CN115819396A - Alcohol removing method and device for crown ether additive for lithium battery electrolyte - Google Patents
Alcohol removing method and device for crown ether additive for lithium battery electrolyte Download PDFInfo
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- CN115819396A CN115819396A CN202211455688.3A CN202211455688A CN115819396A CN 115819396 A CN115819396 A CN 115819396A CN 202211455688 A CN202211455688 A CN 202211455688A CN 115819396 A CN115819396 A CN 115819396A
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- Prior art keywords
- crown ether
- alcohol
- crown
- rectifying tower
- lithium battery
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- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003792 electrolyte Substances 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000654 additive Substances 0.000 title claims abstract description 19
- 230000000996 additive effect Effects 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000012544 monitoring process Methods 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 7
- -1 aliphatic crown ether Chemical class 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZICJVWKUZQNARJ-UHFFFAOYSA-N 1,4,7,10,13,16,19,22,25,28-decaoxacyclotriacontane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCOCCOCCO1 ZICJVWKUZQNARJ-UHFFFAOYSA-N 0.000 description 1
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 1
- XKEHLMZHBXCJGZ-UHFFFAOYSA-N 1,4,7,10,13,16,19-heptaoxacyclohenicosane Chemical compound C1COCCOCCOCCOCCOCCOCCO1 XKEHLMZHBXCJGZ-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- LNNVNAOXLAULPK-UHFFFAOYSA-N 17-tert-butyl-2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene Chemical compound O1CCOCCOCCOCCOC2=CC(C(C)(C)C)=CC=C21 LNNVNAOXLAULPK-UHFFFAOYSA-N 0.000 description 1
- HOWRGZDIVIHRJM-UHFFFAOYSA-N 2,3,5,6-tetrahydro-1,4,7-benzotrioxonine Chemical compound O1CCOCCOC2=CC=CC=C21 HOWRGZDIVIHRJM-UHFFFAOYSA-N 0.000 description 1
- BWSWAIJRFXRRFY-UHFFFAOYSA-N 2,5,8,11,14,17,20,23,26,29-decaoxabicyclo[28.4.0]tetratriaconta-1(34),30,32-triene Chemical compound O1CCOCCOCCOCCOCCOCCOCCOCCOCCOC2=CC=CC=C21 BWSWAIJRFXRRFY-UHFFFAOYSA-N 0.000 description 1
- OUAWYEKLKCARAD-UHFFFAOYSA-N 2,5,8,11,14,17,20,23,26-nonaoxabicyclo[25.4.0]hentriaconta-1(31),27,29-triene Chemical compound O1CCOCCOCCOCCOCCOCCOCCOCCOC2=CC=CC=C21 OUAWYEKLKCARAD-UHFFFAOYSA-N 0.000 description 1
- NJYSMUZHMILTRA-UHFFFAOYSA-N 2,5,8,11,14,17,20,23-octaoxabicyclo[22.4.0]octacosa-1(28),24,26-triene Chemical compound O1CCOCCOCCOCCOCCOCCOCCOC2=CC=CC=C21 NJYSMUZHMILTRA-UHFFFAOYSA-N 0.000 description 1
- DZWYQRMUCPSDQK-UHFFFAOYSA-N 2,5,8,11,14,17,20-heptaoxabicyclo[19.4.0]pentacosa-1(25),21,23-triene Chemical compound O1CCOCCOCCOCCOCCOCCOC2=CC=CC=C21 DZWYQRMUCPSDQK-UHFFFAOYSA-N 0.000 description 1
- DSFHXKRFDFROER-UHFFFAOYSA-N 2,5,8,11,14,17-hexaoxabicyclo[16.4.0]docosa-1(22),18,20-triene Chemical compound O1CCOCCOCCOCCOCCOC2=CC=CC=C21 DSFHXKRFDFROER-UHFFFAOYSA-N 0.000 description 1
- GQRWGIWRQMNZNT-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadecane Chemical compound O1CCOCCOCCOCCOC2CCCCC21 GQRWGIWRQMNZNT-UHFFFAOYSA-N 0.000 description 1
- OAJNZFCPJVBYHB-UHFFFAOYSA-N 2,5,8,11-tetraoxabicyclo[10.4.0]hexadeca-1(16),12,14-triene Chemical compound O1CCOCCOCCOC2=CC=CC=C21 OAJNZFCPJVBYHB-UHFFFAOYSA-N 0.000 description 1
- GHYKVVHGPCZVOG-UHFFFAOYSA-N 6,7,9,10,12,13,15,16,23,24,26,27,29,30-tetradecahydrodibenzo[b,n][1,4,7,10,13,16,19,22,25]nonaoxacycloheptacosine Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 GHYKVVHGPCZVOG-UHFFFAOYSA-N 0.000 description 1
