CN214299711U - Ternary precursor waste water mother liquor processing system - Google Patents
Ternary precursor waste water mother liquor processing system Download PDFInfo
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- CN214299711U CN214299711U CN202022648950.9U CN202022648950U CN214299711U CN 214299711 U CN214299711 U CN 214299711U CN 202022648950 U CN202022648950 U CN 202022648950U CN 214299711 U CN214299711 U CN 214299711U
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Abstract
The utility model belongs to the technical field of waste water treatment, concretely relates to ternary precursor waste water mother liquor processing system, including the mother liquor unit of connection, precipitation unit, the filter-pressing unit, deamination unit and evaporation-crystallization unit, through the method of above-mentioned system processing ternary precursor waste water mother liquor, the comprehensive recycle of ternary precursor waste water mother liquor has been realized, heavy metal ion can be detached, the filtrating obtains the by-product sodium sulfate through the evaporation crystallization, and the ammonia water is directly retrieved to the deamination, the steam condensate of evaporation crystallization process can be reused in current production in addition, the outer mother liquor that arranges of MVR returns mother liquor unit circulation and handles, the closed cycle of resource in the waste water has been realized, the simplified process flow, and the production cost is reduced.
Description
Technical Field
The utility model belongs to the technical field of waste water treatment, concretely relates to ternary precursor waste water mother liquor processing system.
Background
In recent years, the power lithium battery using ternary material as the anode material gradually occupies an increasingly important position in the power battery industry by virtue of important advantages of high capacity, large energy density, good cycle stability, moderate cost and the like. At present, the industrial ternary cathode material is generally prepared by taking hydroxides of three elements of Ni, Co and Mn as precursors, and calcining the hydroxides with lithium. The main process for generating the ternary material precursor is a coprecipitation method, wherein a solution with a certain concentration of mixed metal ions is prepared, NaOH is used as a precipitator, ammonia water is used as a complexing agent, and the mixed metal ions are added in a parallel flow manner to produce the sphere-like ternary hydroxide precursor through coprecipitation. The process can easily control the particle size, specific surface area, morphology and tap density of the precursor, but wastewater such as high salt, high ammonia and the like can be generated in the production process, for example, mother liquor generated after solid-liquid separation of slurry generated by a reaction kettle, alkaline wash liquor after aging of dilute alkali and MVR discharged mother liquor and the like are used in the post-treatment of the ternary precursor, and the wastewater is collectively called the mother liquor. The mother liquor is also characterized by containing a certain amount of solids, which accounts for about 1-5% of the total weight. The production amount of the mother liquor of one ton of the product is 9-20 cubic per ton of the industrial experience. With the increase of the production capacity, the amount of the generated mother liquor is huge, and the high-salt high-ammonia and nickel-cobalt-containing metal have great influence on the surrounding environment and have the potential hazard of environmental pollution accidents. In the existing production process, after the partial mother liquor is subjected to pH regulation, precipitation and filtration, acid is added to regulate the pH value to reach the discharge standard, solid matters are treated as waste materials, few parts of re-dissolution and purification are returned to a salt solution production line for use, and the comprehensive treatment efficiency is not high.
SUMMERY OF THE UTILITY MODEL
The utility model aims to overcome the defects of the prior art and provide a ternary precursor production wastewater mother liquor treatment system which can reduce the production cost and can collect resources.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
a ternary precursor production wastewater mother liquor treatment system comprises a mother liquor unit, a precipitation unit, a filter pressing unit, a deamination unit and an evaporation-crystallization unit which are sequentially connected.
Further, the mother liquor unit is a mother liquor storage tank, the precipitation unit is a pH adjusting tank, and the specification of the pH adjusting tank is 5-25 m3。
Further, the size of the pH adjusting tank is 20m3。
Further, the filter pressing unit is a diaphragm plate and frame filter press, and the specification of the diaphragm plate and frame filter press is 90m2Or 120m2。
Further, the deamination unit consists of an ammonia still front liquid storage tank and an ammonia still which are sequentially connected.
Further, the evaporation-crystallization unit comprises an MVR system and a condensate water collecting tank in sequence, and a heat exchanger is installed in the condensate water collecting tank, so that water loss can be reduced, and environmental pollution caused by white smoke emitted by the periphery of the evaporation-crystallization unit when the air temperature is low can be prevented.
