithium of recycling, including it is following
Step：
Step 1: waste and old phosphoric acid vanadium lithium is aoxidized 0.5-3h in 300-600 DEG C under the conditions of in the stove for being passed through air, pressed after oxidation
According to 1:10-1:Water is added in 3 solid-to-liquid ratio, obtains the first slurry；
Step 2: calcium salt is added into the first slurry obtained by step 1, the solution of lithium-containing compound is then obtained by filtration, contains vanadium
With the filter residue of calcium phosphate；
Step 3: into the filter residue containing vanadium and calcium phosphate obtained by step 2 according to solid-to-liquid ratio be 1:7-1:2 addition water are made the
Two slurries；
Step 4: sodium carbonate or sodium hydroxide are added into the second slurry obtained by step 3, the pH value of solution is made to rise to
Then 12.6-14.0 filters up to sodium vanadate solution and calcium phosphate filter residue, sodium vanadate solution condensing crystallizing is obtained positive vanadium
Sour sodium crystal.
Preferably, after step 2 obtains the solution of lithium-containing compound, the pH of sodium hydrate regulator solution is continuously added
It is 10, then filters, the filtrate being obtained by filtration fully is reacted with sodium carbonate and is concentrated by evaporation up to lithium carbonate.The use of lithium carbonate
It is relatively broad on the way, it can be used for producing compound, lithium metal and its isotope of various lithiums, and in semiconductor, ceramics, TV, doctor
Also there is application in medicine and atomic energy industry.
The waste and old phosphoric acid vanadium lithium is obtained by following methods：It disassembles waste and old phosphoric acid vanadium lithium battery to obtain positive electrode, so
By crushing, sieve to obtain the final product.
Wherein, calcium salt described in step 2 is selected from the mixture of one or both of calcium chloride or calcium sulfate.
Preferably, the molar ratio of phosphate anion is in calcium ion and first slurry in calcium salt described in step 2
1.6-1.8。
Preferably, the solid-to-liquid ratio between the filter residue and water containing vanadium and calcium phosphate in step 3 is 1:5.
Compared to the prior art, the invention has the advantages that：Technique is relatively simple, can return waste and old phosphoric acid vanadium lithium
Receipts obtain the solution and sodium vanadate crystal of lithium-containing compound.The solution of lithium-containing compound can be used for preparing all kinds of lithium compounds,
Such as sodium hydroxide is added into the solution of lithium-containing compound, and then filter, the filtrate being obtained by filtration and sodium carbonate is fully anti-
Should and be concentrated by evaporation and obtain lithium carbonate, the purposes of lithium carbonate is relatively broad, can be used for producing the compounds of various lithiums, lithium metal and
Its isotope, and also have application in semiconductor, ceramics, TV, medicine and atomic energy industry；Sodium vanadate crystal can be used for work
The desulfurization and decarburization of industry gas, corrosion inhibiter, pharmaceuticals industry, the manufacture of photography, ink is printed and dyed and the inoculation etc. of plant.In the present invention
The method of the waste and old phosphoric acid vanadium lithium of recycling can obtain the phosphoric acid vanadium lithium Powder Recovery in phosphoric acid vanadium lithium cell positive material
The higher sodium vanadate crystal of solution and purity of lithium-containing compound, realizes the recycling of waste and old resource, alleviates environment dirt
Dye has extremely wide application prospect.
Specific implementation mode
Embodiment is given below so that the present invention to be specifically described, it is necessary to which indicated herein is following embodiment
It is used to further illustrate the present invention, should not be understood as limiting the scope of the invention, the ordinary skill in the field
Personnel still fall within protection scope of the present invention to the nonessential improvement of some made of the invention or adjustment according to this embodiment.
