CN115818858A - LiFSI wastewater treatment method - Google Patents
LiFSI wastewater treatment method Download PDFInfo
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- CN115818858A CN115818858A CN202210675847.4A CN202210675847A CN115818858A CN 115818858 A CN115818858 A CN 115818858A CN 202210675847 A CN202210675847 A CN 202210675847A CN 115818858 A CN115818858 A CN 115818858A
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910010941 LiFSI Inorganic materials 0.000 title claims abstract description 95
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000003513 alkali Substances 0.000 claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002351 wastewater Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000011552 falling film Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 34
- 229910052808 lithium carbonate Inorganic materials 0.000 description 24
- 239000012535 impurity Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 3
- 238000003795 desorption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The application relates to a treatment method of LiFSI wastewater. A treatment method of LiFSI wastewater comprises the following steps: adsorption: adsorbing the LiFSI wastewater by using resin to obtain LiFSI-adsorbed resin; and (3) analysis: washing the resin adsorbing the LiFSI with alkali liquor to obtain LiFSI solution; concentration: heating and concentrating the LiFSI analytic solution to obtain a lithium-containing concentrated solution; neutralizing: adding acid into the lithium-containing concentrated solution for neutralization to obtain a neutralized solution; and (3) lithium deposition: adding carbonate and/or carbon dioxide into the neutralized solution to react to obtainAnd (4) carbonate precipitation. The application solves the problem of FSI in the prior wastewater treatment process ‑ Can not decompose a large amount of existing problems, and meanwhile, the lithium resource is fully recovered, so that the method is more environment-friendly and has high economic benefit.
Description
Technical Field
The application relates to the field of wastewater treatment, in particular to a treatment method of LiFSI wastewater.
Background
Lithium is an important metal element, is a novel energy source and strategic resource with great prospect, and is widely applied to the industries of electronics, metallurgy, medicine, glass, ceramics, batteries, new energy sources and the like. With the rapid development of new energy industries in recent years, the demand of lithium is driven to increase rapidly.
LiFSI (lithium bis (fluorosulfonyl) imide) as a novel lithium battery electrolyte has the advantages of high stability, excellent low-temperature performance, good hydrolytic stability and the like, and gradually replaces LiPF 6 (lithium hexafluorophosphate), with the increasing maturity of the LiFSI production technology, the cost is reduced continuously, in recent years, the number of LiFSI manufacturers for new construction, reconstruction and extension production is not increased, the yield is increased rapidly, and in addition, the recycling and dismantling amount of waste lithium batteries is increased. No matter a large amount of LiFSI-containing wastewater (LiFSI content is 1000-20000 ppm) or LiFSI-containing wastewater generated by recycling and disassembling waste lithium batteries is generated in the production process (generated LiFSI filter residue is cleaned, production equipment is cleaned and packaging barrels are cleaned), if the LiFSI is not extracted and recycled by the existing sewage treatment process, the FSI in the LiFSI cannot be extracted and recycled by the existing sewage treatment process - Decomposition, resulting in FSI-remaining in the water, while FSI - (bis-fluorosulfonyl imide acid ion) remains in water and seriously affects LAS (anionic surfactant, national first-class water quality requirement is lower than 0.5 ppm) of water quality, and a large amount of lithium resources are wasted.
The invention is therefore proposed.
Disclosure of Invention
The invention mainly aims to provide a LiFSI wastewater treatment method, which solves the problem of FSI in the existing wastewater treatment process - Can not decompose a large amount of existing problems, and meanwhile, the lithium resource is fully recovered, so that the method is more environment-friendly and has high economic benefit.
In order to achieve the above object, the present invention provides the following technical solutions.
A treatment method of LiFSI wastewater comprises the following steps:
adsorption: adsorbing the LiFSI wastewater by using resin to obtain LiFSI-adsorbed resin;
and (3) analysis: washing the resin adsorbing the LiFSI with alkali liquor to obtain LiFSI solution;
concentration: heating and concentrating the LiFSI analytic solution to obtain a lithium-containing concentrated solution;
neutralizing: adding acid into the lithium-containing concentrated solution for neutralization to obtain a neutralized solution;
and (3) lithium deposition: and adding carbonate and/or carbon dioxide into the neutralization solution for reaction to obtain carbonate precipitate.