- RCIDBLLMZGGECJ-UHFFFAOYSA-N 9-crown-3 Chemical group C1COCCOCCO1 RCIDBLLMZGGECJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QSBFECWPKSRWNM-UHFFFAOYSA-N dibenzo-15-crown-5 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 QSBFECWPKSRWNM-UHFFFAOYSA-N 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- JKCQOMAQPUYHPL-UHFFFAOYSA-N dibenzo-21-crown-7 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 JKCQOMAQPUYHPL-UHFFFAOYSA-N 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- MXCSCGGRLMRZMF-UHFFFAOYSA-N dibenzo-30-crown-10 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C2OCCOCCOCCOCCOC2=CC=CC=C21 MXCSCGGRLMRZMF-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XPSQBNPZMNWIPV-UHFFFAOYSA-N ethenoxyperoxyethene Chemical compound C=COOOC=C XPSQBNPZMNWIPV-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for removing alcohol from crown ether additive for lithium battery electrolyte, alcohol-containing crown ether is firstly esterified by alcohol through specific anhydride reaction, then neutralized by alkali, and finally decompressed and rectified to obtain alcohol-free crown ether. The method has the following advantages: 1) The alcohol removing efficiency is high, and the alcohol content in the crown ether can be reduced to below 20ppm by one-time treatment; 2) The material loss is small, the front fraction and the heavy components are repeatedly used in the system, and the comprehensive yield of the alcohol-free crown ether can reach more than 97 percent; 3) The waste is less, the alkali liquor can be repeatedly used for many times, and the generated solid waste amount is only equivalent to the alcohol content.
Description
Technical Field
The invention relates to a dealcoholization method, in particular to a dealcoholization method and a dealcoholization device of a crown ether additive for a lithium battery electrolyte.
Background
In general, in a lithium battery, graphite is used as a negative electrode, a transition metal oxide of lithium is used as a positive electrode, and organic substances such as alkyl carbonate are used as an electrolyte solvent, and the compatibility among the materials becomes one of important factors affecting the performance of the battery.
The aliphatic crown ether is crown ether with a molecular structure unit of epoxy vinyl ether (CH 3CH 3O), has the effects of fuzzy phase interface, compatibility improvement, solubility improvement, ionization degree and conductivity improvement through coordination with metal cations and the like, and is mainly composed of 12-crown ether-4, 15-crown ether-5, 18-crown ether 6 and the like.
The lithium battery electrolyte that is currently the mainstream is lithium hexafluorophosphate (LiPF) 6 ) The electrolyte is prepared by adding various additives into lithium salt containing fluorine as a solute and carbonates as a solvent, and the addition of the aliphatic crown ether can improve the compatibility of the electrolyte and the electrolyte with anode, cathode and diaphragm materials, and has the effects of inhibiting irregular precipitation of metals, forming a film on the surface of an electrode, reducing side reactions of the solvent, solubilizing the electrolyte, improving the ionic conductivity, improving the performance of the solid electrolyte and the like.
Lithium hexafluorophosphate reacts with active hydrogen-containing substances such as moisture, alcohols, and carboxylic acids to generate harmful hydrogen fluoride, which lowers the charge/discharge capacity of the lithium battery, and therefore the electrolyte solution generally needs to have a moisture, alcohol, and carboxylic acid content of 20ppm or less. Wherein, the moisture can be removed by a molecular sieve adsorption mode, and the method is a conventional operation in the field of electrolyte additives. However, when the company respectively produces 18-crown-6 and 15-crown-5 by using patent technologies CN103275059B and CN104230881B, triethylene glycol is adopted as a principle, and triethylene glycol residue exceeding 500ppm can be detected in the finished crown ether product, so that the use requirement of the electrolyte is difficult to meet.
