CN110331286B - Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine - Google Patents
Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine Download PDFInfo
- Publication number
- CN110331286B CN110331286B CN201910619651.1A CN201910619651A CN110331286B CN 110331286 B CN110331286 B CN 110331286B CN 201910619651 A CN201910619651 A CN 201910619651A CN 110331286 B CN110331286 B CN 110331286B
- Authority
- CN
- China
- Prior art keywords
- phosphine oxide
- extraction
- lithium
- salt lake
- alkyl phosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 29
- 239000012267 brine Substances 0.000 title claims abstract description 27
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 27
- -1 alkyl phosphine oxide compound Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 33
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 150000003613 toluenes Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical group CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- NLORAJAXZBEDKS-UHFFFAOYSA-N dicyclopentylphosphorylcyclopentane Chemical group C1CCCC1P(C1CCCC1)(=O)C1CCCC1 NLORAJAXZBEDKS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- KJLLKLRVCJAFRY-UHFFFAOYSA-N mebutizide Chemical compound ClC1=C(S(N)(=O)=O)C=C2S(=O)(=O)NC(C(C)C(C)CC)NC2=C1 KJLLKLRVCJAFRY-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/532—Cycloaliphatic phosphine oxides or thioxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
-
- 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
-
- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/382—Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses application of an alkyl phosphine oxide compound and a method for extracting lithium from salt lake brine, belonging to the technical field of extraction. The organic phase of the extraction system comprises alkyl phosphine oxide compounds which have phosphine oxide groups and Li+Coordinate with Li+And (4) extracting. Compared with the prior art, the extraction method has the characteristics of low cost, simple operation, high extraction efficiency, cleanness, environmental protection and the like, and most importantly, the extractant can not be hydrolyzed under the extraction condition, can be effectively used for a long time, and has important application value.
Description
Technical Field
The invention relates to the technical field of extraction, in particular to application of alkyl phosphine oxide compounds and a method for extracting lithium from salt lake brine.
Background
Lithium is used as a new strategic resource and is widely applied to the fields of medicine, aerospace, batteries, nuclear fusion power generation and the like. Lithium resources in nature mainly comprise solid ores and salt lake brine, the reserves of the salt lake resources in China are extremely rich, and the reserved amount of the lithium resources only found in the area of the Lidamia reaches over two million tons (measured by LiCl). With the increasing market demand, the extraction of lithium in salt lake brine has important strategic significance.
In the salt lake, lithium is associated with alkali metals and alkaline earth metals such as sodium, magnesium, potassium and the like mainly in an ion form, particularly the associated magnesium content is very high, and the magnesium/lithium ratio (mass ratio) in the brine is as high as 40-1200, so that the lithium is very difficult to separate and extract. Therefore, the efficient separation of lithium and magnesium is the key problem for extracting lithium from salt lake brine.
So far, the extraction method is one of the most promising methods for extracting lithium from brine, and the system with better effect is a tributyl phosphate-ferric chloride-kerosene system, and the system is relatively suitable for extracting lithium from the salt lake with high magnesium-lithium ratio. In the system, tributyl phosphate is extremely easy to hydrolyze, and a hydrolysate is easy to polymerize to form a complex solid oil substance which is insoluble in water and organic solvent, and the substance floats on the upper layer of the system and is extremely easy to block a pipeline, so that the extractant needs to be replaced in a short time, and the use cost is greatly increased.
The above problems still exist in the case of amide compounds and phosphate compounds as mixed extractants.
Because the salt lake in China has the characteristic of high magnesium-lithium ratio, the extraction method is one of the most effective modes with the most industrialized application prospect, and the lithium is required to be effectively extracted. However, due to the problems of the prior extractants, it is one of the most critical problems to find a new, mild extraction system or a substitute for an extractant
Disclosure of Invention
The technical task of the invention is to provide the application of alkyl phosphine oxide compounds aiming at the defects of the prior art.
A further technical task of the present invention is to provide a process for extracting lithium from salt lake brine.
The technical task of the invention is realized by the following modes:
the application of alkyl phosphine oxide compounds shown in formula (I) in lithium extraction,
wherein R is1、R2、R3Each independently is C4-C6Cycloalkyl or phenyl.
