CN108754141B - Extracted organic phase and application thereof - Google Patents

Extracted organic phase and application thereof Download PDF

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CN108754141B
CN108754141B CN201810960718.3A CN201810960718A CN108754141B CN 108754141 B CN108754141 B CN 108754141B CN 201810960718 A CN201810960718 A CN 201810960718A CN 108754141 B CN108754141 B CN 108754141B
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modifier
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alkyl
compound shown
organic phase
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CN108754141A (en
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张伟
徐永昌
张丽君
胡金波
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses an extracted organic phase and application thereof. The extraction organic phase comprises a diluent, a modifier and a compound shown as a formula (I), wherein the concentration of the compound shown as the formula (I) in the extraction organic phase is 0.05-2 mol/L; the concentration of the modifier in the extracted organic phase is 0.05 mol/L-2 mol/L. The application can comprise the following steps: and extracting the aqueous phase containing lithium ions by using the extraction organic phase, layering, and collecting the organic phase. The extraction organic phase and the extraction method for extracting lithium provided by the invention have the advantages of high lithium ion extraction efficiency, easiness in phase separation and simplicity and convenience in operation method, and simultaneously have excellent lithium sodium and lithium potassium separation coefficients, and can realize high-selectivity separation of lithium and other alkali metals.

Description

Extracted organic phase and application thereof
Technical Field
The invention relates to an extracted organic phase and application thereof.
Background
Lithium is the metal element with the smallest density in nature, has the smallest atomic radius, and the simple metal substance and the compound thereof have different chemical and physical properties from many other metal elements, thereby having wide industrial application. The application of lithium and its compound relates to the fields of glass, ceramics, medicine, smelting and refrigeration. Especially in the new energy field, lithium is honored as "energy element", is the important raw materials of lithium cell, and global demand is increasing fast with 8 ~ 10% speed every year. On the other hand, lithium-6 and lithium-7, two stable isotopes of the lithium element, lithium-6 being an essential raw material in nuclear fusion reactors, and lithium-7 being a regulator and coolant in fission reactors, have important applications in the nuclear power field. Therefore, the method has very important social and economic benefits for the comprehensive development and utilization of lithium resources, particularly for the production and recovery of lithium by adopting an extraction method.
At present, lithium resources at home and abroad mainly come from lithium ores and lithium resources in salt lake brine. The technological process of extracting lithium salt from salt lake brine includes mainly precipitation, solvent extraction, ion exchange adsorption, carbonization, calcination, leaching, electrodialysis, etc.
The solvent extraction method is an efficient technology for separating and extracting lithium from a solution (such as lithium-containing brine, lithium-containing wastewater, lithium-precipitating mother liquor and the like), and has the advantages of simple process and equipment, continuous operation, easy realization of automatic control and the like. Among the common systems for extracting lithium reported in the prior art are: (1) tributyl phosphate TBP-ferric chloride extraction system; (2) extracting systems such as diketone thiophene formyl trifluoroacetone TTA, benzoylacetone HBA and the like; (3) pyrazolone chelate HPMBP-TBP system; (4) crown compound 15 crown 5, etc.; (5) neutral amide N-503 extraction system. However, the existing lithium extraction systems have problems, including low extraction efficiency and low lithium ion selectivity; the extractant has large water solubility and much loss; the density difference of two phases is small, and the phases are difficult to separate; the back extraction acidity is too large, and the consumption of reagents is large; the organic phase lithium load is too small; severe corrosion of equipment, etc.
Therefore, a high efficiency and high selectivity extraction method is needed.
Disclosure of Invention
The invention solves the technical problems of low efficiency and low selectivity in the existing method for recovering lithium, and provides an extraction organic phase and application thereof.
The invention solves the technical problems through the following technical scheme.
