CN108754141A - A kind of extraction organic phase and its application - Google Patents
A kind of extraction organic phase and its application Download PDFInfo
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- CN108754141A CN108754141A CN201810960718.3A CN201810960718A CN108754141A CN 108754141 A CN108754141 A CN 108754141A CN 201810960718 A CN201810960718 A CN 201810960718A CN 108754141 A CN108754141 A CN 108754141A
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- 0 C*c(c(*)c1C2=Nc3c(*)c(*)c(*)c(*)c3*2)c(*)c(*)c1O Chemical compound C*c(c(*)c1C2=Nc3c(*)c(*)c(*)c(*)c3*2)c(*)c(*)c1O 0.000 description 1
- RMQYTISVZBXKKM-UHFFFAOYSA-N Oc(c(Cl)cc(Cl)c1)c1C1=NC2C=CC=CC2O1 Chemical compound Oc(c(Cl)cc(Cl)c1)c1C1=NC2C=CC=CC2O1 RMQYTISVZBXKKM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of extraction organic phase and its applications.The extraction organic phase includes diluent, modification agent and such as formula (I) compound represented, a concentration of 0.05mol/L~2mol/L such as formula (I) compound represented in extracting organic phase；A concentration of 0.05mol/L~2mol/L of the modification agent in extracting organic phase.The application may include subordinate's step：Contain the water phase extraction of lithium ion with the extraction organic extractant phase, organic phase is collected in layering.The extraction organic phase and extracting process of extraction lithium provided by the invention have the advantages that lithium ion extraction efficiency height, easy split-phase, operating method are easy, also there is outstanding lithium sodium, lithium potassium separation simultaneously, can realize that lithium is detached with the highly selective of otheralkali metal.
Description
Technical field
The present invention relates to a kind of extraction organic phase and its applications.
Background technology
Lithium is the metallic element of density minimum in nature, has minimum atomic radius, metal simple-substance and its chemical combination
Object has the chemical and physical features different from many other metallic elements, industrial use extensive.The application of lithium and its compound
It is related to the multiple fields such as glass, ceramics, medicine, smelting, refrigeration.Especially in new energy field, lithium is known as " energy source element ",
It is the important source material of lithium battery, global demand amount is just quickly increased with annual 8~10% speed.On the other hand, elemental lithium has
The two kinds of stable isotope lithiums -6 and lithium -7 having have important purposes in nuclear energy field, and lithium -6 is must not in fusion reactor
The raw material that can lack, lithium -7 is conditioning agent and coolant in fission reactor.Therefore, to the comprehensive development and utilization of lithium resource, spy
It is not that there is highly important Social benefit and economic benefit with recycling lithium using the method production of extraction.
Currently, lithium resource both domestic and external is essentially from lithium mine and salt lake bittern lithium resource.Lithium salts is extracted from salt lake bittern
Technology method, mainly have the precipitation method, solvent extraction, ion exchange adsorption, carbonizatin method, calcining leaching method, electric osmose
Analysis method etc..
Solvent extraction is the efficient of (such as brine containing lithium, waste water containing lithium, sinker mother liquor) separation and Extraction lithium from solution
Technology, it has many advantages, such as simple technique and equipment, operation serialization, is easily achieved and automatically controls.In existing report, often
The system for the extraction lithium seen has：(1) tributyl phosphate TBP- ferric trichlorides extraction system；(2) diketone class thenoyl trifluoropropyl
The extraction systems such as ketone TTA, benzoyl acetone HBA；(3) pyrazolone chelates class HPMBP-TBP systems；(4) crown compound 15
The systems such as hat 5；(5) neutral amides N-503 extraction systems.But these existing extraction lithium systems there is also some problems, wrap
Include extraction efficiency is low, lithium ion selectivity it is not high；Extractant is water-soluble big, and loss is more；Two-phase density contrast is small, difficult split-phase；Back extraction
Acidity is excessive, and reagent consumption is big；The load capacity of organic phase lithium is too small；Equipment seriously corroded etc..
