CN115072905A - Treatment method of battery wastewater and method for recycling high-purity iron phosphate from battery wastewater - Google Patents
Treatment method of battery wastewater and method for recycling high-purity iron phosphate from battery wastewater Download PDFInfo
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 136
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 134
- 239000002351 wastewater Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000004064 recycling Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000693 micelle Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 30
- 238000004062 sedimentation Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010979 pH adjustment Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 claims description 4
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 29
- 238000004065 wastewater treatment Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000010170 biological method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 159000000003 magnesium salts Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage 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
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02F2001/007—Processes including a sedimentation step
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- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
A method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater relate to the technical field of battery wastewater treatment and battery washing wastewater resource recycling. The invention aims to solve the problems that the treatment cost is high due to the fact that exogenous substances are additionally added when the wastewater generated by iron phosphate production is treated by a biological method, and the treatment cost is high and secondary pollution to a water body is caused when the wastewater generated by iron phosphate production is treated by magnesium oxide or magnesium salt. According to the invention, the micelle agent is utilized to realize rapid recovery of iron phosphate resources from waste iron phosphate production wastewater, the iron phosphate production wastewater is fully utilized, the total yield of iron phosphate is improved, the waste of a large amount of iron phosphate resources is avoided, the difficulty in subsequent iron phosphate wastewater treatment is reduced, iron phosphate products with economic value are recovered, and the micelle agent has double advantages of environmental protection and economy. The invention can obtain a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater.
Description
Technical Field
The invention relates to the technical field of battery wastewater treatment and battery washing wastewater resource recycling, in particular to a battery wastewater treatment method and a method for recycling high-purity iron phosphate from battery wastewater.
Background
The ferric phosphate is a key precursor of the lithium iron phosphate which is the anode material of the storage battery at present. With the rapid development trend of new energy sales markets, the requirements on power batteries, energy storage materials and machine equipment are getting larger and larger, and the demand on iron phosphate is rapidly increased. One of the traditional iron phosphate preparation methods is that a ferrous salt (such as ferrous sulfate) reacts with ammonium hydrogen phosphate, phosphoric acid, ammonia water, hydrogen peroxide and the like to synthesize the iron phosphate, and meanwhile, the iron phosphate can go through a generator, washing water and other process flows in the whole production and manufacturing process, so the generated mother liquor and the washing water caused by the iron phosphate are high-salt inorganic wastewater with metal ions, sulfate ions, iron phosphate ions and part of iron phosphate particles with different concentrations, and are difficult to effectively recycle and treat, while the direct release of the wastewater can bring serious damage and harm to the surrounding natural environment, and meanwhile, the yield of the iron phosphate is generally low.
At present, a biological method is common in the treatment method of the wastewater generated in the production of the iron phosphate, but the wastewater generated in the production of the iron phosphate by the biological method contains higher sulfate radicals and a small amount of metal ions which are inhibitors for the growth of microorganisms, and the wastewater needs to be pretreated before biochemical treatment; during the later biochemical treatment, proper carbon source is required to be added and proper pH is required to be adjusted to enable the microorganisms to grow, but the addition of a large amount of exogenous substances increases the cost of wastewater treatment, so that the wastewater is not suitable for biological treatment.
The phosphorus content and the ammonia nitrogen content in the wastewater generated in the iron phosphate production are higher, a large amount of magnesium oxide or magnesium salt needs to be added into the wastewater containing phosphorus and nitrogen, and the cost for treating the wastewater generated in the iron phosphate production is additionally increased. In addition, after magnesium salt treatment, secondary pollution of water is caused additionally, and the wastewater still can not reach the discharge standard.
Disclosure of Invention
The invention aims to solve the problems that the treatment cost is high due to the fact that exogenous substances are additionally added when the wastewater generated in the iron phosphate production is treated by adopting a biological method, and the treatment cost is high and secondary pollution of a water body is caused when the wastewater generated in the iron phosphate production is treated by using magnesium oxide or magnesium salt, and provides a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater.