The invention provides an extraction organic phase, which comprises a diluent, a modifier and a compound shown as a formula (I), wherein the concentration of the compound shown as the formula (I) in the extraction organic phase is 0.05-2 mol/L; the concentration of the modifier in the extracted organic phase is 0.05 mol/L-2 mol/L;
Figure BDA0001773701630000021
wherein X is an O atom or an S atom;
R1、R2、R3、R4、R5、R6、R7and R8Each independently of the other being hydrogen, halogen (e.g. fluorine, chlorine, bromine or iodine), nitro, unsubstituted or halogen (e.g. fluorine, chlorine, bromine or iodine, and also for example fluorine) -substituted C1-6Alkyl (said C)1-6The alkyl group is preferably C1-4Alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, more preferably tert-butyl), unsubstituted or R1 -1Substituted phenyl (said R1-1May be one or more, when there are more than one R1-1When R is said1-1Same or different), halogen substituted C1-6Alkyl (e.g. trifluoromethyl) or R7、R8Together with the carbon to which they are attached to form
Figure BDA0001773701630000022
Said R1-1Is C1-6Alkyl (preferably C)1-4Alkyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl) or halogen (for example, fluorine, chlorine, bromine or iodine); the R is7a、R7b、R7cAnd R7dIs as defined for R1；
The modifier is one or more of alkyl sulfonium salt, quaternary ammonium salt compound and phosphorus oxide compound.
The diluent can be a conventional diluent in the extraction field, and is preferably one or more of kerosene, heptane, octane, cyclohexane, n-hexane, amyl alcohol, octanone, dodecane, chloroform, petroleum ether, carbon tetrachloride, toluene, xylene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, trichlorobenzene and diphenyl ether.
The concentration of the compound shown in the formula (I) in the extracted organic phase is preferably 0.1mol/L-1 mol/L, for example, 0.11mol/L, 0.50mol/L or 0.60 mol/L.
The concentration of the modifier in the extracted organic phase is 0.1mol/L to 1.0mol/L, for example, 0.11mol/L, 0.30mol/L, 0.60mol/L or 0.50 mol/L.
Said R1Hydrogen is preferred.
Said R2Hydrogen is preferred.
Said R3Preferably hydrogen, C1-6Alkyl or halogen substituted C1-6An alkyl group.
Said R4Hydrogen is preferred.
Said R5Preferably hydrogen or halogen.
Said R6Hydrogen is preferred.
Said R7Preferably hydrogen or halogen.
Said R8Hydrogen is preferred.
Said R7aHydrogen is preferred.
Said R7bHydrogen is preferred.
Said R7cHydrogen is preferred.
Said R7dHydrogen is preferred.
In some preferred embodiments, R1、R2And R4Is hydrogen, R3Is hydrogen or halogen substituted C1-6Alkyl, X is O or S, R5And R7Independently of one another is hydrogen or chlorine, R6And R8Independently of one another, said halogen substituted C1-6The alkyl group is preferably trifluoromethyl.
In some preferred embodiments, R1、R2、R4、R5And R6Is hydrogen, R3Is hydrogen or C1-6Alkyl, X is O or S,
Figure BDA0001773701630000031
is composed of
Figure BDA0001773701630000032
Said C1-6The alkyl group is preferably a tert-butyl group.
The compound shown in the formula (I) is preferably one or more of the following compounds:
Figure BDA0001773701630000041
the cation of the alkyl sulfonium salt is preferably
Figure BDA0001773701630000042
RcAnd RdIndependently is C8-10Alkyl groups (e.g., octyl, nonyl, or decyl). Said C is8-10The alkyl group is octyl, nonyl or decyl, preferably octyl or nonyl
The anion of the alkyl sulfonium salt may be an anion conventional in the art for alkyl sulfonium salts, preferably a halide ion (e.g., fluoride, chloride, bromide or iodide, and further e.g., chloride or bromide).
The alkyl sulfonium salt is preferably dioctyl methyl sulfonium chloride and/or dinonyl methyl sulfonium chloride.
The cation of the quaternary ammonium salt is preferably
Figure BDA0001773701630000043
ReIs C1-4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl) or C8-18Alkyl radical, RfAnd RgIndependently is benzyl, phenyl or C8-18Alkyl (preferably C)8-12Alkyl groups, for example, octyl, nonyl, decyl, undecyl or dodecyl).
The anion of the quaternary ammonium salt may be an anion conventional in the art for quaternary ammonium salts, preferably a halide (e.g., fluoride, chloride, bromide, or iodide, and further e.g., fluoride) or sulfate.
In the quaternary ammonium salt, when the anion is halide ion,
Figure BDA0001773701630000044
in (1), the R isePreferably methyl, octyl, nonyl or decyl, said RfAnd RgIndependently preferably methylBenzyl, phenyl, dodecyl, octyl, nonyl, decyl or octadecyl.
In the quaternary ammonium salt, when the anion is sulfate,
Figure BDA0001773701630000045
in (1), the R ise、RfAnd RgIndependently is preferably C8-10Alkyl groups (e.g., octyl, nonyl, or decyl).