Therefore, there is an urgent need for a kind of high efficiency, highly selective extracting process.
Invention content
The present invention is that there are efficiency is low, selectivity in the method for overcome existing recycling lithium practical the technical issues of solving
Not high defect provides a kind of extraction organic phase and its application, by the extraction of the extractant and water phase lithium ion, back extraction,
It can realize the high efficiency of lithium ion, highly selective extraction, there is higher economic benefit.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of extraction organic phases comprising diluent, modification agent and such as formula (I) compound represented,
A concentration of 0.05mol/L~the 2mol/L such as formula (I) compound represented in extracting organic phase；The modification agent
A concentration of 0.05mol/L~2mol/L in extracting organic phase；
Wherein, X is O atom or S atom；
R1、R2、R3、R4、R5、R6、R7And R8It is each independently hydrogen, halogen (such as fluorine, chlorine, bromine or iodine), nitro, do not take
The C of generation or halogen (such as fluorine, chlorine, bromine or iodine, in another example fluorine) substitution1-6Alkyl (the C1-6Alkyl is preferably C1-4Alkyl,
For example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl or tertiary butyl, more preferably tertiary butyl), unsubstituted or R1 -1Substituted phenyl (the R1-1Number can be one or more, when there are multiple R1-1When, the R1-1It is identical or not
Together), the C of halogen substitution1-6Alkyl (for example, trifluoromethyl) or R7、R8Coupled carbon is formed together
The R1-1For C1-6Alkyl (preferably C1-4Alkyl, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl or
Tertiary butyl) or halogen (such as fluorine, chlorine, bromine or iodine)；The R7a、R7b、R7cAnd R7dThe same R of definition1；
The modification agent is one or more in alkyl sulfonium, quarternary ammonium salt compound and phosphoric-oxygenic compound.
The diluent can be extraction field conventional thinner, preferably kerosene, heptane, octane, hexamethylene, just oneself
Alkane, amylalcohol, octanone, dodecane, chloroform, petroleum ether, carbon tetrachloride, toluene, dimethylbenzene, diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitro
It is one or more in methane, 2- methyl cyclohexanones, methylisobutylketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes and diphenyl ether.
It is described if concentration of formula (I) compound represented in extracting organic phase is preferably 0.1mol/L~1mol/L,
For example, 0.11mol/L, 0.50mol/L or 0.60mol/L.
A concentration of 0.1mol/L~1.0mol/L of the modification agent in extracting organic phase, for example, 0.11mol/L,
0.30mol/L, 0.60mol/L or 0.50mol/L.
The R1Preferably hydrogen.
The R2Preferably hydrogen.
The R3Preferably hydrogen, C1-6Alkyl or the C of halogen substitution1-6Alkyl.
The R4Preferably hydrogen.
The R5Preferably hydrogen or halogen.
The R6Preferably hydrogen.
The R7Preferably hydrogen or halogen.
The R8Preferably hydrogen.
The R7aPreferably hydrogen.
The R7bPreferably hydrogen.
The R7cPreferably hydrogen.
The R7dPreferably hydrogen.
In some preferred embodiments, R1、R2And R4For hydrogen, R3For the C of hydrogen or halogen substitution1-6Alkyl, X are O or S, R5And R7
It independently is hydrogen or chlorine, R6And R8It independently is hydrogen, the C of halogen substitution1-6Alkyl is preferably trifluoromethyl.
In some preferred embodiments, R1、R2、R4、R5And R6For hydrogen, R3For hydrogen or C1-6Alkyl, X are O or S,ForThe C1-6Alkyl is preferably tertiary butyl.