The alkyl phosphine oxide compound shown in formula (I) has phosphine oxide group and Li+Coordinate with Li+And the compound can be well applied to the extraction of lithium.
As a preferenceSaid R is1、R2、R3Both are cyclopentyl or both are phenyl.
The method for extracting lithium from salt lake brine is characterized in that an organic phase of an extraction system comprises alkyl phosphine oxide compounds shown as a formula (I).
Furthermore, the organic phase of the extraction system can also comprise a diluent so as to reduce the viscosity of the system, increase the extraction rate and accelerate the clarification time. The volume ratio of the diluent to the alkyl phosphine oxide compound in the extraction system is (0.9-4.5): 1, preferably (2-3): 1.
The diluent is solvent gasoline, sulfonated kerosene, toluene or xylene and the like.
The volume ratio of the organic phase to the raw brine (aqueous phase) in the extraction system is (0.9-2.1): 1, preferably (0.9-1.5): 1.
The concentration of lithium ions in the raw material brine is preferably (1.1-4.5) g/L.
In order to achieve a good extraction effect, the mass ratio of magnesium to lithium in the raw material brine is preferably (15-85): 1.
The alkyl phosphine oxide compound is an alkyl phosphine oxide compound with phosphine oxide groups, which is obtained by one-step oxidation reaction by taking trialkyl phosphine as a raw material.
The synthesis method comprises the following steps:
a. taking trialkyl phosphine as a starting material to perform oxidation reaction to generate alkyl phosphine oxide compounds;
b. adding a reducing substance to quench the reaction;
c. adding an organic reagent for extraction to obtain a crude product;
d. recrystallizing the crude product to obtain the pure product of alkyl phosphine oxide compounds.
The reaction process is as follows:
the specific method of step a is preferably: dissolving trialkyl phosphine serving as a starting material in an organic solvent, dropwise adding an oxidant, and reacting to generate the alkyl phosphine oxide compound.
The molar ratio of trialkylphosphine to oxidant is preferably 1: (1-1.5).
The substituent R of the trialkyl phosphine1、R2、R3Each independently is C4-C6Cycloalkyl or phenyl.
The oxidant can be hydrogen peroxide or potassium dichromate, and hydrogen peroxide is preferred.
The specific method of step b is preferably: a saturated solution of the reducing agent was slowly added dropwise to the reaction of a under ice bath.
The reducing substance in step b may be sodium sulfite, sodium iodide, sodium thiosulfate, or the like, and is preferably sodium sulfite.
The mol ratio of sodium sulfite to hydrogen peroxide is preferably (0.5-1): 1.
the specific method of step c is preferably: and c, adding an organic solvent into the system obtained in the step b, layering, collecting an organic phase, drying and concentrating to obtain the alkyl phosphine oxide compound.
The organic solvent may be dichloromethane, ethyl acetate, dichloroethane, etc., preferably dichloroethane.
The drying preferably removes the water from the organic phase with anhydrous sodium sulfate.
And the concentration is to remove the organic solvent by vacuum distillation of the dried solution, and to obtain a crude product after vacuum drying at 50 ℃ to constant weight.
The specific method of step d is preferably: and c, dissolving the crude product obtained in the step c in an organic solvent at a higher temperature, and reducing the temperature to obtain a pure product.
The organic solvent is toluene, xylene, etc., preferably toluene.
The higher temperature is the boiling point of the solvent.
And the temperature is reduced to-10-0 ℃.
Compared with the prior art, the application of the alkyl phosphine oxide compound and the method for extracting lithium from salt lake brine have the following outstanding beneficial effects:
the diluent is solvent gasoline, sulfonated kerosene, toluene or xylene, and the extraction cost is low.
The (di) alkyl phosphine oxide compound has extremely stable chemical structure, acid and alkali resistance, can not be decomposed in the extraction and back extraction processes, prolongs the service cycle, reduces the extraction cost, and is easier to popularize and apply and industrial production.
And (III) the single extraction rate of more than 50 percent can be achieved by shorter extraction time.
Detailed Description
The use of the alkylphosphine compounds of the present invention and the method of extracting lithium from salt lake brine are described in detail below with specific examples.
Unless otherwise specified, the contents of the respective components used below are weight percent contents.
