CN108929956A - A kind of processing method of discarded LiFePO4 middle material - Google Patents
A kind of processing method of discarded LiFePO4 middle material Download PDFInfo
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- CN108929956A CN108929956A CN201810757717.9A CN201810757717A CN108929956A CN 108929956 A CN108929956 A CN 108929956A CN 201810757717 A CN201810757717 A CN 201810757717A CN 108929956 A CN108929956 A CN 108929956A
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- Prior art keywords
- lifepo4
- obtains
- filter residue
- added
- phosphate
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 52
- 238000003672 processing method Methods 0.000 title claims abstract description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 36
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 34
- 239000000706 filtrate Substances 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 27
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 21
- 230000008020 evaporation Effects 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940056319 ferrosoferric oxide Drugs 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000010438 heat treatment Methods 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 19
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000005955 Ferric phosphate Substances 0.000 description 7
- 229940032958 ferric phosphate Drugs 0.000 description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical class [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of processing methods of discarded LiFePO4 middle material.After discarded LiFePO4 middle material is collected, pure water is added and carries out pulp, is filtered after then passing to carbon dioxide, filter residue is washed, and filtrate obtains dried feed by spray drying；Filter residue is poured into sealing reaction kettle, ammonium hydroxide reaction is added, reducing agent reduction, then temperature reaction is then added, pressure release, and release material, it is filtered, obtains ferroso-ferric oxide filter residue and phosphorous filtrate, phosphorous filtrate crystallizes to obtain phosphate by concentration and evaporation, after ferroso-ferric oxide filter residue dries pulverizing, electromagnetic separation is carried out after screening, obtains electromagnetic separation material；After obtained phosphate is mixed with electromagnetic separation material, it is put into calcining in rotary kiln, obtains anhydrous iron phosphate；After dried feed is mixed with anhydrous iron phosphate, sintering obtains LiFePO4.Present invention process is simple, and the rate of recovery of the recycling and each component that realize each component is high.
Description
Technical field
The present invention relates to a kind of processing methods of discarded LiFePO4 middle material, belong to circular economy technical field.
Background technique
LiFePO4 (molecular formula:LiFePO4；English: Lithiumironphosphate；Also known as iron lithium phosphate, lithium iron
Phosphorus；Abbreviation LFP), it is a kind ofLithium ion batteryPositive electrode.The NTT Japanese from 1996 discloses AyMPO4 for the first time, and (A isAlkali Metal, M is the combination of both CoFe: LiFeCOPO4)OlivineStructureAnode material of lithium batteryLater, the U.S. in 1997The state university in TexasIt is de- that the research group such as John.B.Goodenough has also then reported reversibly moving into for LiFePO4
The characteristic of lithium out, the U.S. and Japan coincidentally deliver olivine structural (LiMPO4), so that the material receives greatly
Pay attention to, and causes widely to study and rapidly development.With it is traditionalLithium ion secondary batteryPositive electrode,SpinelleStructure
LiMn2O4 is compared with the LiCoO2 of layer structure, and the raw material source of LiMPO4 is more extensive, price is less expensive and dirty without environment
Dye.
The application field of LiFePO4 mainly has:
(1) energy storage device
The energy storage device of solar energy, wind generator system, uninterrupted power system UPS, cooperationSolar batteryUsed as storage
It can equipment (BYD is producing such battery)；
(2) electric tool class
High power electric tool (wireless), electric drill,WeederDeng；
(3) lightweight electric powered vehicles
Electric motor car,Electric bicycle, recreation vehicle, golf cart, electric lift truck,Clean vehicle,Hybrid vehicle
(HEV), the target of recent 2-3；
(4) small device
Medical Devices:Electric wheel-chair vehicle,Electric bicycle), toy (remote controlElectric airplane, vehicle, ship)；
(5) other compact electric apparatus
Mine lamp, the medical instrument (LiFePO4 is non-toxic, and only iron lithium can be met the requirements lithium battery) of implantable, substitutes lead
Acid, ni-mh, ni-Cd, lithium cobalt, application of the lithium manganese class battery on compact electric apparatus.
