CN116374965A - Heterogeneous catalysis synthesis method of lithium bis (fluorosulfonyl) imide key intermediate - Google Patents
Heterogeneous catalysis synthesis method of lithium bis (fluorosulfonyl) imide key intermediate Download PDFInfo
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- CN116374965A CN116374965A CN202310413445.1A CN202310413445A CN116374965A CN 116374965 A CN116374965 A CN 116374965A CN 202310413445 A CN202310413445 A CN 202310413445A CN 116374965 A CN116374965 A CN 116374965A
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000007210 heterogeneous catalysis Methods 0.000 title abstract description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 24
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 20
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005194 fractionation Methods 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 239000011964 heteropoly acid Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- XEWRAXNFTRRVSY-UHFFFAOYSA-N n-(oxomethylidene)sulfamoyl chloride;sulfurochloridic acid Chemical compound OS(Cl)(=O)=O.ClS(=O)(=O)N=C=O XEWRAXNFTRRVSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003930 superacid Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 description 5
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a heterogeneous catalysis synthesis method of a key intermediate (chemical name: dichloro sulfonyl imide) of difluoro sulfonyl imide lithium electrolyte. The heterogeneous catalytic process comprises: the chlorosulfonic acid reacts with chlorosulfonyl isocyanate under the action of heterogeneous catalyst, the catalyst is directly filtered after the reaction is finished, and the filtered mother liquor is subjected to vacuum fractionation to collect target intermediate dichloro-sulfonyl-imide fraction in the next batch of synthesis reaction. Compared with the prior art, the invention has the advantages of repeated application of the catalyst, less kettle residue, less three wastes, low cost and extremely high industrial application value, and also accords with the upgrading of the green chemical industry alternative industry.
Description
Technical Field
The invention relates to the field of electrolytes for lithium batteries, in particular to a preparation method of a key intermediate of lithium bis (fluorosulfonyl) imide, namely bis (chlorosulfonyl) imide.
Background
The lithium bis (fluorosulfonyl) imide is hopeful to gradually replace the lithium hexafluorophosphate (LiPF) widely applied to the current lithium ion battery electrolyte due to the advantages of excellent conductivity, thermal stability and the like 6 ). In the prior art, the technology for preparing lithium bis (fluorosulfonyl) imide by taking bis (chlorosulfonyl) imide as a raw material through fluorination and salifying is most mature, and the industrial chemical raw material sources are sufficient.
Synthesis of a bischlorosulfonimide compound, the reaction of chlorosulfonic acid with chlorosulfonyl isocyanate in the absence of a catalyst in one step is reported in the earlier literature (Chem.Ber.1962, 95,625;Chem.Ber.1962,95,1753), and the fraction is collected by distillation in a moderate yield.
Chinese patent CN106044728B discloses that lewis acid (FeCl 3, niCl2, etc.) or protonic acid (concentrated sulfuric acid, etc.) is used as a catalyst to promote the reaction of chlorosulfonic acid and chlorosulfonyl isocyanate, and the yield is greatly improved by about 10% compared with the condition without catalyst.
Examples in U.S. patent No. 9096502B2 disclose that in the absence of a catalyst, when chlorosulfonic acid is in excess (molar ratio N (Chlorosulfonic acid) /N (chlorosulfonyl isocyanate) =1.1/0.7), the fractional yield of bischlorosulfonimide was only 51%.
The bis (fluorosulfonyl) imide lithium key intermediate bis (chlorosulfonyl) imide process can preliminarily meet the development requirements of the current lithium battery industry, but still has the industrial development bottleneck problems that the catalyst cannot be recovered and reused, a large amount of distillation still residues are left, the environmental protection disposal cost is high, and the like. Therefore, there is a strong need in the art for a more green method for preparing bischlorosulfonimide for process technology replacement upgrades.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for recycling heterogeneous catalyst by utilizing heterogeneous catalysis technology, thereby reducing the use cost of single batch of catalyst, and greatly reducing the generation of residue in a rectifying kettle at the same time, so as to solve the defects in the prior art.
