CN115521015A - System and method for treating lithium iron phosphate battery mother liquor wastewater - Google Patents
System and method for treating lithium iron phosphate battery mother liquor wastewater Download PDFInfo
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- CN115521015A CN115521015A CN202211343565.0A CN202211343565A CN115521015A CN 115521015 A CN115521015 A CN 115521015A CN 202211343565 A CN202211343565 A CN 202211343565A CN 115521015 A CN115521015 A CN 115521015A
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- mother liquor
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- iron phosphate
- lithium iron
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 208
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 54
- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 239000003337 fertilizer Substances 0.000 claims abstract description 21
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000004062 sedimentation Methods 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 31
- 229910052748 manganese Inorganic materials 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000000701 coagulant Substances 0.000 claims description 22
- 238000000108 ultra-filtration Methods 0.000 claims description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001223 reverse osmosis Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- -1 ammonium sulfate compound Chemical class 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 5
- 229910000616 Ferromanganese Inorganic materials 0.000 abstract description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000008237 rinsing water Substances 0.000 description 20
- 229910000398 iron phosphate Inorganic materials 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002515 guano Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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Abstract
The invention relates to the technical field of wastewater treatment, in particular to a system and a method for treating mother liquor wastewater of a lithium iron phosphate battery, wherein the system for treating the mother liquor wastewater of the lithium iron phosphate battery comprises a pretreatment unit which aerates the mother liquor to ensure that the mother liquor is mixed uniformly, oxidizes ferromanganese in the mother liquor, precipitates heavy metal in the mother liquor, outputs the pretreated mother liquor and produces slow release fertilizer; a separation unit for removing particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor and outputting the mother liquor after separation treatment; a concentration unit for concentrating the mother liquor after separation treatment and outputting a concentrated solution; and a crystallization unit for crystallizing and precipitating ammonium sulfate salt in the concentrated solution. The method can convert the lithium iron phosphate battery mother liquor wastewater into high-purity ammonium sulfate salt; realizes resource recycling and zero emission, and has low cost and high benefit.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a system and a method for treating lithium iron phosphate battery mother liquor wastewater.
Background
The lithium iron phosphate battery is a lithium ion battery using lithium iron phosphate (LiFePO 4) as a positive electrode material and carbon as a negative electrode material, and has the advantages of high working voltage, high energy density, long cycle life, good safety performance, small self-discharge rate and no memory effect. During charging, part of lithium ions in the lithium iron phosphate are removed and transferred to the negative electrode through the electrolyte, and meanwhile, electrons are released from the positive electrode and reach the negative electrode from an external circuit to maintain the balance of chemical reaction; during discharging, lithium ions are extracted from the negative electrode and reach the positive electrode through the electrolyte, and meanwhile, electrons are released from the negative electrode and reach the positive electrode from an external circuit to provide energy for the outside
The production process of the iron phosphate battery mainly comprises the following steps: pre-dissolving, synthesizing, filter pressing and washing, high-temperature aging, filter pressing and washing, drying, crushing and packaging. In the process, mother liquor and rinsing water are generated, wherein the mother liquor is mainly generated by rough washing and filter pressing first washing of the synthesis tank, and the rinsing water is mainly generated by filter pressing second washing. The main component of the mother liquor discharged by the iron phosphate device is SO 4 2- 、PO 4 3- 、NH 4 + Fe; the rest contains heavy metal elements such as F, K, mg, ca, cu, zn, co, cd and the like. The existing water treatment process and system have low salt production purity when treating the mother liquor and the rinsing water, and cannot give consideration to low cost, high benefit and zero emission.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a system and a method for treating lithium iron phosphate battery mother liquor wastewater, which can convert the lithium iron phosphate battery mother liquor wastewater into high-purity ammonium sulfate; realizes resource recycling and zero emission, and has low cost and high benefit.
In order to achieve the purpose, the invention provides the following technical scheme:
lithium iron phosphate battery mother liquor wastewater's processing system includes:
the pretreatment unit is used for aerating the mother liquor to ensure that the mother liquor is mixed uniformly and oxidizing iron and manganese in the mother liquor; heavy metal in the mother liquor is precipitated and output to the pretreated mother liquor and the slow release fertilizer is produced;
the separation unit is used for removing particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor and outputting the separated mother liquor;
the concentration unit is used for concentrating the mother liquor after the separation treatment and outputting a concentrated solution;
and a crystallization unit for crystallizing and precipitating ammonium sulfate salt in the concentrated solution.