The quaternary ammonium salt is preferably an alkyl quaternary ammonium salt, and preferably the quaternary ammonium salt is one or more of ditridecyldimethylammonium bromide, dimethylbenzylphenylammonium chloride, trioctylmethylammonium sulfate, dodecyldimethylbenzylammonium chloride, trioctylmethylammonium chloride, trinonylmethylammonium chloride, tridecylmethylammonium chloride, tetramethylammonium chloride, dimethyldioctadecylammonium chloride and trioctylmethylammonium sulfate.
The phosphorus-oxygen compound is preferably
Figure BDA0001773701630000051
And one or more of bisphosphates; said RhIs C1-4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl), said RiAnd RjIndependently is C1-4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl) or C1-4Alkoxy (e.g., methoxy, ethoxy, n-oxopropyl, iso-oxopropyl, n-butoxy, sec-butoxy or tert-butoxy); said Rk、RlAnd RmIndependently is C8-10Alkyl (e.g., n-octyl, n-nonyl, or n-decyl).
Said
Figure BDA0001773701630000052
Preferably one or more of tributyl phosphate, dibutyl butyl phosphonate and dibutyl butyl phosphate. Said
Figure BDA0001773701630000053
Trioctylphosphine oxide is preferred. The diphosphonate compound is preferably methylene tetrabutyl diphosphonate.
The molar ratio of the compound shown as the formula (I) to the modifier is preferably 0.3: 1-2: 1, for example, 0.8: 1-1.2: 1 or 1.2: 1-2: 1, and further for example, 1:1 or 5: 3.
In a preferred embodiment, the compound of formula (I) is
Figure BDA0001773701630000054
The modifier is trioctylmethylammonium chloride. The molar ratio of the compound shown as the formula (I) to the modifier is preferably 0.8: 1-1.2: 1, and more preferably 1: 1.
In a preferred embodiment, the compound of formula (I) is
Figure BDA0001773701630000055
The modifier is trioctyl ammonium methyl sulfate. The molar ratio of the compound shown as the formula (I) to the modifier is preferably 1.2: 1-2: 1, and more preferably 5: 3.
In a preferred embodiment, the compound of formula (I) is
Figure BDA0001773701630000061
The modifier is dibutyl butylphosphonate. The molar ratio of the compound shown as the formula (I) to the modifier is preferably 0.8: 1-1.2: 1, and more preferably 1: 1.
In a preferred embodiment, the compound of formula (I) is
Figure BDA0001773701630000062
The modifier is dioctyl methyl sulfonium chloride. The molar ratio of the compound shown as the formula (I) to the modifier is preferably 0.8: 1-1.2: 1, and more preferably 1: 1.
In a preferred embodiment, the compound of formula (I) is
Figure BDA0001773701630000063
The modifier is trinonyl methyl ammonium chloride. The molar ratio of the compound shown as the formula (I) to the modifier is preferably 0.8: 1-1.2: 1, and more preferably 1: 1.
In a preferred embodiment, the compound of formula (I) is
Figure BDA0001773701630000064
The modifier is tetramethylammonium chloride. The molar ratio of the compound shown as the formula (I) to the modifier is preferably 0.8: 1-1.2: 1, and more preferably 1: 1.
The extraction organic phase is a lithium extraction organic phase.
The invention provides application of the compound shown as the formula (I) in extraction. The extraction is preferably lithium extraction.
The invention provides an application of the extracting agent in extraction. The extraction is preferably lithium extraction. The application may comprise the steps of: and extracting the aqueous phase containing lithium ions by using the extraction organic phase, layering, and collecting the organic phase.
The pH of the aqueous phase containing lithium ions may be a pH as conventional in the art, preferably 9 to 14, for example, 12 to 13 or 13 to 14. The pH value of the lithium ion-containing solution can be adjusted by adding an alkali metal hydroxide, ammonia water, or the like. The alkali metal hydroxide is preferably one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
The volume ratio of the aqueous phase to the extractant can be conventional in the art, and preferably is 30:1 to 1:30, for example, 1: 1.
In the aqueous phase containing lithium ions, the concentration of the lithium ions may be a concentration conventional in the art, preferably 0.01mol/L to 4.0mol/L, more preferably 0.05mol/L to 0.2mol/L, for example, 0.05mol/L, 0.1mol/L or 0.2 mol/L.