A method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater are carried out according to the following steps:
step 1: introducing the battery wastewater into an adjusting tank, and adjusting the pH value to 6.0-8.0; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding a micelle agent, stirring and reacting for 30-60 min, carrying out solid-liquid separation on the battery wastewater through an inclined plate settler after the reaction is finished to obtain iron phosphate slag, and washing, drying and calcining the iron phosphate slag to obtain high-purity iron phosphate;
step 2: adding washing water for washing the iron phosphate slag in the step 1 into the battery wastewater after solid-liquid separation, and then introducing the battery wastewater into an acidolysis regulating tank to regulate the pH value to 10-11; then introducing the battery wastewater after the pH adjustment into a sedimentation tank, adding a ferrous medicament, stirring and reacting for 30-90 min, adding an oxidant, continuously stirring and reacting for 30-90 min, and standing for 1-2 h after the reaction is finished to obtain battery wastewater containing flocs;
and step 3: performing filter pressing on the battery wastewater containing the flocs obtained in the step 2 by using a filter press to obtain supernatant and sludge; and (3) introducing the supernatant into a sedimentation tank, adding an ammonia nitrogen remover while continuously stirring, continuously stirring for 30-60 min, standing for 30-90 min after stirring is finished, and finally performing filter pressing through a filter press until clear water is separated out, so that the treatment of the battery wastewater is completed.
The invention has the beneficial effects that:
according to the method for treating the battery wastewater and the method for recovering the high-purity iron phosphate from the battery wastewater, disclosed by the invention, the micelle agent is utilized to realize the rapid recovery of the iron phosphate resource from the waste iron phosphate production wastewater, the iron phosphate production wastewater is fully utilized, the total yield of the iron phosphate is improved, the waste of a large amount of iron phosphate resources is avoided, the difficulty in subsequent iron phosphate wastewater treatment is reduced, the treatment cost is reduced, the iron phosphate product with economic value is recovered, and the method has the double advantages of environmental protection and economy.
The micelle agent is an organic polymer material, and mainly changes the interfacial tension in the production wastewater to increase the stability of colloid, so that the Zeta potential of the water body is changed, and in addition, the micelle agent also has a structure capable of forming a space net (honeycomb) and can capture ultrafine particles in water. Therefore, after the micelle agent is added into the production wastewater, the micelle agent and the ferric phosphate in the water body form micelle to be rapidly precipitated. The recovered iron phosphate slag is calcined in the subsequent treatment, and the micelle agent can be removed in the calcining process, so that the purity of the subsequent iron phosphate is not influenced.
After the iron phosphate production wastewater enters the iron phosphate and is recycled, ultrafine particles in a water body are reduced, the water body is clear before treatment, in addition, the standard discharge of total phosphorus is realized by adding ferrous iron and an oxidant, the removal of high-concentration ammonia nitrogen is realized by adding an ammonia nitrogen remover calcium hypochlorite, and the standard discharge of the wastewater is realized.
The invention provides a method for efficiently recycling superfine particle iron phosphate in mother liquor and washing water in iron phosphate wastewater by utilizing a micelle agent, and simultaneously enabling total phosphorus and ammonia nitrogen effluent of the wastewater to reach the standard by using a chemical method in the subsequent wastewater treatment process. The method improves the resource utilization rate and the yield of the iron phosphate in production, improves the economic benefit, reduces the difficulty in treating the subsequent production wastewater, and conforms to the national strategic requirements on efficient resource recycling.
The invention can obtain a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater.
Drawings
Fig. 1 is a process flow diagram of a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater according to the present invention.
Figure 2 is an XRD pattern of the iron phosphate recovered in example 1.
Fig. 3 is a scanning electron micrograph of the iron phosphate recovered in example 1.
Figure 4 is an XRD pattern of the iron phosphate recovered in example 2.
Fig. 5 is a scanning electron micrograph of the iron phosphate recovered in example 2.
