CN105555381B - Method for treating mixed solution - Google Patents
Method for treating mixed solution Download PDFInfo
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- CN105555381B CN105555381B CN201480051798.0A CN201480051798A CN105555381B CN 105555381 B CN105555381 B CN 105555381B CN 201480051798 A CN201480051798 A CN 201480051798A CN 105555381 B CN105555381 B CN 105555381B
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- tetramethyl
- ammonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Secondary Cells (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Primary Cells (AREA)
Abstract
Provided is a method with which it is possible to safely and cost-effectively treat a mixed solution including a specific fluorine-containing electrolyte and a carbonic acid ester. A tetramethylammonium compound (except for tetramethylammonium salts of fluorocomplexes) is added to a mixed solution including a carbonic acid ester and at least one type of compound selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, sodium hexafluorophosphate, lithium hexafluoroarsenate, and lithium hexafluoroantimonate; the tetramethylammonium salt(s) of the fluorocomplex(es) is/are precipitated; and then the precipitate is removed.
Description
Technical field
The present invention relates to the processing method of mixed solution, more particularly to can advantageously process the electrolysis as lithium battery etc.
The method of the mixed solution of liquid.
Background technology
All the time, using mixed solution of the carbonates as solvent and comprising electrolyte such as lithium hexafluoro phosphates in lithium electricity
Electrolyte is widely used as in pond, lithium ion battery, lithium-ion capacitor etc., the mixed solution is in lithium ion battery etc.
In manufacturing process, or in replacement, generation of faulty goods for manufacturing species etc., discharge in large quantities as waste liquid.
Herein, the electrolyte such as in above-mentioned electrolyte, lithium hexafluoro phosphate (hereinafter referred to as fluorine-containing electrolyte) are contained in heat
Chemically be unstable compound, therefore will comprising its mixed solution directly for incineration disposal when, can produce poisonous
And the high hydrogen fluoride gas of corrosivity.However, so far, it is also square without (process) is effectively disposed in addition to incineration disposal
Method, therefore the discharge such as the waste liquid as electrolyte, the mixed solution comprising fluorine-containing electrolyte are with other waste liquids, fuel etc.
The state of mixing is by every time marginally for incineration disposal.
In the incineration disposal of the present situation, the disposal ability of hydrogen fluoride gas becomes bottleneck (obstruction), therefore such as one
During the substantial amounts of mixed solution of secondary generation, occur that because receiving restriction etc. the situation of total amount cannot be processed, the place of replacement cannot be found
The problems such as reason mode.Even if in addition, by the mixed solution comprising fluorine-containing electrolyte mixing with other waste liquids, fuel etc.
State every time marginally for incineration disposal in the case of, cannot also avoid the equipment that the hydrogen fluoride gas for producing cause from (burning
Stove etc.) burn into deterioration etc., therefore there is a problem of compared with generally device damage in a short time.
On the other hand, has indefatigable incinerator as to hydrogen fluoride gas, it is known to can will include fluorine compounds
The incinerator of the type that sludge is utilized as solid fuel, is adopted by cement production plants etc..In the situation using this incinerator
Under, in order to the mixed solution comprising fluorine-containing electrolyte and carbonates is made into solid fuel, need described with slaked lime process
Mixed solution is so as to changing into the form of the low stable salt of reactivity.
However, not only making fluorine-containing electrolyte in mixed solution extremely rapidly using the process of slaked lime as described above
Decompose, the carbonates for also making the solvent as fluorine-containing electrolyte also extremely rapidly decompose, become high because of above-mentioned reaction heat
Temperature state so as to catch fire etc. it is dangerous increase, therefore the extremely difficult problem of if then operation.In addition, in the process using slaked lime
In method, aforementioned decomposition reaction causes the release of energy to lose big, and as product the little calcium fluoride of fuel heat, carbon are obtained
Sour calcium, in view of the viewpoint of energy regenerating, molten with regard to processing the mixing comprising fluorine-containing electrolyte and carbonates using slaked lime
Liquid, it has to say that its value is extremely low.
On the other hand, fluorine-containing electrolyte can also decompose because of the contact with water, produce water miscible Fluohydric acid..Also may be used
To consider to process the mixed solution comprising fluorine-containing electrolyte using the property, but in the process, the hydrogen that will be produced is needed
Being fixed of alkali such as fluoric acid slaked lime are implementing harmless treatment.In addition, generally because of fluorine-containing electricity that the contact with water causes
The speed of the decomposition of solution matter is slow, needs substantial amounts of water and time, therefore problem is there is also in terms of cost.
In addition, in patent documentation 1 (Japanese Unexamined Patent Publication 6-170380 publication), as useless comprising fluorophosphoric acid radical ion
The fluorine fixing meanss of liquid, it is proposed that be applied in combination the method for sulphuric acid and calcium compounds.However, as described above, closed using calcification
Processing method of thing, the mixed solution comprising fluorine-containing electrolyte and carbonates contains and is difficult to for products therefrom to be used as fuel
Problem, as the processing method of the mixed solution, it is now desirable to establishing a kind of beyond incineration disposal, safe and economical side
Method.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 6-170380 publication
The content of the invention
Problems to be solved by the invention
Herein, the present invention made as background with the fact, its problem to be solved is, there is provided can using as
The waste liquid of lithium battery etc. the is discharged, mixed solution comprising specific fluorine-containing electrolyte and carbonates is safely and economically
The method of process.
For solution to problem
Then, the present inventor etc. are for the processing method comprising specific fluorine-containing electrolyte and the mixed solution of carbonates
Furtherd investigate, as a result found, by the tetramethyl-ammonium compound for adding regulation in the mixed solution, thus, it is possible to press down
The decomposition of carbonates processed, and the tetramethyl-ammonium that the fluorine-containing electrolyte included in mixed solution can be coordinated with stable fluorine
The form of the solid of salt is separated out, so as to complete the present invention.That is, it is a gist of the present invention that a kind of process of mixed solution
Method, it is characterised in that comprising selected from lithium hexafluoro phosphate, LiBF4, sodium hexafluoro phosphate, hexafluoroarsenate lithium and hexafluoro
Add in the compound of one or more of group and the mixed solution of carbonates of metaantimmonic acid lithium composition tetramethyl-ammonium compound (but
The tetramethyl ammonium of fluorine coordination is not included.), after salting out the tetramethyl-ammonium that fluorine is coordinated, remove gained precipitate.
