CN220579111U - Treatment system for battery disassembly wastewater - Google Patents
Treatment system for battery disassembly wastewater Download PDFInfo
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- CN220579111U CN220579111U CN202322263334.5U CN202322263334U CN220579111U CN 220579111 U CN220579111 U CN 220579111U CN 202322263334 U CN202322263334 U CN 202322263334U CN 220579111 U CN220579111 U CN 220579111U
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- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 230000008929 regeneration Effects 0.000 claims abstract description 57
- 238000011069 regeneration method Methods 0.000 claims abstract description 57
- 238000000197 pyrolysis Methods 0.000 claims abstract description 35
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- 238000001556 precipitation Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims description 52
- 239000011574 phosphorus Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 45
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- 238000004062 sedimentation Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 18
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 230000009466 transformation Effects 0.000 claims description 13
- 238000001226 reprecipitation Methods 0.000 claims description 9
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 6
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 71
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
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- 238000000034 method Methods 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000010802 sludge Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002826 coolant Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
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- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000010979 pH adjustment Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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Abstract
The utility model provides a treatment system of battery disassembly wastewater, which comprises a heavy precipitation unit, an adsorption dephosphorization unit, a pH adjusting unit, an adsorption lithium removal unit, a dephosphorization precipitation unit and a biochemical treatment unit which are sequentially connected along the water flow direction; the adsorption dephosphorization unit comprises a dephosphorization resin device and a dephosphorization regeneration concentrated solution storage device; the water outlet of the dephosphorization resin device is connected with a pH adjusting unit; the regeneration concentrated solution outlet of the dephosphorization resin device is connected with a dephosphorization regeneration concentrated solution storage device; the outlet of the dephosphorization regeneration concentrated solution storage device is connected with the pyrolysis unit; and the outlet of the pyrolysis unit is respectively connected with the pH adjusting unit and the dephosphorization regeneration concentrated solution storage device. The treatment system provided by the utility model can decompose lithium hexafluorophosphate and intermediate products thereof into phosphate which is easy to treat, so that the purification and recovery of lithium salt are realized, the discharge of waste liquid and secondary pollution are avoided, and the investment cost and the operation cost are reduced.
Description
Technical Field
The utility model relates to the technical field of lithium ion battery recovery, in particular to a treatment system for battery disassembly wastewater.
Background
With the rapid development of new energy electric automobile industry, the demand of power batteries is continuously increased, and a large number of waste batteries are generated. The electrolyte is used as one of four materials of the lithium battery, is a carrier for ion transmission in the lithium battery, and plays a role in conducting lithium ions between the anode and the cathode. The electrolyte mainly comprises the following components: lithium hexafluorophosphate (LiPF) 6 ) Ethylene carbonate (C) 3 H 4 O 3 ) Propylene carbonate (C) 4 H 6 O 3 ) Diethyl carbonate (C) 5 H 10 O 3 ) Dimethyl carbonate (C) 3 H 6 O 3 ) And methyl ethyl carbonate (C) 4 H 8 O 3 ). Wherein, lithium hexafluorophosphate (LiPF) 6 ) The electrolyte has the advantages of good ionic conductivity, good electrochemical stability, safety, environmental protection and the like, and is the lithium ion electrolyte which is most widely used at present.
In the process of disassembling the battery, firstly, the battery shell is disassembled, and then the battery is soaked and discharged; and then crushing the discharged battery, dissolving part of electrolyte obtained by crushing in water to form electrolyte wastewater, absorbing tail gas generated by crushing by using a spray tower to obtain absorption wastewater, wherein the two types of wastewater are commonly called battery dismantling wastewater. LiPF in battery disassembly wastewater 6 The hydrolysis behavior of the solution is difficult to judge, the treatment steps are complex, and the LiPF 6 Easy to hydrolyze to form LiF and PF 5 、OPF 3 Or HF and other substances exist in various forms in water, so that the treatment difficulty is high, the recycling is difficult, the treatment cost is high, the treatment effect is poor, and especially the content of phosphorus in the treated water is still high.
At present, COD in the battery disassembly wastewater can generally reach over 20000mg/L, and both lithium element and phosphorus element can reach over 1000 mg/L. The existing treatment method generally comprises the steps of firstly removing heavy metal elements, then diluting the treated battery dismantling wastewater with other wastewater, performing biochemical treatment, and finally sending the diluted battery dismantling wastewater into an MVR evaporator for concentration to obtain concentrated solution for outward transportation. However, the investment cost of this method is enormous and the running cost is high.
Therefore, aiming at the battery disassembly wastewater, the development of a treatment system for removing organic matters, phosphorus and heavy metals more economically and practically has important significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the utility model aims to provide a treatment system for battery disassembly wastewater, which can reduce energy consumption and medicament consumption, reduce investment cost and operation cost, realize purification and recovery of lithium salt and avoid discharge of waste liquid and secondary pollution.