The composition of the raw brine used in the experiments of the invention is shown in table 1:
TABLE 1 composition of brine (Qinghai salt lake boron extraction brine) (g/L)
The first embodiment is as follows:
the extractant is tricyclopentylphosphine oxide, and the structural formula is as follows:
36.2ml (35.7g, 0.122mol) (molecular weight 238.3, density 0.986) of tricyclopentylphosphine is added into a 500ml round-bottom flask, 150ml of absolute ethyl alcohol is added into the flask, the temperature of the system is reduced to 0 to-5 ℃, 30 percent hydrogen peroxide 0.139mol (15.8ml) is dropwise added into the system, the dropping speed is slow, and the temperature of the system cannot be higher than 5 ℃ in the whole dropping process. After the dropwise addition, the mixture was stirred at this temperature for 10min, and then the system was allowed to warm to room temperature and stirred for 4 hours. A saturated aqueous solution of sodium sulfite (13.5g, 0.107mol) was added dropwise to the system in an ice bath, and the reaction was quenched, and after the addition, stirring was continued at room temperature for 15 min.
The above solution was rotary evaporated to remove ethanol, 150ml of dichloromethane was added to the remaining aqueous solution, extracted, and the organic phase was extracted three times with 150ml of dichloromethane respectively, and the organic phases were combined. To the organic phase was added 23g of anhydrous magnesium sulfate, stirred for one hour, filtered with suction, rotary evaporated and the organic phase and remaining small amount of water removed. The temperature is reduced to minus ten degrees, and the white needle-shaped crystals are obtained after suction filtration, wherein the white needle-shaped crystals are 26.66g (69.1%). HMNR (400MH, deuterated toluene) δ 1.62, 9H; δ 1.55, 6H; δ 1.51,6H, δ 1.,49, 6H.31P(1H) NMR (202MH, deuterated toluene) delta 46.31.
[ EXTRACTION METHOD ]
Adding a volume of salt lake brine as shown in table 1 into a liquid separating funnel, adding a volume of organic phase (compared with O/A1), wherein the volume ratio of tricyclopentylphosphine oxide to sulfonated kerosene is 1:3, shaking for 2.5 minutes, standing and layering. Measurement of Li in the equilibrium aqueous phase+The single extraction rate of lithium was calculated to be 61.69%.
Example two:
the extracting agent is triphenylphosphine oxide, and the structural formula is as follows:
adding 22.15g of 84.4mmol of triphenylphosphine into a 500ml round-bottom flask, adding 300ml of absolute ethyl alcohol into the flask, cooling the system to 0 to-5 ℃, dropwise adding 8.4ml of 30% hydrogen peroxide into the system, wherein the dropwise adding speed is slow, and the system temperature cannot be higher than 5 ℃ in the whole dropwise adding process. After the dropwise addition, the mixture was stirred at this temperature for 10min, and then the system was allowed to warm to room temperature and stirred for 4 hours. Saturated aqueous sodium sulfite (13.5g, 63.4mmol) was added dropwise to the system under ice bath conditions, the reaction was quenched, and stirring was continued at room temperature for 15min after the addition.
The solution was rotary evaporated to remove ethanol, 250ml dichloromethane was added to the remaining aqueous solution, extracted, the organic phase was extracted three times with 250ml dichloromethane respectively and the organic phases were combined. To the organic phase was added 23g of anhydrous magnesium sulfate, and the mixture was stirred for one hourSuction filtering, rotary evaporating to eliminate organic phase and residual water. The temperature is reduced to minus ten degrees, and the white needle-shaped crystals are obtained after suction filtration, wherein 22.08g (94.7 percent) of white needle-shaped crystals are obtained. HMNR (400MH, deuterated toluene) δ 7.4-7.29, 15H.31P(1H) NMR (202MH, deuterated chloroform) delta-5.35.
[ EXTRACTION METHOD ]
Adding a volume of salt lake brine as shown in table 1 into a liquid separating funnel, adding a volume of organic phase (compared with O/A1), wherein the volume ratio of triphenylphosphine oxide to sulfonated kerosene is 1:3, shaking for 2 minutes, standing and layering. Measurement of Li in the equilibrium aqueous phase+The single extraction rate of lithium was calculated to be 62.15%.