(6) mobile power source
Solid phase method becomes the prevailing technology of the production of present LiFePO4, is mixed using ferric phosphate, lithium carbonate and glucose
After carry out it is levigate, dry after be sintered, due to each process, upper material process before such as levigate process, drying process and sintering all exists
It is certain to gather dust material and ground scatters material, while cleaning equipment can also generate certain useless middle material, according to statistics, each ton of phosphorus
Sour iron lithium product can generate useless middle material 5kg or so, be produced per year for 20,000 tons of LiFePO4 workshop according to one, and generation is given up
Middle material can achieve 100 tons or so, these useless middle materials are most of after calcining at present, be sold to the producer of recycling lithium, often
The price of ton is cheap less than 5000 yuan, and sintering process can generate energy consumption with manually, be worth lower.
Summary of the invention
In view of this, the present invention provides a kind of processing method of discarded LiFePO4 middle material, simple process, cost
Low, the added value of product recycled is high, is the raw material of LiFePO4, realizes the recycling of each component and each component
The rate of recovery it is high, can be sintered to obtain LiFePO4 again after finally carrying out ingredient again.
The present invention solves above-mentioned technical problem by following technological means:
A kind of processing method of discarded LiFePO4 middle material of the invention, is following steps:
(1) after collecting discarded LiFePO4 middle material, pure water is added and carries out pulp, then passes to carbon dioxide to filter residue
In lithium content be lower than 200ppm, be filtered, filter residue is washed；
(2) filter residue after washing that step (1) obtains is poured into sealing reaction kettle, ammonium hydroxide is added, adjusts the pH of solution
For 8-8.5, it is 30-45 DEG C of reaction 15-30min in temperature, reducing agent is then added and is restored to ferric iron and ferrous iron in material
Molar ratio be 2:1.01-1.02, then heat to temperature be 95-105 DEG C, be stirred to react 2-4 hours, be subsequently cooled to temperature
For 30 DEG C hereinafter, pressure release, and material is released；
(3) material that step (2) release is filtered, obtains ferroso-ferric oxide filter residue and phosphorous filtrate, by four oxidations
After pure water is added in three-iron filter residue, dried in vacuum drying oven, then after air-flow crushing is crushed, through being sieved
Electromagnetic separation is carried out after point, obtains electromagnetic separation material；
(4) filtrate that step (1) is obtained by filtration obtains dried feed, the inlet air temperature of spray drying by spray drying
At 120-160 DEG C, drop temperature is controlled at 70 DEG C or less for control；
(5) phosphorous filtrate that step (3) obtains is crystallized to obtain phosphate by concentration and evaporation, by obtained phosphate with
After the mixing of electromagnetic separation material, adds phosphate or molysite makes the iron phosphorus molar ratio in mixture be 1:1, be put into rotary kiln
Interior calcining, being fired to temperature is 550-690 DEG C, and calcination time is 12-15 hours, obtains anhydrous iron phosphate；
(6) after mixing the dried feed that step (4) obtains with the anhydrous iron phosphate that step (5) obtains, mixing, mill are carried out
Carefully, it is then placed in sintering in sintering furnace, obtains LiFePO4.
Solid-to-liquid ratio is 1:3-4 when step (1) pulp, and the washing water that washing filter residue obtains and the filtrate being obtained by filtration are mixed
It is combined together.
The reducing agent being added in the step (2) is hydrazine hydrate, and pressure leak process, it is molten that the gas that pressure release is come out passes through phosphoric acid
Liquid absorbs, when the pH for being absorbed into phosphoric acid solution is 5.5-6.5, with the progress concentration and evaporation crystallization admixed together of phosphorous filtrate.
When carrying out vacuum drying in the step (3), drying temperature is 75-85 DEG C, vacuum degree is -0.09~-
0.08MPa, the partial size of air-flow crushing to ferroso-ferric oxide are 150-250 μm, cross 200-250 mesh, electromagnetism when electromagnetic separation
Intensity is 8000-10000 Gauss.