To achieve the purpose, the utility model adopts the following technical scheme:
the utility model provides a treatment system for battery disassembly wastewater, which comprises a heavy removal precipitation unit, an adsorption dephosphorization unit, a pH adjustment unit, an adsorption lithium removal unit, a dephosphorization precipitation unit and a biochemical treatment unit which are sequentially connected along the water flow direction; the adsorption dephosphorization unit comprises a dephosphorization resin device and a dephosphorization regeneration concentrated solution storage device; the water outlet of the dephosphorization resin device is connected with a pH adjusting unit; the regeneration concentrated solution outlet of the dephosphorization resin device is connected with a dephosphorization regeneration concentrated solution storage device; the outlet of the dephosphorization regeneration concentrated solution storage device is connected with the pyrolysis unit; and the outlet of the pyrolysis unit is respectively connected with the pH adjusting unit and the dephosphorization regeneration concentrated solution storage device.
Preferably, the pyrolysis unit comprises an acid regulating device, a pyrolysis device and a heat exchange device which are sequentially connected along the water flow direction; the outlet of the dephosphorization regeneration concentrated solution storage device is respectively connected with the inlet of the acid regulating device and the cold water inlet of the heat exchange device; the cold water outlet of the heat exchange device is connected with a dephosphorization regeneration concentrated solution storage device; the outlet of the pyrolysis device is connected with the hot water inlet of the heat exchange device; and a hot water outlet of the heat exchange device is connected with the pH adjusting unit.
Preferably, the heavy removal sedimentation unit comprises a first heavy removal reaction tank, a second heavy removal reaction tank and a heavy removal sedimentation tank which are sequentially connected along the water flow direction.
Preferably, a first filtering unit is arranged between the heavy precipitation unit and the adsorption dephosphorization unit; the outlet of the heavy removal sedimentation tank is connected with a first filtering unit; the outlet of the first filtering unit is connected with the dephosphorization resin device.
Preferably, the adsorption lithium removal unit comprises a lithium removal resin device and a lithium removal regeneration concentrated solution storage device; the water outlet of the lithium resin removing device is connected with a phosphorus removing precipitation unit; the regenerated concentrated solution outlet of the lithium removal resin device is connected with a lithium removal regenerated concentrated solution storage device; the transformation waste liquid outlet of the lithium resin removing device is connected with a heavy precipitation removing unit.
Preferably, a second filtering unit is arranged between the pH adjusting unit and the adsorption lithium removing unit; the outlet of the pH adjusting unit is connected with the second filtering unit; and the outlet of the second filtering unit is connected with the lithium resin removing device.
Preferably, the dephosphorization precipitation unit comprises a first dephosphorization reaction tank, a second dephosphorization reaction tank, a third dephosphorization reaction tank and a dephosphorization precipitation tank which are sequentially connected along the water flow direction.
Preferably, the biochemical treatment unit comprises a UASB treatment device, an anaerobic tank, an aerobic tank and a secondary sedimentation tank which are sequentially connected along the water flow direction.
Preferably, the outlet of the aerobic tank is also connected with an anaerobic tank; the outlet of the secondary sedimentation tank is also respectively connected with the anaerobic tank and the aerobic tank.
Preferably, the transformation waste liquid outlet of the dephosphorization resin device is connected with a reprecipitation unit.
Compared with the prior art, the utility model has the beneficial effects that:
(1) The treatment system provided by the utility model can avoid using an MVR evaporator, reduce investment cost and operation cost, enrich and concentrate phosphorus in wastewater, decompose lithium hexafluorophosphate and intermediate products thereof into easy-to-treat phosphate through pyrolysis, thereby realizing recovery of lithium, improving the yield of lithium, avoiding outward transport and secondary pollution of waste liquid, reducing energy consumption and dosage of medicaments, and realizing standard treatment of wastewater.
(2) The treatment system provided by the utility model combines biochemical technology to remove pollutants, especially organic pollutants, and has lower operation cost.
(3) The processing system provided by the utility model can automatically run, reduces the manpower consumption, and is simple to operate and convenient to maintain.
Drawings
FIG. 1 is a schematic diagram of a processing system according to embodiment 1 of the present utility model;
in the figure: 1-a first weight removing reaction tank; 2-a second weight removing reaction tank; 3-removing heavy sedimentation tank; 4-a first filtration unit; 5-a dephosphorization resin device; 6-dephosphorizing regeneration concentrated solution storage device; 7-an acid regulating device; 8-pyrolysis device; 9-a heat exchange device; 10-a pH adjusting unit; 11-a lithium removal regeneration concentrate storage device; 12-a second filtration unit; 13-a lithium removal resin device; 14-a first dephosphorization reaction tank; 15-a second dephosphorization reaction tank; 16-a third dephosphorization reaction tank; 17-a dephosphorization sedimentation tank; 18-UASB processing means; 19-an anaerobic tank; 20-an aerobic tank; 21-a secondary sedimentation tank; 22-pyrolysis unit.