The method firstly enriches LiFSI in the wastewater by adsorption and desorption methods, and then heats the LiFSI to enable alkali liquor in the wastewater to react with the LiFSI, thereby leading the FSI to be converted into the LiFSI - Decomposition to FSO 3- 、SO 4 2- And F - Thus fundamentally solving the problem of FSI in the wastewater - The problem of high content; and finally, adding a lithium precipitating agent such as carbonate and carbon dioxide after neutralization so as to convert lithium ions in the lithium precipitating agent into lithium carbonate for precipitation, thereby recovering lithium in the wastewater.
It can be seen that the treatment method of the present invention not only fundamentally removes FSI - And moreover, metal lithium is recovered, and the economic benefit of wastewater treatment is improved.
Tested and detected by the test, the FSI treatment method of the invention is utilized - The decomposition rate reaches at least 99.6%, and the lithium recovery rate reaches at least 93%.
The operating conditions and the types of raw materials in the five main steps in the above treatment process can be further optimized to increase the decomposition rate, increase the lithium recovery rate, shorten the reaction time or reduce the cost, etc., as exemplified below.
In some embodiments, the alkali solution is an inorganic strong alkali solution, preferably at least one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, and aluminum hydroxide aqueous solution.
The inorganic strong base can not introduce exogenous impurities or impurities which are not easy to remove, and has strong basicity, and can rapidly analyze and decompose the FSI - 。
In some embodiments, the lye is at least one of a potassium hydroxide solution or a sodium hydroxide solution. Because different salt ions have different ionic strengths and have different chemical balance influences on the decomposition reaction and the lithium precipitation reaction, the similar potassium hydroxide solution or sodium hydroxide solution is more beneficial to the quick and full progress of the decomposition reaction and the lithium precipitation reaction, therefore, the potassium hydroxide solution or sodium hydroxide solution is preferred, and potassium hydroxide is more preferred.
In some embodiments, the concentration of the lye is between 3% and 10%. In view of the combination of reaction rate and cost, the alkali solution concentration is preferably 3% to 10%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., and more preferably 5% to 8%, etc.
In some embodiments, the temperature for the heat concentration is 80 to 100 ℃, preferably 95 to 100 ℃. When heated to 80-100 ℃, FSI - The decomposition rate is substantially maximized without producing other by-products, wherein a more preferred temperature range is 95-100 ℃.
In some embodiments, the equipment for heating and concentrating is one or more of a double-effect evaporator, a triple-effect evaporator, a falling-film evaporator, a thin-film evaporator and a distillation tower which are used in series or in parallel.
The evaporators have the advantages of high evaporation efficiency, high heat exchange rate and the like, and the heating and concentration process can simultaneously improve the reaction rate and reduce the energy consumption.
In some embodiments, the resin is a neutral resin or a weakly basic resin, preferably a PD201 resin.
Neutral resins or weakly basic resins have a high adsorption coefficient for LiFSI in LiFSI wastewater, with PD201 resin being preferred.
In some embodiments, the adsorption is followed by achieving LiFSI content in the LiFSI wastewater of less than 0.2ppm.
When the adsorption is carried out until the LiFSI content reaches below 0.2ppm, on the one hand, the FSI in the resin effluent is - Has satisfied the national standard requirement, on the other hand can guarantee that LiFSI is almost totally enriched.
In some embodiments, the endpoint pH of the neutralization reaches 6.5 to 7.0.
When the pH value is neutralized to 6.5-7.0, lithium carbonate precipitation can be quickly formed after the lithium precipitation agent is added. In the actual treatment process, the end point pH value cannot be controlled to a constant specific value completely, and a slight fluctuation range, such as 6.5 to 6.8, 6.8 to 7.0, etc., is generally allowed, and even for the treatment of a large amount of wastewater, the end point pH value can be allowed to fluctuate within a wide range of 6.5 to 7.0.
In some embodiments, the neutralizing added acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, hypochlorous acid, formic acid.
Similar to alkali liquor, the acid type added during neutralization needs to simultaneously take into account a plurality of factors such as no impurity or less impurity introduction, fast reaction rate and the like, and sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, hypochlorous acid and formic acid can all meet the requirements, wherein the sulfuric acid is preferred. In addition, these acids can be added as a solution or by passing an acid gas during the treatment.
In some embodiments, the carbonate salt is at least one of sodium carbonate and potassium carbonate.