The temperature of the extraction may be a temperature conventional in the art, preferably 10 ℃ to 40 ℃.
The use further comprises stripping, which is a conventional stripping process for such operations, preferably comprising the steps of: and mixing a stripping agent with the lithium ion-loaded organic phase, and balancing to obtain a lithium ion-loaded aqueous solution and an organic phase.
In the back extraction, the back extractant can be added at one time or in multiple times, and is preferably added in multiple times.
In the stripping, the mixing may be performed in a manner conventional in the art. Preferably by shaking.
The acid may be an acid conventional in the art, and preferably is an inorganic acid. The inorganic acid may be an inorganic acid conventional in the art, and preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.
In the aqueous solution of the acid, H+May be H as is conventional in the art+The concentration of (B) is preferably 0.1 to 10mol/L, for example, 2.0mol/L or 4.0 mol/L.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
Reagents used in the present invention are commercially available, and part of the raw material synthesis can be referred to chem.
The positive progress effects of the invention are as follows:
(1) the compound shown as the formula (I) has the advantages of convenient source, low cost, excellent oil solubility and low water solubility.
(2) The modifier has the characteristics of high polarity and easy dissolution in an organic phase, and can improve the solubility of an extracting agent and an extracted lithium complex; on the other hand, the modifier has phase transfer capacity and can promote the transfer of lithium ions from the water phase into the organic phase, thereby greatly improving the extraction rate of the lithium ions.
(3) The extraction organic phase and the extraction method provided by the invention have the advantages of high extraction efficiency, easiness in phase separation and simplicity and convenience in operation method, and simultaneously have excellent lithium sodium and lithium potassium separation coefficients, so that the selective separation of lithium and other alkali metals can be realized.
(4) The extracted organic phase is easy to back extract, regenerate and recycle, and has higher economic benefit.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Preparing an extraction organic phase, and mixing the following components:
Figure BDA0001773701630000081
the concentration is 0.11 mol/L; modifying agent: trioctylmethylammonium chloride at a concentration of 0.11 mol/L; diluent agent: chloroform. In the aqueous phase containing lithium, the concentration of lithium ion was 0.05mol/L and that of chloride ion was 0.05 mol/L.
The extraction method comprises the following steps: and adding a certain amount of NaOH into the lithium-containing water phase, adjusting the pH value to 12-13, and fully contacting the organic phase and the water phase of the extracting agent according to the ratio of 1:1 to perform single-stage extraction. After standing and phase splitting, 2mol/L hydrochloric acid is used as stripping liquid, and an organic phase system after stripping is recycled, so that a stripping lithium product is obtained. The concentration of lithium ions in the extracted organic phase was measured to be 0.042mol/L, and the single-stage extraction rate of lithium was 84%.
Example 2
Preparing an extraction organic phase, and mixing the following components:
Figure BDA0001773701630000082
the concentration is 0.50 mol/L; modifying agent: trioctylmethylammonium sulfate, the concentration is 0.30 mol/L; diluent agent: 2-octanone. In the aqueous phase containing lithium, the concentration of lithium ion was 0.20mol/L and the concentration of sulfate ion was 0.10 mol/L.
The extraction method comprises the following steps: and adding a certain amount of NaOH into the lithium-containing water phase, adjusting the pH value to 13-14, and fully contacting the organic phase and the water phase of the extracting agent according to the ratio of 1:1 to perform single-stage extraction. After standing and phase splitting, 2mol/L hydrochloric acid is used as stripping liquid, and an organic phase system after stripping is recycled, so that a stripping lithium product is obtained. The concentration of lithium ions in the extracted organic phase was measured to be 0.17mol/L, and the single-stage extraction rate of lithium was 85%.
Example 3
Preparing an extraction organic phase, and mixing the following components:
Figure BDA0001773701630000091
the concentration is 0.60 mol/L; modifying agent: dibutyl butyl phosphonate, the concentration is 0.60 mol/L; diluent agent: and (3) sulfonated kerosene. In the lithium-containing aqueous phase, the concentration of lithium ions is 0.15mol/L, the concentration of sulfate ions is 0.05mol/L, and the concentration of hydroxide ions is 0.05 mol/L.
The extraction method comprises the following steps: adding a certain amount of NaOH into the lithium-containing aqueous phase, adjusting the pH value to 14, and fully contacting the organic phase and the aqueous phase of the extracting agent according to the ratio of 1:1 to perform single-stage extraction. And (3) after standing and phase splitting, using 2mol/L sulfuric acid as stripping solution, and recycling the organic phase system after stripping to obtain a stripping lithium product. The concentration of lithium ions in the organic phase of the extractant was measured to be 0.096mol/L, and the single-stage extraction rate of lithium was 64%.
Example 4
Preparing an extraction organic phase, and mixing the following components:
Figure BDA0001773701630000092
the concentration is 0.60 mol/L; modifying agent: dioctyl methyl sulfonium chloride with the concentration of 0.60 mol/L; diluent agent: and (3) sulfonated kerosene. In the aqueous phase containing lithium, the concentration of lithium ion was 0.10mol/L and the concentration of sulfate ion was 0.05 mol/L.
The extraction method comprises the following steps: adding a certain amount of KOH into the lithium-containing water phase, adjusting the pH value to 13-14, and fully contacting the organic phase and the water phase of the extracting agent according to the ratio of 1:1 to perform single-stage extraction. After standing and phase splitting, 2mol/L hydrochloric acid is used as stripping liquid, and an organic phase system after stripping is recycled, so that a stripping lithium product is obtained. The lithium ion concentration in the organic phase of the extractant was found to be 0.083mol/L, and the single-stage extraction rate of lithium was found to be 83%.
Example 5
Preparing an extraction organic phase, and mixing the following components:
Figure BDA0001773701630000093
the concentration is 0.60 mol/L; modifying agent: trinonyl methylammonium chloride, concentration 0.60moL/L; diluent agent: and (3) sulfonated kerosene. In the aqueous phase containing lithium, the concentration of lithium ion was 0.10mol/L and the concentration of chloride ion was 0.10 mol/L.
The extraction method comprises the following steps: adding a certain amount of ammonia water into the lithium-containing water phase, adjusting the pH value to 13-14, and fully contacting the organic phase and the water phase of the extracting agent according to the ratio of 1:1 to perform single-stage extraction. And (3) after standing and phase splitting, using 2mol/L sulfuric acid as stripping solution, and recycling the organic phase system after stripping to obtain a stripping lithium product. The lithium ion concentration in the organic phase of the extractant is measured to be 0.072mol/L, and the single-stage extraction rate of lithium is 72 percent.
Example 6
Preparing an extraction organic phase, and mixing the following components:
Figure BDA0001773701630000101
the concentration is 0.50 mol/L; modifying agent: tetramethylammonium chloride with a concentration of 0.50 mol/L; diluent agent: dichlorobenzene. In the lithium-containing industrial wastewater, the concentration of lithium ions is 0.15mol/L, the concentration of sodium ions is 0.85mol/L, the concentration of potassium ions is 0.32mol/L, the concentration of sulfate ions is 0.55mol/L, the concentration of chloride ions is 0.20mol/L, and the concentration of bromide ions is 0.02.
The extraction method comprises the following steps: adding a certain amount of ammonia water into the lithium-containing water phase, adjusting the pH value to 13-14, fully contacting the extracted organic phase system with the water phase according to the ratio of 1:1, performing single-stage extraction, standing and phase splitting. And (3) taking 2mol/L hydrochloric acid as a back extraction solution, recycling the back extracted organic phase system, obtaining a back extraction lithium product, and simultaneously measuring the concentration of sodium ions and potassium ions in the back extraction solution. The experimental result shows that the extracting agent has excellent lithium sodium and lithium potassium separating effect, and the lithium sodium separating coefficient beta is 5.1 multiplied by 102The separation coefficient of lithium and potassium is 1.3 × 103. Therefore, when other alkali metal ions coexist with lithium ions, the extracting agent can extract and separate the lithium ions from a complex alkali metal mixed solution with high selectivity.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (22)

1. An extraction organic phase is characterized by comprising a diluent, a modifier and a compound shown as a formula (I), wherein the concentration of the compound shown as the formula (I) in the extraction organic phase is 0.05 mol/L-2 mol/L; the concentration of the modifier in the extracted organic phase is 0.05 mol/L-2 mol/L;
Figure FDA0002708247130000011
wherein X is an O atom or an S atom;
R1、R2、R3、R4、R5、R6、R7and R8Each independently hydrogen, halogen, nitro, unsubstituted or halogen-substituted C1-6Alkyl, unsubstituted or R1-1Substituted phenyl, halogen substituted C1-6Alkyl or R7、R8Together with the carbon to which they are attached to form
Figure FDA0002708247130000012
Said R1-1Is C1-6Alkyl or halogen; the R is7a、R7b、R7cAnd R7dIs as defined for R1；
The modifier is one or more of alkyl sulfonium salt, quaternary ammonium salt compound and phosphorus oxide compound.