Detailed Description
The technical scheme of the utility model is further described below by the specific embodiments with reference to the accompanying drawings.
The present utility model will be described in further detail below. The following examples are merely illustrative of the present utility model and are not intended to represent or limit the scope of the utility model as defined in the claims.
It is to be understood that in the description of the present utility model, the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the drawings, are merely for convenience in describing the present utility model and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus are not to be construed as limiting the present utility model. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present utility model, unless otherwise indicated, the meaning of "a plurality" is two or more.
It should be noted that, in the description of the present utility model, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present utility model can be understood by those of ordinary skill in the art in a specific case.
It will be appreciated by those skilled in the art that the present utility model necessarily includes the necessary piping, conventional valves and general pumping equipment for achieving the process integrity, but the foregoing is not a major inventive aspect of the present utility model, and that the present utility model is not particularly limited thereto as the layout may be added by themselves based on the process flow and the equipment configuration options.
In one embodiment, the utility model provides a treatment system of battery disassembly wastewater, as shown in fig. 1, wherein the treatment system comprises a heavy precipitation unit, an adsorption dephosphorization unit, a pH adjusting unit 10, an adsorption lithium removal unit, a dephosphorization precipitation unit and a biochemical treatment unit which are sequentially connected along the water flow direction; the adsorption dephosphorization unit comprises a dephosphorization resin device 5 and a dephosphorization regeneration concentrated solution storage device 6; the water outlet of the dephosphorization resin device 5 is connected with a pH adjusting unit 10; the regenerated concentrated solution outlet of the dephosphorization resin device 5 is connected with a dephosphorization regenerated concentrated solution storage device 6; the outlet of the dephosphorization regeneration concentrated solution storage device 6 is connected with a pyrolysis unit 22; the outlet of the pyrolysis unit 22 is respectively connected with the pH adjusting unit 10 and the dephosphorization regeneration concentrated solution storage device 6, and the pH adjusting unit 10 is a pH adjusting tank.
In the utility model, heavy metals and suspended matters are removed by a heavy precipitation removal unit; then removing phosphorus element in the battery disassembly wastewater by adsorption through an adsorption phosphorus removal unit, wherein the phosphorus element in the water after phosphorus removal obtained by adsorption can be reduced to below 1mg/L, the adsorption phosphorus removal unit is provided with a phosphorus removal resin device 5, generally a phosphorus removal resin adsorption tower, the resin adopted by the phosphorus removal resin device 5 is acid regeneration and alkali transformation resin, the water after phosphorus removal is generated after phosphorus removal by adsorption and enters a pH adjustment unit 10, the phosphorus removal resin after phosphorus removal is regenerated and transformed to respectively generate phosphorus removal regeneration concentrated solution and transformed waste liquid, the phosphorus removal regeneration concentrated solution contains lithium hexafluorophosphate and decomposition intermediates thereof, the phosphorus removal regeneration concentrated solution enters a pyrolysis unit 22, and the lithium hexafluorophosphate and the decomposition intermediates thereof are decomposed into phosphate in the pyrolysis unit 22 and then enter the pH adjustment unit 10 and the water after phosphorus removal for mixing; then, recovering a lithium source through an adsorption lithium removal unit, and removing phosphate through a phosphorus removal precipitation unit; finally, most of organic matters, total phosphorus and total nitrogen are removed through a biochemical treatment unit. Through the treatment process, the utility model can realize the standard discharge of the wastewater, and the waste liquid is not required to be transported outwards after being concentrated, so that the secondary pollution is avoided.
In the utility model, the water quality condition of the battery disassembly wastewater is generally as follows: the heavy metal elements comprise nickel, cobalt, manganese and copper, and the concentrations are 5-20mg/L, 1-5mg/L and 1-5mg/L respectively; the concentration of lithium is 1-2g/L, and the concentration of phosphorus is 1-2g/L; COD value is 20-60g/L.
In some embodiments, the pyrolysis unit 22 comprises an acid regulating device 7, a pyrolysis device 8 and a heat exchange device 9 which are sequentially connected along the water flow direction; the outlet of the dephosphorization regeneration concentrated solution storage device 6 is respectively connected with the inlet of the acid regulating device 7 and the cold water inlet of the heat exchange device 9; the cold water outlet of the heat exchange device 9 is connected with the dephosphorization regeneration concentrated solution storage device 6; the outlet of the pyrolysis device 8 is connected with the hot water inlet of the heat exchange device 9; the hot water outlet of the heat exchange device 9 is connected with a pH adjusting unit 10.