Both of these salts can react with lithium ions to rapidly form lithium carbonate precipitate. The amount of carbonate added is generally determined depending on the lithium content in the solution, and an excess amount is appropriately added.
In some embodiments, in the lithium precipitating step, after the reaction, the lithium is further filtered, and the filtering device is preferably one or a combination of a plate-and-frame filter, a bag filter, a candle filter, a scraper centrifuge, a horizontal centrifuge, a drawstring centrifuge, a siphon centrifuge and a pusher centrifuge.
Filtering to remove precipitate, and treating the effluent as industrial water or other sewage. The filtering equipment used for filtering, such as a plate-frame filter, a bag filter, a candle filter, a scraper centrifuge, a horizontal centrifuge, a drawstring centrifuge, a siphon centrifuge and a pusher centrifuge, can be used for treating large-flow sewage.
In summary, compared with the prior art, the invention at least achieves the following technical effects:
(1) The FSI in the wastewater is fundamentally removed through decomposition reaction - ；
(2) The metallic lithium in the wastewater is recovered, and the economic benefit of sewage treatment is improved;
(3) Only common safe and nontoxic chemical reagents such as inorganic alkali, inorganic acid, carbonate and the like are used in the treatment process, so that the safety of sewage treatment capacity is improved, and the cost of raw materials is reduced;
(4) Optimizes the operation conditions in each step and provides prerequisites for further improving the efficiency and economic benefit of wastewater treatment.
The foregoing description is only an overview of the technical solutions of the present application, and the present application can be implemented according to the content of the description in order to make the technical means of the present application more clearly understood, and the following detailed description of the present application is given in order to make the above and other objects, features, and advantages of the present application more clearly understandable.
Detailed Description
Embodiments of the present invention will be described in detail below. The following examples are merely used to more clearly illustrate the technical solutions of the present application, and therefore are only examples, and the protection scope of the present application is not limited thereby.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having," and any variations thereof, in the description and claims of this application and the foregoing description are intended to cover non-exclusive inclusions.
In the description of the embodiments of the present application, the technical terms "first", "second", and the like are used only for distinguishing different objects, and are not to be construed as indicating or implying relative importance or implicitly indicating the number, specific order, or primary-secondary relationship of the technical features indicated. In the description of the embodiments of the present application, "a plurality" means two or more unless specifically defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is only one kind of association relationship describing an associated object, and means that three relationships may exist, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter associated objects are in an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" refers to two or more (including two), and similarly, "plural sets" refers to two or more (including two), and "plural pieces" refers to two or more (including two).
In the description of the embodiments of the present application, unless otherwise explicitly stated or limited, the terms "mounted," "connected," "fixed," and the like are used in a broad sense, and for example, may be fixedly connected, detachably connected, or integrated; mechanical connection or electrical connection is also possible; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the embodiments of the present application can be understood by those of ordinary skill in the art according to specific situations.
As described in the background, FSI exists in the existing LiFSI wastewater treatment processes - The content does not reach the standard, and the invention provides a safe and economic treatment method. The method mainly relates to five key steps of adsorption, desorption, concentration, neutralization and lithium precipitation which are carried out in sequence, and part of the steps are listedThe following describes the treatment effect of the present invention (it should be noted that, after a certain condition before lithium deposition is changed, the content of ions participating in the lithium deposition reaction may be different, and the amount of the lithium deposition agent is also different to ensure that the lithium deposition agent is excessive).
Example 1
Taking PD201 resin 4.5m 3 Packing into resin column at 3m 3 The flow rate of the reaction is that 2500ppm (indicating the content of LiFSI, which is explained in the same way below) LiFSI wastewater enters from the top of a resin column, the LiFSI wastewater is discharged from the bottom and circulates back to a raw water pool, the LiFSI content of effluent at the bottom is sampled and detected, the LAS is monitored on line and is less than or equal to 0.2ppm, and when the LiFSI content is less than 0.2ppm, the wastewater is discharged; and when the LiFSI content of the bottom effluent is more than 0.2ppm or the LAS is more than 0.2ppm by on-line monitoring, stopping water inflow, drying the water in the resin column by using air, and repeating the treatment until the LiFSI content of the bottom effluent is less than or equal to 0.2ppm.