It should be noted that the preferred first scheme in the processing method of this mixed solution of the invention
In, aforementioned tetramethyl-ammonium compound be strongly alkaline compound, by the strongly alkaline compound be modulated into pH less than 14 water
The form of solution is added in aforementioned mixed solution.
In addition, in the preferred alternative plan in the processing method of mixed solution of the invention, aforementioned tetramethyl
Ammonium compoundss are strongly alkaline compound, and the strongly alkaline compound is worked as with water with 1 with being modulated into：The ratio of 1 (volume ratio)
The pH of water phase during mixing less than 14, using organic solvent as the solution of solvent form add.
Herein, in preferred each scheme of the invention described above, it is advantageous to which aforementioned strongly alkaline compound is hydroxide four
Ammonium methyl.
In addition, in the preferred third program in the processing method of mixed solution of the invention, while heating adds
Added with the aforementioned mixed solution of aforementioned tetramethyl-ammonium compound, while the tetramethyl-ammonium for making aforementioned fluorine coordination is salted out, by mistake
Filter is processed and removes the tetramethyl ammonium of the fluorine coordination for separating out, and the filtrate obtained by the filtration treatment by distillation is back and forth
Receive aforementioned carbonates.
And, in the preferred fourth program in the processing method of mixed solution of the invention, at filtration
Manage and remove the tetramethyl ammonium of the aforementioned fluorine coordination for separating out, and heat the filtrate obtained by the filtration treatment, and by steaming
Evaporate the filtrate after the heating to reclaim aforementioned carbonates.
The effect of invention
Thus, the processing method of mixed solution of the invention is comprising specific fluorine-containing electrolyte and carbonates
Add the tetramethyl-ammonium compound of regulation in mixed solution, the decomposition of carbonates can be suppressed, and fluorine-containing electrolysis can be made
The solid form of the tetramethyl ammonium that matter is coordinated with stable fluorine is separated out.Therefore, by the precipitate of the removal solid, can
Effectively the fluorine composition from fluorine-containing electrolyte is removed from the mixed solution of treated object, marginally burnt every time with conventional
Burn the method for processing to compare, the processing method of the present invention is safe and economical.
In addition, by the tetramethyl ammonium of the fluorine for separating out in solid form coordination and from specific fluorine-containing electrolyte
The removed mixed solution of fluorine composition (main component is carbonates) both is higher as the heat of fuel, from
From the aspect of upper, they can carry out effectively utilizes as fuel.Thus, the processing method of mixed solution of the invention from
It is also very excellent from the viewpoint of the recycling of energy.
Specific embodiment
Herein, in the processing method of mixed solution of the invention, the solution dealt with objects as it is comprising specific
Fluorine-containing electrolyte and carbonates mixed solution (below, it is also possible to be properly termed as " processed solution ".).
Herein, the fluorine-containing electrolyte for including in processed solution is selected from lithium hexafluoro phosphate (LiPF6), LiBF4
(LiBF4), sodium hexafluoro phosphate (NaPF6), hexafluoroarsenate lithium (LiAsF6) and hexafluoro-antimonic acid lithium (LiSbF6) composition group in one
Plant the compound of the above.In addition, as the carbonates included in processed solution, ethylene carbonate, carbonic acid can be exemplified
Sub- propyl ester, butylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid di-n-propyl ester, diisopropyl carbonate, carbonic acid n-pro-pyl
Isopropyl esters, Ethyl methyl carbonate, methyl n-pro-pyl ester, carbonic acid normal-butyl methyl ester, carbonic acid isobutyl methyl ester, carbonic acid uncle
Butyl methyl ester, carbonic acid ethyl n-pro-pyl ester, carbonic acid normal-butyl ethyl ester, isobutyl carbonate butyl ethyl ester, carbonic acid t-butylethyl
Ester etc..In the present invention, comprising specific fluorine-containing electrolyte and each more than one the mixed solution of carbonates process object is become.
More specifically, as the mixed solution, the quilt in lithium battery, lithium ion battery, lithium-ion capacitor etc. can be exemplified
The mixed solution of electrolyte is widely used as, can be molten to the mixing discharged when the manufacture process of these batteries etc., waste treatment etc.
Liquid is advantageously using the processing method of the present invention.
It should be noted that the mixing even for the composition comprising specific fluorine-containing electrolyte and beyond carbonates is molten
Liquid, as long as the composition does not hinder the effect of the present invention, and its content does not hinder the effect of the present invention, it is possible to according to this
Bright processing method is being processed.
And, the processing method of the mixed solution of the present invention is significantly technically characterized in that, as described above to processed
Tetramethyl-ammonium compound beyond the tetramethyl ammonium of solution addition fluorine removal coordination.That is, if adding tetramethyl in processed solution
Base ammonium compoundss (but do not include the tetramethyl ammonium of fluorine coordination.), then can suppress the decomposition of carbonates, and specifically contain
Fluorine electrolyte is susceptible to neutralization reaction or salt exchange reaction with the tetramethyl-ammonium compound of above-mentioned regulation, and separates out stable fluorine
The solid of the tetramethyl ammonium of coordination.By removing the precipitate, advantageously can remove from fluorine-containing from processed solution
The fluorine composition of electrolyte.