It is worth noting that in the utility model, part of the phosphorus removal regenerated concentrated solution is sent into the acid regulating device 7, the pH value can be regulated to be less than or equal to 1.0 by adding concentrated sulfuric acid (the mass fraction is generally 98%), a large amount of heat released by dilution of the concentrated sulfuric acid is utilized to increase the water temperature of the regenerated concentrated solution, the consumption of subsequent steam is saved, then the regenerated concentrated solution with the pH value less than or equal to 1.0 is sent into the pyrolysis device 8, the water temperature is increased to 80-100 ℃ by steam heating, lithium hexafluorophosphate and a decomposition intermediate thereof are gradually decomposed into phosphate at the pH value less than or equal to 1.0 and the temperature of 80-100 ℃, the decomposed regenerated concentrated solution enters the heat exchanging device 9, the heat exchanging device 9 can adopt part of the phosphorus removal regenerated concentrated solution as a cooling medium for heat exchanging, the temperature of the regenerated concentrated solution after pyrolysis can be reduced, the influence on the subsequent treatment working section is avoided, the temperature of the regenerated concentrated solution after heat exchanging by the cooling medium is increased, the consumption of the subsequent steam is saved, the consumption of the subsequent steam can be increased, the lithium is not only can be increased, but also the energy consumption and the equipment investment cost and the secondary pollution are greatly reduced is avoided.
According to the utility model, the dephosphorization regeneration concentrated solution subjected to heat exchange and the dephosphorization water are mixed in the pH adjusting unit 10, on one hand, because the water yield of the heat exchange device 9 is small and the temperature is high, the water yield of the dephosphorization water is large and the temperature is low, the water temperature can be further reduced through the mixing of the two, and the influence on the operation of the subsequent working section is avoided; on the other hand, as the pH value of the water discharged from the heat exchange device 9 is lower, the pH value of the water after dephosphorization is higher, the acid and alkali neutralization effect can be achieved through the mixing of the water and the phosphorus removal device, and the consumption of acid and alkali is reduced. The pH adjusting unit 10 generally adjusts the pH to 8-9 by using sodium hydroxide solution (mass fraction is generally 30%) or concentrated sulfuric acid (mass fraction is generally 98%), so that the addition of calcium chloride in the subsequent dephosphorization and precipitation unit can be avoided to make the wastewater acidic.
In the utility model, the adopted cooling medium of the heat exchange device 9 is dephosphorization regeneration concentrated solution, and the cooling medium flows into the heat exchange device 9 from a cold water inlet and flows out from a cold water outlet; the heat exchange device 9 is used for cooling the pyrolyzed dephosphorized regenerated concentrated solution, and the pyrolyzed dephosphorized regenerated concentrated solution flows into the heat exchange device 9 from a hot water inlet of the heat exchange device 9 and flows out from a hot water outlet. In the present utility model, a stirrer is generally disposed in the pyrolysis device 8, so as to increase stirring of the water body.
In some embodiments, the heavy removal sedimentation unit comprises a first heavy removal reaction tank 1, a second heavy removal reaction tank 2 and a heavy removal sedimentation tank 3 which are sequentially connected along the water flow direction.
In the utility model, the pH value of the battery disassembly wastewater can be adjusted to 8-10 by adding sodium hydroxide solution (generally 30% by mass) into the first weight removal reaction tank 1, so that metal ions such as nickel, aluminum, copper and the like in the battery disassembly wastewater form hydroxide precipitates; the polyacrylamide solution (generally with the mass fraction of 0.1%) is added into the second weight removing reaction tank 2, so that small-particle hydroxide precipitates in the battery dismantling wastewater can be aggregated, and large-particle flocs are formed; finally, the sludge enters a heavy removal sedimentation tank 3 for sludge-water separation, the generated sludge is subjected to periodical filter pressing and outward transportation treatment, and the filtrate enters the next working section for treatment.
In some embodiments, a first filtering unit 4 is arranged between the reprecipitation unit and the adsorption dephosphorization unit; the outlet of the heavy removal sedimentation tank 3 is connected with a first filtering unit 4; the outlet of the first filtering unit 4 is connected with the dephosphorization resin device 5, and the first filtering unit 4 is a first filter.
In the utility model, suspended matters can be removed by arranging the first filtering unit 4 between the reprecipitation unit and the adsorption dephosphorization unit, so that the subsequent adsorption resin is prevented from being blocked, and the filtering precision of the first filtering unit 4 is generally 1-5 mu m.