Introducing 5% potassium hydroxide solution into the resin column, soaking for 2h, continuing to use 2m 3 The flow rate of the solution is pumped into the alkali liquor and is 2m from the bottom 3 Discharging alkali liquor at flow rate/h, continuously feeding alkali liquor for 2h, stopping feeding alkali liquor, and drying the alkali liquor in the resin column to obtain about 6m 3 Li + The content of the alkali liquor is 1-2%, and the next LiFSI adsorption can be carried out after the resin column is desorbed.
Concentrating the alkali liquor at 92-95 ℃ until the volume of the alkali liquor is 50% of the original volume, stopping concentration, filtering, conveying to a neutralization kettle for stirring, slowly adding hydrochloric acid with the mass fraction of 3% for neutralization, adjusting the pH value to 6.5-7, then adding deionized water and adjusting Li in the solution + The concentration is 2%; pump in 5m 3 Adjusted to 2% Li + And (3) putting the solution with the concentration into an alkalization kettle, then pouring 760kg of sodium carbonate, stirring for 3-4 h to obtain a lithium carbonate turbid solution, and finally carrying out centrifugal dehydration on the lithium carbonate turbid solution by a scraper centrifuge to obtain 548kg of lithium carbonate powder. The lithium carbonate content in the lithium carbonate powder was 90.2%, the water content was 8.3%, and the impurity content was 1.5%.
Example 2
The main difference from example 1 is that the alkali solution is replaced by sodium hydroxide, and the amount of sodium carbonate added during lithium precipitation is different, which is specifically as follows.
Taking PD201 resin 4.5m 3 Packing into resin column at 3m 3 2500ppm LiFSI wastewater enters from the top of a resin column at a flow rate of/h, is discharged from the bottom and circulates back to a raw water tank, the LiFSI content of bottom effluent is sampled and detected, the LAS is monitored on line and is less than 0.2ppm, and when the LiFSI content is less than 0.2ppm, water is discharged outside; and when the LiFSI content of the bottom effluent is more than 0.2ppm or the LAS is more than 0.2ppm by on-line monitoring, stopping water inflow, drying the water in the resin column by using air, and repeating the treatment until the LiFSI content of the bottom effluent is less than or equal to 0.2ppm.
Introducing 5% sodium hydroxide solution into the resin column, soaking for 2h, continuing to use 2m 3 The flow rate of the solution is pumped into the alkali liquor and is 2m from the bottom 3 Discharging alkali liquor at a flow rate of/h, continuously feeding alkali liquor for 2h, stopping feeding alkali liquor, and drying the alkali liquor in the resin column to obtain about 6m3 Li + The content of the alkali liquor is 1-2%, and the next LiFSI adsorption can be carried out after the resin column is desorbed.
Concentrating the alkali liquor at 92-95 ℃ until the volume of the alkali liquor is 50% of the volume of the original alkali liquor, stopping concentration, filtering, conveying to a neutralization kettle for stirring, slowly adding hydrochloric acid with the mass fraction of 3% for neutralization, adjusting the PH value to 6.5-7, then adding deionized water and adjusting Li in the solution + The concentration is 2%; pump in 5m 3 Adjusted to 2% Li + And (3) putting the solution with the concentration into an alkalization kettle, then pouring 760kg of sodium carbonate, stirring for 3-4 h to obtain a lithium carbonate turbid solution, and finally carrying out centrifugal dehydration on the lithium carbonate turbid solution by a scraper centrifuge to obtain 603kg of lithium carbonate powder, wherein the lithium carbonate content is 78.7%, the water content is 10.5%, and the impurity content is 10.8%.
Example 3
The main difference from example 1 is that the acid added during neutralization is replaced by sulfuric acid, which corresponds to the difference in the amount of sodium carbonate added during lithium precipitation, and the following is specific.
Taking PD201 resin 4.5m 3 Packing into resin column at 3m 3 2500ppm LiFSI wastewater enters from the top of the resin column at a flow rate of/h, is discharged from the bottom and circulates back to the raw water tank, and is discharged from the bottom after sampling detectionThe LiFSI content of water and online monitoring LAS are less than 0.2ppm, and when the LiFSI content is less than 0.2ppm, the water is discharged; and when the LiFSI content of the bottom effluent is more than 0.2ppm or the LAS is more than 0.2ppm by on-line monitoring, stopping water inflow, drying the water in the resin column by using air, and repeating the treatment until the LiFSI content of the bottom effluent is less than or equal to 0.2ppm.
Introducing 5% by mass of potassium hydroxide solution into the resin column, soaking for 2h, continuing to take 2m 3 The flow rate of the solution is pumped into the alkali liquor and is 2m from the bottom 3 Discharging alkali liquor at a flow rate of/h, continuously feeding alkali liquor for 2h, stopping feeding alkali liquor, and drying the alkali liquor in the resin column to obtain about 6m3 Li + The content of the alkali liquor is 1-2%, the next LiFSI adsorption can be carried out after the resin column is desorbed, and the treatment is repeated until the LiFSI content of the effluent at the bottom is less than or equal to 0.2ppm.
Concentrating the alkali liquor at 92-95 ℃ to 50% of the volume of the original alkali liquor, stopping concentration, filtering, conveying to a neutralization kettle for stirring, slowly adding sulfuric acid with the mass fraction of 4% for neutralization, adjusting the pH value to 6.5-7, then adding deionized water and adjusting Li in the solution + The concentration is 2%; pump in 5m 3 Adjusted to 2% of Li + And (3) putting the solution with the concentration into an alkalization kettle, then pouring 760kg of sodium carbonate, stirring for 3-4 h to obtain a lithium carbonate turbid solution, and finally, carrying out centrifugal dehydration on the lithium carbonate turbid solution through a scraper centrifuge to obtain 551kg of lithium carbonate powder, wherein the lithium carbonate content is 91.2%, the water content is 6.7%, and the impurity content is 2.1%, and repeating the treatment until the LiFSI content of the effluent at the bottom is less than or equal to 0.2ppm.
Example 4
The main difference from example 1 is that the concentration of the alkali solution is increased to 10%, which is adapted to the difference in the amount of sodium carbonate added during the precipitation of lithium, and is as follows.
Taking PD201 resin 4.5m 3 Packing into resin column at 3m 3 2500ppm LiFSI wastewater enters from the top of a resin column at a flow rate of/h, is discharged from the bottom and circulates back to a raw water pool, the LiFSI content of bottom effluent is detected by sampling, the LAS is less than 0.2ppm by online monitoring, and when the LiFSI content is less than 0.2ppm, water is discharged; when the LiFSI content of the bottom effluent is more than 0.2ppm or the LAS is more than 0.2ppm by on-line monitoring, stopping water inflow and using airAnd (4) drying the water in the resin column by using air, and repeatedly treating until the LiFSI content of the effluent at the bottom is less than or equal to 0.2ppm.
Introducing 10% potassium hydroxide solution into the resin column, soaking for 2h, continuing to use 2m 3 The flow rate of the solution is pumped into the alkali liquor and is 2m from the bottom 3 Discharging alkali liquor at flow rate/h, continuously feeding alkali liquor for 2h, stopping feeding alkali liquor, and drying the alkali liquor in the resin column to obtain about 6m 3 Li + The content of the alkali liquor is 1-2%, and the next LiFSI adsorption can be carried out after the resin column is desorbed.
Concentrating the alkali liquor at 92-95 ℃ to 50% of the volume of the original alkali liquor, stopping concentrating, filtering, conveying to a neutralization kettle for stirring, slowly adding hydrochloric acid with the mass fraction of 3% for neutralization, adjusting the PH value to 6.5-7, then adding deionized water and adjusting Li in the solution + The concentration is 1%; pumping 5m3 of adjusted 1% Li + And (3) putting the solution with the concentration into an alkalization kettle, then pouring 380kg of sodium carbonate, stirring for 3-4 h to obtain a lithium carbonate turbid solution, and finally carrying out centrifugal dehydration on the lithium carbonate turbid solution by a scraper centrifuge to obtain 270kg of lithium carbonate powder, wherein the lithium carbonate content is 85.3%, the water content is 7.8%, and the impurity content is 6.9%.
Example 5
The main difference from example 1 is that the lithium precipitating agent is replaced by carbon dioxide, as follows.
Taking PD201 resin 4.5m 3 Packing into resin column at 3m 3 2500ppm LiFSI wastewater enters from the top of a resin column at a flow rate of/h, is discharged from the bottom and circulates back to a raw water tank, the LiFSI content of bottom effluent is sampled and detected, the LAS is monitored on line and is less than 0.2ppm, and when the LiFSI content is less than 0.2ppm, water is discharged outside; and when the LiFSI content of the bottom effluent is more than 0.2ppm or the LAS is more than 0.2ppm by on-line monitoring, stopping water inflow, drying the water in the resin column by using air, and repeating the treatment until the LiFSI content of the bottom effluent is less than or equal to 0.2ppm.
Introducing 5% potassium hydroxide solution into the resin column, soaking for 2h, continuing to use 2m 3 The flow rate of the solution is pumped into the alkali liquor and is 2m from the bottom 3 Discharging alkali liquor at a flow rate of/h, continuously feeding alkali liquor for 2h, stopping feeding alkali liquor, and press-drying resinAlkali liquor in the column to obtain about 6m 3 Li + The content of the alkali liquor is 1-2%, and the next LiFSI adsorption can be carried out after the resin column is desorbed.
Concentrating the alkali liquor at 92-95 ℃ to 50% of the volume of the original alkali liquor, stopping concentrating, filtering, conveying to a neutralization kettle for stirring, slowly adding hydrochloric acid with the mass fraction of 3% for neutralization, adjusting the PH value to 6.5-7, then adding deionized water and adjusting Li in the solution + The concentration is 2%; pump in 5m 3 The solution with the concentration of 2 percent Li + is adjusted to an alkalization kettle, 350kg of carbon dioxide is slowly introduced into the alkalization kettle, the feeding is continued for 2 hours after the completion, the lithium carbonate turbid liquid is obtained, and finally the lithium carbonate turbid liquid is centrifugally dewatered by a scraper centrifuge to obtain 606kg of lithium carbonate powder, wherein the lithium carbonate content is 85.8 percent, the water content is 13.8 percent, and the impurity content is 0.4 percent.
Example 6
The only difference from example 1 is that the lye potassium hydroxide is replaced by magnesium hydroxide and the remaining operations and conditions remain unchanged.
This example gives 545kg of lithium carbonate powder. The lithium carbonate content in the lithium carbonate powder was 86.3%, the water content was 8.5%, and the impurity content was 5.2%.
Examples 7 to 10
The only difference from example 1 is the concentration of the potassium hydroxide solution, which is 2%, 3%, 8%, 12%, respectively, and the remaining operations and conditions remain unchanged. As a result, it was found that examples 7 to 8, in which the concentration was decreased, had poor resolving effects, resulting in that the resin reached saturation quickly when repeatedly used, and thus the total resolving time was prolonged; on the other hand, examples 9 to 10 with increased concentrations showed better results in rapid and complete analysis, and the adsorption amount of the resin increased when it was used repeatedly. In addition, since the lithium ion concentration was quantified to 2% in the lithium deposition in all examples, there was no significant difference in the amount of lithium carbonate and the impurity content.
Examples 11 to 14
The difference from example 1 is only that the temperature during heating concentration is different, and the temperature is controlled to 70-73 ℃, 80-85 ℃, 97-100 ℃, 105-110 ℃, and the rest operation and conditions are kept unchanged. As a result, it was found that the temperature was lowered11-12 FSI - The decomposition effect becomes poor, resulting in an increase in the amount of acid used in neutralization; while examples 13-14, in which the temperature was increased, showed a better decomposition effect and the amount of acid used for neutralization was reduced. In addition, since the lithium ion concentration was quantified to 2% in the lithium deposition in all examples, there was no significant difference in the amount of lithium carbonate and the impurity content.
Example 15
The difference from example 1 is only the type of resin used for adsorption, and the details are as follows.
Taking LX-363 resin 4.5m 3 Packing into resin column at 3m 3 The flow rate of the reaction is that 2500ppm (indicating the content of LiFSI, which is explained in the same way below) LiFSI wastewater enters from the top of a resin column, the LiFSI wastewater is discharged from the bottom and circulates back to a raw water pool, the LiFSI content of effluent at the bottom is sampled and detected, the LAS is monitored on line and is less than or equal to 0.2ppm, and when the LiFSI content is less than 0.2ppm, the wastewater is discharged; and when the LiFSI content of the bottom effluent is more than 0.2ppm or the LAS is more than 0.2ppm by on-line monitoring, stopping water inflow, drying the water in the resin column by using air, and repeating the treatment until the LiFSI content of the bottom effluent is less than or equal to 0.2ppm.
Introducing 5% potassium hydroxide solution into the resin column, soaking for 2h, continuing to use 2m 3 The flow rate of the solution is pumped into the alkali liquor and is 2m from the bottom 3 Discharging alkali liquor at flow rate/h, continuously feeding alkali liquor for 2h, stopping feeding alkali liquor, and drying the alkali liquor in the resin column to obtain about 6m 3 Li + The content is 0.02-0.05% alkali liquor, and the next LiFSI adsorption can be carried out after the resin column is desorbed.
Concentrating the alkali liquor to Li at 92-95 DEG C + The concentration is 2.3% -2.5%; stopping concentration, filtering, conveying to a neutralization kettle, stirring, slowly adding hydrochloric acid with the mass fraction of 3% for neutralization, adjusting the pH value to 6.5-7, and then adjusting Li by using deionized water + To 2%; pump in 5m 3 Adjusted to 2% of Li + And (3) putting the solution with the concentration into an alkalization kettle, then pouring 760kg of sodium carbonate, stirring for 3-4 h to obtain a lithium carbonate turbid solution, and finally performing centrifugal dehydration on the lithium carbonate turbid solution through a scraper centrifuge to obtain 548kg of lithium carbonate powder. The lithium carbonate content in the lithium carbonate powder was 65.2%, the water content was 12.3%, and the impurity content was 22%.5％。
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present disclosure, and the present disclosure should be construed as being covered by the claims and the specification. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein but is to cover all embodiments that may fall within the scope of the appended claims.
Claims (12)
1. A method for treating LiFSI wastewater, comprising the steps of:
adsorption: adsorbing the LiFSI wastewater by using resin to obtain LiFSI-adsorbed resin;
and (3) analysis: washing the resin adsorbing the LiFSI with alkali liquor to obtain LiFSI solution;
concentration: heating and concentrating the LiFSI analytic solution to obtain a lithium-containing concentrated solution;
neutralizing: adding acid into the lithium-containing concentrated solution for neutralization to obtain a neutralized solution;
and (3) lithium deposition: and adding carbonate and/or carbon dioxide into the neutralization solution for reaction to obtain carbonate precipitate.
2. The method for treating LiFSI wastewater as claimed in claim 1, wherein the alkaline solution is an inorganic strong alkaline solution, preferably at least one or more of the group consisting of aqueous solutions of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, and aluminum hydroxide.
3. The method of treating LiFSI wastewater as recited in claim 2, wherein said alkali solution is at least one of a potassium hydroxide solution or a sodium hydroxide solution.
4. The method of LiFSI wastewater treatment according to any of the claims 1 to 3, wherein the concentration of said alkali solution is 3% to 10%.
5. The process for the treatment of LiFSI wastewater as claimed in claim 1, wherein the temperature of said heating concentration is 80-100 ℃, preferably 95-100 ℃.
6. The LiFSI wastewater treatment method according to claim 1 or 5, wherein the heating and concentrating equipment is one or more of a double-effect evaporator, a triple-effect evaporator, a falling film evaporator, a thin film evaporator and a distillation tower, which are used in series or in parallel.
7. The LiFSI wastewater treatment process according to claim 1, wherein said resin is a neutral resin or a weakly basic resin, preferably a PD201 resin.
8. The method of treating LiFSI wastewater as claimed in claim 1 or claim 7 wherein the LiFSI content of the LiFSI wastewater after said adsorption is below 0.2ppm.
9. The method of treating LiFSI wastewater as claimed in claim 1, wherein said terminal pH of neutralization is 6.5-7.0.
10. The method of LiFSI wastewater treatment according to claim 1 or 9, wherein said acid added for neutralization is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, hypochlorous acid, and formic acid.
11. The method of treating LiFSI wastewater of claim 1, wherein said carbonate is at least one of sodium carbonate and potassium carbonate.
12. The LiFSI wastewater treatment method as claimed in claim 1, wherein in the lithium precipitation step, after the reaction, the wastewater is further filtered, and the filtering device is preferably one or a combination of plate and frame filter, bag filter, candle filter, scraper centrifuge, horizontal centrifuge, draw belt centrifuge, siphon centrifuge and pusher centrifuge.
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| CN213388194U (en) * | 2020-06-02 | 2021-06-08 | 四川恩特普环保科技有限公司 | Lithium carbonate waste water's processing system |
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| CN114380305A (en) * | 2022-01-29 | 2022-04-22 | 宁德时代新能源科技股份有限公司 | Method for recovering raw and auxiliary materials in production of lithium bis (fluorosulfonyl) imide |
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