Example three:
the extractant is tributyl phosphine oxide, and the structural formula is as follows:
40.1ml (32.77g, 0.162mmol) (molecular weight 202.3, density 0.817) of tributylphosphine is added into a 500ml round-bottom flask, 200ml of absolute ethyl alcohol is added into the flask, the temperature of the system is reduced to 0 to-5 ℃, 30 percent hydrogen peroxide 0.185mol (21ml) is dropwise added into the system, the dropping speed is slow, and the temperature of the system cannot be higher than 5 ℃ in the whole dropping process. After the dropwise addition, the mixture was stirred at this temperature for 10min, and then the system was allowed to warm to room temperature and stirred for 4 hours. And (3) dropwise adding a saturated sodium sulfite (18g, 0.142mol) aqueous solution into the system under the ice bath condition, quenching the reaction, and continuously stirring at room temperature for 15min after the dropwise adding is finished.
The above solution was rotary evaporated to remove ethanol, 200ml of dichloromethane was added to the remaining aqueous solution, extracted, and the organic phase was extracted three times with 200ml of dichloromethane respectively, and the organic phases were combined. To the organic phase was added 30g of anhydrous magnesium sulfate, stirred for one hour, filtered with suction, rotary evaporated and the organic phase and remaining small amount of water removed. The temperature was reduced to-ten degrees and suction filtration was carried out to obtain 25.46g (72.1%) of white needle-like crystals. HMNR (400MH, deuterated toluene) δ 1.23, 6H; δ 1.22, 6H; δ 0.89, 9H.31P(1H)NMR(202MH, deuterated toluene) delta 46.47.
[ EXTRACTION METHOD ]
Adding a volume of salt lake brine as shown in table 1 into a liquid separating funnel, adding a volume of organic phase (compared with O/A1), wherein the volume ratio of tributylphosphine oxide to sulfonated kerosene is 1:3, shaking for 3 minutes, and standing for layering. Measurement of Li in the equilibrium aqueous phase+The single extraction rate of lithium was calculated to be 58.71%.
From the first, second and third examples, it can be seen that the effect of cycloalkyl and aryl substituted oxyphosphorus compounds in salt lake brine extraction of lithium is better than that of long chain alkane substituted oxyphosphorus compounds.
Claims (1)
1. The method for extracting lithium from salt lake brine is characterized by comprising the following steps: mixing the raw material brine with the organic phase, shaking, standing and layering, wherein the volume ratio of the organic phase to the raw material brine is (0.9-2.1): 1,
the organic phase consists of an extracting agent and a diluting agent,
the extractant is an alkyl phosphine oxide compound shown in a formula (I),
wherein R is1、R2、R3Each independently is C4-C6A cycloalkyl group or a phenyl group of (a),
the diluent is solvent gasoline, sulfonated kerosene, toluene or xylene, and the volume ratio of the diluent to the alkyl phosphine oxide compound is (0.9-4.5): 1;
the concentration of lithium ions in the raw material brine is (1.1-4.5) g/L, and the mass ratio of magnesium to lithium is (15-85): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910619651.1A CN110331286B (en) | 2019-07-10 | 2019-07-10 | Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910619651.1A CN110331286B (en) | 2019-07-10 | 2019-07-10 | Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110331286A CN110331286A (en) | 2019-10-15 |
| CN110331286B true CN110331286B (en) | 2021-05-04 |
Family
ID=68145600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910619651.1A Expired - Fee Related CN110331286B (en) | 2019-07-10 | 2019-07-10 | Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110331286B (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770085A (en) * | 1991-06-12 | 1998-06-23 | Idaho Research Foundation, Inc. | Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts |
| JP4275795B2 (en) * | 1999-03-30 | 2009-06-10 | 高砂香料工業株式会社 | Phosphine derivatives having a vinyl group, polymers using the same, and transition metal complexes thereof |
| CN102312110B (en) * | 2010-07-09 | 2013-10-09 | 何涛 | Method for extracting alkali metal from salt lake brine and seawater through membrane extraction-back extraction |
| CN102516295A (en) * | 2011-11-01 | 2012-06-27 | 黑龙江大学 | Fluorenyl aromatic phosphine oxide, preparation method thereof and application thereof |