In some of these embodiments, the adsorption lithium removal unit comprises a lithium removal resin device 13 and a lithium removal regeneration concentrate storage device 11; the water outlet of the lithium removal resin device 13 is connected with a phosphorus removal precipitation unit; the regenerated concentrated solution outlet of the lithium removal resin device 13 is connected with a lithium removal regenerated concentrated solution storage device 11; the transformation waste liquid outlet of the lithium removal resin device 13 is connected with a reprecipitation unit.
According to the utility model, the adsorption lithium removing unit is arranged, so that lithium elements in the battery disassembly wastewater can be recovered, and the lithium yield is improved.
In some of these embodiments, a second filtration unit 12 is disposed between the pH adjustment unit 10 and the adsorption lithium removal unit; the outlet of the pH adjusting unit 10 is connected with a second filtering unit 12; the outlet of the second filter unit 12 is connected with a lithium removing resin device 13, and the second filter unit 12 is a second filter.
In the present utility model, suspended matters in water can be removed by providing the second filter unit 12, and subsequent resin clogging is avoided, and the filtering accuracy of the second filter unit 12 is generally 1-5 μm.
In some embodiments, the dephosphorization and precipitation unit comprises a first dephosphorization reaction tank 14, a second dephosphorization reaction tank 15, a third dephosphorization reaction tank 16 and a dephosphorization and precipitation tank 17 which are sequentially connected along the water flow direction.
In the utility model, the calcium chloride solution (generally 30% by mass) is added into the first dephosphorization reaction tank 14, so that phosphorus elements can be primarily removed; adding a polyaluminium chloride solution (generally 10% by mass) into the second dephosphorization reaction tank 15, so that phosphorus elements can be removed secondarily; the addition of the polyacrylamide solution (typically 0.1% by mass) in the third dephosphorization reaction tank 16 can aggregate small particle suspensions to form large particle flocs; finally, the sludge enters a dephosphorization sedimentation tank 17 for sludge-water separation, the sludge is subjected to periodical filter pressing and outward transportation treatment, and the filtrate enters the next working section for treatment.
In some embodiments, the biochemical treatment unit includes a UASB treatment device 18, an anaerobic tank 19, an aerobic tank 20, and a secondary sedimentation tank 21, which are sequentially connected in the water flow direction.
In the utility model, most of organic matters, part of total phosphorus and total nitrogen in the wastewater can be removed by arranging the UASB processing device 18, namely an upflow anaerobic sludge reaction device; the combined device of the anaerobic tank 19, the aerobic tank 20 and the secondary sedimentation tank 21 can further realize the removal of organic matters, total phosphorus and total nitrogen.
In some embodiments, the outlet of the aerobic tank 20 is also connected with an anaerobic tank 19; the outlet of the secondary sedimentation tank 21 is also respectively connected with the anaerobic tank 19 and the aerobic tank 20.
In the utility model, the outlet of the aerobic tank 20 is also connected with the anaerobic tank 19, so that the reflux of nitrified liquid can be realized, and the outlet of the secondary sedimentation tank 21 is respectively connected with the anaerobic tank 19 and the aerobic tank 20, so that the reflux of sludge can be realized, and the further removal of organic matters, total phosphorus and total nitrogen can be realized.
In some of these embodiments, the conversion waste outlet of the dephosphorization resin apparatus 5 is connected to a reprecipitation unit.
In the present utility model, by discharging the transformation waste liquid into the inlet of the reprecipitation unit, typically the inlet of the first reprecipitation reaction tank 1, lithium element and the like in the transformation waste liquid can be recovered, and contaminants in the transformation waste liquid can be further removed.
