CN114751546A - Pretreatment process for lithium battery electrolyte production wastewater - Google Patents
Pretreatment process for lithium battery electrolyte production wastewater Download PDFInfo
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- CN114751546A CN114751546A CN202210338236.0A CN202210338236A CN114751546A CN 114751546 A CN114751546 A CN 114751546A CN 202210338236 A CN202210338236 A CN 202210338236A CN 114751546 A CN114751546 A CN 114751546A
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- battery electrolyte
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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
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Abstract
The invention relates to a pretreatment process of lithium battery electrolyte production wastewater, which comprises the following steps: s1, adding Ca (OH) into the wastewater2And maintaining the reaction pH at 12-13; s2, adding a PAM flocculating agent into the wastewater, and discharging precipitates; s3, adding CaCl into the wastewater2NaOH, maintaining the reaction pH at 12-13, and raising the temperature of the wastewater; s4, adding a PAC flocculant into the wastewater, and discharging precipitates; s5, adding HCl into the wastewater, adjusting the pH value to 7.5-8.5, adding a PAM flocculating agent, and discharging precipitates. The temperature of the waste water in S1 and S2 is 35-45 ℃, and the temperature of the waste water in S3 and S4 is 75-85 ℃. The invention breaks through the technical barriers of advanced fluorine and phosphorus removal pretreatment of the lithium battery electrolyte production wastewater, can achieve the purpose of pretreatment process with fluorine less than 6ppm and phosphorus less than 1ppm, and enters a biochemical treatment system after pretreatment to enter a biochemical treatment systemAnd deep removal of COD, ammonia nitrogen and total nitrogen is performed.
Description
Technical Field
The invention belongs to the field of environmental protection, relates to an industrial wastewater pretreatment process, and particularly relates to a pretreatment process of lithium battery electrolyte production wastewater.
Background
Lithium batteries are a new industry, and as an important component of new energy industry, the global demand of lithium batteries is gradually increased year by year along with the continuous expansion of application fields. The lithium battery comprises a positive electrode, a negative electrode,The electrolyte is a medium for lithium ion migration and charge transfer, and is similar to blood of a lithium ion battery. The electrolyte is prepared from solute, solvent and additive according to a certain proportion; the solute is the core of the electrolyte, lithium hexafluorophosphate (LiPF)6) The excellent combination of properties makes it the most commercially used lithium salt for such electrolytes. However, lithium hexafluorophosphate has the disadvantages of poor thermal stability in the electrolyte and easy hydrolysis, which results in a decrease in battery performance to some extent. In view of such circumstances, more and more novel lithium salts (lithium bis (fluorosulfonyl imide) and fluoroethylene carbonate having improved discharge capacity, which are desirable in conductivity, stability, high and low temperature performance, etc., are used in combination as important additives for electrolytes.
In view of the complex composition of the production raw materials of the electrolyte, a large amount of refractory wastewater containing fluorine, phosphorus and high organic concentration can be generated in the production process, and the electrolyte has the characteristics of complex components, high salinity, irregular discharge and strong corrosivity.
The physicochemical precipitation defluorination and dephosphorization process widely applied in the field of wastewater treatment at present can only remove the fluoride ions and the total phosphorus of fluorine-containing organic matters, fluorine-oxygen phosphoric acids (lithium hexafluorophosphate hydrolysate), sulfonated substances (mainly substances such as fluorosulfonate, lithium bis (fluorosulfonyl) imide and the like) aiming at free fluoride ions and orthophosphate with little effect, and adds great difficulty to the wastewater treatment. Through published literature data inquiry, the technical vacuum exists in domestic treatment research or engineering application aiming at the wastewater, and with the increasing strictness of the wastewater discharge standard, the requirements of deep fluorine and phosphorus removal of the wastewater are more urgent.
Chinese patent document CN112607917A discloses a method and a system for treating fluorine-containing wastewater by Ca (OH)2The wastewater is treated by combining the precipitate with an oxidant, the process can remove fluorine, but the total phosphorus content is 5-6 ppm (mg/L), and the total phosphorus content cannot reach lower water contentAnd (7) flattening.
Disclosure of Invention
The invention aims to provide a pretreatment process for lithium battery electrolyte production wastewater, which solves the problems of fluorine and phosphorus removal of lithium battery electrolyte production wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that:
The invention provides a pretreatment process for production wastewater of lithium battery electrolyte, which comprises the following steps:
s1, adding Ca (OH) into the wastewater2And maintaining the reaction pH at 12-13;
s2, adding a PAM flocculating agent into the wastewater, and discharging precipitates;
s3, adding CaCl into the wastewater2NaOH, maintaining the reaction pH value at 12-13, and raising the temperature of the waste water;
s4, adding a PAC flocculant into the wastewater, and discharging precipitates;
s5, adding HCl into the wastewater, adjusting the pH value to 7.5-8.5, adding PAM flocculant, and discharging precipitates;
the temperature of the wastewater in S1 and S2 is 35-45 ℃, and the temperature of the wastewater in S3 and S4 is 75-85 ℃.