2. The organic phase of claim 1, wherein,
said R1Is hydrogen;
and/or, said R2Is hydrogen;
and/or, said R3Is hydrogen, C1-6Alkyl or halogen substituted C1-6An alkyl group;
and/or, said R4Is hydrogen;
and/or, said R5Is hydrogen or halogen;
and/or, said R6Is hydrogen;
and/or, said R7Is hydrogen or halogen;
and/or, said R8Is hydrogen;
and/or, said R7aIs hydrogen;
and/or, said R7bIs hydrogen;
and/or, said R7cIs hydrogen;
and/or, said R7dIs hydrogen;
and/or the diluent is one or more of kerosene, heptane, octane, cyclohexane, n-hexane, amyl alcohol, octanone, dodecane, chloroform, petroleum ether, carbon tetrachloride, toluene, xylene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, trichlorobenzene and diphenyl ether;
and/or the concentration of the compound shown as the formula (I) in the extracted organic phase is 0.1-1 mol/L;
and/or the concentration of the modifier in the extracted organic phase is 0.1-1.0 mol/L;
and/or the molar ratio of the compound shown as the formula (I) to the modifier is 0.3: 1-2: 1.
3. The organic phase of claim 2,
the molar ratio of the compound shown as the formula (I) to the modifier is 0.8: 1-1.2: 1 or 1.2: 1-2: 1.
4. The organic phase of claim 1, wherein,
when R is1、R2、R3、R4、R5、R6、R7And R8When each is independently halogen, the halogen is fluorine, chlorine, bromine or iodine;
and/or, said halogen substituted C1-6Halogen in the alkyl is fluorine, chlorine, bromine or iodine;
and/or, said halogen substituted C1-6C in alkyl1-6Alkyl is C1-4An alkyl group;
and/or, said halogen substituted C1-6Alkyl is trifluoromethyl;
and/or, when said R is1-1Is C1-6When alkyl, said C1-6Alkyl is C1-4An alkyl group;
and/or, when said R is1-1When the halogen is fluorine, chlorine, bromine or iodine;
and/or, the cation of said alkyl sulfonium salt is
Figure FDA0002708247130000021
RcAnd RdIndependently is C8-10An alkyl group;
and/or, the anion of the alkyl sulfonium salt is a halide ion;
and/or, the cation of the quaternary ammonium salt is
Figure FDA0002708247130000022
ReIs C1-4Alkyl or C8-18Alkyl radical, RfAnd RgIndependently is benzyl, phenyl or C8-18An alkyl group;
and/or, the anion of the quaternary ammonium salt is halide ion or sulfate ion;
and/or the phosphorus-oxygen compound is
Figure FDA0002708247130000031
And one or more of bisphosphates; said RhIs C1-4Alkyl, said RiAnd RjIndependently is C1-4Alkyl or C1-4An alkoxy group; said Rk、RlAnd RmIndependently is C8-10An alkyl group.
5. The organic phase of claim 4,
said halogen substituted C1-6C in alkyl1-6Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl;
and/or, when said R is1-1Is C1-6When alkyl, said C1-6Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
6. The organic phase of claim 4,
said halogen substituted C1-6C in alkyl1-6The alkyl group is a tert-butyl group.
7. The organic phase of claim 4,
said RcAnd RdIn (A), the C8-10Alkyl is octyl or nonyl;
and/or, said Re、RfAnd RgIn (b), the C1-4Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, said Re、RfAnd RgSaid C is8-18Alkyl is C8-12An alkyl group;
and/or, in the anion of the quaternary ammonium salt, the halide ion is fluoride ion, chloride ion, bromide ion or iodide ion;
and/or, when the anion of the quaternary ammonium salt is a halide ion,
Figure FDA0002708247130000032
in, ReIs methyl, octyl, nonyl or decyl, RfAnd RgIndependently benzyl, phenyl, dodecyl, octyl, nonyl, decyl, or octadecyl;
and/or the presence of a gas in the gas,
Figure FDA0002708247130000033
when said R ishIs C1-4When alkyl, said C1-4Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl;
and/or the presence of a gas in the gas,
Figure FDA0002708247130000041
when said R isiAnd RjIndependently is C1-4When alkyl, said C1-4Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl;
and/or the presence of a gas in the gas,
Figure FDA0002708247130000042
when said R isiAnd RjIndependently is C1-4At alkoxy, said C1-4Alkoxy is methoxy, ethoxy, n-oxopropyl, iso-oxopropyl, n-butoxy, sec-butoxy or tert-butoxy;
and/or the presence of a gas in the gas,
Figure FDA0002708247130000043
in (b), the C8-10Alkyl is n-octyl, n-nonyl or n-decyl;
and/or the diphosphonate compound is methylene tetrabutyl diphosphonate.