It is described such as formula (I) compound represented, it is one or more in preferably following compound：
The cation of the alkyl sulfonium is preferablyRcAnd RdIt independently is C8-10Alkyl is (for example, octyl, nonyl
Base or decyl).The C8-10Alkyl is octyl, nonyl or decyl, preferably octyl or nonyl
The anion of the alkyl sulfonium can be the anion of this field alkyl sulfonium routine, preferably halogen ion (example
Such as, fluorine ion, chlorion, bromide ion or iodide ion, in another example chlorion or bromide ion).
The alkyl sulfonium is preferably chlorination dioctyl Methylsulfonium Salt and/or chlorination dinonyl Methylsulfonium Salt.
The cation of the quaternary ammonium salt is preferablyReFor C1-4Alkyl is (for example, methyl, ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group or tertiary butyl) or C8-18Alkyl, RfAnd RgIt independently is benzyl, phenyl or C8-18Alkyl is (preferably
C8-12Alkyl, for example, octyl, nonyl, decyl, undecyl or dodecyl).
The anion of the quaternary ammonium salt can be the anion of this field quaternary ammonium salt routine, and preferably halogen ion is (for example, fluorine
Ion, chlorion, bromide ion or iodide ion, in another example fluorine ion) or sulfate ion.
In the quaternary ammonium salt, when anion is halogen ion,In, the RePreferably methyl, octyl, nonyl
Base or decyl, the RfAnd RgIndependent is preferably methyl, benzyl, phenyl, dodecyl, octyl, nonyl, decyl or octadecane
Base.
In the quaternary ammonium salt, when anion is sulfate radical,In, the Re、RfAnd RgIt is preferably independently
C8-10Alkyl (for example, octyl, nonyl or decyl).
The quaternary ammonium salt is preferably alkyl quaternary ammonium salts, preferably, the quaternary ammonium salt is bromination didecyl Dimethy
Ammonium, chlorodimethyl benzyl phenyl ammonium, tricaprylmethyl ammonium sulfate, dodecyl dimethyl benzyl ammonium chloride, chlorination trioctylphosphine
Methyl ammonium, three nonanylmethyl ammonium of chlorination, three decyl methyl ammonium of chlorination, tetramethyl ammonium chloride, dimethyl two (N- octadecyls) chlorine
Change one or more in ammonium and tricaprylmethyl ammonium sulfate.
The phosphoric-oxygenic compound is preferablyWith one kind in bis phosphoric acid ester type compound or more
Kind；The RhFor C1-4Alkyl (for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl or tertiary butyl), it is described
RiAnd RjIt independently is C1-4Alkyl (for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl or tertiary butyl) or
C1-4Alkoxy (for example, methoxyl group, ethyoxyl, positive oxygen propyl group, different oxygen propyl group, n-butoxy, sec-butoxy or tert-butoxy)；
The Rk、RlAnd RmIt independently is C8-10Alkyl (for example, n-octyl, n-nonyl or positive decyl).
DescribedPreferably in tributyl phosphate, dibutyl-butylphosphonate and dibutylphosphoric acid butyl ester it is a kind of or
It is a variety of.DescribedPreferably trioctyl phosphine oxide.The bis phosphoric acid ester type compound is preferably that the methylene tetrabutyl is double
Phosphate.
The described molar ratio such as formula (I) compound represented and the modification agent is preferably 0.3:1~2:1, for example,
0.8:1~1.2:1 or 1.2:1~2:1, in another example, 1:1 or 5:3.
In a preferred embodiment, described as formula (I) compound represented isModification agent is chlorination
Tricaprylmethylammonium.The described molar ratio such as formula (I) compound represented and the modification agent is preferably 0.8:1~1.2:
1, more preferably 1:1.
In a preferred embodiment, described as formula (I) compound represented isModification agent is three pungent
Ammonium methyl sulfate.The described molar ratio such as formula (I) compound represented and the modification agent is preferably 1.2:1~2:1,
More preferably 5:3.