In the processing method of the mixed solution of the present invention, as tetramethyl-ammonium compound, except specifically not containing with above-mentioned
Tetramethyl ammonium (for example, hexafluorophosphoric acid tetramethyl-ammonium, the Tetrafluoroboric acid tetramethyl-ammonium of the fluorine coordination that fluorine electrolyte reacts
Deng) beyond, it is possible to use all of tetramethyl-ammonium compound.As the tetramethyl-ammonium compound that can be used in the present invention, can be with
Exemplify tetramethyl ammonium hydroxide, tetramethyl ammonium chloride, nitric acid tetramethyl-ammonium, sulphuric acid tetramethyl-ammonium, phosphoric acid tetramethyl-ammonium, acetic acid
Tetramethyl-ammonium, tetramethylammonium bromide, iodate tetramethyl-ammonium etc..
In addition, can be according in the processed solution to the addition of the tetramethyl-ammonium compound of the solution that is processed
The content of specific fluorine-containing electrolyte suitably determining, equivalent to the mole of the fluorine-containing electrolyte included in processed solution
During less than 1 equivalent (mol ratio), the fluorine composition from fluorine-containing electrolyte can be remained in the processed solution after process.Therefore, it is
Fluorine removal composition is fully removed from processed solution, relative to the mole of the fluorine-containing electrolyte included in processed solution, with 1
Add tetramethyl-ammonium compound more than equivalent (mol ratio), preferably with the ratio of amounts more than 1.1 equivalents (mol ratio).
In the present invention, as described above, it is stipulated that tetramethyl-ammonium compound it is of course possible to by the tetramethyl-ammonium of solid, shaped
Compound is directly appended in processed solution, can be with the form of the aqueous solution being dissolved in the water or to be dissolved in regulation
The form of the solution in organic solvent is added.It should be noted that using as basicity acetic acid tetramethyl-ammonium is not strong
Tetramethyl-ammonium compound in the case of, use compared to the form with aqueous solution, preferably directly use the tetramethyl of solid, shaped
Ammonium compoundss.This is because, by using the tetramethyl-ammonium compound of solid, shaped, obtain after treatment, fluorine composition is removed
And using carbonates as the processed solution of main component in, the content of moisture is suppressed relatively low, and this moisture is low
Processed solution and moisture more than processed solution ratio, not only caloric value is big, and greatly facilitates and steamed
Evaporate cost cutting when regeneration carrys out recycling design (carbonates), yield to improve.
On the other hand, the tetramethyl-ammonium compound being added in processed solution is the strong basicities such as tetramethyl ammonium hydroxide
In the case of compound, preferably be modulated into pH less than 14 aqueous solution form or be modulated into when with water with 1：1 (body
Product ratio) ratio mix when water phase pH less than 14, organic solvent is added to as the form of the solution of solvent and is located
In reason solution.In addition, particularly preferably be modulated into aqueous solutions of the pH less than 13 form or be modulated into when with water with
1：The pH of the water phase when ratio of 1 (volume ratio) mixes less than 13, add organic solvent as the form of the solution of solvent
To in processed solution.It should be noted that in the case of with the form of solution using tetramethyl-ammonium compound, as modulation
The organic solvent used during the solution, can exemplify methanol etc..
So add tetramethyl-ammonium compound in the state of basicity is reduced, thus, it is possible to effectively suppress processed solution
In the decomposition of carbonates that includes, and can effectively reclaim the carbonates of Oil repellent reduction.It should be noted that
In the case that tetramethyl-ammonium compound is strongly alkaline compound, by it with the form of solid or with aqueous solution that pH is more than 14
Form or with when with water with 1：The pH of the water phase when ratio of 1 (volume ratio) mixes be more than 14, organic solvent is made
When being added in processed solution for the form of the solution of solvent, there is following risk：The decomposition reaction of carbonates is significantly
Carry out, the yield of carbonates is reduced；Or reaction heat during decomposition reaction rises liquid temperature.Further, since carbonates
Decomposition, produce the low alcohols of flash-point, there is the dangerous risk for increasing caught fire, light a fire.
As described above, when alkaline tetramethyl-ammonium compound is used with the form of aqueous solution or solution, preferably will
Compound for reducing its basicity is added in aqueous solution or solution.As this compound, as long as can reduce as strong
The basicity of the tetramethyl-ammonium compound of alkali compoundss, is not hindering in the range of the purpose of the present invention, it is possible to using anyization
Compound.Specifically, mineral acid, organic acid can be enumerated and is equal to their compound, for example, as mineral acid or be had
Machine acid, can enumerate nitric acid, hydrochloric acid, sulphuric acid, phosphoric acid, acetic acid, oxalic acid etc., in addition, as these sour compounds are equal to, can
Decomposed and compound of generation acid etc. by the reaction with alkali with enumerating o-methyl-benzene formyl chloride, caproyl chloride, stearyl chloride etc..Especially
Its, according to aftermentioned method, it is including in reclaiming processed solution, from the lithium of specific fluorine-containing electrolyte when, preferably use
Acetic acid or nitric acid are used to reduce the basicity of alkaline tetramethyl-ammonium compound.
It should be noted that forming the chemical combination of stable salt as energetically reacting with above-mentioned specific fluorine-containing electrolyte
Thing, in addition to the tetramethyl-ammonium compound of above-mentioned regulation, can enumerate for example the quaternary ammonium compound such as tetraethyl ammonium compound, three
The tertiary amine compounds such as methylamine and inorganic ammonium compoundss etc..However, using in addition to the tetramethyl-ammonium compound of above-mentioned regulation
During quaternary ammonium compound, can be dissolved in large quantities in carbonates with the quaternary ammonium salt of the fluorine-containing fluorine coordination for being electrolysed qualitative response and generating,
Fluorine removal composition can not be fully removed from processed solution.In addition, during using tertiary amine compound, inorganic ammonium compoundss, existing and containing
The risk that the reaction of fluorine electrolyte is deficiently carried out, and with the reaction of fluorine-containing electrolyte and generate fluorine coordination ammonium salt meeting
It is dissolved in large quantities in carbonates, it is impossible to fully remove fluorine removal composition from processed solution.
In addition, in the processing method of the present invention, the tetramethyl-ammonium compound of regulation is added in processed solution, institute is made
Tetramethyl-ammonium compound and specific fluorine-containing electrolysis qualitative response are stated, the time separated out required for the tetramethyl ammonium of fluorine coordination can root
Suitably change according to the amount of the fluorine-containing electrolyte included in processed solution, but separate out generally from both mixing through several points
Terminate after clock~a few hours.