Concentration and evaporation crystallization process in the step (5), the Baume degrees for being concentrated into solution is 50-52, is subsequently cooled to temperature
Degree is 25-30 DEG C, then carries out centrifuge dripping, fluidized bed drying, the mother liquor recycle after drying using the calcium into mother liquor from
When the sum of son, magnesium ion are greater than 100ppm, ammonium fluoride removing calcium and magnesium is added, the solution after removing calcium and magnesium returns again to use.
Step (6) dried feed and anhydrous iron phosphate mixed process, by be additionally added anhydrous iron phosphate, lithium carbonate or
Carbon source, maintain the lithium in mixture, iron, phosphorus molar ratio be 1.01-1.02:1:1, while maintaining the LiFePO4 that finally prepares
The mass fraction of middle carbon is 1-2%.
The present invention pass through pulping and washing after be passed through carbon dioxide again, due to carbon source be it is soluble, dissolve after washing
Into water, and it is passed through carbon dioxide, realizes the process for converting lithium carbonate to lithium bicarbonate, after filtering, realizes solid-liquid
Separation, then by the mixed solution of carbon source and lithium bicarbonate by being spray-dried, lithium bicarbonate is dry and decomposition obtains lithium carbonate, from
And the recycling of carbon source and lithium carbonate is realized, ammonium hydroxide is added, realizes precipitating conversion, iron hydroxide is converted by ferric phosphate, adds
Enter reducing agent and convert ferrous hydroxide for part iron hydroxide, carries out dehydration at high temperature and obtain ferroso-ferric oxide, into
After row is separated by solid-liquid separation, obtained solution is ammonium dibasic phosphate solution, crystallizes to obtain the crystal of diammonium hydrogen phosphate by concentration and evaporation,
By obtained ferroso-ferric oxide after vacuum drying, air-flow crushing, using electromagnetic separation, due to the magnetic of ferroso-ferric oxide
Property, it is easy to it is separated with nonmagnetic other impurities, so that molysite has been purified, and the mother liquor that concentration and evaporation crystallizes follows
Ring several times after, detect impurity therein, continued to use after removal of impurities after impurity is high, that is, ensure that purity, and improve product
The rate of recovery, then obtained ferroso-ferric oxide is calcined at high temperature with diammonium hydrogen phosphate, obtains anhydrous iron phosphate, and ammonium root passes through
It crosses high-temperature calcination to volatilize to obtain ammonia, returns and use after phosphoric acid solution absorbs, avoid the pollution of environment, realize simultaneously
The recycling of each component.
Each component is subjected to mix again, additionally increases carbon source, lithium salts, phosphate, source of iron, according to a certain percentage
It is calcined after mixing, and LiFePO4 can be prepared, fully achieve recycling for waste material.
The rate of recovery of finally obtained carbon source is greater than 99%, and the rate of recovery of lithium carbonate is greater than 98%, the rate of recovery of ferric phosphate
> 97%, each performance of the LiFePO4 finally prepared is identical as the performance of LiFePO4 prepared using new raw material, phase
Compare and sold as waste material, this technique middle material per ton can recycle nearly 710 kilograms of ferric phosphate, and lithium carbonate nearly 170 is public
Jin, nearly 95 kilograms of carbon source, according to current market price, benefit is up to 3.3 ten thousand, much larger than the price sold.