The ternary precursor production wastewater mother liquor treatment method based on the treatment system comprises the following steps:
(1) storing, collecting and transferring ternary precursor production wastewater mother liquor which is conveyed in a workshop in a classified manner in a mother liquor unit;
(2) carrying out precipitation reaction on the mother liquor through a precipitation unit to precipitate most of free heavy metal ions;
(3) the mother liquor of the wastewater after heavy metal ion precipitation enters a filter pressing unit for filtration, the filter residue is subjected to treatment such as re-dissolution purification and the like, the filter residue can be mixed into a normal salt solution production line, and the filtrate enters a liquid storage tank before an ammonia still for storage, collection and transfer;
(4) separating ammonia from filtrate in a liquid storage tank in front of an ammonia still through the ammonia still, evaporating and crystallizing concentrated solution of the ammonia from the filtrate in an MVR system to obtain sodium sulfate crystal particles, and storing and collecting MVR condensed water in a condensed water collecting tank;
the working conditions of the ammonia still are as follows: introducing steam, wherein the steam pressure is 0.4-0.5 MPa, the temperature is more than or equal to 150 ℃, introducing ammonia-containing steam into a tower top condenser, condensing by using circulating cooling water to obtain ammonia water, and recovering the ammonia water, wherein the mass concentration of the ammonia water is 18-25%;
(5) and returning the MVR discharged mother liquor to the mother liquor unit for circular treatment.
Further, the content of ionic heavy metal in the wastewater mother liquor after heavy metal ion precipitation is as follows: ni is less than or equal to 0.5mg/L, Co is less than or equal to 1mg/L, and Mn is less than or equal to 1 mg/L.
And further, returning the MVR condensed water in the condensed water collecting tank to a washing water storage tank, and performing reverse osmosis on the MVR condensed water by an RO membrane to obtain reclaimed water.
Further, the pH control range of the precipitation reaction is 9.5-11.5, because the pH cannot be controlled too high, the yield of ammonia can be reduced due to too high pH, and incomplete precipitation of metal ions is caused due to too low pH.
The utility model discloses with the heavy metal of mother liquor removal, evaporate ammonia, evaporation crystallization, RO membrane reverse osmosis. Removing heavy metals from the mother liquor, recovering solids, and returning the mother liquor to a salt solution production line for use after re-dissolution and purification; recovering ammonia and sodium sulfate by an ammonia still, MVR and other equipment; and (5) preparing the MVR condensed water into reclaimed water through reverse osmosis of an RO membrane.
Compared with the prior art, the utility model discloses a comprehensive recycle of ternary precursor waste water production mother liquor can detach heavy metal ion, and the filtrating obtains the by-product sodium sulfate through the evaporation crystallization to the aqueous ammonia is directly retrieved in the deamination, and the steam condensate of evaporation crystallization process can be used back in current production in addition, and the outer mother liquor that arranges of MVR returns mother liquor unit circulation and handles, has realized the closed cycle of resource in the waste water, simplifies process flow, reduction in production cost.
Drawings
FIG. 1 is a schematic structural view of a ternary precursor production wastewater mother liquor treatment system.
The notations in FIG. 1 have the following meanings: 1-mother liquor storage tank, 2-pH adjusting tank, 3-diaphragm plate and frame filter press, 4-ammonia still front liquor storage tank, 5-ammonia still, 6-MVR system, 7-condensed water collecting tank and 8-washing water storage tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts all belong to the protection scope of the present invention.
It should be noted that, in the present invention, the embodiments and the features of the embodiments may be combined with each other without conflict.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the invention.
Example 1
A ternary precursor production wastewater mother liquor treatment system comprises a mother liquor unit, a precipitation unit, a filter pressing unit, a deamination unit and an evaporation-crystallization unit which are sequentially connected.
The mother liquor unit is a mother liquor storage tank 1, the precipitation unit is a pH adjusting tank 2, a stirring mechanism is arranged in the pH adjusting tank 2, and the specification of the pH adjusting tank 2 is 20m3。
The filter pressing unit is a diaphragm plate and frame filter press 3, and the specification of the diaphragm plate and frame filter press 3 is 120m2。
The deamination unit consists of an ammonia still front liquid storage tank 4 and an ammonia still 5 which are connected in sequence.
The evaporation-crystallization unit comprises an MVR system 6 and a condensate collecting tank 7 in sequence, and a heat exchanger is installed in the condensate collecting tank 7, so that water loss can be reduced, and environmental pollution caused by white smoke on the periphery of the evaporation-crystallization unit when the temperature is low can be prevented.
Example 2
A method for treating a ternary precursor industrial wastewater mother liquor using the ternary precursor industrial wastewater mother liquor treatment system of example 1, comprising the steps of:
(1) the ternary precursor production wastewater mother liquor which is conveyed in a workshop classification manner is stored, collected and transferred in a mother liquor storage tank 1;
(2) the mother liquor is subjected to precipitation reaction through a pH adjusting tank 2 to precipitate most of free heavy metal ions;
(3) the wastewater mother liquor after heavy metal ion precipitation enters a membrane plate-and-frame filter press 3 for filtration, filter residue is subjected to treatment such as re-dissolution purification and the like, the filter residue can be mixed into a normal salt solution production line, and filtrate enters a liquid storage tank 4 in front of an ammonia still for collection and transfer;
the characteristic values of the filtered wastewater mother liquor after heavy metal ion precipitation are shown in table 1 below:
TABLE 1 characteristic values of filtered wastewater mother liquor after heavy metal ion precipitation
(4) Ammonia is separated from a liquid storage tank 4 in front of the ammonia still through an ammonia still 5, concentrated liquid of the ammonia is evaporated and crystallized in an MVR system 6 to prepare sodium sulfate crystal particles, and MVR condensed water enters a condensed water collecting tank 7 for storage and collection;
the working conditions of the ammonia still are as follows: introducing steam, wherein the steam pressure is 0.48MPa, the temperature is 180 ℃, the ammonia-containing steam enters a tower top condenser, circulating cooling water is used for condensing to obtain ammonia water, and the ammonia water is recovered, wherein the mass concentration of the ammonia water is 20.5%;
(5) and returning the MVR discharged mother liquor to the mother liquor storage tank 1 for circular treatment.