As a preferred scheme of the treatment system for the lithium iron phosphate battery mother liquor wastewater, the pretreatment unit comprises a water tank, heat exchange equipment, a primary efficient sedimentation tank and a secondary efficient sedimentation tank which are sequentially connected;
the water tank is used for aerating the mother liquor to ensure that the mother liquor is mixed uniformly, so that iron and manganese in the mother liquor are oxidized;
the heat exchange equipment is used for carrying out heat exchange on the mother liquor and outputting the mother liquor with the temperature of 15-35 ℃ to the primary efficient sedimentation tank;
the first-stage efficient sedimentation tank is used for removing heavy metals and Ca ions through sedimentation;
and the secondary efficient sedimentation tank is used for further sedimentation of the mother liquor, so that most of polyvalent metal ions and phosphorus in the mother liquor are converted into sediment and the slow release fertilizer is produced.
As a preferable scheme of the system for treating the lithium iron phosphate battery mother liquor wastewater, the separation unit includes:
the manganese sand filter tank is used for performing manganese removal, turbidity removal and filtration on the pretreated mother liquor;
the ultrafiltration unit is used for performing molecular filtration on the filtrate output by the manganese sand filter;
the ion exchange resin unit is used for adsorbing most of polyvalent metal ions in the ultrafiltration product water output by the ultrafiltration unit to obtain mother liquor after separation treatment; the stable operation of the reverse osmosis membrane device is protected.
As a preferable scheme of the system for treating the lithium iron phosphate battery mother liquor wastewater, the concentration unit comprises a high-pressure reverse osmosis unit.
As a preferable scheme of the system for treating the lithium iron phosphate battery mother liquor wastewater, the crystallization unit comprises an evaporative crystallization device.
As a preferable scheme of the treatment system for the lithium iron phosphate battery mother liquor wastewater, the pH value in the first-stage efficient sedimentation tank is 7.5-8, and the pH value in the second-stage efficient sedimentation tank is 9-9.5.
As a preferred scheme of the treatment system for the lithium iron phosphate battery mother liquor wastewater, a recapture agent, a coagulant and a flocculant are added into the primary high-efficiency sedimentation tank; adding a coagulant and a flocculant into the secondary high-efficiency sedimentation tank; the coagulant is PAC and the flocculant is PAM.
As a preferable scheme of the treatment system for the lithium iron phosphate battery mother liquor wastewater, a water pump is arranged between the ultrafiltration unit and the ion exchange resin unit and is used for lifting the filtered mother liquor into the ion exchange resin unit.
A method for treating lithium iron phosphate battery mother liquor wastewater comprises the following steps:
(1) Injecting the lithium iron phosphate battery mother liquor into a pretreatment unit (10) for aeration to ensure that the mother liquor is mixed uniformly, and oxidizing iron and manganese in the mother liquor; precipitating heavy metals in the mother liquor, outputting the pretreated mother liquor and producing the slow release fertilizer;
(2) Injecting the pretreated mother liquor into a separation unit (20) to remove particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a concentration unit (30) for concentration, and outputting a concentrated solution;
(4) And injecting the concentrated solution into a crystallization unit (40) to crystallize and separate out ammonium sulfate salt.
As a preferable scheme of the method for treating the lithium iron phosphate battery mother liquor wastewater,
the method comprises the following steps:
(1) Injecting the lithium iron phosphate battery mother liquor into a water tank for aeration to ensure that the lithium iron phosphate battery mother liquor is mixed uniformly, and oxidizing iron and manganese in the mother liquor; then injecting the mother liquor into a first-stage efficient sedimentation tank, adding ammonia water to adjust the pH value to 7.5-8, and simultaneously adding a heavy-duty agent, a coagulant and a flocculant to precipitate and remove heavy metals and Ca ions; after the precipitation in the first-stage high-efficiency sedimentation tank, the heavy metal flows into a second-stage high-efficiency sedimentation tank by gravity, the pH value is adjusted to 9-9.5, and simultaneously, a coagulant and a flocculant are added, so that the heavy metal in the mother liquor is precipitated and output to the pretreated mother liquor, and the slow release fertilizer is produced;
(2) Injecting the pretreated mother liquor into a manganese sand filter tank and an ultrafiltration unit for filtering, lifting the filtered water into an ion exchange resin unit through a water pump to remove particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor, outputting the separated mother liquor, and protecting the stable operation of a reverse osmosis membrane device;
(3) Injecting the separated mother liquor into a high-pressure reverse osmosis unit for concentration, concentrating the mother liquor to 150000-160000 PPM, and outputting a concentrated solution;
(4) And injecting the concentrated solution into an evaporative crystallization device to crystallize and separate out ammonium sulfate salt, drying and packaging for later use, and further crystallizing and drying the crystallized residual liquid to obtain the ammonium phosphate and ammonium sulfate compound fertilizer.