The operation and treatment effect of the treatment system are specifically described below by way of example 1 and comparative example 1:
example 1
The embodiment provides a treatment system for battery disassembly wastewater, the structural schematic diagram of which is shown in fig. 1, wherein the treatment system comprises a reprecipitation unit, an adsorption dephosphorization unit, a pH adjustment unit 10, an adsorption lithium removal unit, a dephosphorization precipitation unit and a biochemical treatment unit which are sequentially connected along the water flow direction;
the adsorption dephosphorization unit comprises a dephosphorization resin device 5 and a dephosphorization regeneration concentrated solution storage device 6, wherein a water outlet of the dephosphorization resin device 5 is connected with a pH adjusting unit 10, a regeneration concentrated solution outlet of the dephosphorization resin device 5 is connected with the dephosphorization regeneration concentrated solution storage device 6, an outlet of the dephosphorization regeneration concentrated solution storage device 6 is connected with a pyrolysis unit 22, an outlet of the pyrolysis unit 22 is respectively connected with the pH adjusting unit 10 and the dephosphorization regeneration concentrated solution storage device 6, the pyrolysis unit 22 comprises an acid adjusting device 7, a pyrolysis device 8 and a heat exchange device 9 which are sequentially connected along the water flow direction, an outlet of the dephosphorization regeneration concentrated solution storage device 6 is respectively connected with an inlet of the acid adjusting device 7 and a cold water inlet of the heat exchange device 9, a cold water outlet of the heat exchange device 9 is connected with the dephosphorization regeneration concentrated solution storage device 6, an outlet of the pyrolysis device 8 is connected with a hot water inlet of the heat exchange device 9, and a hot water outlet of the heat exchange device 9 is connected with the pH adjusting unit 10;
the heavy removal sedimentation unit comprises a first heavy removal reaction tank 1, a second heavy removal reaction tank 2 and a heavy removal sedimentation tank 3 which are sequentially connected along the water flow direction, wherein the outlet of the heavy removal sedimentation tank 3 is connected with a first filtering unit 4, and the outlet of the first filtering unit 4 is connected with a phosphorus removal resin device 5;
the adsorption lithium removal unit comprises a lithium removal resin device 13 and a lithium removal regeneration concentrated solution storage device 11, a water outlet of the lithium removal resin device 13 is connected with a phosphorus removal precipitation unit, a regeneration concentrated solution outlet of the lithium removal resin device 13 is connected with the lithium removal regeneration concentrated solution storage device 11, a transformation waste liquid outlet of the lithium removal resin device 13 is connected with a heavy precipitation unit, an outlet of the pH adjustment unit 10 is connected with a second filtering unit 12, an outlet of the second filtering unit 12 is connected with the lithium removal resin device 13, and a transformation waste liquid outlet of the phosphorus removal resin device 5 is connected with the heavy precipitation unit;
the dephosphorization precipitation unit comprises a first dephosphorization reaction tank 14, a second dephosphorization reaction tank 15, a third dephosphorization reaction tank 16 and a dephosphorization precipitation tank 17 which are sequentially connected along the water flow direction;
the biochemical treatment unit comprises a UASB treatment device 18, an anaerobic tank 19, an aerobic tank 20 and a secondary sedimentation tank 21 which are sequentially connected along the water flow direction, wherein the outlet of the aerobic tank 20 is also connected with the anaerobic tank 19, and the outlet of the secondary sedimentation tank 21 is also respectively connected with the anaerobic tank 19 and the aerobic tank 20.
The treatment system provided by the embodiment is used for treating the battery dismantling wastewater, wherein the heavy metal elements in the battery dismantling wastewater comprise nickel, cobalt, manganese and copper, and the concentrations of the heavy metal elements are 17.77mg/L, 1.72mg/L, 1.89mg/L and 3.11mg/L respectively; the concentration of lithium is 1.62g/L, and the concentration of phosphorus is 1.84g/L; COD value is 59788mg/L, and the operation process is as follows:
(1) The method comprises the steps that battery disassembly wastewater enters a first weight removal reaction tank 1, a sodium hydroxide solution with the mass fraction of 30% is added into the first weight removal reaction tank 1, the pH value of the battery disassembly wastewater is adjusted to be 9, metal ions such as nickel, aluminum and copper in the wastewater form hydroxide precipitates, then the battery disassembly wastewater enters a second weight removal reaction tank 2, a PAM solution with the mass fraction of 0.1% is added into the second weight removal reaction tank 2, and the hydroxide precipitates of small and medium particles in the wastewater are aggregated, so that large-particle flocs are formed; then, the battery disassembly wastewater enters a heavy removal sedimentation tank 3 for mud-water separation, and filtrate obtained by separation enters a first filtering unit 4; filtering in the first filter unit 4 with a filtering accuracy of 2 μm;
(2) The filtered battery disassembly wastewater enters a dephosphorization resin device 5, phosphorus in the wastewater is adsorbed by utilizing the ion exchange performance of the resin to obtain dephosphorized water, the concentration of the phosphorus in the dephosphorized water is less than or equal to 1mg/L, and the dephosphorized water enters a pH adjusting unit 10; regenerating the dephosphorized resin by adopting acid liquor to obtain dephosphorized regenerated concentrated solution, transforming the regenerated resin by adopting alkali liquor to obtain transformed waste liquid, enabling the dephosphorized regenerated concentrated solution to enter a dephosphorized regenerated concentrated solution storage device 6, and enabling the transformed waste liquid to enter a first weight-removing reaction tank 1;