Detailed Description
The first embodiment is as follows: the embodiment provides a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater, which are carried out according to the following steps:
step 1: introducing the battery wastewater into an adjusting tank, and adjusting the pH to 6.0-8.0; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding a micelle agent, stirring and reacting for 30-60 min, carrying out solid-liquid separation on the battery wastewater through an inclined plate settler after the reaction is finished to obtain iron phosphate slag, and washing, drying and calcining the iron phosphate slag to obtain high-purity iron phosphate;
step 2: adding washing water for washing the iron phosphate slag in the step 1 into the battery wastewater after solid-liquid separation, and then introducing the battery wastewater into an acidolysis regulating tank to regulate the pH value to 10-11; then introducing the battery wastewater after the pH adjustment into a sedimentation tank, adding a ferrous medicament, stirring and reacting for 30-90 min, adding an oxidant, continuously stirring and reacting for 30-90 min, and standing for 1-2 h after the reaction is finished to obtain battery wastewater containing flocs;
and step 3: performing filter pressing on the battery wastewater containing the flocs obtained in the step 2 by using a filter press to obtain supernatant and sludge; and (3) introducing the supernatant into a sedimentation tank, adding an ammonia nitrogen remover while continuously stirring, continuously stirring for 30-60 min, standing for 30-90 min after stirring is finished, and finally performing filter pressing through a filter press until clear water is separated out, so that the treatment of the battery wastewater is completed.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the micelle agent in the step 1 is a polymer micelle agent JS-2, and the addition amount of the micelle agent is 2-3 g/L.
Other steps are the same as those in the first embodiment.
The third concrete implementation mode: the first or second differences from the present embodiment are as follows: and (3) washing the iron phosphate slag in the step (1) for 10-30 min.
The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: in the step 1, the iron phosphate slag is dried for 500-900 min at the temperature of 100-200 ℃.
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the step 1, the iron phosphate slag is calcined at the temperature of 500-700 ℃ for 500-900 min.
The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: in the step 2, 0.1mol/L sodium hydroxide solution is used for adjusting the pH value of the battery wastewater to 10-11.
The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the ferrous medicament in the step 2 is ferrous sulfate heptahydrate, and the addition amount of the ferrous medicament is 0.4-0.5 g/L.
The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and the first to seventh embodiments is: the oxidant in the step 2 is hydrogen peroxide with the mass fraction of 30%.
The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the ratio of the ferrous sulfate heptahydrate to the hydrogen peroxide is (1-6): 2.
the other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the ammonia nitrogen remover in the step 3 is 500-600 ppm of calcium hypochlorite.
The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater are carried out according to the following steps:
in this example, an iron phosphate production mother liquor and rinse water from a home battery anode material precursor iron phosphate production plant in somewhere in Sichuan were selected for experiments. The water quality index of the water body is as follows: COD: 3370mg/L, ammonia nitrogen: 3690mg/L, total phosphorus: 1400mg/L, SS: 750mg/L and pH 9.
Step 1: introducing the battery wastewater (production mother liquor and flushing water) into an adjusting tank, and adjusting the pH to 7.0; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding 2g/L micelle agent, stirring and reacting for 30min, carrying out solid-liquid separation on the battery wastewater through an inclined plate settler after the reaction is finished to obtain iron phosphate slag, washing the iron phosphate slag for 30min by using clear water, wherein the purpose of washing is to remove ions on the surface of the iron phosphate slag and prevent the ions from influencing the subsequent iron phosphate production purity and electronic material preparation, and the washing requirement is to basically remove NH on the surface of the iron phosphate + 、SO 4 2- 、Fe 3+ Ions. The washed iron phosphate slag is sent to a drying room and dried at the temperature of 150 DEG CDrying for 600min to remove crystal water, and calcining the dried iron phosphate slag at 700 ℃ for 600min to obtain high-purity iron phosphate; and (4) detecting the purity of the recovered iron phosphate by a scanning electron microscope and an X-ray diffractometer.