| CN103801194B (en) * | 2012-11-05 | 2017-08-29 | 中国科学院上海有机化学研究所 | A kind of extractant and its application for being used to separate lithium isotope |
| CN103086848B (en) * | 2013-01-28 | 2014-09-03 | 烟台德润液晶材料有限公司 | Dicyclohexylalkyl ether terminal olefines liquid crystal compound and preparation method thereof |
| CN106544506B (en) * | 2015-09-16 | 2018-10-26 | 金发科技股份有限公司 | A kind of extractant composition and the preparation method and application thereof |
| CN105331817B (en) * | 2015-12-01 | 2018-08-31 | 中国科学院青海盐湖研究所 | It is a kind of extraction alkali or alkaline earth metal extraction system and its application |
| CN106319244B (en) * | 2016-09-09 | 2018-08-14 | 山东省医学科学院药物研究所 | The application of functional ionic liquids and the method that lithium is extracted from salt lake bittern |
| CN106498184B (en) * | 2016-12-07 | 2019-04-26 | 青海柴达木兴华锂盐有限公司 | A kind of extraction system of lithium |
| CN107779612B (en) * | 2017-12-08 | 2019-12-13 | 中国科学院青海盐湖研究所 | Process for extracting lithium from alkaline brine |
| CN108004420B (en) * | 2017-12-08 | 2020-04-28 | 中国科学院青海盐湖研究所 | Centrifugal extractor-based process for extracting lithium from lithium-containing alkaline brine |
| CN108085490B (en) * | 2017-12-26 | 2020-04-28 | 青海恒信融锂业科技有限公司 | Extraction composition and method for enriching lithium |
-
2019
- 2019-07-10 CN CN201910619651.1A patent/CN110331286B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN110331286A (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Tailoring hydrophobic deep eutectic solvent for selective lithium recovery from the mother liquor of Li2CO3 | |
| CN106498184B (en) | A kind of extraction system of lithium | |
| Ashby et al. | The composition of “mixed hydride” reagents. A study of the Schlesinger reaction | |
| CN109438488A (en) | A kind of preparation method of liquid Lithium bis (oxalate) borate salt | |
| CN106521190A (en) | Purpose and method of amido-contained neutral phosphine extracting agent for extracting and separating zirconium and/or hafnium | |
| CN113736995A (en) | Application of carboxylic acid compound as extracting agent and metal ion extraction method | |
| CN109517985B (en) | Method for extracting and separating light rare earth elements by using bifunctional ionic liquid | |
| CN105561790A (en) | Application of benzo-azacrown ether compounds to separation of lithium isotopes | |
| CN105018753B (en) | A kind of method of composite extractant and the composite extractant extract and separate recovery indium | |
| CN110218866B (en) | P204Preparation method and application of polythiophene-doped light rare earth solid phase extractant | |
| CN114804048A (en) | Method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag | |
| CN110331286B (en) | Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine | |
| Zhao et al. | Extracting Li+ from high Na/Li solution and comparing the affinity of nonylphenol oxygen anion to Na+ and Li+ | |
| CN115197266B (en) | Method for purifying tri (2-cyanoethyl) phosphate | |
| CN113072573B (en) | Method for preparing chelated boron-based lithium salt by recycling electrolyte from waste lithium ion battery | |
| Li et al. | Dialkyl phosphinic acids: Synthesis and applications as extractant for nickel and cobalt separation | |
| CN106544506B (en) | A kind of extractant composition and the preparation method and application thereof | |
| CN110643836B (en) | Extraction system, extraction method and application for separating magnesium from magnesium-containing brine by using secondary amide/alkyl ester composite solvent to extract lithium | |
| CN102690286A (en) | Synthetic method of high-purity asymmetrical dialkyl phosphinic acid | |
| CN107619935B (en) | Extraction composition, extraction system and application thereof | |
| CN107619951B (en) | Extraction composition, extraction system and application thereof | |
| Liu et al. | Cobalt recovery from lithium battery leachate using hydrophobic deep eutectic solvents: Performance and mechanism | |
| CN107447118B (en) | Extraction composition, extraction system, extraction method and back extraction method | |
| CN107619933B (en) | Extraction composition, extraction system and application thereof | |
| CN107441767B (en) | Extraction composition, extraction system and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210504 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |