CN102328954A - Method for recovering vanadium from lithium vanadium phosphate power battery for electric automobile - Google Patents
Method for recovering vanadium from lithium vanadium phosphate power battery for electric automobile Download PDFInfo
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- CN102328954A CN102328954A CN201110222393A CN201110222393A CN102328954A CN 102328954 A CN102328954 A CN 102328954A CN 201110222393 A CN201110222393 A CN 201110222393A CN 201110222393 A CN201110222393 A CN 201110222393A CN 102328954 A CN102328954 A CN 102328954A
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- Prior art keywords
- vanadium
- power battery
- filtrating
- filter residue
- sodium
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 65
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 37
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 38
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 17
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 235000017550 sodium carbonate Nutrition 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 9
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 4
- 229910052744 lithium Inorganic materials 0.000 claims 4
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 4
- 230000001376 precipitating effect Effects 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 abstract 1
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RFRIWRLHYDZFRS-UHFFFAOYSA-N [Na].[Na].[Na].P(O)(O)(O)=O Chemical compound [Na].[Na].[Na].P(O)(O)(O)=O RFRIWRLHYDZFRS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Abstract
The invention discloses a method for recovering vanadium from a lithium vanadium phosphate power battery for an electric automobile. The method comprises the following steps of: firstly, disassembling the lithium vanadium phosphate power battery to obtain an anode material, crushing and screening the anode material to obtain powder; secondly, adding an ionic compound of sodium in the powder, fully mixing and backing; thirdly, leaching the backed material with solvent and filtering to obtain leachate and filter residue; fourthly, adding an ionic compound of calcium, adjusting the pH value, stirring and mixing, precipitating to separate out calcium vanadate and filtering to obtain filtrate and filter residue; fifthly, washing the filter residue, adding the washed filter residue in a sodium salt solution and stirring, introducing carbon diode into the solution and filtering to obtain filtrate and filter residue; sixthly, adding soluble villaumite in the filtrate, precipitating and filtering to obtain filtrate; seventhly, adding ammonium salt in the filtrate and adjusting the pH value to obtain ammonium metavanadate precipitation; and eighthly, calcining the ammonium metavanadate to obtain vanadic oxide. The recovering method disclosed by the invention has a simple process and high recovery rate.
Description
Technical field
The present invention relates to a kind of method that reclaims vanadium, particularly a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium.
Background technology
Estimate that according to " electromobile development in science and technology " 12 " ad hoc planning " electromobile is the emphasis of following automobile industry development, Chinese electromobile recoverable amount in 2015 plan reaches 1,000,000.As the electromobile most important parts, the power cell limit is a system electromobile development key factor.
The automobile power cell that success is at present gone into operation mainly contains ni-mh and lithium ion battery, and as main phosphoric acid vanadium lithium of the anode material for lithium-ion batteries of power cell and nickle cobalt lithium manganate, because their technology maturation, SF are high.Yet all there is the low and insufficient problem of cycle life of energy density in existing automobile battery, and scientist and scholars are researching and developing new battery material to improve the performance of power cell always.
Phosphoric acid vanadium lithium has higher specific energy and satisfactory stability property, security, is considered to very promising power battery anode material.Have a plurality of research institutions developing the phosphoric acid vanadium lithium positive electrode material both at home and abroad, the shallow company of soup of Japan announces successfully to develop vanadium lithium phosphate power battery especially, and will put goods on the market in 2012.Believe along with what study to deepen continuously and technological improvement that vanadium lithium phosphate power battery will occupy a tiny space in electromobile market afterwards.
For the industrial chain of environment protection and perfect motive battery, the recovery technology of exploitation phosphoric acid vanadium lithium positive electrode material seems quite necessary.Because after power cell is scrapped, if do not deal carefully with recovery, not only can cause the wasting of resources, also can do great damage to physical environment.The technology that the research vanadium lithium phosphate power battery is recycled can be avoided polluting afterwards earlier and administer, and recycles all very meaningful to protection environment and reasonable resources.
Vanadium belongs to the dispersion rare elements, usually and ore association such as iron ore.Vanadium grade in mineral products is very low, generally is lower than 1%, and it is low to reclaim the difficulty and the recovery.And in phosphoric acid vanadium lithium, vanadium has accounted for 25% of total quality.It is thus clear that no matter from the angle of resource and environment, it is all very meaningful from the phosphoric acid vanadium lithium positive electrode material, to reclaim vanadium.
Also do not have at present to the technology and the patent that reclaim vanadium from vanadium lithium phosphate power battery.Patent CN 101058853A has announced that a kind of utilization contains the method for the industrial slag recovery Chemicals of vanadium, chromium, iron and phosphorus.Through the raw material roasting; The grog lixiviate of heating; Red stone with contain vanadium; Chromium; Phosphorus solution separates; The preparatory dephosphorization of solution crystallization; Deep phosphorous removal; Desiliconization; Contain vanadium; The adjustment of chromium solution potential of hydrogen; Extracting vanadium; Chromium separates; The reextraction vanadium; The vanadium deposition; The ammonium meta-vanadate roasting; The chromium reduction; Chromium hydroxide precipitation; Chromium hydroxide separates with sodium sulfate; Deamination; Sulfate crystal separates; Sodium sulfate separates mother liquor purification; The raw phosphoric acid trisodium is made with extra care the resin absorption vanadium; Chromium; Trisodium phosphate solution and phosphatase reaction; The tripoly phosphate sodium STPP drying and roasting; The heat exchange operation is from containing vanadium; Chromium; Extract vanadium in the industrial slag of iron and phosphorus; Chromium; Iron and phosphorus product are also isolated ammoniacal liquor and the sodium sulfate sub product.This technology is many because reclaim metal species, and route is comparatively complicated, is not suitable for the recovery of phosphoric acid vanadium lithium.
Publication number be the patent of CN101121962A disclose a kind of from contain the vanadium chromium solution method of Separation and Recovery vanadium and chromium; This method is earlier with at first using brothers varies extraction agent vanadium; Be strippant then with alkali lye, through the counter current contact mode with vanadium from rich vanadium organic phase back extraction in water; Use the ammonium salt precipitator method with vanadium isolated in form with ammonium meta-vanadate from solution again; Adopt highly efficient distilling technical finesse precipitation supernatant to obtain ammonium meta-vanadate at last.What this method was directed against is to contain the vanadium chromium solution, not exclusively suitable to the solid phosphoric acid vanadium lithium.
Publication number is that the patent of CN101200335A discloses a kind of cupric, vanadium waste comprehensive recovering process; This method is with the preparatory adjust pH to 2.5 of the waste water of cupric, vanadium～4.5; Add oxygenant with the vanadium oxidation, the feed liquid of gained must be born vanadium resin and absorption back liquid through anionite-exchange resin absorption vanadium; Negative vanadium resin is then used the NaOH desorb, and the stripping liquid that obtains adds NH after transferring pH value to 8.0～9.0
4The CL precipitation obtains deposition vanadium mother liquid and ammonium meta-vanadate, ammonium meta-vanadate calcine product V
2O
5Adopt resin to absorb in this procedure, efficient is low, and cost is very high.
Summary of the invention
The object of the present invention is to provide a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium.