In a preferred embodiment, described as formula (I) compound represented isModification agent is
Dibutyl-butylphosphonate.The described molar ratio such as formula (I) compound represented and the modification agent is preferably 0.8:1~
1.2:1, more preferably 1:1.
In a preferred embodiment, described as formula (I) compound represented isModification agent is chlorination
Dioctyl Methylsulfonium Salt.The described molar ratio such as formula (I) compound represented and the modification agent is preferably 0.8:1~
1.2:1, more preferably 1:1.
In a preferred embodiment, described as formula (I) compound represented isModification agent is chlorination
Three nonanylmethyl ammoniums.The described molar ratio such as formula (I) compound represented and the modification agent is preferably 0.8:1~1.2:
1, more preferably 1:1.
In a preferred embodiment, described as formula (I) compound represented isModification agent is tetramethyl
Ammonium chloride.The described molar ratio such as formula (I) compound represented and the modification agent is preferably 0.8:1~1.2:1, more
Preferably 1:1.
The extraction organic phase is that lithium extracts organic phase.
The present invention provides a kind of applications such as formula (I) compound represented in terms of extraction as previously described.Described
Extract preferred lithium extraction.
The present invention provides a kind of application of foregoing extractant in terms of extraction.The preferred lithium extraction of the extraction
It takes.The application may include following step：The water phase extraction for containing lithium ion with the extraction organic extractant phase, is layered,
Collect organic phase.
The pH value of the water phase containing lithium ion can be this field routine pH value, preferably 9~14, for example,
12~13 or 13~14.The pH value containing lithium ion can pass through the progress such as the hydroxide of addition alkali metal or ammonium hydroxide
It adjusts.The hydroxide of the alkali metal is preferably one or more in sodium hydroxide, potassium hydroxide and lithium hydroxide.
The water phase and the volume ratio of the extractant can be that this field is conventional, and the volume ratio of preferably the two is
30:1~1:30, for example, 1:1.
In the water phase containing lithium ion, the concentration of the lithium ion can be the concentration of this field routine, compared with
It is goodly 0.01mol/L~4.0mol/L, more preferably 0.05mol/L~0.2mol/L, for example, 0.05mol/L, 0.1mol/L
Or 0.2mol/L.
The temperature of the extraction can be this field routine temperature, preferably 10 DEG C -40 DEG C.
The application still further comprises back extraction, and the conventional stripping method for being stripped generic operation thus preferably wraps
Include following steps：Back washing agent and load the organic of lithium ion are mixed, balanced, the aqueous solution of load lithium ion is obtained
With organic phase.
In the back extraction, the back washing agent can be added disposably or by several times, preferably be added by several times.
In the back extraction, the mode of the mixing can be the mode of this field routine.It is preferred that oscillation mixing.
The acid can be the acid of this field routine, preferably inorganic acid.The inorganic acid can be that this field is conventional
Inorganic acid, it is preferably one or more in hydrochloric acid, sulfuric acid and nitric acid.
In the aqueous solution of the acid, H+Concentration can be this field routine H+Concentration, preferably 0.1mol/L~
10mol/L, such as 2.0mol/L, 4.0mol/L.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition can be combined arbitrarily each preferably to get the present invention
Example.
Agents useful for same of the present invention is commercially available, and part material, which synthesizes, can refer to Chem.Commun., and 2015,51,191-
194。
The positive effect of the present invention is that：
(1) present invention such as formula (I) compound represented convenient sources, it is at low cost, have oil-soluble excellent, water-soluble low
Advantage.
(2) modification agent of the invention has the characteristics that polarity is big, is soluble in organic phase, can improve extractant and extraction
Take the dissolubility of lithium complex；On the other hand, modification agent has phase transfer ability, lithium ion can be promoted to be transferred into from water phase
Organic phase, thus substantially increase the extraction yield of lithium ion.
(3) extraction organic phase provided by the invention and extracting process have extraction efficiency height, easy split-phase, operating method easy
The advantages of, while also there is outstanding lithium sodium, lithium potassium separation, it can realize the Selective Separation of lithium and otheralkali metal.