The micelle agent is a commercial product purchased from Houchen environmental protection energy (Guangzhou) Co.Ltd, and the product model is a polymer micelle agent JS-2. The main component of the water-based polymer is an organic high molecular polymer, has an organic high molecular structure, can form a spatial mesh (honeycomb) structure, and can capture ultrafine particles in water.
The plate pipe of the inclined plate settler and the horizontal plane form an angle of 60 degrees, the height of a clear water area in the inclined plate sedimentation tank is 1.0-1.5 m, and the height of a water distribution area at the bottom of the sedimentation tank is not less than 1.0 m. In addition, the flow velocity of the wastewater passing through the inclined plate is about 10-20 mm/s, iron phosphate slag recovered in water is obliquely accumulated into a thin mud layer on the surface area of the bottom side of the inclined pipe by utilizing the inclined plate sedimentation, and the iron phosphate slag slides into the mud collection hopper under the action of gravity, so that the iron phosphate slag can be rapidly recovered.
Step 2: adding washing water for washing the iron phosphate slag in the step 1 into the battery wastewater after solid-liquid separation, then introducing the battery wastewater into an acidolysis regulating tank, and regulating the pH to 10 by using 0.1mol/L sodium hydroxide solution; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding 0.4g/L ferrous sulfate heptahydrate, stirring and reacting for 30min, adding 30% hydrogen peroxide, and continuously stirring and reacting for 30min, wherein the step is mainly to remove phosphate radicals, iron ions and the like in the wastewater; standing for 1h after the reaction is finished, and allowing a large amount of flocs to appear in the sedimentation tank to obtain battery wastewater containing the flocs; the ratio of the amounts of the ferrous sulfate heptahydrate to the hydrogen peroxide is 1: 1.
and step 3: performing filter pressing on the battery wastewater containing the flocs obtained in the step 2 by using a filter press to obtain supernatant and sludge; storing the sludge, introducing the supernatant into a settling tank, adding 600ppm of calcium hypochlorite while continuously stirring, and continuously stirring for 30min, wherein the step is mainly to remove ammonium ions in the wastewater. Standing for 30min after stirring is finished, and finally performing filter pressing through a filter press until clear water is separated out, so that the treatment of the battery wastewater is completed. At the moment, the total phosphorus and ammonia nitrogen in the clear water basically meet the emission standard and can be discharged.
The water quality of the water body after the recovery and treatment in the embodiment is as follows: COD: 400mg/L, ammonia nitrogen: 23mg/L, total phosphorus: 8mg/L, SS: 62mg/L, pH: about 800g of iron phosphate solid particles per ton of water were recovered in this example, with a recovery rate of about 23%.
Figure 2 is an XRD pattern of the iron phosphate recovered in example 1; the anhydrous iron phosphate powder recovered in this example was tested using an X-ray diffractometer (XRD), and the obtained results are shown in fig. 1, where the peaks of iron phosphate can both correspond to the standard cards one to one, so that the quality of iron phosphate prepared by this method meets the requirements of practical applications.
FIG. 3 is a scanning electron micrograph of the iron phosphate recovered in example 1; as shown in fig. 2, the size of the product iron phosphate is smaller, the lithium iron phosphate prepared by the carbothermic method can reach a finer grade, and the prepared lithium iron phosphate has better conductivity.
Example 2: a method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater are carried out according to the following steps:
in this example, an iron phosphate production mother liquor and rinse water from a home battery anode material precursor iron phosphate production plant in somewhere in Sichuan were selected for experiments. The water body has the following water inlet quality indexes: COD: 5671mg/L, ammonia nitrogen: 6827mg/L, Total phosphorus: 3892mg/L, SS: 1520mg/L, pH 8.5.