The technical scheme that the present invention taked is:
A kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium may further comprise the steps:
1) disassembles vanadium lithium phosphate power battery and obtain positive electrode material and pulverizing, sieve, obtain powder;
2) ionic compound of adding sodium in powder, roasting behind the thorough mixing;
3) material after the roasting is used solvent extraction, filter and obtain leach liquor and filter residue;
4) add the ionic compound of calcium in the leach liquor, the pH value of regulating leach liquor is 9～11, mixes, and deposition is separated out vanadic acid calcium, filters to obtain filtrating and filter residue;
5) washing step 4) in the filter residue that obtains, join again in the sodium salt solution, stir and toward solution in, feed carbonic acid gas, filter and obtain filtrating and solid insoluble;
6) add the solubility villiaumite in the filtrating that obtains in the step 5), deposition is filtered and is obtained filtrating;
7) in the filtrating that step 6) obtains, add ammonium salt, regulating the pH value is 8～9, obtains the ammonium meta-vanadate deposition;
8) calcining step 7) in the ammonium meta-vanadate that obtains obtain Vanadium Pentoxide in FLAKES.
Step 2) in, the ionic compound of described sodium is at least a in sodium hydroxide, yellow soda ash and the sodium-chlor, and the ratio of the amount of substance of the sodium ion in the ionic compound of sodium and the amount of substance of the vanadium in the powder is 2～4:1.
In the step 3), the quality of the material after the roasting and the volume ratio of solvent are 1g:30～50ml.
In the step 4), the ionic compound of described calcium is a quicklime, the amount of substance and the step 2 of calcium ion in the quicklime) in powder in the ratio of amount of substance of vanadium be 1.5～3:1.
In the step 5), described sodium salt is yellow soda ash or sodium hydrogencarbonate, the amount of substance and the step 2 of yellow soda ash or sodium hydrogencarbonate) in powder in the ratio of amount of substance of vanadium be 4～5:1.
In the step 7), described ammonium salt is an ammonium chloride, and its add-on is: the ammonium chloride 40-50g in the corresponding step 7) of the filtrating in the 1L step 5).
After step 3) obtains filter residue, detect the content of the vanadium in the filter residue, if the amount that contains vanadium greater than 0.5wt%, then with filter residue as step 2) in powder.
After obtaining filtrating in the step 4), in filtrating, add sour neutralization filtrate, making its pH is 6.5～7.5, and the filtrating after then will neutralizing is as the solvent in the step 3).
After step 5) obtains solid insoluble, detect the content of the vanadium in the solid insoluble, if the amount that contains vanadium greater than 0.5wt%, then with this solid insoluble as step 2) in powder.
The invention has the beneficial effects as follows: recovery method technology of the present invention is simple, and the chemical that process adopts is cheap and easy to get, the vanadium in can efficient recovery phosphoric acid vanadium lithium positive electrode material, and the recovery reaches more than 90%, and the Vanadium Pentoxide in FLAKES purity of preparation is more than 99.5%.Optimized technical process, the waste water of minimizing and the discharging of solid waste.
Embodiment
A kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium may further comprise the steps:
1) disassembles vanadium lithium phosphate power battery and obtain positive electrode material and pulverizing, sieve, obtain powder, detect the V element content in the powder;
2) in powder, add the ionic compound (in sodium hydroxide, yellow soda ash and the sodium-chlor at least a) of sodium, behind the thorough mixing 500～800 ℃ of following roastings 0.5～2 hour; Wherein, the ratio of the amount of substance of sodium ion and the vanadium amount of substance in the powder is 2～4:1;
3) with the material after the roasting with 70～90 ℃ solvent extraction 1～2 hour, filter and obtain leach liquor and filter residue; The quality of the material after the roasting and the volume ratio of solvent are 1g:30～50ml;
4) add quicklime in the leach liquor, regulate pH value to 9～11 of leach liquor, mix, deposition is separated out vanadic acid calcium, filters to obtain filtrating and filter residue; Wherein, the amount of substance and the step 2 of the calcium ion in the quicklime) in powder in the ratio of vanadium amount of substance be 1.5～3:1;
5) washing step 4) in the filter residue that obtains, join yellow soda ash or sodium hydrogen carbonate solution that volumetric molar concentration is 1 ~ 2mol/L again, stirring and feeding flow in the solution is the carbonic acid gas 1-2h of 30-60L/h, filters to obtain filtrating and solid insoluble; Wherein, the amount of substance and the step 2 of the yellow soda ash of adding or sodium hydrogencarbonate) in powder in the ratio of amount of substance of vanadium be 4～5:1;
6) add the solubility villiaumite in the filtrating that obtains in the step 5), the calcium ions and magnesium ions in the deposition filtrating filters and obtains filtrating; Wherein, the amount of substance and the step 2 of the fluorine in the solubility villiaumite) in powder in the ratio of amount of substance of vanadium be 0.8～1.2:1;
7) in the filtrating that step 6) obtains, add ammonium chloride, regulating the pH value is 8～9, obtains the ammonium meta-vanadate deposition, and its add-on is: the ammonium chloride 40-50g in the corresponding step 7) of the filtrating in the 1L step 5);
8) ammonium meta-vanadate that obtains under 300～500 ℃, calcining step 7) obtained Vanadium Pentoxide in FLAKES 1～2 hour, and is preferred, can be before calcining with deionized water wash 1～3 time;
Preferably, the solvent described in the step 3) is preferably water, perhaps also can be the inorganic salt solution of Na, K.