Compared with the prior art, the invention has the beneficial effects that: the mother liquor treated by the method is high-concentration salt water, and the mother liquor wastewater of the lithium iron phosphate battery can be converted into high-purity ammonium sulfate; realizes resource recycling and zero emission, and has low cost and high benefit.
(1) The treatment system for the lithium iron phosphate battery mother liquor wastewater can convert the lithium iron phosphate battery mother liquor wastewater into high-purity ammonium sulfate; the produced salt has high purity.
(2) The method has the advantages of simple process, low cost and high benefit, and can fully realize resource recycling and zero emission.
(3) The invention produces the slow release fertilizer after the precipitation of the secondary efficient sedimentation tank, and realizes the resource recovery of the slow release fertilizer.
(4) The invention has two kinds of evaporation crystallization products, one is high-purity ammonium sulfate, and the other is unrecoverable miscellaneous salt.
(5) The invention effectively solves the problems of material resource waste, large sludge yield and low water resource utilization rate when the conventional technology is used for treating the wastewater of the iron phosphate battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts. Wherein:
FIG. 1 is a schematic diagram of a processing system according to the present invention;
FIG. 2 is a schematic flow diagram of the treatment process of the present invention;
FIG. 3 is a schematic flow chart of example 2 of the treatment method of the present invention;
FIG. 4 is a schematic flow chart of example 3 of the treatment method of the present invention;
reference numbers in the figures: : 10. a pre-processing unit; 20. a separation unit; 30. a concentration unit; 40. and (5) a crystallization unit.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it should be understood that they are presented herein only to illustrate and explain the present invention and not to limit the present invention.
The invention relates to a 20-million ton/year iron phosphate battery new material precursor project. Receiving mother liquor and rinsing water discharged by an iron phosphate device. The main component of the coming water of the mother liquor (pH0.8-1.5. TDS 66000PPm) of the invention is SO 4 2- （4～6%）、PO 4 3- （0.45～0.59%）、NH 4 + (1.03%), fe (500 ppm); the rest contains F, K, mg and CaAnd heavy metal elements such as Cu, zn, co, cd and the like. The mother liquor is high-concentration brine.
Example 1
Referring to fig. 1 and 2, a first embodiment of the present invention provides a system for treating lithium iron phosphate battery mother liquor wastewater, which comprises a pretreatment unit, a separation unit, a concentration unit, and a crystallization unit;
preferably, the pretreatment unit 10 is used for aerating the mother liquor to enable the mother liquor to be mixed uniformly, and oxidizing iron and manganese in the mother liquor; heavy metal in the mother liquor is precipitated and output to the pretreated mother liquor and the slow release fertilizer is produced; the system comprises a water tank, heat exchange equipment, a primary efficient sedimentation tank and a secondary efficient sedimentation tank which are sequentially connected;
the water tank is used for aerating the mother liquor to ensure that the mother liquor is uniformly mixed, so that iron and manganese in the mother liquor are oxidized;
the heat exchange equipment is used for carrying out heat exchange on the mother liquor and outputting the mother liquor with the temperature of 15-35 ℃ to the primary efficient sedimentation tank;
the primary high-efficiency sedimentation tank is used for removing heavy metals and Ca ions through sedimentation; heavy metals are captured. The pH value in the first-stage high-efficiency sedimentation tank is 7.5-8, and the pH value in the second-stage high-efficiency sedimentation tank is 9-9.5. Adding a recapture agent, a coagulant and a flocculant into the first-stage efficient sedimentation tank; the coagulant is PAC and the flocculant is PAM.