Step 1: introducing the battery wastewater (production mother liquor and flushing water) into an adjusting tank, and adjusting the pH to 8.0; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding 3g/L micelle agent, stirring and reacting for 30min, carrying out solid-liquid separation on the battery wastewater through an inclined plate settler after the reaction is finished to obtain iron phosphate slag, washing the iron phosphate slag for 30min by using clear water, wherein the purpose of washing is to remove ions on the surface of the iron phosphate slag and prevent the ions from influencing the subsequent iron phosphate production purity and electronic material preparation, and the washing requirement is to basically remove NH on the surface of the iron phosphate + 、SO 4 2- 、Fe 3+ Ions. The washed iron phosphate slag is sent to a drying room and dried at the temperature of 200 DEG CDrying for 600min to remove crystal water, and calcining the dried iron phosphate slag at the temperature of 500 ℃ for 600min to obtain high-purity iron phosphate; and (4) detecting the purity of the recovered iron phosphate by a scanning electron microscope and an X-ray diffractometer.
The micelle agent is a commercial product purchased from Houchen environmental protection energy (Guangzhou) Co.Ltd, and the product model is a polymer micelle agent JS-2. The main component of the water-based paint is organic high molecular polymer which has an organic high molecular structure, can form a spatial mesh (honeycomb) structure, and can capture ultrafine particles in water.
The plate pipe of the inclined plate settler and the horizontal plane form an angle of 60 degrees, the height of a clear water area in the inclined plate sedimentation tank is 1.0-1.5 m, and the height of a water distribution area at the bottom of the sedimentation tank is not less than 1.0 m. In addition, the flow velocity of the wastewater passing through the inclined plate is about 10-20 mm/s, iron phosphate slag recovered in water is obliquely accumulated into a thin mud layer on the surface area of the bottom side of the inclined pipe by utilizing the inclined plate sedimentation, and the iron phosphate slag slides into the mud collection hopper under the action of gravity, so that the iron phosphate slag can be rapidly recovered.
Step 2: adding washing water for washing the iron phosphate slag in the step 1 into the battery wastewater after solid-liquid separation, then introducing the battery wastewater into an acidolysis regulating tank, and regulating the pH to 11 by using 0.1mol/L sodium hydroxide solution; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding 0.5g/L ferrous sulfate heptahydrate, stirring and reacting for 30min, adding 30% hydrogen peroxide, and continuously stirring and reacting for 30min, wherein the step is mainly to remove phosphate radicals, iron ions and the like in the wastewater; standing for 1h after the reaction is finished, and allowing a large amount of flocs to appear in the sedimentation tank to obtain battery wastewater containing the flocs; the ratio of the amounts of the ferrous sulfate heptahydrate to the hydrogen peroxide is 1: 2.
and step 3: performing filter pressing on the battery wastewater containing the flocs obtained in the step 2 by using a filter press to obtain supernatant and sludge; storing the sludge, introducing the supernatant into a settling tank, adding 500ppm of calcium hypochlorite while continuously stirring, and continuously stirring for 30min, wherein the step is mainly to remove ammonium ions in the wastewater. Standing for 30min after stirring is finished, and finally performing filter pressing through a filter press until clear water is separated out, so that the treatment of the battery wastewater is completed. At the moment, the total phosphorus and ammonia nitrogen in the clear water basically meet the emission standard and can be discharged.
The water quality of the water body after the recovery and treatment in the embodiment is as follows: COD: 560mg/L, ammonia nitrogen: 56mg/L, total phosphorus: 10mg/L, SS: 132mg/L, pH: 7.5, in this example approximately 1450g of iron phosphate solid particles per ton of water were recovered, with a recovery rate of approximately 23%.
Figure 4 is an XRD pattern of the iron phosphate recovered in example 2; the anhydrous iron phosphate powder recovered in this example was tested using an X-ray diffractometer (XRD), and the obtained results are shown in fig. 4, where the peaks of iron phosphate and standard cards can both correspond to each other one by one, so that the quality of iron phosphate prepared by this method meets the requirements of practical application.