Triethylene glycol and crown ether have similar structures and boiling points, are difficult to separate by rectification, extraction, adsorption, crystallization and other modes, and a removal method is not reported in a published document.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an alcohol-free crown ether obtained by firstly esterifying alcohol by using specific anhydride reaction, then neutralizing by using alkali and finally carrying out vacuum rectification, and is a method and a device for removing alcohol from a crown ether additive for lithium battery electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
the alcohol removing method of the crown ether additive for the lithium battery electrolyte comprises the following steps:
(1) adding excessive anhydride according to the content of alcoholic hydroxyl in the crown ether, and heating to 120-200 ℃ to convert alcohol into ester;
(2) adding the mixed solution containing alkali metal hydroxide to neutralize acidic substances;
(3) and carrying out vacuum rectification to obtain a purified product.
Preferably, the crown ether in step (1) has an alcohol content of 100 to 10000ppm; the acid anhydride is one or more of acetic anhydride, propionic anhydride, malonic anhydride, butyric anhydride, succinic anhydride and benzoic anhydride.
Preferably, the alkali metal hydroxide in step (2) is one or more of sodium hydroxide and potassium hydroxide.
Preferably, after the material in the step (2) is heated to 150 ℃, starting a vacuum system for vacuum rectification, wherein the reflux ratio is 8-12; for 15-crown ether-5, the outlet temperature under reduced pressure is 160 ℃ or lower, the front fraction is the product fraction at 160-190 ℃; for 18-crown ether-6, the outlet temperature under reduced pressure is 180 ℃ or lower to obtain front fraction, and the outlet temperature under reduced pressure is 180-210 ℃ to obtain product fraction;
after the rectification is completed, the front cut fraction and the residual liquid are mixed to be used as the mixed liquid containing the alkali metal hydroxide in the step (2).
Preferably, the molar ratio of the added anhydride to the alcohol contained in the crown ether is 1 to 3.
The utility model provides a device that removes alcohol of crown ether additive for lithium cell electrolyte, includes presss from both sides cover reation kettle (3), rectifying column cauldron (5), condenser (10) and vacuum system (9), it is connected with rectifying column cauldron (5) to press from both sides cover reation kettle (3), the upper portion of rectifying column cauldron (5) is equipped with ceramic packing layer (8), condenser (10) and ceramic packing layer (8) are mutually linked, vacuum system (9) link to each other with condenser (10).
Preferably, the rectifying tower kettle (5) is filled with alcohol-containing crown ether and alkali metal hydroxide powder, and is stirred to form a suspension (7);
mixing alcohol-containing crown ether with anhydride in the jacketed reaction kettle (3), heating and stirring to complete esterification, pressing the reaction material to a rectifying tower kettle (5) by using nitrogen, heating and stirring;
after the rectifying tower kettle (5) is heated to 150 ℃, starting a vacuum system (9), condensing gas flowing out of the top of the rectifying tower kettle (5) through a condenser (10), adjusting the proportion of a reflux material and a distillate material, and collecting a front fraction; and (3) after the temperature of the material at the top outlet of the rectifying tower kettle (5) reaches the target temperature, replacing the receiving tank and collecting the target crown ether product.
Preferably, the pH value of the distillation tower bottom (5) is monitored, the pH value is maintained to be more than 10, when the pH value is reduced to be less than 10, after the distillation is finished, the suspension (7) of the distillation tower bottom (5) is sent out and cooled to 50 ℃, the solid is removed by filtration, the filtrate is sent back to the distillation tower bottom (5), and alkali metal hydroxide powder is supplemented.
Preferably, if the pH is less than 10, the alkali metal hydroxide is immediately supplemented.
Preferably, the vacuum system has an adjusted reflux ratio of 10; the mixed liquid in the jacket reaction kettle enters the rectifying tower under the pressure difference.