Beneficial effects of the present invention: simple process and low cost, it is LiFePO4 that the added value of product recycled is high
Raw material, the rate of recovery of the recycling and each component that realize each component is high, can be sintered again after finally carrying out ingredient again
Obtain LiFePO4.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail: in a kind of discarded LiFePO4 of the present embodiment
Between the processing method expected, be following steps:
(1) after collecting discarded LiFePO4 middle material, pure water is added and carries out pulp, then passes to carbon dioxide to filter residue
In lithium content be lower than 200ppm, be filtered, filter residue is washed；
(2) filter residue after washing that step (1) obtains is poured into sealing reaction kettle, ammonium hydroxide is added, adjusts the pH of solution
For 8-8.5, it is 30-45 DEG C of reaction 15-30min in temperature, reducing agent is then added and is restored to ferric iron and ferrous iron in material
Molar ratio be 2:1.01-1.02, then heat to temperature be 95-105 DEG C, be stirred to react 2-4 hours, be subsequently cooled to temperature
For 30 DEG C hereinafter, pressure release, and material is released；
(3) material that step (2) release is filtered, obtains ferroso-ferric oxide filter residue and phosphorous filtrate, by four oxidations
After pure water is added in three-iron filter residue, dried in vacuum drying oven, then after air-flow crushing is crushed, through being sieved
Electromagnetic separation is carried out after point, obtains electromagnetic separation material；
(4) filtrate that step (1) is obtained by filtration obtains dried feed, the inlet air temperature of spray drying by spray drying
At 120-160 DEG C, drop temperature is controlled at 70 DEG C or less for control；
(5) phosphorous filtrate that step (3) obtains is crystallized to obtain phosphate by concentration and evaporation, by obtained phosphate with
After the mixing of electromagnetic separation material, adds phosphate or molysite makes the iron phosphorus molar ratio in mixture be 1:1, be put into rotary kiln
Interior calcining, being fired to temperature is 550-690 DEG C, and calcination time is 12-15 hours, obtains anhydrous iron phosphate；
(6) after mixing the dried feed that step (4) obtains with the anhydrous iron phosphate that step (5) obtains, mixing, mill are carried out
Carefully, it is then placed in sintering in sintering furnace, obtains LiFePO4.
Solid-to-liquid ratio is 1:3-4 when step (1) pulp, and the washing water that washing filter residue obtains and the filtrate being obtained by filtration are mixed
It is combined together.
The reducing agent being added in the step (2) is hydrazine hydrate, and pressure leak process, it is molten that the gas that pressure release is come out passes through phosphoric acid
Liquid absorbs, when the pH for being absorbed into phosphoric acid solution is 5.5-6.5, with the progress concentration and evaporation crystallization admixed together of phosphorous filtrate.
When carrying out vacuum drying in the step (3), drying temperature is 75-85 DEG C, vacuum degree is -0.09~-
0.08MPa, the partial size of air-flow crushing to ferroso-ferric oxide are 150-250 μm, cross 200-250 mesh, electromagnetism when electromagnetic separation
Intensity is 8000-10000 Gauss.
Concentration and evaporation crystallization process in the step (5), the Baume degrees for being concentrated into solution is 50-52, is subsequently cooled to temperature
Degree is 25-30 DEG C, then carries out centrifuge dripping, fluidized bed drying, the mother liquor recycle after drying using the calcium into mother liquor from
When the sum of son, magnesium ion are greater than 100ppm, ammonium fluoride removing calcium and magnesium is added, the solution after removing calcium and magnesium returns again to use.
Step (6) dried feed and anhydrous iron phosphate mixed process, by be additionally added anhydrous iron phosphate, lithium carbonate or
Carbon source, maintain the lithium in mixture, iron, phosphorus molar ratio be 1.01-1.02:1:1, while maintaining the LiFePO4 that finally prepares
The mass fraction of middle carbon is 1-2%.