FIG. 5 is a scanning electron micrograph of the iron phosphate recovered in example 2; as shown in fig. 5, the size of the product iron phosphate is smaller, the lithium iron phosphate prepared by the carbothermic method can reach a finer grade, and the prepared lithium iron phosphate has better conductivity.
In summary, according to the method for treating the battery wastewater and the method for recovering the high-purity iron phosphate from the battery wastewater, disclosed by the invention, the micelle agent is utilized to realize the rapid recovery of the iron phosphate resource from the waste iron phosphate production wastewater, the iron phosphate production wastewater is fully utilized, the total yield of the iron phosphate is improved, the waste of a large amount of iron phosphate resources is avoided, the difficulty in subsequent iron phosphate wastewater treatment is reduced, the treatment cost is reduced, and the iron phosphate product with economic value is recovered.
Claims (10)
1. A method for treating battery wastewater and a method for recovering high-purity iron phosphate from the battery wastewater are characterized by comprising the following steps:
step 1: introducing the battery wastewater into an adjusting tank, and adjusting the pH to 6.0-8.0; then introducing the battery wastewater after pH adjustment into a sedimentation tank, adding a micelle agent, stirring and reacting for 30-60 min, carrying out solid-liquid separation on the battery wastewater through an inclined plate settler after the reaction is finished to obtain iron phosphate slag, and washing, drying and calcining the iron phosphate slag to obtain high-purity iron phosphate;
step 2: adding washing water for washing the iron phosphate slag in the step 1 into the battery wastewater after solid-liquid separation, and then introducing the battery wastewater into an acidolysis regulating tank to regulate the pH value to 10-11; then introducing the battery wastewater after the pH adjustment into a sedimentation tank, adding a ferrous medicament, stirring and reacting for 30-90 min, adding an oxidant, continuously stirring and reacting for 30-90 min, and standing for 1-2 h after the reaction is finished to obtain battery wastewater containing flocs;
and step 3: performing filter pressing on the battery wastewater containing the flocs obtained in the step 2 by using a filter press to obtain supernatant and sludge; and (3) introducing the supernatant into a sedimentation tank, adding an ammonia nitrogen remover while continuously stirring, continuously stirring for 30-60 min, standing for 30-90 min after stirring is finished, and finally performing filter pressing through a filter press until clear water is separated out, so that the treatment of the battery wastewater is completed.
2. The method for treating the battery wastewater and the method for recovering the high-purity iron phosphate from the battery wastewater according to claim 1, wherein the micelle agent in the step 1 is a polymer micelle agent JS-2, and the addition amount of the micelle agent is 2-3 g/L.
3. The method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 1, wherein the washing time of the iron phosphate slag in step 1 is 10-30 min.
4. The method for treating the battery wastewater and the method for recovering the high-purity iron phosphate from the battery wastewater according to claim 1, wherein the iron phosphate slag in the step 1 is dried at a temperature of 100-200 ℃ for 500-900 min.
5. The method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 1, wherein the iron phosphate slag in step 1 is calcined at a temperature of 500-700 ℃ for 500-900 min.
6. The method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 1, wherein the pH of the battery wastewater is adjusted to 10-11 in step 2 by using 0.1mol/L sodium hydroxide solution.
7. The method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 1, wherein the ferrous iron in the step 2 is ferrous sulfate heptahydrate, and the addition amount of the ferrous iron is 0.4-0.5 g/L.
8. The method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 1, wherein the oxidant in the step 2 is hydrogen peroxide with a mass fraction of 30%.
9. The method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 7 or 8, wherein the ratio of the amounts of ferrous sulfate heptahydrate to hydrogen peroxide is (1-6): 2.
10. the method for treating battery wastewater and the method for recovering high-purity iron phosphate from battery wastewater according to claim 1, wherein the ammonia nitrogen remover in the step 3 is calcium hypochlorite with a concentration of 500-600 ppm.
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