Embodiment 1
A method of the waste and old phosphoric acid vanadium lithium of recycling includes the following steps：
Step 1: the waste and old phosphoric acid vanadium lithiums of 1kg are aoxidized 3h in 300 DEG C under the conditions of in the stove for being passed through air, by the powder after oxidation
End is placed in container, and the water of 3L is added into container, obtains the first slurry；
Step 2: calcium chloride dihydrate 1.5kg is added into the first slurry obtained by step 1, filtered after being stirred continuously reaction 1h,
Solution 600ml, the filter residue containing vanadium and calcium phosphate for obtaining lithium-containing compound are closed by flame atomic absorption spectrometry test containing lithiumation
The content of lithium in the solution of object, result 8.3g/L, the quality that lithium in the solution of lithium-containing compound thus can be calculated are
4.98g；
Step 3: into the filter residue containing vanadium and calcium phosphate obtained by step 2 according to solid-to-liquid ratio be 1:The second slurry is made in 3 addition water
Material；
Step 4: sodium hydrate solid is added into the second slurry obtained by step 3, the pH value of solution is set to rise to 13.0, so
After filter up to sodium vanadate solution and calcium phosphate filter residue, sodium vanadate solution condensing crystallizing is obtained into sodium vanadate crystal, will
Sodium vanadate solution condensing crystallizing obtains sodium vanadate crystal, and the purity of the sodium vanadate crystal is 99.6%.
Embodiment 2
A method of the waste and old phosphoric acid vanadium lithium of recycling includes the following steps：
Step 1: the waste and old phosphoric acid vanadium lithiums of 1kg are aoxidized 0.5h in 600 DEG C under the conditions of in the stove for being passed through air, after oxidation
Powder is placed in container, and the water of 3L is added into container, obtains the first slurry；
Step 2: calcium chloride dihydrate 1.5kg is added into the first slurry obtained by step 1, filtered after being stirred continuously reaction 1h,
Solution 600ml, the filter residue containing vanadium and calcium phosphate for obtaining lithium-containing compound are closed by flame atomic absorption spectrometry test containing lithiumation
The content of lithium in the solution of object, result 8.3g/L, the quality that lithium in the solution of lithium-containing compound thus can be calculated are
4.98g；
Step 3: into the filter residue containing vanadium and calcium phosphate obtained by step 2 according to solid-to-liquid ratio be 1:The second slurry is made in 5 addition water
Material；
Step 4: sodium hydrate solid is added into the second slurry obtained by step 3, the pH value of solution is set to rise to 12.6, so
After filter up to sodium vanadate solution and calcium phosphate filter residue, sodium vanadate solution condensing crystallizing is obtained into sodium vanadate crystal, will
Sodium vanadate solution condensing crystallizing obtains sodium vanadate crystal, and the purity of the sodium vanadate crystal is 99.4%.
Embodiment 3
A method of the waste and old phosphoric acid vanadium lithium of recycling includes the following steps：
Step 1: the waste and old phosphoric acid vanadium lithiums of 1kg are aoxidized 1h in 400 DEG C under the conditions of in the stove for being passed through air, by the powder after oxidation
End is placed in container, and the water of 3L is added into container, obtains the first slurry；
Step 2: calcium chloride dihydrate 1.5kg is added into the first slurry obtained by step 1, filtered after being stirred continuously reaction 1h,
Solution 600ml, the filter residue containing vanadium and calcium phosphate for obtaining lithium-containing compound are closed by flame atomic absorption spectrometry test containing lithiumation
The content of lithium in the solution of object, result 8.4g/L, the quality that lithium in the solution of lithium-containing compound thus can be calculated are
5.04g；
Step 3: into the filter residue containing vanadium and calcium phosphate obtained by step 2 according to solid-to-liquid ratio be 1:The second slurry is made in 10 addition water
Material；
Step 4: sodium hydrate solid is added into the second slurry obtained by step 3, the pH value of solution is set to rise to 14.0, so
After filter up to sodium vanadate solution and calcium phosphate filter residue, sodium vanadate solution condensing crystallizing is obtained into sodium vanadate crystal, will
Sodium vanadate solution condensing crystallizing obtains sodium vanadate crystal, and the purity of the sodium vanadate crystal is 99.4%.