8. The organic extract phase of claim 7, wherein R ise、RfAnd RgSaid C is8-18The alkyl group is octyl, nonyl, decyl, undecyl or dodecyl.
9. The organic phase for extraction according to any one of claims 1 to 8,
the compound shown in the formula (I) is one or more of the following compounds:
Figure FDA0002708247130000044
and/or, the alkyl sulfonium salt is dioctyl methyl sulfonium chloride and/or dinonyl methyl sulfonium chloride;
and/or the quaternary ammonium salt is one or more of ditridecyldimethylammonium bromide, dimethylbenzylammonium chloride, trioctylmethylammonium methosulfate, dodecyldimethylbenzylammonium chloride, trioctylmethylammonium chloride, trinonylmethylammonium chloride, tridecylmethylammonium chloride, tetramethylammonium chloride, dimethyldi (N-octadecyl) ammonium chloride and trioctylmethylammonium methosulfate;
and/or the phosphorus-oxygen compound is one or more of tributyl phosphate, dibutyl butyl phosphate, tri-n-octyl phosphine oxide and methylene tetra-butyl diphosphate.
10. The organic phase of claim 1, wherein,
the compound shown as the formula (I) is
Figure FDA0002708247130000051
The modifier is trioctylmethylammonium chloride;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000052
The modifier is trioctyl ammonium methyl sulfate;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000053
The modifier is dibutyl butylphosphonate;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000054
The modifier is dioctyl methyl sulfonium chloride;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000055
The modifier is trisnonyl ammonium methyl chloride;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000056
The modifier is tetramethylammonium chloride.
11. The organic phase of claim 10, wherein,
the compound shown as the formula (I) is
Figure FDA0002708247130000057
The modifier is trioctylmethylammonium chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 0.8: 1-1.2: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000058
The modifier is trioctyl ammonium methyl sulfate; the molar ratio of the compound shown as the formula (I) to the modifier is 1.2: 1-2: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000061
The modifier is dibutyl butylphosphonate; the molar ratio of the compound shown as the formula (I) to the modifier is 0.8: 1-1.2: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000062
The modifier is dioctyl methyl chlorideA sulfonium salt; the molar ratio of the compound shown as the formula (I) to the modifier is 0.8: 1-1.2: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000063
The modifier is trisnonyl ammonium methyl chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 0.8: 1-1.2: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000064
The modifier is tetramethylammonium chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 0.8: 1-1.2: 1.
12. The organic phase of claim 10, wherein,
the compound shown as the formula (I) is
Figure FDA0002708247130000065
The modifier is trioctylmethylammonium chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 1: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000066
The modifier is trioctyl ammonium methyl sulfate; the molar ratio of the compound shown as the formula (I) to the modifier is 5: 3;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000067
The modifier is dibutyl butylphosphonate; the molar ratio of the compound shown as the formula (I) to the modifier is 1: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000068
The modifier is dioctyl methyl sulfonium chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 1: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000071
The modifier is trisnonyl ammonium methyl chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 1: 1;
or, the compound shown as the formula (I) is
Figure FDA0002708247130000072
The modifier is tetramethylammonium chloride; the molar ratio of the compound shown as the formula (I) to the modifier is 1: 1.
13. Use of a compound of formula (I) according to any one of claims 1 to 12 for extraction.
14. Use according to claim 13, wherein the extraction is lithium extraction.
15. Use of an organic phase according to any one of claims 1 to 12 for extraction, said extraction being lithium extraction.
16. The use of claim 15, wherein said use comprises the steps of: and extracting the aqueous phase containing lithium ions by using the extraction organic phase, layering, and collecting the organic phase.