Preferably, the wastewater is treated in the form of circulating fluidization in S1 and/or S2 and/or S3 and/or S4 and/or S5.
Further, the circulating fluidization velocity in S1 and/or S3 and/or S4 is maintained at 2-4m/h, and the reaction residence time is 3-4 h.
Further, the circulating fluidization velocity in S2 and/or S5 is maintained at 0.5-1m/h, and the reaction residence time is 3-4 h.
Preferably, the waste water is heated by passing steam into the waste water.
Preferably, the complete mixed solution in S1, S3 and S4 is subjected to the next treatment procedure, and the supernatant in S2 and S5 is subjected to the next treatment procedure.
Further, S1, S2, S3, S4 and S5 are all carried out in different containers and are connected in series.
Preferably, each of S1, S2, S3, S4 and S5 is provided with a waste gas treatment process, and the collected waste gas is subjected to comprehensive treatment of oxidation spraying, alkali spraying and biological deodorization.
Preferably, S1, S2, S3, S4 and S5 are used for treating wastewater by a sequencing batch fluidized bed or a reaction kettle.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the pretreatment process for the lithium battery electrolyte production wastewater breaks through the technical barriers of the deep fluorine and phosphorus removal pretreatment of the lithium battery electrolyte production wastewater, can achieve the purpose of the pretreatment process with fluorine less than 6ppm and phosphorus less than 1ppm, and enters a biochemical treatment system for deep removal of COD, ammonia nitrogen and total nitrogen after pretreatment.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
FIG. 1 is a diagram of the steps of a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of a series continuous flow fluidized bed configuration employed in a preferred embodiment of the present invention;
wherein the reference numerals are as follows:
1. 1# reaction fluidized bed;
2. 2# precipitation fluidized bed;
3. 3# reaction fluidized bed;
4. 4# reaction fluidized bed;
5. no. 5 precipitation fluidized bed.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The pretreatment process of the lithium battery electrolyte production wastewater shown in fig. 1 comprises the following steps:
s1, adding Ca (OH) into the wastewater2Maintaining the reaction pH value at 12-13, introducing steam into the wastewater to heat the wastewater to 35-45 ℃, and adopting a circulating fluidization mode, wherein the circulating fluidization speed is kept at 2-4m/h, and the reaction retention time is 3-4 h;
s2, adding a PAM flocculating agent into the wastewater, introducing steam into the wastewater to maintain the wastewater temperature at 35-45 ℃, and discharging precipitates (CaF)2、Ca3（PO 4）2The circulating fluidization speed is kept between 0.5 and 1m/h, and the reaction residence time is between 3 and 4 h;
s3, adding strong electrolyte CaCl into the wastewater2NaOH, maintaining the reaction pH value at 12-13, introducing steam into the wastewater to raise the temperature of the wastewater to 75-85 ℃, keeping the circulating fluidization speed at 2-4m/h, and keeping the reaction residence time at 3-4 h;
s4, adding a PAC flocculant into the wastewater, introducing steam into the wastewater to maintain the wastewater temperature at 75-85 ℃, keeping the circulating fluidization speed at 2-4m/h, keeping the reaction retention time at 3-4h, and discharging precipitates;
s5, adding HCl into the wastewater, adjusting the pH value to 7.5-8.5, adding a PAM flocculating agent, and discharging precipitates (complex precipitates consisting of fluorine, phosphorus, calcium, aluminum and the like).
S1, S2, S3, S4 and S5 are reacted in sequence in a series continuous flow fluidized bed (a No. 1 reaction fluidized bed, a No. 2 precipitation fluidized bed, a No. 3 reaction fluidized bed, a No. 4 reaction fluidized bed and a No. 5 precipitation fluidized bed) as shown in FIG. 2. The water inlet of the next fluidized bed is connected with the upper overflow port of the previous fluidized bed. The 2# precipitation fluidized bed and the 5# precipitation fluidized bed are provided with inclined plate precipitation mechanisms. Each fluidized bed is formed in a circulating fluidized form in the tank by a pump mechanism. S1, S3 and S4 are that the complete mixed solution enters the next stage, S2 and S5 are that the sludge and water of the mixed solution are separated, and the supernatant enters the next stage.
The heating mode that this example adopted is directly to let in steam heating in aqueous, and steam utilization ratio is high like this to the comdenstion water directly gets into waste water and does not need extra collection processing, easy operation.