The crown ethers are aliphatic crown ethers and derivatives thereof, for example, the crown ether is 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, 30-crown-10, benzo-9-crown-3, benzo-12-crown-4, benzo-15-crown-5, benzo-18-crown-6, benzo-21-crown-7, benzo-24-crown-8, benzo-27-crown-9, benzo-30-crown-10, dibenzo-9-crown-3, dibenzo-12-crown-4, dibenzo-9-crown-4, or dibenzo-15-crown-5, dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, dibenzo-27-crown-9, dibenzo-30-crown-10, cyclohexyl-9-crown-3, cyclohexyl-12-crown-4, cyclohexyl-15-crown-5, cyclohexyl-18-crown-6, cyclohexyl-21-crown-7, cyclohexyl-24-crown-8, cyclohexyl-27-crown-9, cyclohexyl-30-crown-10, dicyclohexyl-9-crown-3, cyclohexyl-21-crown-9, cyclohexyl-9-crown-10, cyclohexyl-9-crown-3, and mixtures thereof, <xnotran> -12- -4, -15- -5, -18- -6, -21- -7, -24- -8, -27- -9, -30- -10, -9- -3, -12- -4, -15- -5, -18- -6, -21- -7, -24- -8, -27- -9, -30- -10, -9- -3, -12- -4, -15- -5, -18- -6, -21- -7, -24- -8, -27- -9, -30- -10, -9- -3, -12- -4, -15- -5, -18- -6, -21- -7, -24- -8, -27- -9, </xnotran> Dodecyl-30-crown-10, 4-tert-butylbenzo-9-crown-3, 4-tert-butylbenzo-12-crown-4, 4-tert-butylbenzo-15-crown-5, 4-tert-butylbenzo-18-crown-6, 4-tert-butylbenzo-21-crown-7, 4-tert-butylbenzo-24-crown-8, 4-tert-butylbenzo-27-crown-9, 4-tert-butylbenzo-30-crown-10, 4' -di-tert-butyldibenzo-9-crown-3, 4' -di-tert-butyldibenzo-12-crown-4, 4' -di-tert-butyldibenzo-15-crown-5, etc 4,4' -di-tert-butyldibenzo-18-crown-6, 4' -di-tert-butyldibenzo-21-crown-7, 4' -di-tert-butyldibenzo-24-crown-8, 4' -di-tert-butyldibenzo-27-crown-9, 4' -di-tert-butyldibenzo-30-crown-10, and mixtures thereof 4,4' -di-tert-butylcyclohexa-9-crown-3, 4-tert-butylcyclohexa-12-crown-4, 4-tert-butylcyclohexa-15-crown-5, 4-tert-butylcyclohexa-18-crown-6, 4-tert-butylcyclohexa-21-crown-7, 4-tert-butylcyclohexa-24-crown-8, 4-tert-butylcyclohexa-27-crown-9, 4-tert-butylcyclohexa-30-crown-10, 4' -di-tert-butylcyclohexa-12-crown-4, 4' -di-tert-butylcyclohexa-15-crown-5 4,4' -di-tert-butylcyclohexa-18-crown-6, 4' -di-tert-butylcyclohexa-21-crown-7, 4' -di-tert-butylcyclohexa-24-crown-8, 4' -di-tert-butylcyclohexa-27-crown-9, 4' -di-tert-butylcyclohexa-30-crown-10.
The jacketed reaction kettle in the step (1) can be heated by steam or heat conducting oil.
And (3) the pressure difference of the mixed liquid in the jacket reaction kettle in the step (2) can be realized by filling nitrogen into the polymerization kettle or starting a vacuum system of the rectifying tower.
The rectifying tower is divided into an upper part and a lower part, the inner diameter of a tower kettle at the lower part is larger, a stirring and heating jacket is arranged, the inner diameter of the upper part of the rectifying tower is relatively smaller, and ceramic filler is arranged. Under heating, the material distilled from the top of the rectification column is condensed by a condenser and then collected. The gas phase pipeline on the upper part of the condenser is connected with a vacuum system, and the pressure in the rectifying tower is controlled by a valve.
The pH of the bottom liquid of the rectification column is monitored. After neutralization, the mixed liquid in the tower bottom is centrifuged, the supernatant is skimmed off, and the residual solid is prepared into 1% aqueous solution. If the pH value is reduced to 10-11, the tower bottom liquid is sent out and cooled to 50 ℃ after the rectification is finished, the solid is removed by filtration, the filtrate is sent back to the tower bottom, and alkali metal hydroxide is supplemented; if the pH is less than 10, the alkali metal hydroxide is added immediately.