Embodiment 1
A kind of processing method of discarded LiFePO4 middle material, is following steps:
(1) after collecting discarded LiFePO4 middle material, pure water is added and carries out pulp, then passes to carbon dioxide to filter residue
In lithium content be lower than 200ppm, be filtered, filter residue is washed；
(2) filter residue after washing that step (1) obtains is poured into sealing reaction kettle, ammonium hydroxide is added, adjusts the pH of solution
It is 8.3, is 41 DEG C of reaction 19min in temperature, reducing agent is then added and is restored to ferric iron and ferrous molar ratio in material
For 2:1.015, then heating to temperature is 99 DEG C, is stirred to react 3.2 hours, and being subsequently cooled to temperature is 30 DEG C hereinafter, pressure release,
And material is released；
(3) material that step (2) release is filtered, obtains ferroso-ferric oxide filter residue and phosphorous filtrate, by four oxidations
After pure water is added in three-iron filter residue, dried in vacuum drying oven, then after air-flow crushing is crushed, through being sieved
Electromagnetic separation is carried out after point, obtains electromagnetic separation material；
(4) filtrate that step (1) is obtained by filtration obtains dried feed, the inlet air temperature of spray drying by spray drying
At 155 DEG C, drop temperature is controlled at 70 DEG C or less for control；
(5) phosphorous filtrate that step (3) obtains is crystallized to obtain phosphate by concentration and evaporation, by obtained phosphate with
After the mixing of electromagnetic separation material, adds phosphate or molysite makes the iron phosphorus molar ratio in mixture be 1:1, be put into rotary kiln
Interior calcining, being fired to temperature is 590 DEG C, and calcination time is 13 hours, obtains anhydrous iron phosphate；
(6) after mixing the dried feed that step (4) obtains with the anhydrous iron phosphate that step (5) obtains, mixing, mill are carried out
Carefully, it is then placed in sintering in sintering furnace, obtains LiFePO4.
Solid-to-liquid ratio is 1:3.5 when step (1) pulp, and the washing water that washing filter residue obtains and the filtrate being obtained by filtration are mixed
It is combined together.
The reducing agent being added in the step (2) is hydrazine hydrate, and pressure leak process, it is molten that the gas that pressure release is come out passes through phosphoric acid
Liquid absorbs, when the pH for being absorbed into phosphoric acid solution is 6.2, with the progress concentration and evaporation crystallization admixed together of phosphorous filtrate.
When carrying out vacuum drying in the step (3), drying temperature is 75-85 DEG C, and vacuum degree is -0.083MPa, air-flow
The partial size for being crushed to ferroso-ferric oxide is 210 μm, crosses 225 meshes, and electromagnetism intensity when electromagnetic separation is 8500 Gausses.
Concentration and evaporation crystallization process in the step (5), the Baume degrees for being concentrated into solution is 51, and being subsequently cooled to temperature is
28 DEG C, then carry out centrifuge dripping, fluidized bed drying, mother liquor recycle after drying using into mother liquor calcium ion, magnesium from
When the sum of son is greater than 100ppm, ammonium fluoride removing calcium and magnesium is added, the solution after removing calcium and magnesium returns again to use.
Step (6) dried feed and anhydrous iron phosphate mixed process, by be additionally added anhydrous iron phosphate, lithium carbonate or
Carbon source, maintain the lithium in mixture, iron, phosphorus molar ratio be 1.015:1:1, while maintaining carbon in the LiFePO4 that finally prepares
Mass fraction be 1.8%.
The rate of recovery of final products is as follows:
The rate of recovery 99.1% of carbon source, the rate of recovery 98.2% of lithium carbonate, the rate of recovery 97.5% of ferric phosphate.
Embodiment 2
A kind of processing method of discarded LiFePO4 middle material, is following steps:
(1) after collecting discarded LiFePO4 middle material, pure water is added and carries out pulp, then passes to carbon dioxide to filter residue
In lithium content be lower than 200ppm, be filtered, filter residue is washed；
(2) filter residue after washing that step (1) obtains is poured into sealing reaction kettle, ammonium hydroxide is added, adjusts the pH of solution
It is 8.3, is 42 DEG C of reaction 19min in temperature, reducing agent is then added and is restored to ferric iron and ferrous molar ratio in material
For 2:1.013, then heating to temperature is 101 DEG C, is stirred to react 3.2 hours, and being subsequently cooled to temperature is 30 DEG C hereinafter, letting out
Pressure, and material is released；
(3) material that step (2) release is filtered, obtains ferroso-ferric oxide filter residue and phosphorous filtrate, by four oxidations
After pure water is added in three-iron filter residue, dried in vacuum drying oven, then after air-flow crushing is crushed, through being sieved
Electromagnetic separation is carried out after point, obtains electromagnetic separation material；
(4) filtrate that step (1) is obtained by filtration obtains dried feed, the inlet air temperature of spray drying by spray drying
At 145 DEG C, drop temperature is controlled at 70 DEG C or less for control；
(5) phosphorous filtrate that step (3) obtains is crystallized to obtain phosphate by concentration and evaporation, by obtained phosphate with
After the mixing of electromagnetic separation material, adds phosphate or molysite makes the iron phosphorus molar ratio in mixture be 1:1, be put into rotary kiln
Interior calcining, being fired to temperature is 580 DEG C, and calcination time is 14 hours, obtains anhydrous iron phosphate；
(6) after mixing the dried feed that step (4) obtains with the anhydrous iron phosphate that step (5) obtains, mixing, mill are carried out
Carefully, it is then placed in sintering in sintering furnace, obtains LiFePO4.