(4) extraction organic phase of the invention is easy to back extraction regeneration, recycles, and has higher economic benefit.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Embodiment 1
Prepare extraction organic phase, compound：A concentration of 0.11mol/L；Modification agent：Chlorination trioctylphosphine first
Base ammonium, a concentration of 0.11mol/L；Diluent：Chloroform.In water phase containing lithium, lithium concentration 0.05mol/L, chlorine ion concentration
0.05mol/L。
Extracting process：A certain amount of NaOH is added in water phase containing lithium, adjusts pH value=12~13, extractant organic phase and water phase
According to compared to 1:1, come into full contact with single-stage extraction.After standing split-phase, use the hydrochloric acid of 2mol/L as strip liquor, organic phase after back extraction
System recycling cycle, and obtain back extraction lithium product.Measure lithium concentration 0.042mol/L in extraction organic phase, the single-stage extraction of lithium
It is 84% to take rate.
Embodiment 2
Prepare extraction organic phase, compound：A concentration of 0.50mol/L；Modification agent：Tricaprylmethyl sulphur
Sour ammonium, a concentration of 0.30mol/L；Diluent：Methyln-hexyl ketone.In water phase containing lithium, lithium concentration 0.20mol/L, sulfate ion
Concentration 0.10mol/L.
Extracting process：A certain amount of NaOH is added in water phase containing lithium, adjusts pH value=13~14, extractant organic phase and water phase
According to compared to 1:1, come into full contact with single-stage extraction.After standing split-phase, use the hydrochloric acid of 2mol/L as strip liquor, organic phase after back extraction
System recycling cycle, and obtain back extraction lithium product.Measure lithium concentration 0.17mol/L in extraction organic phase, the single-stage extraction of lithium
It is 85% to take rate.
Embodiment 3
Prepare extraction organic phase, compound：A concentration of 0.60mol/L；Modification agent：Butyl phosphonic acids
Dibutyl ester, a concentration of 0.60mol/L；Diluent：Sulfonated kerosene.In water phase containing lithium, lithium concentration 0.15mol/L, sulfate radical
Ion concentration 0.05mol/L, hydroxide ion concentration 0.05mol/L.
Extracting process：A certain amount of NaOH is added in water phase containing lithium, adjusts pH value=14, extractant organic phase and water phase according to
Compared to 1:1, come into full contact with single-stage extraction.After standing split-phase, use the sulfuric acid of 2mol/L as strip liquor, organic phase system after back extraction
Recycling cycle, and obtain back extraction lithium product.Measure lithium concentration 0.096mol/L in extractant organic phase, the single-stage extraction of lithium
Rate is 64%.
Embodiment 4
Prepare extraction organic phase, compound：A concentration of 0.60mol/L；Modification agent：Chlorination dioctyl first
Base sulfonium salt, a concentration of 0.60mol/L；Diluent：Sulfonated kerosene.In water phase containing lithium, lithium concentration 0.10mol/L, sulfate radical
Ion concentration 0.05mol/L.
Extracting process：A certain amount of KOH is added in water phase containing lithium, adjusts pH value=13~14, extractant organic phase and water phase
According to compared to 1:1, come into full contact with single-stage extraction.After standing split-phase, use the hydrochloric acid of 2mol/L as strip liquor, organic phase after back extraction
System recycling cycle, and obtain back extraction lithium product.Measure lithium concentration 0.083mol/L in extractant organic phase, the single-stage of lithium
Extraction yield is 83%.
Embodiment 5
Prepare extraction organic phase, compound：A concentration of 0.60mol/L；Modification agent：Three nonyl first of chlorination
Base ammonium, a concentration of 0.60mol/L；Diluent：Sulfonated kerosene.In water phase containing lithium, lithium concentration 0.10mol/L, chlorion is dense
Spend 0.10mol/L.