(3) Part of the dephosphorization regeneration concentrated solution in the dephosphorization regeneration concentrated solution storage device 6 enters an acid regulating device 7, sulfuric acid with the mass fraction of 98% is added into the acid regulating device 7, the pH value of the dephosphorization regeneration concentrated solution is regulated to be lower than 1.0, then the effluent of the acid regulating device 7 enters a pyrolysis device 8, the water body is stirred in the pyrolysis device 8, the water temperature is raised to 90 ℃ by adopting steam heating, lithium hexafluorophosphate and decomposition intermediates thereof are gradually decomposed into phosphate, the effluent of the pyrolysis device 8 enters a heat exchange device 9, part of the dephosphorization regeneration concentrated solution in the dephosphorization regeneration concentrated solution storage device 6 is used as a cooling medium of the heat exchange device 9, the effluent of the pyrolysis device 8 is cooled, the cooled effluent of the heat exchange device 9 enters a pH regulating unit 10, and the cooling medium after temperature rise returns to the dephosphorization regeneration concentrated solution storage device 6;
(4) Adding 30% sodium hydroxide solution or 98% concentrated sulfuric acid into the pH adjusting unit 10, adjusting the pH value of the water body to 8, and then filtering the effluent in the pH adjusting unit 10 by the second filtering unit 12 with the filtering precision of 2 mu m;
(5) The effluent of the second filtering unit 12 enters a lithium removal resin device 13, lithium in the wastewater is adsorbed by utilizing the ion exchange performance of the resin to obtain water after lithium removal, the resin after lithium removal is regenerated by acid liquor to obtain lithium removal regeneration concentrated solution, the regenerated resin is transformed by alkali liquor to obtain transformation waste liquid, the lithium removal regeneration concentrated solution enters a lithium removal regeneration concentrated solution storage device 11, so that lithium is recovered, and the transformation waste liquid enters a first weight removal reaction tank 1; after lithium removal, water enters a first phosphorus removal reaction tank 14, calcium chloride solution with the mass fraction of 30% is added into the first phosphorus removal reaction tank 14 for preliminary phosphorus removal, then enters a second phosphorus removal reaction tank 15, PAC solution with the mass fraction of 10% is added into the second phosphorus removal reaction tank 15 for secondary phosphorus removal, then enters a third phosphorus removal reaction tank 16, PAM solution with the mass fraction of 0.1% is added into the third phosphorus removal reaction tank 16, and small particle suspended matters in wastewater are aggregated, so that large particle flocs are formed; finally, the wastewater enters a dephosphorization sedimentation tank 17 for sludge-water separation to obtain filtrate;
(6) The filtrate enters a UASB treatment device 18 to remove most of organic matters and partial total phosphorus and total nitrogen in the wastewater, and meanwhile, macromolecular organic matters in the wastewater are degraded into micromolecular organic matters, the effluent of the UASB treatment device 18 sequentially enters an anaerobic tank 19, an aerobic tank 20 and a secondary sedimentation tank 21, nitrifying liquid flows back to the water inlet end of the anaerobic tank 19 from the tail end of the aerobic tank 20, sludge flows back to the water inlet ends of the anaerobic tank 19 and the aerobic tank 20 from the secondary sedimentation tank 21, and treated water is discharged from the secondary sedimentation tank 21.
By adopting the operation process, the treated water is discharged in the quality of water: the heavy metal elements comprise nickel, cobalt, manganese and copper, and the concentrations are respectively 0.09mg/L, 0.08mg/L, 0.11mg/L and 0.07mg/L; the concentration of lithium is 0.136g/L, and the concentration of phosphorus is 0.93mg/L; COD value was 386mg/L and recovery rate of lithium was 92.6%.
Comparative example 1
This comparative example provides a treatment system for battery disassembly wastewater, which differs from example 1 only in that a dephosphorization regeneration concentrate storage device and a pyrolysis unit are not provided.
The treatment system provided in this comparative example was used for treating the battery disassembly wastewater, and was different from example 1 only in that the water entering the pH adjusting unit was only the post-dephosphorization water, and the dephosphorization regeneration concentrate was not treated.
By adopting the treatment system and the operation process of the comparative example, the effluent quality of the treated water is as follows: the heavy metal elements comprise nickel, cobalt, manganese and copper, and the concentrations are respectively 0.1mg/L, 0.09mg/L, 0.12mg/L and 0.09mg/L; the concentration of lithium is 0.136/L, and the concentration of phosphorus is 0.95mg/L; COD value was 377mg/L and recovery rate of lithium was 47.8%.
The operation results of the embodiment 1 and the comparative example 1 show that the treatment system provided in the embodiment 1 not only realizes the standard treatment of the battery disassembly wastewater, but also realizes the treatment of the dephosphorization regeneration concentrated solution, avoids secondary pollution, reduces the treatment cost, and can fully recover the lithium in the dephosphorization regeneration concentrated solution due to the existence of partial phosphorus and lithium compounds in the dephosphorization regeneration concentrated solution, thereby remarkably improving the recovery rate of the lithium in the embodiment 1.