Solid-to-liquid ratio is 1:3.2 when step (1) pulp, and the washing water that washing filter residue obtains and the filtrate being obtained by filtration are mixed
It is combined together.
The reducing agent being added in the step (2) is hydrazine hydrate, and pressure leak process, it is molten that the gas that pressure release is come out passes through phosphoric acid
Liquid absorbs, when the pH for being absorbed into phosphoric acid solution is 5.9, with the progress concentration and evaporation crystallization admixed together of phosphorous filtrate.
When carrying out vacuum drying in the step (3), drying temperature is 78 DEG C, and vacuum degree is -0.082MPa, air-flow crushing
Partial size to ferroso-ferric oxide is 212 μm, crosses 200 meshes, and electromagnetism intensity when electromagnetic separation is 9000 Gausses.
Concentration and evaporation crystallization process in the step (5), the Baume degrees for being concentrated into solution is 51, and being subsequently cooled to temperature is
28 DEG C, then carry out centrifuge dripping, fluidized bed drying, mother liquor recycle after drying using into mother liquor calcium ion, magnesium from
When the sum of son is greater than 100ppm, ammonium fluoride removing calcium and magnesium is added, the solution after removing calcium and magnesium returns again to use.
Step (6) dried feed and anhydrous iron phosphate mixed process, by be additionally added anhydrous iron phosphate, lithium carbonate or
Carbon source, maintain the lithium in mixture, iron, phosphorus molar ratio be 1.015:1:1, while maintaining carbon in the LiFePO4 that finally prepares
Mass fraction be 1.9%.
The rate of recovery of final products is as follows:
The rate of recovery 99.2% of carbon source, the rate of recovery 98.1% of lithium carbonate, the rate of recovery 97.3% of ferric phosphate.
Embodiment 3
A kind of processing method of discarded LiFePO4 middle material, is following steps:
(1) after collecting discarded LiFePO4 middle material, pure water is added and carries out pulp, then passes to carbon dioxide to filter residue
In lithium content be lower than 200ppm, be filtered, filter residue is washed；
(2) filter residue after washing that step (1) obtains is poured into sealing reaction kettle, ammonium hydroxide is added, adjusts the pH of solution
It is 8.1, is 35 DEG C of reaction 19min in temperature, reducing agent is then added and is restored to ferric iron and ferrous molar ratio in material
For 2:1.017, then heating to temperature is 99 DEG C, is stirred to react 3.2 hours, and being subsequently cooled to temperature is 30 DEG C hereinafter, pressure release,
And material is released；
(3) material that step (2) release is filtered, obtains ferroso-ferric oxide filter residue and phosphorous filtrate, by four oxidations
After pure water is added in three-iron filter residue, dried in vacuum drying oven, then after air-flow crushing is crushed, through being sieved
Electromagnetic separation is carried out after point, obtains electromagnetic separation material；
(4) filtrate that step (1) is obtained by filtration obtains dried feed, the inlet air temperature of spray drying by spray drying
At 150 DEG C, drop temperature is controlled at 70 DEG C or less for control；
(5) phosphorous filtrate that step (3) obtains is crystallized to obtain phosphate by concentration and evaporation, by obtained phosphate with
After the mixing of electromagnetic separation material, adds phosphate or molysite makes the iron phosphorus molar ratio in mixture be 1:1, be put into rotary kiln
Interior calcining, being fired to temperature is 610 DEG C, and calcination time is 14 hours, obtains anhydrous iron phosphate；
(6) after mixing the dried feed that step (4) obtains with the anhydrous iron phosphate that step (5) obtains, mixing, mill are carried out
Carefully, it is then placed in sintering in sintering furnace, obtains LiFePO4.