Extracting process：A certain amount of ammonium hydroxide is added in water phase containing lithium, adjusts pH value=13~14, extractant organic phase and water phase
According to compared to 1:1, come into full contact with single-stage extraction.After standing split-phase, use the sulfuric acid of 2mol/L as strip liquor, organic phase after back extraction
System recycling cycle, and obtain back extraction lithium product.Measure lithium concentration 0.072mol/L in extractant organic phase, the single-stage of lithium
Extraction yield is 72%.
Embodiment 6
Prepare extraction organic phase, compound：A concentration of 0.50mol/L；Modification agent：Tetramethyl chlorination
Ammonium, a concentration of 0.50mol/L；Diluent：Dichloro-benzenes.In industrial wastewater containing lithium, lithium concentration 0.15mol/L, sodium ion is dense
0.85mol/L, potassium concentration 0.32mol/L, sulfate ion concentration 0.55mol/L, chlorine ion concentration 0.20mol/L are spent,
Bromide ion concentration 0.02.
Extracting process：Be added a certain amount of ammonium hydroxide in water phase containing lithium, adjust pH value=13~14, extract organic phase system with
Water phase is according to compared to 1:1, single-stage extraction is come into full contact with, split-phase is stood.Gained organic phase uses the hydrochloric acid of 2mol/L as back extraction
Liquid, organic phase system recycling cycle after back extraction, and back extraction lithium product is obtained, while measuring sodium in strip liquor, potassium concentration.It is real
Test the result shows that, the extractant have excellent lithium sodium, lithium potassium separating effect, lithium sodium separation β=5.1 × 102, lithium potassium point
From factor beta=1.3 × 103.Therefore, when there is otheralkali metal ion to be coexisted with lithium ion, which can be from complexity
In alkali metal mixed solution, highly selective extraction and separation lithium ion.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (11)
1. a kind of extraction organic phase, which is characterized in that it includes diluent, modification agent and such as formula (I) compound represented, described
A concentration of 0.05mol/L~2mol/L such as formula (I) compound represented in extracting organic phase；The modification agent is extracting
Take a concentration of 0.05mol/L~2mol/L in organic phase；
Wherein, X is O atom or S atom；
R1、R2、R3、R4、R5、R6、R7And R8It is each independently the C that hydrogen, halogen, nitro, unsubstituted or halogen replace1-6Alkyl,
Unsubstituted or R1-1The C of substituted phenyl, halogen substitution1-6Alkyl or R7、R8Coupled carbon is formed togetherThe R1-1For C1-6Alkyl or halogen；The R7a、R7b、R7cAnd R7dThe same R of definition1；
The modification agent is one or more in alkyl sulfonium, quarternary ammonium salt compound and phosphoric-oxygenic compound.
2. extraction organic phase as described in claim 1, which is characterized in that
The R1For hydrogen；
And/or the R2For hydrogen；
And/or the R3For hydrogen, C1-6Alkyl or the C of halogen substitution1-6Alkyl；
And/or the R4For hydrogen；
And/or the R5For hydrogen or halogen；
And/or the R6For hydrogen；
And/or the R7For hydrogen or halogen；
And/or the R8For hydrogen；
And/or the R7aFor hydrogen；
And/or the R7bFor hydrogen；
And/or the R7cFor hydrogen；
And/or the R7dFor hydrogen；
And/or the diluent is kerosene, heptane, octane, hexamethylene, n-hexane, amylalcohol, octanone, dodecane, chloroform, stone
Oily ether, carbon tetrachloride, toluene, dimethylbenzene, diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitromethane, 2- methyl cyclohexanones, methyl tert-butyl
It is one or more in ketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes and diphenyl ether；
And/or a concentration of 0.1mol/L~1mol/L such as formula (I) compound represented in extracting organic phase；
And/or a concentration of 0.1mol/L~1.0mol/L of the modification agent in extracting organic phase；
And/or it is described if formula (I) compound represented and the molar ratio of the modification agent are 0.3:1~2:1, for example,
0.8:1~1.2:1 or 1.2:1~2:1.