17. The use according to claim 16,
the pH value of the water phase containing the lithium ions is 9-14;
and/or the pH value of the aqueous phase containing the lithium ions is adjusted by adding hydroxide of alkali metal or ammonia water;
and/or the volume ratio of the water phase containing lithium ions to the extraction organic phase is 30: 1-1: 30;
and/or, in the water phase containing lithium ions, the concentration of the lithium ions is 0.001-4.0 mol/L;
and/or the temperature of the extraction is 10-40 ℃.
18. The use according to claim 17,
the hydroxide of the alkali metal is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide;
and/or, in the water phase containing the lithium ions, the concentration of the lithium ions is 0.05 mol/L-0.2 mol/L.
19. The use according to any one of claims 16 to 18, wherein said use further comprises stripping.
20. The use according to claim 19, wherein said stripping comprises the steps of: mixing a stripping agent with the lithium ion-loaded organic phase, and balancing to obtain a lithium ion-loaded aqueous solution and a blank organic phase; the stripping agent is an aqueous solution of acid.
21. The use of claim 20, wherein the acid in the aqueous acid solution is an inorganic acid;
and/or, in said stripping, in said aqueous acid solution, H+The concentration of (b) is 0.1mol/L to 10.0 mol/L.
22. The use of claim 20, wherein the acid in the aqueous acid solution is one or more of hydrochloric acid, sulfuric acid and nitric acid.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101193867A (en) * 2004-12-01 2008-06-04 Osi医药有限公司 N-substituted benzimidazolyl c-Kit inhibitors and combinatorial benzimidazole library
CN102089269A (en) * 2008-07-10 2011-06-08 罗地亚管理公司 Method for separating a carboxylic acid in salified form bearing at least one halogen atom.
CN102659708A (en) * 2012-05-21 2012-09-12 北京化工大学 Structure and preparation method for heterocyclic aryl acetylene compounds containing benzoxazole and benzothiazole groups
CN103044414A (en) * 2012-12-05 2013-04-17 天津科技大学 Benzothiazole derivative, preparation method and application thereof
CN103102314A (en) * 2012-01-12 2013-05-15 四川大学 Benzothiazole, benzimidazole, benzoxazole derivatives and preparation method and application thereof
CN105111161A (en) * 2015-09-18 2015-12-02 浙江农林大学暨阳学院 Method for efficiently synthesizing 2-phenylbenzoxazole and derivatives of 2-phenylbenzoxazole through coupling and series connection
WO2016109492A1 (en) * 2014-12-31 2016-07-07 Angion Biomedica Corp Methods and agents for treating disease
CN106565629A (en) * 2016-10-27 2017-04-19 温州大学 Synthesis method of 2-phenylselenic benzothiazole compound
CN108103317A (en) * 2017-12-22 2018-06-01 中国科学院上海有机化学研究所 A kind of method that lithium is recycled from waste liquid containing lithium

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101193867A (en) * 2004-12-01 2008-06-04 Osi医药有限公司 N-substituted benzimidazolyl c-Kit inhibitors and combinatorial benzimidazole library
CN102089269A (en) * 2008-07-10 2011-06-08 罗地亚管理公司 Method for separating a carboxylic acid in salified form bearing at least one halogen atom.
CN103102314A (en) * 2012-01-12 2013-05-15 四川大学 Benzothiazole, benzimidazole, benzoxazole derivatives and preparation method and application thereof
CN102659708A (en) * 2012-05-21 2012-09-12 北京化工大学 Structure and preparation method for heterocyclic aryl acetylene compounds containing benzoxazole and benzothiazole groups
CN103044414A (en) * 2012-12-05 2013-04-17 天津科技大学 Benzothiazole derivative, preparation method and application thereof
WO2016109492A1 (en) * 2014-12-31 2016-07-07 Angion Biomedica Corp Methods and agents for treating disease
CN105111161A (en) * 2015-09-18 2015-12-02 浙江农林大学暨阳学院 Method for efficiently synthesizing 2-phenylbenzoxazole and derivatives of 2-phenylbenzoxazole through coupling and series connection
CN106565629A (en) * 2016-10-27 2017-04-19 温州大学 Synthesis method of 2-phenylselenic benzothiazole compound
CN108103317A (en) * 2017-12-22 2018-06-01 中国科学院上海有机化学研究所 A kind of method that lithium is recycled from waste liquid containing lithium

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