Preferably,, after step 3) obtains filter residue, detect the content of the vanadium in the filter residue for recycle, if the amount that contains vanadium greater than 0.5wt%, then with filter residue as step 2) in powder, be less than or equal to 0.5wt% if contain the amount of vanadium, then as offal treatment.
Preferably, for recycle, after obtaining in the step 4) filtrating, in filtrating, add acid (being preferably HCl) neutralization filtrate, making its pH is 6.5～7.5, and the filtrating after then will neutralizing is as the solvent in the step 3).
Preferably,, after step 5) obtains solid insoluble, detect the content of the vanadium in the solid insoluble for recycle, if the amount that contains vanadium greater than 0.5wt%, then with this solid insoluble as step 2) in powder; Be less than or equal to 0.5wt% if contain the amount of vanadium, then as offal treatment.
The Determination on content that it should be noted that the vanadium that relates to adopts flame atomic absorption spectrometry (GBT 6730.58-2004).
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
1) disassemble after the discharge of waste and old used for electric vehicle vanadium lithium phosphate power battery, obtain battery anode slice, be put into then in the vertical and high-speed rotary mill and pulverize, the pulverizing time is 10 minutes.Material after the pulverizing sieves with 80 purpose standard sieves, gets the undersized powder of 50g and puts into crucible (through the flame atomic absorption spectrometry determination and analysis, the quality of V element is 6.62g in the powder of 50g);
2) add sodium hydroxide powder 10.4g in the beaker, mix, pour mixed powder into crucible, put into process furnace, obtain the material 13.1g after the roasting 500 ℃ of following roastings 1 hour;
3) material after the roasting being put into the 400ml temperature is that 90 ℃ hot water leached 1 hour, filters then and obtains filtrating;
4) in filtrating, add quicklime 11g, add the pH value to 9 of sodium hydrate regulator solution again, mix, deposition is separated out vanadic acid calcium, filters and obtains filter residue;
5) with the filter residue that obtains of step on the deionized water rinsing three times, the sodium carbonate solution 500ml that puts into volumetric molar concentration then and be 1mol/L dissolves, and stirs and feed in the solution flow and be the carbonic acid gas 1.5 hours of 40L/h, filters to obtain filtrating;
6) add Sodium Fluoride 4.4g in the filtrating that obtains in the step 5), stir, the precipitated calcium mg ion filters and obtains filtrating;
7) in the filtrating that step 6) obtains, add ammonium chloride 16g and stirring, adding sodium hydroxide adjusting pH value in addition is 8, separates out the ammonium meta-vanadate deposition;
8) precipitate 1 time with the deionized water wash ammonium meta-vanadate, place crucible, put into process furnace then, calcined 3 hours down, obtain Vanadium Pentoxide in FLAKES at 300 ℃.