The crown ether dealcoholization method can bring hundreds ppm of ester compounds into the finished crown ether product, and does not cause obvious negative effects on the electrolyte and does not need further purification.
The invention provides a method for removing alcohol from crown ether additive for lithium battery electrolyte, which has the following advantages:
1) The alcohol removing efficiency is high, and the alcohol content in the crown ether can be reduced to below 20ppm by one-time treatment;
2) The material loss is small, the front fraction and the heavy components are repeatedly used in the system, and the comprehensive yield of the alcohol-free crown ether can reach more than 97 percent;
3) The waste is less, the alkali liquor can be repeatedly used for many times, and the generated solid waste amount is only equivalent to the alcohol content.
Drawings
FIG. 1 is a flow diagram of the alcohol removal process of the present invention.
Description of reference numerals: 1. an alcohol-containing crown ether; 2. an acid anhydride; 3. a jacket reaction kettle; 4. reaction materials; 5. a rectifying tower kettle; 6. an alkali metal hydroxide powder; 7. suspending liquid; 8. a ceramic packing layer; 9. a vacuum system; 10. a condenser; 11. refluxing the material; 12. distilling the materials; 13. and (4) ejecting the material from the opening.
Detailed Description
The invention is further described by the following detailed description in conjunction with the accompanying drawings.
Example 1:1kg of 18-crown ether-6 with the triethylene glycol content of 1840ppm and 2.5g of acetic anhydride are mixed in a jacketed reaction kettle, heated to 140 ℃, kept warm and reacted for 2 hours, nitrogen is pressed to a rectifying tower kettle filled with 200g of 18-crown ether-6 and 10g of anhydrous potassium hydroxide powder mixed suspension, the temperature is raised to 150 ℃ by stirring, and the pH value of the rectifying tower kettle is monitored to be 12.91.
Starting the vacuum system, and adjusting the reflux ratio to be 10. Heating the kettle of the rectifying tower to 220 ℃, collecting 44g of front fraction with the outlet temperature below 180 ℃, continuing heating the kettle of the rectifying tower to 240 ℃ after collecting the crown ether product, and stopping rectifying after collecting 1000g of the crown ether product.
The obtained crown ether product was not detected by gas chromatography, and the detection limit was 10ppm, as follows.
Example 2:
1kg of 15-crown ether-5 with triethylene glycol content of 1280ppm and 5.8g of benzoic anhydride are mixed in a jacketed reaction kettle, heated to 160 ℃, kept warm and reacted for 2 hours, nitrogen is pressed to a rectifying tower kettle filled with 200g of 15-crown ether-5 and 10g of anhydrous sodium hydroxide powder mixed suspension, the temperature is raised to 150 ℃ by stirring, and the pH value of the rectifying tower kettle is monitored to be 13.47.
Starting the vacuum system, and adjusting the reflux ratio to be 10. Heating the kettle of the rectifying tower to 190 ℃, collecting 36g of front fraction with the outlet temperature below 160 ℃, continuing heating the kettle of the rectifying tower to 220 ℃ after collecting the crown ether product, and stopping rectifying after collecting 1000g of the crown ether product.
The obtained crown ether product was not detected by gas chromatography.
Example 3:
in example 2, the suspension in the bottom of the rectifying column was reused for 7 times, and the pH of the bottom of the rectifying column was monitored to be 11.28, and the obtained crown ether product was not detected by gas chromatography. According to the calculation of 7 times of alcohol removal loss 200g 15-crown ether-5, the comprehensive yield of the alcohol-free crown ether reaches 97 percent.
Comparative example 1:
the other process was the same as example 1 except that the temperature of the esterification reaction was adjusted from 140 ℃ to 120 ℃ and the obtained crown ether product was found to have a triethylene glycol content of 1140ppm by gas chromatography.