In summary, the treatment system provided by the utility model can realize the recovery of lithium, improve the yield of lithium, reduce the energy consumption and the dosage of medicaments, reduce the investment cost and the operation cost, realize the standard treatment of wastewater, and avoid the discharge of waste liquid and secondary pollution.
The applicant declares that the above is only a specific embodiment of the present utility model, but the scope of the present utility model is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present utility model disclosed by the present utility model fall within the scope of the present utility model and the disclosure.
Claims (10)
1. The treatment system for the battery disassembly wastewater is characterized by comprising a heavy precipitation unit, an adsorption dephosphorization unit, a pH adjusting unit (10), an adsorption lithium removal unit, a dephosphorization precipitation unit and a biochemical treatment unit which are sequentially connected along the water flow direction;
the adsorption dephosphorization unit comprises a dephosphorization resin device (5) and a dephosphorization regeneration concentrated solution storage device (6);
the water outlet of the dephosphorization resin device (5) is connected with a pH adjusting unit (10);
the regenerated concentrated solution outlet of the dephosphorization resin device (5) is connected with a dephosphorization regenerated concentrated solution storage device (6);
the outlet of the dephosphorization regeneration concentrated solution storage device (6) is connected with a pyrolysis unit (22);
the outlet of the pyrolysis unit (22) is respectively connected with the pH adjusting unit (10) and the dephosphorization regeneration concentrated solution storage device (6).
2. The system for treating the battery disassembly wastewater according to claim 1, wherein the pyrolysis unit (22) comprises an acid regulating device (7), a pyrolysis device (8) and a heat exchange device (9) which are sequentially connected along the water flow direction;
the outlet of the dephosphorization regeneration concentrated solution storage device (6) is respectively connected with the inlet of the acid regulating device (7) and the cold water inlet of the heat exchange device (9);
the cold water outlet of the heat exchange device (9) is connected with a dephosphorization regeneration concentrated solution storage device (6);
the outlet of the pyrolysis device (8) is connected with the hot water inlet of the heat exchange device (9);
the hot water outlet of the heat exchange device (9) is connected with a pH adjusting unit (10).
3. The system for treating the battery disassembly wastewater according to claim 1, wherein the weight removing precipitation unit comprises a first weight removing reaction tank (1), a second weight removing reaction tank (2) and a weight removing precipitation tank (3) which are sequentially connected along the water flow direction.
4. A treatment system of battery dismantling waste water according to claim 3, characterized in that a first filtering unit (4) is arranged between the heavy precipitation unit and the adsorption dephosphorization unit;
the outlet of the heavy removal sedimentation tank (3) is connected with a first filtering unit (4);
the outlet of the first filtering unit (4) is connected with a dephosphorization resin device (5).
5. The system for treating battery disassembly wastewater according to claim 1, wherein the adsorption lithium removal unit comprises a lithium removal resin device (13) and a lithium removal regeneration concentrate storage device (11);
the water outlet of the lithium removal resin device (13) is connected with a phosphorus removal precipitation unit;
the regenerated concentrated solution outlet of the lithium removal resin device (13) is connected with a lithium removal regenerated concentrated solution storage device (11);
the transformation waste liquid outlet of the lithium removal resin device (13) is connected with a heavy precipitation removal unit.
6. The system for treating the battery disassembly wastewater according to claim 5, wherein a second filter unit (12) is arranged between the pH adjusting unit (10) and the adsorption lithium removing unit;
the outlet of the pH adjusting unit (10) is connected with the second filtering unit (12);
the outlet of the second filtering unit (12) is connected with a lithium removing resin device (13).
7. The system for treating the battery disassembly wastewater according to claim 1, wherein the dephosphorization precipitation unit comprises a first dephosphorization reaction tank (14), a second dephosphorization reaction tank (15), a third dephosphorization reaction tank (16) and a dephosphorization precipitation tank (17) which are sequentially connected along the water flow direction.
8. The system for treating the battery disassembly wastewater according to claim 1, wherein the biochemical treatment unit comprises a UASB treatment device (18), an anaerobic tank (19), an aerobic tank (20) and a secondary sedimentation tank (21) which are sequentially connected in the water flow direction.
9. The system for treating the battery dismantling wastewater according to claim 8, wherein an outlet of the aerobic tank (20) is also connected with an anaerobic tank (19);
the outlet of the secondary sedimentation tank (21) is also respectively connected with the anaerobic tank (19) and the aerobic tank (20).
10. The system for treating waste water from cell disassembly according to claim 1, wherein the transformation waste liquid outlet of the dephosphorization resin device (5) is connected with a reprecipitation unit.
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