The processing method of the mixed solution of the present invention for example can be implemented according to following steps.First, it is (anti-in reactive tank
Answer container) in input as processed solution, the mixed solution comprising specifically fluorine-containing electrolyte and carbonates.Then,
By the tetramethyl-ammonium compound of regulation directly with solid, shaped either with pH through the form of the aqueous solution of regulation or specifying
Organic solvent be used as the form of solution of solvent and put in reactive tank, stirring is added with the tetramethyl-ammonium compound of regulation
Processed solution (hereinafter also referred to as reactant liquor), thus makes specific fluorine-containing electrolyte react with tetramethyl-ammonium compound.So
Afterwards, by the processed solution comprising the product (tetramethyl ammonium of fluorine coordination) separated out by the reaction according to known in the past
Method filtered, be thus separated into filtrate and solid content (product), and reclaimed respectively.
Tetramethyl ammonium reclaimed in the form of solid content by filtration treatment, fluorine coordination is under typical operating conditions
For stable compound, and from having as fuel from the aspect of certain heat, can use as solid fuel.Need
It is noted that used in the processing method as the present invention, the solution of tetramethyl-ammonium compound comprising regulation for example may be used
With using the waste liquid discharged in the matting of quasiconductor etc., by using the waste liquid, can further reduce comprising fluorine-containing
The processing cost of the mixed solution of electrolyte and carbonates.
On the other hand, the filtrate reclaimed by filtration treatment is fully eliminated from specific from processed solution
Fluorine-containing electrolyte it is fluorine composition, using the carbonates both existed from the processed solution of before processing as main component filter
Liquid, but also the decomposition of carbonates is restrained effectively, consider that effectively utilizes can be carried out as fuel from the above.Need
It is bright, even if filtrate includes substantial amounts of water, by mixing with the mixed liquor comprising various water-soluble solvents, surfactant etc.
Close, thus fuel can use as an alternative.
Thus, the filtrate reclaimed by filtration treatment be using carbonates as main component filtrate, from top
Face consideration, by filtrate described in distillation purifying, can reclaim carbonates.
Herein, according to the opinion of the acquisitions such as the present inventor, according to the species of the mixed solution as processed solution, pass through
The filtrate (eliminating the reactant liquor of the tetramethyl ammonium of fluorine coordination) that filtration treatment is obtained has very strong acidity sometimes.This
Person of good sense etc. thinks, in order to improve the characteristic as electrolyte, in the waste liquid (electrolyte) as the lithium battery etc. of processed solution
The situation of the other compositions being added with addition to fluorine-containing electrolyte, carbonates is more, due to the presence of the composition, on
State filtrate and show very strong acidity.
When implementing distillation process to this filtrate for showing very strong acidity, due to showing strong acidity, treatment fluid (filter
Liquid) and/or process after residue in the stillage residue in device and exist distilling apparatus corrosion risk.In order to be effectively reduced process
The acidity of liquid (filtrate) and/or stillage residue, corrosion of distilling apparatus etc. is prevented, it is preferred i) while heating is added with the tetramethyl of regulation
The processed solution (reactant liquor) of base ammonium compoundss while make the fluorine-containing electrolysis qualitative response of the tetramethyl-ammonium compound and regulation,
The tetramethyl-ammonium that fluorine is coordinated is salted out, remove precipitate by filtration treatment, and to being obtained by the filtration treatment
Filtrate is implemented distillation and is processed；Ii) the processed solution from the tetramethyl-ammonium compound for being added with regulation is gone by filtration treatment
Except the tetramethyl ammonium of the fluorine coordination for separating out, and filtrate is heated, distillation is implemented to the filtrate after the heating and is processed.
It should be noted that it is above-mentioned i) in reactant liquor heating condition and above-mentioned ii) in the heating condition of filtrate can respectively
Suitably determined according to composition included in the mixed solution as processed solution etc., but usually as heating-up temperature, adopted
With 40~80 DEG C, as heat time heating time, using 1~10 hour or so.In addition, in order to reduce alkaline tetramethyl-ammonium compound
Basicity and when using acidic aqueous solution, substantial amounts of water is included in filtrate, consider from the above, such as preferably by regulation
Filtrate after heating stands, and after point liquid is organic faciess and water phase, the organic faciess to obtaining are implemented distillation and processed.
On the other hand, according to the present invention, in order to reduce the basicity of alkaline tetramethyl-ammonium compound, using acetic acid or nitre
Acid comprising the lithium salts as fluorine-containing electrolyte to (being selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium and hexafluoro-antimonic acid lithium
One or more of compound) mixed solution processed, thus, it is possible to using from the lithium salts as fluorine-containing electrolyte
Lithium is advantageously recovered in the form of the water miscible Quilonorm (SKB) that generates between acetic acid or nitric acid or lithium nitrate and eliminates fluorine and match somebody with somebody
In the water phase of the reactant liquor (filtrate) of the tetramethyl ammonium of position.Herein, if not using for reducing alkaline tetramethyl-ammonium
The acid of the basicity of compound, then the generated carbonic acid of carbonates hydrolysis and lithium reaction, the carbon low so as to generate the dissolubility to water
Sour lithium, it is difficult in being recovered to water phase.Even if in addition, using phosphorus to reduce the basicity of alkaline tetramethyl-ammonium compound
Acid, generates the lithium phosphate low to the dissolubility of water, it is also difficult in being recovered to water phase.It should be noted that as from aqueous solution
The method for reclaiming lithium, suitably can select to adopt from known various methods.As reclaiming lithium from aqueous solution
Method, can exemplify using the lithium adsorbent disclosed in Japanese Patent Publication 4-23577 publication, Japanese Unexamined Patent Publication 2001-
The method of the selectivity lithium separating medium disclosed in No. 224957 publications, returning disclosed in Japanese Unexamined Patent Publication 2007-122885 publications
Receiving method etc..