The Vanadium Pentoxide in FLAKES weight that weighing obtains is 11.87g, and the Vanadium Pentoxide in FLAKES purity of preparation is 99.5% simultaneously.
Embodiment 2
1) disassemble after the discharge of waste and old used for electric vehicle vanadium lithium phosphate power battery, obtain battery anode slice, be put into then in the vertical and high-speed rotary mill and pulverize, the pulverizing time is 15 minutes.Material after the pulverizing sieves with 80 purpose standard sieves, gets the undersized powder of 50g and puts into crucible (through the flame atomic absorption spectrometry determination and analysis, the quality of V element is 6.87g in the powder of 50g);
2) add sodium hydroxide powder 21.6g in the beaker, mix, pour mixed powder into crucible, put into process furnace, obtain the material 19.7g after the roasting 600 ℃ of following roastings 2 hours;
3) material after the roasting being put into the 950ml temperature is that 70 ℃ hot water leached 1 hour, filters then and obtains filtrating;
4) in filtrating, add quicklime 23g and stirring, the pH value that adds sodium hydrate regulator solution again is 10, mixes, and deposition is separated out vanadic acid calcium, filters to obtain filter residue;
5) with the filter residue that obtains of step on the deionized water rinsing three times, the sodium carbonate solution of putting into the 340ml volumetric molar concentration then and be 2mol/L dissolves, and stirs and feed in the solution flow and be the carbonic acid gas 1 hour of 60L/h, filters to obtain filtrating;
6) add Sodium Fluoride 6.8g in the filtrating that obtains in the step 5) and stir, the precipitated calcium mg ion filters and obtains filtrating;
7) in the filtrating that step 6) obtains, add ammonium chloride 16g and stirring, adding sodium hydroxide adjusting pH value in addition is 8.5, separates out the ammonium meta-vanadate deposition;
8) precipitate 2 times with the deionized water wash ammonium meta-vanadate, place crucible, put into process furnace then, calcined 2 hours down, obtain Vanadium Pentoxide in FLAKES at 400 ℃.
The Vanadium Pentoxide in FLAKES weight that weighing obtains is 12.32g, and the Vanadium Pentoxide in FLAKES purity of preparation is 99.7% simultaneously.
Embodiment 3
1) disassemble after the discharge of waste and old used for electric vehicle vanadium lithium phosphate power battery, obtain battery anode slice, be put into then in the vertical and high-speed rotary mill and pulverize, the pulverizing time is 20 minutes.Material after the pulverizing sieves with 80 purpose standard sieves, gets the undersized powder of 50g and puts into crucible (through the flame atomic absorption spectrometry determination and analysis, the quality of V element is 6.31g in the powder of 50g);
2) add sodium hydroxide powder 15g in the beaker, mix, pour mixed powder into crucible, put into process furnace, obtain the material 15.6g after the roasting 800 ℃ of following roastings 0.5 hour;
3) material after the roasting being put into the 600ml temperature is that 80 ℃ hot water leached 2 hours, filters then and obtains filtrating;
4) in filtrating, add quicklime 14g, the pH value that adds sodium hydrate regulator solution again is 11, mixes, and deposition is separated out vanadic acid calcium, filters and obtains filter residue;
5) with the filter residue that obtains of step on the deionized water rinsing three times, the sodium carbonate solution of putting into the 400ml volumetric molar concentration then and be 1.5mol/L dissolves, and stirring and feeding flow in the solution is 30L/h carbonic acid gas 2 hours, filters to obtain filtrating;
6) add Sodium Fluoride 6.3g in the filtrating that obtains in the step 5) and stir, the precipitated calcium mg ion filters and obtains filtrating;
7) in the filtrating that step 6) obtains, add ammonium chloride 18g and stirring, adding sodium hydroxide adjusting pH value in addition is 9, separates out the ammonium meta-vanadate deposition.