Claims (5)
1. a kind of method of the waste and old phosphoric acid vanadium lithium of recycling, which is characterized in that include the following steps：
Step 1: waste and old phosphoric acid vanadium lithium is aoxidized 0.5-3h in 300-600 DEG C under the conditions of in the stove for being passed through air, pressed after oxidation
According to 1:10-1:Water is added in 3 solid-to-liquid ratio, obtains the first slurry；
Step 2: calcium salt is added into the first slurry obtained by step 1, the solution of lithium-containing compound is then obtained by filtration, contains vanadium
With the filter residue of calcium phosphate；
Step 3: into the filter residue containing vanadium and calcium phosphate obtained by step 2 according to solid-to-liquid ratio be 1:7-1:2 addition water are made the
Two slurries；
Step 4: sodium carbonate or sodium hydroxide are added into the second slurry obtained by step 3, the pH value of solution is made to rise to
Then 12.6-14.0 filters up to sodium vanadate solution and calcium phosphate filter residue, sodium vanadate solution condensing crystallizing is obtained positive vanadium
Sour sodium crystal.
2. the method for the waste and old phosphoric acid vanadium lithium of recycling according to claim 1, which is characterized in that the waste and old phosphoric acid vanadium lithium by
Following methods obtain：It disassembles waste and old phosphoric acid vanadium lithium battery to obtain positive electrode, then through crushing, sieving to obtain the final product.
3. the method for the waste and old phosphoric acid vanadium lithium of recycling according to claim 1, which is characterized in that calcium salt described in step 2 selects
From the mixture of one or both of calcium chloride or calcium sulfate.
4. the method for the waste and old phosphoric acid vanadium lithium of recycling according to claim 3, which is characterized in that in calcium salt described in step 2
The molar ratio of phosphate anion is 1.6-1.8 in calcium ion and first slurry.
5. the method for the waste and old phosphoric acid vanadium lithium of recycling according to claim 1, which is characterized in that contain vanadium and phosphoric acid in step 3
Solid-to-liquid ratio between the filter residue and water of calcium is 1:5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810942090.4A CN108773847B (en) | 2018-08-17 | 2018-08-17 | Method for recovering waste lithium vanadium phosphate |
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|---|---|---|---|
| CN201810942090.4A CN108773847B (en) | 2018-08-17 | 2018-08-17 | Method for recovering waste lithium vanadium phosphate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115341098A (en) * | 2022-08-12 | 2022-11-15 | 宁波容百新能源科技股份有限公司 | Method for recovering vanadium from waste sodium-ion battery |
| WO2024045513A1 (en) * | 2022-08-29 | 2024-03-07 | 广东邦普循环科技有限公司 | Method for recovering sodium vanadium phosphate positive electrode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328954A (en) * | 2011-08-04 | 2012-01-25 | 佛山市邦普循环科技有限公司 | Method for recovering vanadium from lithium vanadium phosphate power battery for electric automobile |
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2018
- 2018-08-17 CN CN201810942090.4A patent/CN108773847B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328954A (en) * | 2011-08-04 | 2012-01-25 | 佛山市邦普循环科技有限公司 | Method for recovering vanadium from lithium vanadium phosphate power battery for electric automobile |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115341098A (en) * | 2022-08-12 | 2022-11-15 | 宁波容百新能源科技股份有限公司 | Method for recovering vanadium from waste sodium-ion battery |
| WO2024045513A1 (en) * | 2022-08-29 | 2024-03-07 | 广东邦普循环科技有限公司 | Method for recovering sodium vanadium phosphate positive electrode material |
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| CN108773847B (en) | 2021-01-15 |
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Address after: No. 421, Dongjiang Circular Industrial Park, Dongyang City, Hunan Province Patentee after: Hunan Jinkai Recycling Technology Co.,Ltd. Address before: No. 421, Dongjiang Circular Industrial Park, Dongyang City, Hunan Province Patentee before: HUNAN KEYKING CYCLE TECHNOLOGY Co.,Ltd. |