Solid-to-liquid ratio is 1:3.6 when step (1) pulp, and the washing water that washing filter residue obtains and the filtrate being obtained by filtration are mixed
It is combined together.
The reducing agent being added in the step (2) is hydrazine hydrate, and pressure leak process, it is molten that the gas that pressure release is come out passes through phosphoric acid
Liquid absorbs, when the pH for being absorbed into phosphoric acid solution is 6.4, with the progress concentration and evaporation crystallization admixed together of phosphorous filtrate.
When carrying out vacuum drying in the step (3), drying temperature is 82 DEG C, and vacuum degree is -0.088MPa, air-flow crushing
Partial size to ferroso-ferric oxide is 179 μm, crosses 250 meshes, and electromagnetism intensity when electromagnetic separation is 9200 Gausses.
Concentration and evaporation crystallization process in the step (5), the Baume degrees for being concentrated into solution is 51.3, is subsequently cooled to temperature
It is 28 DEG C, then carries out centrifuge dripping, fluidized bed drying, the mother liquor recycle after drying uses calcium ion, the magnesium into mother liquor
When the sum of ion is greater than 100ppm, ammonium fluoride removing calcium and magnesium is added, the solution after removing calcium and magnesium returns again to use.
Step (6) dried feed and anhydrous iron phosphate mixed process, by be additionally added anhydrous iron phosphate, lithium carbonate or
Carbon source, maintain the lithium in mixture, iron, phosphorus molar ratio be 1.012:1:1, while maintaining carbon in the LiFePO4 that finally prepares
Mass fraction be 1.85%.
The rate of recovery of final products is as follows:
The rate of recovery 99.1% of carbon source, the rate of recovery 98.2% of lithium carbonate, the rate of recovery 97.4% of ferric phosphate.
The LiFePO4 of LiFePO4 and the raw material preparation newly purchased prepared by embodiment 1/2/3 is subjected to the ratio in performance
It is as follows compared with result:
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 | Comparative example 3 | |
| Sintering temperature | 770℃ | 770℃ | 770℃ | 770℃ | 770℃ | 770℃ |
| Carbon content | 1.8% | 1.8% | 1.9% | 1.9% | 1.85% | 1.85% |
| Compacted density/g/mL | 2.3641 | 2.3643 | 2.3591 | 2.3590 | 2.3611 | 2.3614 |
| 0.1C head/mAh/g | 161.2 | 160.9 | 161.6 | 161.5 | 160.9 | 161.1 |
| 0.1C head/mAh/g | 157.2 | 157.2 | 157.7 | 157.5 | 157.3 | 157.2 |
| Efficiency | 97.5% | 97.7% | 97.6% | 97.5% | 97.8% | 97.6% |
| BET/m2/g | 14.9 | 14.7 | 15.6 | 15.5 | 15.2 | 15.1 |
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of processing method of discarded LiFePO4 middle material, which is characterized in that be following steps:
(1) after collecting discarded LiFePO4 middle material, pure water is added and carries out pulp, then passes to carbon dioxide into filter residue
Lithium content is lower than 200ppm, is filtered, filter residue is washed；
(2) filter residue after washing that step (1) obtains is poured into sealing reaction kettle, ammonium hydroxide is added, the pH for adjusting solution is 8-
8.5, it is 30-45 DEG C of reaction 15-30min in temperature, then addition reducing agent is restored to ferric iron in material and rubs with ferrous
, than being 2:1.01-1.02, then heating to temperature is 95-105 DEG C, is stirred to react 2-4 hours for you, and being subsequently cooled to temperature is 30
DEG C hereinafter, pressure release, and material is released；
(3) material that step (2) release is filtered, ferroso-ferric oxide filter residue and phosphorous filtrate is obtained, by ferroso-ferric oxide
After pure water is added in filter residue, dried in vacuum drying oven, then after air-flow crushing is crushed, after screening
Electromagnetic separation is carried out, electromagnetic separation material is obtained；
(4) filtrate that step (1) is obtained by filtration obtains dried feed, the inlet air temperature control of spray drying by spray drying
At 120-160 DEG C, drop temperature is controlled at 70 DEG C or less；
(5) the phosphorous filtrate that step (3) obtains is crystallized to obtain phosphate by concentration and evaporation, by obtained phosphate and electromagnetism
After sorting material mixing, adds phosphate or molysite makes the iron phosphorus molar ratio in mixture be 1:1, be put into rotary kiln and forge
It burns, being fired to temperature is 550-690 DEG C, and calcination time is 12-15 hours, obtains anhydrous iron phosphate；
(6) after mixing the dried feed that step (4) obtains with the anhydrous iron phosphate that step (5) obtains, mixing, levigate is carried out, so
After be put into sintering in sintering furnace, obtain LiFePO4.