Embodiment
Below, several embodiments of the invention are shown, the present invention, but the present invention is further illustrated not because of the embodiment
Record and be self-evident by a bit restriction.In addition, it is to be understood that the present invention except following examples and
Beyond above-mentioned specific description, without departing from the spirit and scope of the invention, according to the knowledge of those skilled in the art, can be with
Various changes are added, is changed, improvement etc..
- embodiment 1-
Prepare ethylene carbonate and dimethyl carbonate as solvent and containing lithium hexafluoro phosphate (LiPF6) 10 weight %
The mixed solution 400g of (equivalent to 0.26mol in terms of lithium hexafluoro phosphate, using in terms of Funing tablet equivalent to 7.5 weight %) is used as being located
Reason solution.On the other hand, as the solution comprising tetramethyl-ammonium compound, prepare in tetramethyl ammonium hydroxide known to concentration
(TMAH) appropriate acetic acid is added in aqueous solution (more than pH14) so as to by aqueous solution 180g that pH regulator is 13.0.Need explanation
, the aqueous solution contains the tetramethyl ammonium of the amount equivalent to 0.29mol.
The total amount of the total amount of processed solution and aqueous solution is put into respectively in the reaction vessel for possessing blender and (is held
Amount：1L or so), it is stirred at room temperature 5 minutes in container, processed.Thereafter, the reactant liquor in container is filtered, and is separated back
Receive filtrate and solid content.
By reclaim filtrate stands in container so as to be separated into organic faciess and water phase this 2 liquid phases after, according to JIS-
K-0102：The Oil repellent of these each phases of determination of quantitative analysis specified in 2008 " plant drainage test methods ", and calculate each
The Funing tablet (weight %) and removal efficiency of flouride (%) of phase.It should be noted that removal efficiency of flouride is calculated according to following formula (I)s.
As a result, the Funing tablet in the organic faciess of filtrate is 0.2 weight %, the Funing tablet in water phase is 0.2 weight %, and removal efficiency of flouride is
97%.In addition, carbonates content (g) in the processed solution of measure and carbonates content (g) in the organic faciess of filtrate,
And calculate the response rate of carbonates according to following formula (II)s.These results are shown in into table 1 below.
Formula (1)：
Formula (II)：
- embodiment 2-
Lithium hexafluoro phosphate will be substituted and contain LiBF4 (LiBF4), ethylene carbonate and dimethyl carbonate are made
For solvent mixed solution 400g (using in terms of LiBF4 containing amount) equivalent to 0.26mol as processed solution, except this
In addition, the process of processed solution is carried out according to condition same as Example 1.Fluorine in the organic faciess of the filtrate after process is dense
Spend for 0.1 weight %, the Funing tablet in water phase is 0.2 weight %, and removal efficiency of flouride is 98%.
- embodiment 3~embodiment 5-
Except using each tetramethyl-ammonium (TMA) salt shown in table 1 below as the solution comprising tetramethyl-ammonium compound
Aqueous solution beyond, the process of processed solution is carried out according to condition same as Example 1.It should be noted that being used
Each aqueous solution in terms of tetramethyl ammonium containing amount equivalent to 0.29mol.Filter in 3~embodiment of embodiment 5, after process
Funing tablet in the organic faciess of liquid is 0.2 weight %, and the Funing tablet in water phase is 0.2 weight %, and removal efficiency of flouride is
97%.
- embodiment 6, embodiment 7-
As the solution comprising tetramethyl-ammonium compound, in tetramethyl ammonium hydroxide aqueous solution (pH14 used in embodiment 6
More than) in add appropriate acetic acid so as to by the aqueous solution 167g that pH regulator is 13.0, identical water used in additional embodiment 7
Solution 245g, in addition, according to condition same as Example 1 the process of processed solution is carried out.With regard to the filter after process
Funing tablet in the organic faciess of liquid, embodiment 6 is 0.4 weight %, embodiment 7 is 0.1 weight %, dense with regard to the fluorine in water phase
Degree, embodiment 6 and embodiment 7 are 0.2 weight %, and with regard to removal efficiency of flouride, it is 98% that embodiment 6 is 95%, embodiment 7.
- embodiment 8, embodiment 9-
It is respectively, water-soluble in tetramethyl ammonium hydroxide used in embodiment 8 as the solution comprising tetramethyl-ammonium compound
Appropriate acetic acid is added in liquid (more than pH14) so as to by the aqueous solution that pH regulator is 13.5, in hydrogen used in additional embodiment 9
Appropriate acetic acid is added in oxidation tetramethyl-ammonium aqueous solution (more than pH14) so as to by the aqueous solution that pH regulator is 12.0, except this with
Outward, the process of processed solution is carried out according to condition same as Example 1.Filter in embodiment 8 and embodiment 9, after process
Funing tablet in the organic faciess of liquid is 0.2 weight %, and the Funing tablet in water phase is 0.2 weight %, and removal efficiency of flouride is
97%.
- embodiment 10, embodiment 11-
By comprising tetramethyl-ammonium compound solution usage amount be set as 131g in embodiment 10, in embodiment 11
It is set as 82g, in addition, the process of processed solution is carried out according to condition same as Example 1.With regard to the filter after process
Funing tablet in the organic faciess of liquid, embodiment 10 is 1.8 weight %, embodiment 11 is 4.4 weight %, dense with regard to the fluorine in water phase
Degree, embodiment 6 and embodiment 7 are 0.2 weight %, and with regard to removal efficiency of flouride, it is 49% that embodiment 10 is 78%, embodiment 11.
- embodiment 12-
As comprising tetramethyl-ammonium compound solution, using tetramethyl ammonium hydroxide methanol solution (when with water with
1：The pH of the water phase when ratio of 1 (volume ratio) mixes is more than 14) in add acetic acid so as to reduce solution A 130g of basicity,
In addition, the process of processed solution is carried out according to condition same as Example 1.It should be noted that solution A is worked as and water
With 1：The pH of the water phase when ratio of 1 (volume ratio) mixes is 13.0, is contained equivalent to 0.29mol's in terms of tetramethyl ammonium
Amount.Funing tablet in the organic faciess of the filtrate after process is 0.1 weight %, and removal efficiency of flouride is 98%.