The content of ionic heavy metal in the wastewater mother liquor after heavy metal ion precipitation is as follows: ni is less than or equal to 0.5mg/L, Co is less than or equal to 1mg/L, and Mn is less than or equal to 1 mg/L.
And the MVR condensed water in the condensed water collecting tank 7 returns to the washing water storage tank 8, and reclaimed water is prepared through reverse osmosis of the RO membrane.
The pH control range of the precipitation reaction is 10-11, because the pH cannot be controlled too high, the yield of ammonia can be reduced due to too high pH, and incomplete precipitation of metal ions is caused due to too low pH.
The utility model discloses with the heavy metal of mother liquor removal, evaporate ammonia, evaporation crystallization, RO membrane reverse osmosis. Removing heavy metals from the mother liquor, recovering solids, and returning the mother liquor to a salt solution production line for use after re-dissolution and purification; recovering ammonia and sodium sulfate by an ammonia still, MVR and other equipment; and (5) preparing the MVR condensed water into reclaimed water through reverse osmosis of an RO membrane.
The utility model discloses a comprehensive recycle of ternary precursor waste water production mother liquor can detach heavy metal ion, and the filtrating obtains the by-product sodium sulfate through the evaporation crystallization to the aqueous ammonia is directly retrieved in the deamination, and the steam condensate of evaporation crystallization process can be used back in current production in addition, and the outer mother liquor that arranges of MVR returns mother liquor unit circulation and handles, has realized the closed cycle of resource in the waste water, simplifies process flow, reduction in production cost.
The above-mentioned embodiment is only the preferred embodiment of the present invention, all the basis the utility model discloses a technical entity all belongs to the utility model discloses any simple modification, modification and substitution change to what the above embodiment was done the within range of technical scheme.
Claims (5)
1. A ternary precursor production wastewater mother liquor treatment system is characterized by comprising a mother liquor unit, a precipitation unit, a filter pressing unit, a deamination unit and an evaporation-crystallization unit which are sequentially connected;
the mother liquor unit is a mother liquor storage tank, the precipitation unit is a pH adjusting tank, and the specification of the pH adjusting tank is 5-25 m3。
2. The ternary precursor production wastewater mother liquor treatment system according to claim 1, wherein the specification of the pH adjustment tank is 20m3。
3. The ternary precursor production wastewater mother liquor treatment system according to claim 1, wherein the filter pressing unit is a membrane plate and frame filter press, and the specification of the membrane plate and frame filter press is 90m2Or 120m2。
4. The ternary precursor production wastewater mother liquor treatment system according to any one of claims 1 to 3, wherein the deamination unit comprises an ammonia still front liquor storage tank and an ammonia still which are connected in sequence.
5. The ternary precursor production wastewater mother liquor treatment system according to claim 4, wherein the evaporation-crystallization unit comprises an MVR system and a condensed water collection tank in sequence, and the condensed water collection tank is provided with a heat exchanger.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299638A (en) * | 2020-11-16 | 2021-02-02 | 江西普瑞美新材料科技有限公司 | Ternary precursor production wastewater mother liquor treatment system and treatment method |
| CN114230084A (en) * | 2021-12-29 | 2022-03-25 | 深圳市瑞升华科技股份有限公司 | Ternary precursor wastewater treatment equipment and process |
| WO2023173776A1 (en) * | 2022-03-18 | 2023-09-21 | 广东邦普循环科技有限公司 | Recovery method and recovery system for ternary precursor mother liquor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299638A (en) * | 2020-11-16 | 2021-02-02 | 江西普瑞美新材料科技有限公司 | Ternary precursor production wastewater mother liquor treatment system and treatment method |
| CN114230084A (en) * | 2021-12-29 | 2022-03-25 | 深圳市瑞升华科技股份有限公司 | Ternary precursor wastewater treatment equipment and process |
| WO2023173776A1 (en) * | 2022-03-18 | 2023-09-21 | 广东邦普循环科技有限公司 | Recovery method and recovery system for ternary precursor mother liquor |
| GB2619836A (en) * | 2022-03-18 | 2023-12-20 | Guangdong Brunp Recycling Technology Co Ltd | Recovery method and recovery system for ternary precursor mother liquor |
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