3. extraction organic phase as described in claim 1, which is characterized in that
Work as R1、R2、R3、R4、R5、R6、R7And R8When being each independently halogen, the halogen is fluorine, chlorine, bromine or iodine；
And/or the C of the halogen substitution1-6Halogen in alkyl is fluorine, chlorine, bromine or iodine；
And/or the C of the halogen substitution1-6C in alkyl1-6Alkyl is C1-4Alkyl, further preferred methyl, ethyl, just
Propyl, isopropyl, normal-butyl, sec-butyl or tertiary butyl, more preferably tertiary butyl；
And/or the C of the halogen substitution1-6Alkyl is trifluoromethyl；
And/or as the R1-1For C1-6When alkyl, the C1-6Alkyl is C1-4Alkyl, for example, methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl or tertiary butyl；
And/or as the R1-1For halogen when, the halogen be fluorine, chlorine, bromine or iodine；
And/or the cation of the alkyl sulfonium isRcAnd RdIt independently is C8-10Alkyl；
And/or the anion of the alkyl sulfonium is halogen ion；
And/or the cation of the quaternary ammonium salt isReFor C1-4Alkyl or C8-18Alkyl, RfAnd RgIt independently is benzyl
Base, phenyl or C8-18Alkyl；
And/or the anion of the quaternary ammonium salt is halogen ion or sulfate ion；
And/or the phosphoric-oxygenic compound isWith it is one or more in bis phosphoric acid ester type compound；
The RhFor C1-4Alkyl, the RiAnd RjIt independently is C1-4Alkyl or C1-4Alkoxy；The Rk、RlAnd RmIndependently
For C8-10Alkyl.
4. extraction organic phase as claimed in claim 3, which is characterized in that
The RcAnd RdIn, the C8-10Alkyl is octyl or nonyl；
And/or the Re、RfAnd RgIn, the C1-4Alkyl is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl
Base or tertiary butyl；
And/or the Re、RfAnd Rg, the C8-18Alkyl is C8-12Alkyl, for example, octyl, nonyl, decyl, undecyl
Or dodecyl；
And/or in the anion of the quaternary ammonium salt, the halogen ion is fluorine ion, chlorion, bromide ion or iodide ion；
And/or the anion of the quaternary ammonium salt be halogen ion when,In, ReFor methyl, octyl, nonyl or decyl, Rf
And RgIt independently is benzyl, phenyl, dodecyl, octyl, nonyl, decyl or octadecyl；
And/orIn, as the RhFor C1-4When alkyl, the C1-4Alkyl is methyl, ethyl, n-propyl, different
Propyl, normal-butyl, sec-butyl or tertiary butyl；
And/orIn, as the RiAnd RjIt independently is C1-4When alkyl, the C1-4Alkyl be methyl, ethyl,
N-propyl, isopropyl, normal-butyl, sec-butyl or tertiary butyl；
And/orIn, as the RiAnd RjIt independently is C1-4When alkoxy, the C1-4Alkoxy is methoxy
Base, ethyoxyl, positive oxygen propyl group, different oxygen propyl group, n-butoxy, sec-butoxy or tert-butoxy；
And/orIn, the C8-10Alkyl is n-octyl, n-nonyl or positive decyl；
And/or the bis phosphoric acid ester type compound is methylene tetrabutyl biphosphonate.