- embodiment 13-
Substitute the solution comprising tetramethyl-ammonium compound and use the acetic acid tetramethyl-ammonium 39g of solid, shaped (with tetramethyl-ammonium
Amount of the ion meter equivalent to 0.29mol), the mixing time in reaction vessel is set as into 30 minutes, in addition, according to reality
Applying the identical condition of example 1 carries out the process of processed solution.Funing tablet in the organic faciess of the filtrate after process is 0.5 weight
Amount %, removal efficiency of flouride is 94%.
- embodiment 14-
As the solution comprising tetramethyl-ammonium compound, tetramethyl ammonium hydroxide aqueous solution (more than pH14) is directly used,
In addition, the process of processed solution is carried out according to condition same as Example 1.It should be noted that the hydrogen for being used
Oxidation tetramethyl-ammonium aqueous solution is in terms of tetramethyl ammonium containing the amount equivalent to 0.40mol.The organic faciess of the filtrate after process
In Funing tablet be 0.2 weight %, the Funing tablet in water phase be 0.2 weight %, removal efficiency of flouride is 97%.It should be noted that
The heating that the decomposition of discovery ethylene carbonate and dimethyl carbonate causes in processing procedure, the response rate of carbonates is less than real
Apply 1~embodiment of example 13.
- embodiment 15-
As comprising tetramethyl-ammonium compound solution, directly use tetramethyl ammonium hydroxide methanol solution (when with water
With 1：The pH of the water phase when ratio of 1 (volume ratio) mixes is more than 14), in addition, according to condition same as Example 1
Carry out the process of processed solution.It should be noted that the tetramethyl ammonium hydroxide aqueous solution for being used is with tetramethyl ammonium
Meter is containing the amount equivalent to 0.40mol.Funing tablet in the organic faciess of the filtrate after process is 0.1 weight %, and removal efficiency of flouride is
98%.It should be noted that the heating that the decomposition of discovery ethylene carbonate and dimethyl carbonate causes in processing procedure, carbonic ester
The response rate of class is less than 1~embodiment of embodiment 13.
- embodiment 16-
Lithium hexafluoro phosphate will be substituted and contain sodium hexafluoro phosphate (NaPF6), ethylene carbonate and dimethyl carbonate are made
For solvent mixed solution 400g (using in terms of sodium hexafluoro phosphate containing amount) equivalent to 0.26mol as processed solution, except this
In addition, the process of processed solution is carried out according to condition same as Example 1.Fluorine in the organic faciess of the filtrate after process is dense
Spend for 0.2 weight %, the Funing tablet in water phase is 0.2 weight %, and removal efficiency of flouride is 97%.
Solid content (tetramethyl ammonium of fluorine coordination) and filtrate to obtaining in above-described embodiment is carried out as fuel respectively
Evaluation.Specifically, the automatic bomb calorimeter CA-4AJ types of formula (Shimadzu Scisakusho Ltd's system) and basis are ground using combustion
JIS-M-8814, JIS-K-2279 are determining the caloric value as fuel that solid content and filtrate have.Its result can be true
Recognize, the solid content (tetramethyl ammonium of fluorine coordination) obtained in embodiment is respectively provided with the caloric value of 3000cal/g, and filtrate is equal
Caloric value with 4200cal/g, discovery can be used as fuel effectively utilizes.
- comparative example 1-
Lithium hexafluoro phosphate will be substituted and contain trifluoromethanesulfonic acid lithium (LiCF3SO3), by ethylene carbonate and carbonic acid diformazan
Ester is molten as being processed as the mixed solution 400g (using in terms of trifluoromethanesulfonic acid lithium containing the amount equivalent to 0.26mol) of solvent
Liquid, in addition, according to condition same as Example 1 the process of processed solution is carried out.It should be noted that fluoroform sulphur
Sour lithium is to be mainly directed towards the representational electrolyte used in the electrolyte of 1 primary cell.Even if however, in stirring reaction container
Afterwards, the precipitation of solidss is not found yet.Additionally, it is believed that the major part of the fluorine composition in processed solution residues in organic faciess
In, therefore removal efficiency of flouride is considered as into 0%.
- comparative example 2~comparative example 4-
Substitute the solution comprising tetramethyl-ammonium compound and use the ammonium compoundss of other species shown in table 1 below, remove
Beyond this, the process of processed solution is carried out according to condition same as Example 1.Specifically, respectively, in comparative example 2
Using appropriate acetic acid is added in tetraethyl ammonium hydroxide aqueous solution so as to by the aqueous solution that pH regulator is 13.0, comparative example 3
Used in appropriate acetic acid is added in trimethylamine aqueous solution so as to pH to be modulated into 13.0 aqueous solution, used in comparative example 4
Aqueous ammonium chloride solution.In addition, these each aqueous solutions contain the amount equivalent to 0.29mol in terms of ammonium compoundss.However, comparative example
In 2~comparative example 4, in the stirring reaction container after do not find the precipitation of solidss.Additionally, it is believed that in processed solution
The major part of fluorine composition residue in organic faciess, therefore removal efficiency of flouride is considered as into 0%.
[table 1]
As the result from table 1 is clear and definite, it is found that the processing method of mixed solution of the invention can suppress to make
The decomposition of carbonates that includes in mixed solution for process object and can safely remove from specific fluorine-containing electricity
The fluorine composition of solution matter.
According to the present invention, for the tetramethyl ammonium that the fluorine that precipitation is removed by filtration treatment is coordinated, and from filtrate
Carbonates are reclaimed, following experiment is carried out.
First, as processed solution, 2 kinds of electrolyte (waste liquid of lithium battery) each 400g shown below is prepared.In addition,
As the solution comprising tetramethyl-ammonium compound, prepare in tetramethyl ammonium hydroxide known to concentration (TMAH) aqueous solution (pH14
More than) in add appropriate acetic acid so as to pH to be modulated into 13.0 aqueous solution 180g.It should be noted that the aqueous solution contains
There is the tetramethyl ammonium of the amount equivalent to 0.29mol.
Electrolyte A：Using ethylene carbonate and Ethyl methyl carbonate (EMC) are as solvent and contain lithium hexafluoro phosphate
(LiPF6) 10 weight % (equivalent to 0.26mol in terms of lithium hexafluoro phosphate, equivalent to 7.5 weight % in terms of Funing tablet) electrolysis
Liquid.
Electrolyte B：Using propylene carbonate, ethylene carbonate and Ethyl methyl carbonate (EMC) are as solvent and contain hexafluoro
Lithium phosphate (LiPF6) 10 weight % (equivalent to 0.26mol in terms of lithium hexafluoro phosphate, equivalent to 7.5 weight % in terms of Funing tablet)
Electrolyte.
- embodiment 17-
The total amount of the total amount of electrolyte A and above-mentioned aqueous solution is put into respectively in the reaction vessel for possessing blender and (is held
Amount：1L or so), it is stirred at room temperature 5 minutes in container, processed.Thereafter, the reactant liquor in container is filtered, and is separated back
Receive filtrate and solid content.
Stir 4 hours in the state of the filtrate of recovery is heated to be into 60 DEG C.After the heated and stirred, by filtrate in
Stand in container so as to be separated into organic faciess and water mutually this 2 liquid phases.According to the fluorine of these each phases of above-mentioned determination of quantitative analysis
Content, calculates removal efficiency of flouride, is as a result 97%.By the organic faciess for obtaining distillation, Ethyl methyl carbonate is reclaimed in the form of fraction
(EMC).By the knot of the purity (weight %) of the EMC in the pH and fraction that determine organic faciess, fraction and stillage residue before distillation
Fruit is shown in table 2 below.It should be noted that finding the alcohol of trace in fraction.
- embodiment 18-
Electrolyte A 400g and above-mentioned aqueous solution 180g are put into into respectively (capacity in the reaction vessel for possessing blender：
1L or so), in container for stirring 4 hours in the state of reactant liquor to be heated to be 60 DEG C, thus processed.Thereafter, filter
Reactant liquor in container, and separate and recover filtrate and solid content.
By reclaim filtrate stands in container so as to be separated into organic faciess and water phase this 2 liquid phases.According to above-mentioned quantitative
The Oil repellent of assay these each phases, calculates removal efficiency of flouride, is as a result 97%.By the organic faciess for obtaining distillation, with fraction
Form reclaim Ethyl methyl carbonate (EMC).By in the pH and fraction that determine organic faciess, fraction and stillage residue before distillation
The result of the purity (weight %) of EMC is shown in table 2 below.It should be noted that being found that the alcohol of trace in fraction.
- embodiment 19-
In addition to alternative electrolyte A 400g uses electrolyte B 400g, according to method similarly to Example 17,
It is final that Ethyl methyl carbonate (EMC) is reclaimed in the form of fraction.It should be noted that removal efficiency of flouride is 98%.To determine before distillation
Organic faciess, fraction and stillage residue pH and fraction in the result of purity (weight %) of EMC be shown in table 2 below.Need
Illustrate, the alcohol of trace is found that in fraction.
- embodiment 20-
The filtrate to reclaiming does not implement heat treated, by stand in container make its be separated into organic faciess and water mutually this 2
Individual liquid phase, in addition, according to method similarly to Example 17, finally reclaims Ethyl methyl carbonate (EMC) in the form of fraction.
It should be noted that removal efficiency of flouride is 97%.By in the pH and fraction that determine organic faciess, fraction and stillage residue before distillation
The result of the purity (weight %) of EMC is shown in table 2 below.It should be noted that being found that the alcohol of trace in fraction.
[table 2]
As clear and definite by the table 2, organic faciess and water phase be separated into after heat treated is carried out to filtrate and steamed
Evaporate the embodiment 17 and embodiment 19 of the organic faciess and to reactant liquor one side heated and stirred while being neutralized the reality of process
Apply in example 18 and find, the acidity of stillage residue in device is residued in after the organic faciess and distillation procedure before distillation not extremely
By force.On the other hand, find in the embodiment 20 for not implementing above-mentioned heat treated completely, although the purity of the EMC in fraction is high,
But the organic faciess and stillage residue before distilling show strong acidity, there is the corrosion equivalent risk for causing distilling apparatus.
Then, according to the present invention, in order to removed by filtration treatment precipitation fluorine be coordinated tetramethyl ammonium and from
Filtrate reclaims lithium, has carried out following experiment.
- embodiment 21~embodiment 23-
As processed solution, prepare above-mentioned electrolyte A.In addition, as the solution comprising tetramethyl-ammonium compound, each standard
Standby 180g adds a in tetramethyl ammonium hydroxide known to concentration (TMAH) aqueous solution (more than pH14)) appropriate acetic acid so as to
PH is modulated into 13.0 aqueous solution a, adds b) appropriate nitric acid so as to pH to be modulated into 13.0 aqueous solution b and is added
C) appropriate phosphoric acid so as to pH is modulated into 13.0 aqueous solution c.It should be noted that aqueous solution a~aqueous solution c contains phase
When the tetramethyl ammonium of the amount in 0.29mol.
By the total amount of the electrolyte A of 400g and aqueous solution a in embodiment 21, by the electrolyte of 400g in additional embodiment 22
In the total amount of A and aqueous solution b, and then embodiment 23 total amount of the electrolyte A of 400g and aqueous solution c is put into possess respectively and stir
Mix (capacity in the reaction vessel of machine：1L or so), it is stirred at room temperature 5 minutes in container, processed.Thereafter, container is filtered
Interior reactant liquor, and separate and recover filtrate and solid content.
By reclaim filtrate stands in container so as to be separated into organic faciess and water phase this 2 liquid phases.According to above-mentioned quantitative
The Oil repellent of assay these each phases, calculates removal efficiency of flouride, and the removal efficiency of flouride in acetonideexample 21 is 97%, embodiment
It is 97% that removal efficiency of flouride in 22 is the removal efficiency of flouride in 97%, embodiment 23.Lithium concentration (weight %) root of the water phase for obtaining
Determine according to " atomic absorption analysis general rule " specified in JIS-K-0121.In addition, with regard to the lithium content in water phase, calculate for
As the response rate (%) of the lithium included in the electrolyte A of processed solution.By the lithium concentration (Li concentration) in water phase and recovery
Rate (the Li response rate) is shown in Table 3 below.
[table 3]
As the result from the table 3 is clear and definite, discovery use acetic acid or nitric acid as pH adjusting agent (embodiment 21,
Embodiment 22) compared with phosphoric acid is used as pH adjusting agent (embodiment 23), can more effectively reclaim lithium.
Claims (7)
1. a kind of processing method of mixed solution, it is characterised in that comprising selected from lithium hexafluoro phosphate, LiBF4, six
The compound of one or more of the group of sodium fluorophosphate, hexafluoroarsenate lithium and hexafluoro-antimonic acid lithium composition and the mixing of carbonates are molten
Add tetramethyl-ammonium compound in liquid, after salting out the tetramethyl-ammonium that fluorine is coordinated, remove gained precipitate, wherein, it is described
Tetramethyl-ammonium compound does not include the tetramethyl ammonium of fluorine coordination.
2. the processing method of mixed solution according to claim 1, wherein, the tetramethyl-ammonium compound is strong basicity
Compound, the strongly alkaline compound is added in the mixed solution with the form for being modulated into aqueous solutions of the pH less than 14.
3. the processing method of mixed solution according to claim 1, wherein, the tetramethyl-ammonium compound is strong basicity
Compound, the strongly alkaline compound is worked as with water with volume basis 1 with being modulated into：The pH of water phase when 1 ratio mixes is little
In 14, be added organic solvent as the form of the solution of solvent.
4. the processing method of mixed solution according to claim 2, wherein, the strongly alkaline compound is tetramethylphosphonihydroxide hydroxide
Base ammonium.
5. the processing method of mixed solution according to claim 3, wherein, the strongly alkaline compound is tetramethylphosphonihydroxide hydroxide
Base ammonium.
6. the processing method of the mixed solution according to any one of Claims 1 to 5, wherein, while heating addition is
The mixed solution of tetramethyl-ammonium compound is stated, while the tetramethyl-ammonium for making the fluorine coordination is salted out, by filtration treatment
And the tetramethyl ammonium of the fluorine coordination for separating out is removed, and reclaim described by distilling the filtrate obtained by the filtration treatment
Carbonates.
7. the processing method of the mixed solution according to any one of Claims 1 to 5, wherein, gone by filtration treatment
Except the tetramethyl ammonium of the fluorine coordination for separating out, and the filtrate obtained by the filtration treatment is heated, and it is described by distillation
Filtrate after heating is reclaiming the carbonates.
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| JP2013-192526 | 2013-09-18 | ||
| JP2013192526 | 2013-09-18 | ||
| PCT/JP2014/074052 WO2015041131A1 (en) | 2013-09-18 | 2014-09-11 | Method for treating mixed solution |
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| JP (1) | JP6276281B2 (en) |
| KR (1) | KR20160056870A (en) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06170380A (en) * | 1992-12-10 | 1994-06-21 | Morita Kagaku Kogyo Kk | Fixation of fluorine in waste solution containing fluorophosphate |
| JPH06170381A (en) * | 1991-12-20 | 1994-06-21 | Nec Corp | Treatment of fluorine in waste water |
| CN1121439A (en) * | 1994-05-26 | 1996-05-01 | 多摩化学工业株式会社 | Method for processing acid waste gas |
| JP2000106221A (en) * | 1998-09-28 | 2000-04-11 | Mitsubishi Heavy Ind Ltd | Treatment method of battery |
| CN102856610A (en) * | 2012-08-28 | 2013-01-02 | 奇瑞汽车股份有限公司 | Pretreatment method for recycling scrap lithium ion battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3884407B2 (en) * | 2003-06-03 | 2007-02-21 | 株式会社東芝 | Method and apparatus for treating fluorine-containing water |
| FR2868603B1 (en) * | 2004-04-06 | 2006-07-14 | Recupyl Sa Sa | METHOD FOR RECYCLING BATTERY MIXTURES AND BATTERIES BASED ON LITHIUM ANODE |
| AU2012368870B2 (en) * | 2012-02-10 | 2016-07-21 | Sumitomo Metal Mining Co., Ltd. | Method for recovering lithium |
-
2014
- 2014-09-11 CN CN201480051798.0A patent/CN105555381B/en active Active
- 2014-09-11 JP JP2015537884A patent/JP6276281B2/en active Active
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06170381A (en) * | 1991-12-20 | 1994-06-21 | Nec Corp | Treatment of fluorine in waste water |
| JPH06170380A (en) * | 1992-12-10 | 1994-06-21 | Morita Kagaku Kogyo Kk | Fixation of fluorine in waste solution containing fluorophosphate |
| CN1121439A (en) * | 1994-05-26 | 1996-05-01 | 多摩化学工业株式会社 | Method for processing acid waste gas |
| JP2000106221A (en) * | 1998-09-28 | 2000-04-11 | Mitsubishi Heavy Ind Ltd | Treatment method of battery |
| CN102856610A (en) * | 2012-08-28 | 2013-01-02 | 奇瑞汽车股份有限公司 | Pretreatment method for recycling scrap lithium ion battery |
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| Publication number | Publication date |
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| WO2015041131A1 (en) | 2015-03-26 |
| JP6276281B2 (en) | 2018-02-07 |
| JPWO2015041131A1 (en) | 2017-03-02 |
| TW201527225A (en) | 2015-07-16 |
| KR20160056870A (en) | 2016-05-20 |
| TWI643821B (en) | 2018-12-11 |
| CN105555381A (en) | 2016-05-04 |
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