Comparative example 2:
the other procedure was the same as in example 2 except that benzoic anhydride was replaced with phthalic anhydride, and the obtained crown ether product was not detected in triethylene glycol by gas chromatography, but contained 120ppm of phthalic acid.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The alcohol removing method of the crown ether additive for the lithium battery electrolyte is characterized by comprising the following steps of:
(1) adding excessive anhydride according to the content of alcoholic hydroxyl in the crown ether, and heating to 120-200 ℃ to convert alcohol into ester;
(2) adding the mixed solution containing alkali metal hydroxide to neutralize acidic substances;
(3) and carrying out vacuum rectification to obtain a purified product.
2. The method of claim 1 for removing alcohol from a crown ether additive for a lithium battery electrolyte, wherein:
the alcohol content in the crown ether in the step (1) is 100-10000 ppm; the acid anhydride is one or more of acetic anhydride, propionic anhydride, malonic anhydride, butyric anhydride, succinic anhydride and benzoic anhydride.
3. The method of claim 1 for removing alcohol from a crown ether additive for lithium battery electrolytes, comprising:
in the step (2), the alkali metal hydroxide is one or more of sodium hydroxide and potassium hydroxide.
4. The method of claim 1 for removing alcohol from a crown ether additive for a lithium battery electrolyte, wherein:
after the material in the step (2) is heated to 150 ℃, starting a vacuum system for vacuum rectification, wherein the reflux ratio is 8-12; for 15-crown ether-5, the outlet temperature under reduced pressure is 160 ℃ or lower, the front fraction is the product fraction at 160-190 ℃; for 18-crown ether-6, the outlet temperature under reduced pressure is 180 ℃ or lower to obtain front fraction, and the outlet temperature under reduced pressure is 180-210 ℃ to obtain product fraction;
after the rectification is completed, the front cut fraction and the residual liquid are mixed to be used as the mixed liquid containing the alkali metal hydroxide in the step (2).
5. The method of claim 1 for removing alcohol from a crown ether additive for a lithium battery electrolyte, wherein: wherein the molar ratio of the added amount of the acid anhydride to the alcohol contained in the crown ether is 1-3.
6. The alcohol removing device for the crown ether additive for lithium battery electrolytes as claimed in claim 4, wherein: the device comprises a jacket reaction kettle (3), a rectifying tower kettle (5), a condenser (10) and a vacuum system (9), wherein the jacket reaction kettle (3) is connected with the rectifying tower kettle (5), a ceramic packing layer (8) is arranged on the upper portion of the rectifying tower kettle (5), the condenser (10) is communicated with the ceramic packing layer (8), and the vacuum system (9) is connected with the condenser (10).
7. The alcohol removing device for the crown ether additive for lithium battery electrolytes according to claim 5, wherein:
the rectifying tower kettle (5) is filled with alcohol-containing crown ether and alkali metal hydroxide powder, and is stirred to form a suspension (7);
mixing alcohol-containing crown ether with anhydride in the jacketed reaction kettle (3), heating and stirring to complete esterification, pressing the reaction material to a rectifying tower kettle (5) by using nitrogen, heating and stirring;
after the rectifying tower kettle (5) is heated to 150 ℃, starting a vacuum system (9), condensing gas flowing out of the top of the rectifying tower kettle (5) through a condenser (10), adjusting the proportion of a reflux material and a distillate material, and collecting front fraction; and (3) after the temperature of the material at the top outlet of the rectifying tower kettle (5) reaches the target temperature, replacing the receiving tank and collecting the target crown ether product.
8. The alcohol removing device for the crown ether additive for lithium battery electrolytes as claimed in claim 6, wherein:
monitoring the pH value of the rectifying tower kettle (5), maintaining the pH value to be above 10, when the pH value is reduced to be below 10, sending out suspension (7) of the rectifying tower kettle (5) after the rectification is finished, cooling to 50 ℃, filtering to remove solids, sending filtrate back to the rectifying tower kettle (5) and supplementing alkali metal hydroxide powder.
9. The alcohol removing device for the crown ether additive for lithium battery electrolytes according to claim 8, wherein: if the pH is less than 10, the alkali metal hydroxide is added immediately.
10. The alcohol removing device for the crown ether additive for lithium battery electrolytes according to claim 8, wherein: the reflux ratio of the vacuum system is adjusted to be 10; the mixed liquid in the jacket reaction kettle enters the rectifying tower under the pressure difference.
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