5. as Claims 1 to 4 any one of them extracts organic phase, which is characterized in that
It is described as formula (I) compound represented be in following compound it is one or more：
And/or the alkyl sulfonium is chlorination dioctyl Methylsulfonium Salt and/or chlorination dinonyl Methylsulfonium Salt；
And/or the quaternary ammonium salt is bromination didecyl Dimethy ammonium, chlorodimethyl benzyl phenyl ammonium, tricaprylmethyl
Ammonium sulfate, dodecyl dimethyl benzyl ammonium chloride, tricaprylylmethylammchloride chloride, three nonanylmethyl ammonium of chlorination, three decyl of chlorination
Methyl ammonium, tetramethyl ammonium chloride, (N- octadecyls) ammonium chloride of dimethyl two and one kind or more in tricaprylmethyl ammonium sulfate
Kind；
And/or the phosphoric-oxygenic compound is tributyl phosphate, dibutyl-butylphosphonate, dibutylphosphoric acid butyl ester, three n-octyls
Phosphine oxide and methylene tetrabutyl biphosphonate are one or more.
6. extraction organic phase as described in claim 1, which is characterized in that
It is described as formula (I) compound represented isModification agent is tricaprylylmethylammchloride chloride；It is described as
Formula (I) compound represented and the molar ratio of the modification agent are preferably 0.8:1~1.2:1, more preferably 1:1；
Or, described as formula (I) compound represented isModification agent is tricaprylmethyl ammonium sulfate；Described
If the molar ratio of formula (I) compound represented and the modification agent is preferably 1.2:1~2:1, more preferably 5:3；
Or, described as formula (I) compound represented isModification agent is dibutyl-butylphosphonate；Institute
State if the molar ratio of formula (I) compound represented and the modification agent is preferably 0.8:1~1.2:1, more preferably 1:1；
Or, described as formula (I) compound represented isModification agent is chlorination dioctyl Methylsulfonium Salt；It is described
If the molar ratio of formula (I) compound represented and the modification agent is preferably 0.8:1~1.2:1, more preferably 1:1；
Or, described as formula (I) compound represented isModification agent is three nonanylmethyl ammonium of chlorination；Described
If the molar ratio of formula (I) compound represented and the modification agent is preferably 0.8:1~1.2:1, more preferably 1:1；
Or, described as formula (I) compound represented isModification agent is tetramethyl ammonium chloride；It is described as
Formula (I) compound represented and the molar ratio of the modification agent are preferably 0.8:1~1.2:1, more preferably 1:1.
7. a kind of application as claimed in any one of claims 1 to 6 such as formula (I) compound represented in terms of extraction；Described
Extract preferred lithium extraction.
8. a kind of application of extraction organic phase as claimed in any one of claims 1 to 6 in terms of extraction, the extraction is lithium
Extraction.
9. application as claimed in claim 8, which is characterized in that the application may include following step：With the extraction
Organic extractant phase contains the water phase extraction of lithium ion, and organic phase is collected in layering.
10. application as claimed in claim 9, which is characterized in that
The pH value of the water phase containing lithium ion is 9~14；
And/or the acid-base value of the water phase containing lithium ion is adjusted by the hydroxide or ammonium hydroxide for adding alkali metal
Section；The hydroxide of the alkali metal is preferably one or more in sodium hydroxide, potassium hydroxide and lithium hydroxide；
And/or the water phase containing lithium ion and the volume ratio of the extractant are 30:1~1:30；
And/or in the water phase containing lithium ion, a concentration of 0.001mol/L~4.0mol/ of the lithium ion
L, preferably 0.05mol/L~0.2mol/L；
And/or the temperature of the extraction is 10 DEG C~40 DEG C.
11. the application as described in claim 9 or 10, which is characterized in that the application still further comprises back extraction；Described
Back extraction preferably includes following steps：Back washing agent and load the organic of lithium ion are mixed, balance, obtain load lithium from
The aqueous solution and blank organic phase of son；The back washing agent is the aqueous solution of acid；The acid is preferably inorganic acid, more excellent
It is selected as one or more in hydrochloric acid, sulfuric acid and nitric acid；
And/or in the back extraction, in the aqueous solution of the acid, H+A concentration of 0.1mol/L-10.0mol/L.
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