The secondary high-efficiency sedimentation tank is used for further sedimentation of the mother liquor, and a coagulant and a flocculant are added into the secondary high-efficiency sedimentation tank; most of the polyvalent metal ions and phosphorus in the mother liquor are converted into precipitate and the slow release fertilizer is produced. And recycling the slow release fertilizer. The coagulant is PAC and the flocculant is PAM.
Preferably, the separation unit 20 is configured to remove particulate matter, polyvalent metal ions, and scaling ions in the pretreated mother liquor, and output the separated mother liquor; it includes:
the manganese sand filter tank is used for carrying out manganese removal and turbidity removal filtration on the pretreated mother liquor; the manganese and turbidity removing effect is good.
The ultrafiltration unit is used for performing molecular filtration on the filtrate output by the manganese sand filter; the molecules are subjected to membrane separation. And a water pump is arranged between the ultrafiltration unit and the ion exchange resin unit and used for lifting the filtered mother liquor into the ion exchange resin unit.
And the ion exchange resin unit is used for adsorbing most of polyvalent metal ions in the ultrafiltration produced water output by the ultrafiltration unit to obtain the mother liquor after separation treatment. Can remove scaling ions and protect the stable operation of the reverse osmosis membrane device.
Preferably, the concentration unit 30 is configured to concentrate the separated mother liquor and output a concentrated solution; which includes a high pressure reverse osmosis unit. Ion concentration is achieved. The crystallizing unit 40 is used for crystallizing and separating out ammonium sulfate salt in the concentrated solution. Which comprises an evaporative crystallization device. And the high-purity ammonium sulfate salt is recycled.
The method for treating the lithium iron phosphate battery mother liquor wastewater comprises the following steps:
(1) Injecting the lithium iron phosphate battery mother liquor into the pretreatment unit 10 for aeration to ensure that the lithium iron phosphate battery mother liquor is mixed uniformly, and oxidizing iron and manganese in the mother liquor; heavy metal in the mother liquor is precipitated and output to the pretreated mother liquor and the slow release fertilizer is produced;
(2) Injecting the pretreated mother liquor into a separation unit 20 to remove particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a concentration unit 30 for concentration, and outputting a concentrated solution;
(4) And the concentrated solution is injected into a crystallization unit 40 to crystallize out ammonium sulfate salt.
Preferably, the method for treating the lithium iron phosphate battery mother liquor wastewater comprises the following steps:
(1) Injecting the lithium iron phosphate battery mother liquor into a water tank for aeration to ensure that the lithium iron phosphate battery mother liquor is mixed uniformly, and oxidizing iron and manganese in the mother liquor; after aeration, carrying out heat exchange on the mother liquor by heat exchange equipment and outputting the mother liquor with the temperature of 15-35 ℃ to a primary high-efficiency sedimentation tank; then injecting the mother liquor into a first-stage efficient sedimentation tank, adding ammonia water to adjust the pH value to 7.5-8, simultaneously adding a recapture agent, a coagulant and a flocculant, settling for 5 hours, and settling and removing heavy metals and Ca ions; after the first-stage efficient sedimentation tank is sedimentated, the heavy metal flows into a second-stage efficient sedimentation tank by gravity, the pH value is adjusted to 9-9.5, and simultaneously, a coagulant and a flocculant are added for 1H of sedimentation, so that the heavy metal in the mother liquor is precipitated and output to pretreated mother liquor and the slow release guano stone (Mg (NH 4) [ PO4].6H 2O) is produced;
(2) Adding H into the pretreated mother liquor produced water 2 SO 4 Adjusting pH to 7.5-8, injecting into manganese sand filter tank and ultrafiltration unit, filtering, lifting the filtered water with water pump, introducing into ion exchange resin unit, and adding NH 4 + Removing particles, polyvalent metal ions and scaling ions in the pretreated mother liquor by chemical operation, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a high-pressure reverse osmosis unit for concentration, concentrating the mother liquor to 150000-160000 PPM, and outputting a concentrated solution;
(4) And injecting the concentrated solution into an evaporative crystallization device to crystallize and separate out ammonium sulfate salt, drying and packaging for later use, and further crystallizing and drying the crystallized residual liquid to obtain the ammonium phosphate and ammonium sulfate compound fertilizer.
Example 2
Referring to fig. 3, a second embodiment of the present invention is based on the previous embodiment. The system for treating the lithium iron phosphate battery mother liquor wastewater comprises a pretreatment unit, a separation unit, a concentration unit and a crystallization unit;
specifically, the method for treating the lithium iron phosphate battery mother liquor wastewater comprises the following steps:
(1) The lithium iron phosphate battery mother liquor is aerated through a mother liquor/pure water heat exchanger, a closed water cooling tower and a regulating water tank to be mixed uniformly, so that iron and manganese in the mother liquor are oxidized; then injecting the mother liquor into a first-level efficient sedimentation tank, adding ammonia water to adjust the pH value to 7.5-8, simultaneously adding a heavy-duty agent, a coagulant PAC and a flocculant PAM, settling for 5 hours, and settling and removing heavy metals and Ca ions; after the first-level efficient sedimentation tank is sedimentated, the gravity flows into a second-level efficient sedimentation tank, the pH value is adjusted to 9-9.5, a coagulant PAC and a flocculant PAM are added at the same time, the sedimentation time is 5 hours, heavy metal in the mother liquor is precipitated and output the pretreated mother liquor, and the slow release guanite (Mg (NH 4) [ PO4].6H 2O) is produced;
(2) Adding H into the pretreated mother liquor produced water 2 SO 4 Adjusting pH to 7.5-8, injecting into manganese sand filter tank, self-cleaning filter, external pressure type ultrafiltration device, and ultrafiltration water tank, filtering, lifting filtered water with water pump into ion exchange resin unit (chelate resin), and introducing into NH 4 + Removing particles, polyvalent metal ions and scaling ions in the pretreated mother liquor through chemical operation, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a high-pressure reverse osmosis unit for concentration, concentrating the mother liquor to 150000PPM, and outputting a concentrated solution;
(4) And injecting the concentrated solution into an evaporative crystallization device through a concentrated water buffer tank to crystallize and separate out ammonium sulfate and monoammonium phosphate, drying and packaging for later use, and further crystallizing and drying the crystallized residual liquid to obtain the ammonium phosphate and ammonium sulfate compound fertilizer.
Example 3
Referring to fig. 4, a third embodiment of the present invention is based on the previous embodiment. The invention relates to mother liquid and rinsing water discharged by an iron phosphate device. The system for treating the lithium iron phosphate battery mother liquor wastewater comprises a pretreatment unit, a separation unit, a concentration unit and a crystallization unit;
specifically, the method for treating the lithium iron phosphate battery mother liquor wastewater comprises the following steps:
(1) The lithium iron phosphate battery mother liquor is aerated through a mother liquor/pure water heat exchanger, a closed water cooling tower and a regulating water tank to be mixed uniformly, so that iron and manganese in the mother liquor are oxidized; then injecting the mother liquor into a first-stage efficient sedimentation tank, adding ammonia water to adjust the pH value to 7.5-8, and simultaneously adding a heavy-duty agent, a coagulant and a flocculant to precipitate and remove heavy metals and Ca ions; after the first-stage high-efficiency sedimentation tank is settled, the heavy metal flows into a second-stage high-efficiency sedimentation tank by gravity, the pH value is adjusted to 9-9.5, and simultaneously, a coagulant and a flocculant are added to ensure that the heavy metal in the mother liquor is settled and output the pretreated mother liquor and the slow-release guano (Mg (NH 4) [ PO4].6H 2O) is produced; wherein the first-stage efficient sedimentation tank and the second-stage efficient sedimentation tank adopt plate-and-frame filter pressing.
(2) Adding H into the pretreated mother liquor produced water 2 SO 4 Adjusting pH to 7.5-8, injecting into manganese sand filter tank, self-cleaning filter, external pressure type ultrafiltration device, and ultrafiltration water tank, filtering, lifting filtered water with water pump, introducing into ion exchange resin unit (chelate resin), and introducing into NH 4 + Removing particles, polyvalent metal ions and scaling ions in the pretreated mother liquor by chemical operation, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a high-pressure reverse osmosis unit for concentration, concentrating the mother liquor to 160000PPM, and outputting a concentrated solution;
(4) And injecting the concentrated solution into an evaporative crystallization device through a concentrated water buffer tank to crystallize and separate out ammonium sulfate salt, drying and packaging for later use, and further crystallizing and drying the crystallized residual liquid to obtain the ammonium phosphate and ammonium sulfate compound fertilizer.
Specifically, the method for treating the rinsing water and the mother liquor of the lithium iron phosphate battery comprises the following steps:
rinsing water is subjected to heat exchange through a rinsing water/pure water heat exchanger, is uniformly mixed through a closed water cooling tower and an adjusting water tank, is injected into a sedimentation tank for sedimentation, and is filtered through a manganese sand filter tank, a self-cleaning filter and an ultrafiltration water production tank; then concentrating the rinsing water and the mother liquor by a high-pressure reverse osmosis unit, a high-pressure reverse osmosis water production tank and high-pressure reverse osmosis equipment, and then feeding the concentrated rinsing water and the mother liquor into a pure water tank, wherein the pure water tank is communicated with a rinsing water/pure water heat exchanger and a mother liquor/pure water heat exchanger, the rinsing water and the mother liquor are aerated by the mother liquor/pure water heat exchanger, a closed cooling tower and a regulating water tank to be uniformly mixed, so that ferro-manganese in the rinsing water and the mother liquor is oxidized; then injecting rinsing water and mother liquor into a first-stage efficient sedimentation tank, adding ammonia water to adjust the pH value to 7.5-8, and simultaneously adding a recapture agent, a coagulant and a flocculant to precipitate and remove heavy metals and Ca ions; after the first-stage efficient sedimentation tank is sedimentated, the heavy metal flows into a second-stage efficient sedimentation tank by gravity, the pH value is adjusted to 9-9.5, and simultaneously, a coagulant and a flocculant are added, so that the heavy metal in the rinsing water and the pretreated mother liquor is sedimentated and output to the rinsing water and the pretreated mother liquor; wherein the first-stage efficient sedimentation tank and the second-stage efficient sedimentation tank adopt plate-and-frame filter pressing. Adding H into rinsing water and pretreated mother liquor produced water 2 SO 4 Adjusting the pH value to 7.5-8, injecting into a manganese sand filter chamber, and self-cleaningThe filter, the external pressure type ultrafiltration device and the ultrafiltration water production tank are used for filtering, the filtered water is lifted by the water pump to enter the ion exchange resin unit (chelate resin) by adopting NH 4 + Removing particles, polyvalent metal ions and scaling ions in the clear rinsing water and the pretreated mother liquor by chemical operation, and outputting low-salt rinsing water and the mother liquor; injecting the low-salt rinsing water and the mother liquor into a high-pressure reverse osmosis unit for concentration, concentrating the mother liquor to 150000-160000 PPM, and outputting a concentrated solution; and (3) injecting the concentrated solution into an evaporative crystallization device through a concentrated water buffer tank to crystallize and separate out ammonium sulfate I-type solid, drying and packaging for later use, and further crystallizing and drying the crystallized residual liquid to obtain ammonium phosphate and ammonium sulfate compound fertilizer.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: it is also possible to modify the solutions described in the previous embodiments or to substitute some or all of them with equivalents. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a processing system of lithium iron phosphate battery mother liquor waste water which characterized in that: the method comprises the following steps:
the pretreatment unit (10) is used for aerating the mother liquor to ensure that the mother liquor is mixed and homogenized and oxidizing iron and manganese in the mother liquor; heavy metal in the mother liquor is precipitated and output to the pretreated mother liquor and the slow release fertilizer is produced;
the separation unit (20) is used for removing particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor and outputting the separated mother liquor;
a concentration unit (30) for concentrating the separated mother liquor and outputting a concentrated solution;
a crystallization unit (40) for crystallizing ammonium sulfate salt in the concentrated solution.
2. The system and the method for treating the lithium iron phosphate battery mother liquor wastewater according to claim 1, characterized in that: the pretreatment unit (10) comprises a water tank, heat exchange equipment, a primary efficient sedimentation tank and a secondary efficient sedimentation tank which are sequentially connected;
the water tank is used for aerating the mother liquor to ensure that the mother liquor is uniformly mixed, so that iron and manganese in the mother liquor are oxidized;
the heat exchange equipment is used for carrying out heat exchange on the mother liquor and outputting the mother liquor with the temperature of 15-35 ℃ to the primary efficient sedimentation tank;
the first-stage efficient sedimentation tank is used for removing heavy metals and Ca ions through sedimentation;
and the secondary efficient sedimentation tank is used for further sedimentating the mother liquor, so that most of polyvalent metal ions and phosphorus in the mother liquor are converted into sediments and the slow release fertilizer is produced.