Each of S1, S2, S3, S4, and S5 is provided with an exhaust gas treatment step, and the collected exhaust gas is subjected to comprehensive treatment such as oxidation shower, alkali shower, and biological deodorization.
In the embodiment, a step-by-step temperature rise mode is adopted, the temperature of the wastewater in S1 and S2 is raised to 35-45 ℃, and the temperature of the wastewater in S3, S4 and S5 is raised to 75-85 ℃.
This example uses several tests to test the wastewater treatment results, as shown in the table below.
TABLE 1
Among them, test numbers 1, 4, 5, 8, 12, and 13 are comparative examples. The primary temperature rise of 35-45 ℃ in the No. 1 fluidized bed is mainly used for prolonging the integral temperature rise time, so that the instantaneous flow of steam can be saved, and the instantaneous consumption of the steam can be reduced. The result difference is not great in the first-stage temperature rise region of 35-45 ℃.
The invention breaks through the technical barriers of the advanced fluorine and phosphorus removal pretreatment of the lithium battery electrolyte wastewater, can achieve the purpose of the pretreatment process with fluorine less than 6ppm and phosphorus less than 1ppm, has good fluorine and phosphorus removal effects, and then enters a biochemical treatment system for the advanced removal of COD, ammonia nitrogen and total nitrogen.
The process has the following advantages: the invention adopts the multi-stage series fluidized bed process, the route is simple, the mixing and homogenizing reaction effect is good, and the impact resistance is strong; the process control parameters are few and easy to quantify, the types of medicines are conventional, and the operation cost is low; moreover, automatic operation can be realized, labor cost is greatly saved, and process operation control risk is reduced.
If the invention adopts a series continuous flow fluidized bed process operation, if a sequencing batch fluidized bed or a reaction kettle type operation device is adopted, the pretreatment effect can be achieved by adopting the operation parameters of the invention, but the efficiency is slightly low, and the invention belongs to the simple change of the invention and also falls into the protection scope of the invention.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (9)
1. A pretreatment process for production wastewater of lithium battery electrolyte comprises the following steps:
s1, adding Ca (OH) into the wastewater2And maintaining the reaction pH at 12-13;
s2, adding a PAM flocculating agent into the wastewater, and discharging precipitates;
s3, adding CaCl into the wastewater2NaOH, maintaining the reaction pH at 12-13, and raising the temperature of the wastewater;
s4, adding a PAC flocculant into the wastewater, and discharging precipitates;
s5, adding HCl into the wastewater, adjusting the pH value to 7.5-8.5, adding a PAM flocculating agent, and discharging precipitates;
the temperature of the waste water in S1 and S2 is 35-45 ℃, and the temperature of the waste water in S3 and S4 is 75-85 ℃.
2. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 1, wherein the pretreatment comprises: and S1 and/or S2 and/or S3 and/or S4 and/or S5, treating the wastewater in a circulating fluidization mode.
3. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 2, wherein the pretreatment comprises: the circulating fluidization velocity in S1 and/or S3 and/or S4 is kept between 2 and 4m/h, and the reaction residence time is between 3 and 4 h.
4. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 2, wherein: the circulating fluidization speed in the S2 and/or the S5 is kept between 0.5 and 1m/h, and the reaction residence time is between 3 and 4 h.
5. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 1, wherein: the waste water is heated by introducing steam into the waste water.
6. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 1, wherein the pretreatment comprises: the complete mixed solution in S1, S3 and S4 is processed in the next step, and the supernatant in S2 and S5 is processed in the next step.
7. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 6, wherein the pretreatment comprises: s1, S2, S3, S4 and S5 are all carried out in different containers and are connected in series.
8. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 1, wherein the pretreatment comprises: each of S1, S2, S3, S4, and S5 is provided with an exhaust gas treatment step, and the collected exhaust gas is subjected to comprehensive treatment such as oxidation shower, alkali shower, and biological deodorization.
9. The pretreatment process for wastewater from lithium battery electrolyte production according to claim 1, wherein the pretreatment comprises: s1, S2, S3, S4 and S5 adopt a sequencing batch fluidized bed or a reaction kettle to treat the wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210338236.0A CN114751546A (en) | 2022-04-01 | 2022-04-01 | Pretreatment process for lithium battery electrolyte production wastewater |
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|---|---|---|---|
| CN202210338236.0A CN114751546A (en) | 2022-04-01 | 2022-04-01 | Pretreatment process for lithium battery electrolyte production wastewater |
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| CN114751546A true CN114751546A (en) | 2022-07-15 |
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| CN202210338236.0A Withdrawn CN114751546A (en) | 2022-04-01 | 2022-04-01 | Pretreatment process for lithium battery electrolyte production wastewater |
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- 2022-04-01 CN CN202210338236.0A patent/CN114751546A/en not_active Withdrawn
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