2. a kind of processing method of discarded LiFePO4 middle material according to claim 1, it is characterised in that: the step
(1) solid-to-liquid ratio is 1:3-4 when pulp, and the washing water that washing filter residue obtains and the filtrate being obtained by filtration are admixed together.
3. a kind of processing method of discarded LiFePO4 middle material according to claim 1, it is characterised in that: the step
(2) reducing agent being added in is hydrazine hydrate, and the gas that pressure release comes out is absorbed by phosphoric acid solution, is absorbed by pressure leak process
When the pH of phosphoric acid solution is 5.5-6.5, with the progress concentration and evaporation crystallization admixed together of phosphorous filtrate.
4. a kind of processing method of discarded LiFePO4 middle material according to claim 1, it is characterised in that: the step
(3) when carrying out vacuum drying in, drying temperature is 75-85 DEG C, and vacuum degree is -0.09~-0.08MPa, air-flow crushing to four oxygen
The partial size for changing three-iron is 150-250 μm, crosses 200-250 mesh, and electromagnetism intensity when electromagnetic separation is 8000-10000 Gauss.
5. a kind of processing method of discarded LiFePO4 middle material according to claim 1, it is characterised in that: the step
(5) concentration and evaporation crystallization process in, the Baume degrees for being concentrated into solution is 50-52, and being subsequently cooled to temperature is 25-30 DEG C, then
Carry out centrifuge dripping, fluidized bed drying, mother liquor recycle after drying is greater than using calcium ion, the sum of the magnesium ion into mother liquor
When 100ppm, ammonium fluoride removing calcium and magnesium is added, the solution after removing calcium and magnesium returns again to use.
6. a kind of processing method of discarded LiFePO4 middle material according to claim 1, it is characterised in that: the step
(6) dried feed and anhydrous iron phosphate mixed process maintain mixture by the way that anhydrous iron phosphate, lithium carbonate or carbon source is additionally added
In lithium, iron, phosphorus molar ratio be 1.01-1.02:1:1, while maintaining the mass fraction of carbon in the LiFePO4 that finally prepares
For 1-2%.
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| CN111960396A (en) * | 2020-08-26 | 2020-11-20 | 界首市南都华宇电源有限公司 | Method for preparing soluble phosphate from iron phosphate slag |
| CN112357937A (en) * | 2020-11-12 | 2021-02-12 | 萍乡市拓源实业有限公司 | Method for preparing battery-grade lithium carbonate from lithium iron phosphate |
| WO2022142583A1 (en) * | 2020-12-28 | 2022-07-07 | 湖南邦普循环科技有限公司 | Method for recycling lithium iron phosphate waste and use thereof |
| CN115784190A (en) * | 2022-11-30 | 2023-03-14 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium iron phosphate |
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Effective date of registration: 20201221 Address after: No.557 Tianma Avenue, Yunyang Economic Development Zone, Shiyan City, Hubei Province Patentee after: Hubei Wanrun New Energy Technology Co., Ltd Address before: No.42 Xiashan village, Baita Town, Xianju County, Taizhou City, Zhejiang Province Patentee before: Fang Jiacheng |