3. The system for treating lithium iron phosphate battery mother liquor wastewater as claimed in claim 2, characterized in that: the separation unit (20) comprises:
the manganese sand filter tank is used for carrying out manganese removal and turbidity removal filtration on the pretreated mother liquor;
the ultrafiltration unit is used for performing molecular filtration on the filtrate output by the manganese sand filter;
and the ion exchange resin unit is used for removing scaling ions in the pretreated mother liquor to obtain the separated mother liquor.
4. The system for treating lithium iron phosphate battery mother liquor wastewater as claimed in claim 3, characterized in that: the concentration unit (30) comprises a high pressure reverse osmosis unit.
5. The system for treating the mother liquor wastewater of the lithium iron phosphate battery as claimed in claim 4, wherein: the crystallization unit (40) comprises an evaporative crystallization device.
6. The system for treating lithium iron phosphate battery mother liquor wastewater as claimed in claim 5, characterized in that: the pH value in the first-stage high-efficiency sedimentation tank is 7.5-8, and the pH value in the second-stage high-efficiency sedimentation tank is 9-9.5.
7. The system for treating the mother liquor wastewater of the lithium iron phosphate battery as claimed in claim 6, wherein: adding a recapture agent, a coagulant and a flocculant into the first-stage efficient sedimentation tank; adding a coagulant and a flocculant into the secondary high-efficiency sedimentation tank; the coagulant is PAC, and the flocculant is PAM.
8. The system for treating lithium iron phosphate battery mother liquor wastewater as claimed in claim 6, wherein: and a water pump is arranged between the ultrafiltration unit and the ion exchange resin unit and used for lifting the filtered mother liquor into the ion exchange resin unit.
9. A treatment method of lithium iron phosphate battery mother liquor wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) Injecting the lithium iron phosphate battery mother liquor into a pretreatment unit (10) for aeration to ensure that the lithium iron phosphate battery mother liquor is mixed uniformly, and oxidizing iron and manganese in the mother liquor; precipitating heavy metals in the mother liquor, outputting the pretreated mother liquor and producing the slow release fertilizer;
(2) Injecting the pretreated mother liquor into a separation unit (20) to remove particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a concentration unit (30) for concentration, and outputting a concentrated solution;
(4) And the concentrated solution is injected into a crystallization unit (40) to crystallize and separate out ammonium sulfate salt.
10. The method for treating lithium iron phosphate battery mother liquor wastewater as claimed in claim 9, characterized in that: the method comprises the following steps:
(1) Injecting the lithium iron phosphate battery mother liquor into a water tank for aeration to ensure that the mother liquor is mixed uniformly, and oxidizing iron and manganese in the mother liquor; then injecting the mother liquor into a first-stage efficient sedimentation tank, adjusting the pH value to 7.5-8, simultaneously adding a heavy-duty agent, a coagulant and a flocculant, and carrying out sedimentation removal on heavy metals and Ca ions; after the precipitation in the first-stage high-efficiency sedimentation tank, the heavy metal flows into a second-stage high-efficiency sedimentation tank by gravity, the pH value is adjusted to 9-9.5, and simultaneously, a coagulant and a flocculant are added, so that the heavy metal in the mother liquor is precipitated and output to the pretreated mother liquor, and the slow release fertilizer is produced;
(2) Injecting the pretreated mother liquor into a manganese sand filter and an ultrafiltration unit for filtering, lifting the filtered water into an ion exchange resin unit through a water pump to remove particulate matters, polyvalent metal ions and scaling ions in the pretreated mother liquor, and outputting the separated mother liquor;
(3) Injecting the separated mother liquor into a high-pressure reverse osmosis unit for concentration, concentrating the mother liquor to 150000-160000 PPM, and outputting the concentrated solution;
(4) Injecting the concentrated solution into an evaporative crystallization device to crystallize and separate out ammonium sulfate, drying and packaging for later use; and further crystallizing and drying the crystallization residual liquid to obtain ammonium phosphate and ammonium sulfate compound fertilizer.
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