8) precipitate 3 times with the deionized water wash ammonium meta-vanadate, place crucible, put into process furnace then, calcined 2 hours down, obtain Vanadium Pentoxide in FLAKES at 500 ℃.
The Vanadium Pentoxide in FLAKES weight that weighing obtains is 11.33g, and the Vanadium Pentoxide in FLAKES purity of preparation is 99.6% simultaneously.
Claims (9)
1. method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium may further comprise the steps:
1) disassembles vanadium lithium phosphate power battery and obtain positive electrode material and pulverizing, sieve, obtain powder;
2) ionic compound of adding sodium in powder, roasting behind the thorough mixing;
3) material after the roasting is used solvent extraction, filter and obtain leach liquor and filter residue;
4) add the ionic compound of calcium in the leach liquor, the pH value of regulating leach liquor is 9～11, mixes, and deposition is separated out vanadic acid calcium, filters to obtain filtrating and filter residue;
5) washing step 4) in the filter residue that obtains, join again in the sodium salt solution, stir and toward solution in, feed carbonic acid gas, filter and obtain filtrating and solid insoluble;
6) add the solubility villiaumite in the filtrating that obtains in the step 5), deposition is filtered and is obtained filtrating;
7) in the filtrating that step 6) obtains, add ammonium salt, regulating the pH value is 8～9, obtains the ammonium meta-vanadate deposition;
8) calcining step 7) in the ammonium meta-vanadate that obtains obtain Vanadium Pentoxide in FLAKES.
2. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium according to claim 1; It is characterized in that: step 2) in; The ionic compound of described sodium is at least a in sodium hydroxide, yellow soda ash and the sodium-chlor, and the ratio of the amount of substance of the sodium ion in the ionic compound of sodium and the amount of substance of the vanadium in the powder is 2～4:1.
3. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims lithium according to claim 1, it is characterized in that: in the step 3), the quality of the material after the roasting and the volume ratio of solvent are 1g:30～50ml.
4. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium according to claim 1; It is characterized in that: in the step 4); The ionic compound of described calcium is a quicklime, the amount of substance and the step 2 of calcium ion in the quicklime) in powder in the ratio of amount of substance of vanadium be 1.5～3:1.
5. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium according to claim 1; It is characterized in that: in the step 5); Described sodium salt is yellow soda ash or sodium hydrogencarbonate, the amount of substance and the step 2 of yellow soda ash or sodium hydrogencarbonate) in powder in the ratio of amount of substance of vanadium be 4～5:1.
6. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims vanadium according to claim 1; It is characterized in that: in the step 7); Described ammonium salt is an ammonium chloride, and its add-on is: the ammonium chloride 40-50g in the corresponding step 7) of the filtrating in the 1L step 5).
7. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims lithium according to claim 1; It is characterized in that: after step 3) obtains filter residue; Detect the content of the vanadium in the filter residue, if the amount that contains vanadium greater than 0.5wt%, then with filter residue as step 2) in powder.
8. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims lithium according to claim 1; It is characterized in that: after obtaining filtrating in the step 4); In filtrating, add sour neutralization filtrate, making its pH is 6.5～7.5, and the filtrating after then will neutralizing is as the solvent in the step 3).
9. a kind of method that from the used for electric vehicle vanadium lithium phosphate power battery, reclaims lithium according to claim 1; It is characterized in that: after step 5) obtains solid insoluble; Detect the content of the vanadium in the solid insoluble; If the amount that contains vanadium is greater than 0.5wt%, then with this solid insoluble as step 2) in powder.
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| CN108773847A (en) * | 2018-08-17 | 2018-11-09 | 湖南金凯循环科技有限公司 | A method of the waste and old phosphoric acid vanadium lithium of recycling |
| CN108977665A (en) * | 2018-08-17 | 2018-12-11 | 湖南金凯循环科技有限公司 | A method of recycling waste and old lithium manganese phosphate |
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