The technical scheme of the invention is as follows:
according to the invention, the chemical synthesis steps are as follows:
according to the invention, the method for preparing the dichlor sulfimide by utilizing heterogeneous catalyst catalysis technology comprises the following steps: mixing raw material chlorosulfonic acid with a heterogeneous catalyst to form a heterogeneous mixed system, then heating and dropwise adding chlorosulfonyl isocyanate for reaction, filtering and separating the heterogeneous catalyst after the reaction is finished, directly applying the heterogeneous catalyst to the next batch of reaction, and collecting target intermediate fraction dichloro sulfonyl imide by vacuum rectification of mother liquor.
In the method, the heterogeneous catalyst is a solid super acid heteropolyacid catalyst, and SiO is used for preparing the catalyst 2 Zeolite molecular sieve or MCM-41 as a carrier.
More specifically, the heterogeneous catalyst is commercially available, such as one or more combinations selected from the group consisting of HND-580, HND-587, HND-583, HND-5w, HND-31, HND-64, HND-270, and HND-260.
In the method, the heterogeneous catalyst can be used for at least three times, and the catalytic activity is not obviously reduced.
In the above process, the mass ratio of heterogeneous catalyst to chlorosulfonic acid, m (catalyst) /m (Chlorosulfonic acid) =1/(5 to 200), preferably 1/10 to 1/100.
In the above process, the molar ratio N of chlorosulfonic acid to chlorosulfonyl isocyanate (Chlorosulfonic acid) :N (chlorosulfonyl isocyanate) =1:0.9 to 1:1.5, preferably 1:1.1 to 1:1.3.
In the above method, the reaction temperature of the reaction system is 80 to 140 ℃, preferably 100 to 130 ℃.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the solid super acid heteropolyacid catalyst to realize heterogeneous catalysis, the reaction condition is mild, and the product yield is obviously improved compared with the condition without the catalyst.
(2) The heterogeneous catalyst is separated from the reaction liquid through simple filtering operation, and the catalyst is directly applied to the next batch of reaction, so that the emission of residue in each batch of rectifying still is obviously reduced, and the heterogeneous catalyst is more green and has more advantages in economic cost.
The invention provides an industrialized preparation method for preparing the dichloro sulfonyl imide in a green way.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto. It should be noted that the embodiments and features in the embodiments may be combined with each other.
Example 1
To a dry 500mL reaction flask, 116.5g of chlorosulfonic acid, 6.0g of HND-580 heteropolyacid, nitrogen purging, heating to 80-110℃and starting to dropwise add 184.2g of chlorosulfonyl isocyanate. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. After the reaction is finished, the temperature is reduced to about 40 ℃, the catalyst is filtered, the mother liquor starts high vacuum reduced pressure distillation, after the temperature of the fraction is more than 95 ℃, 188.5g of dichloro-sulfonyl imide fraction is collected, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 88.1%.
Example 2
To a dry 500mL reaction flask, 116.4g of chlorosulfonic acid, 6.0g of HND-31 heteropolyacid, nitrogen purging, heating to 80-110℃and starting to dropwise add 184.3g of chlorosulfonyl isocyanate. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. After the reaction is finished and the temperature is reduced to about 40 ℃, the catalyst is filtered, the mother liquor starts high vacuum reduced pressure distillation, 179.1g of dichloro sulfimide fraction is collected after the fraction temperature is more than 95 ℃, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 83.7%.
Example 3
To a dry 500mL reaction flask, 116.5g of chlorosulfonic acid, 6.0g of HND-260 heteropolyacid, nitrogen purging, heating to 80-110℃and starting to dropwise add 184.1g of chlorosulfonyl isocyanate. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. When the reaction is finished and the temperature is reduced to about 40 ℃, the catalyst is filtered, the mother liquor starts high vacuum reduced pressure distillation, 167.3g of dichloro sulfimide fraction is collected after the fraction temperature is more than 95 ℃, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 78.2%.
Example 4
To a dry 500mL reaction flask, 116.6g of chlorosulfonic acid, 3.0g of HND-580 heteropolyacid, and nitrogen were added, the mixture was evacuated, heated to 80-110℃and 184.5g of chlorosulfonyl isocyanate was added dropwise. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. After the reaction is finished and the temperature is reduced to about 40 ℃, the catalyst is filtered, the mother liquor starts high vacuum reduced pressure distillation, 156.4g of dichloro sulfimide fraction is collected after the fraction temperature is more than 95 ℃, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 73.1%.
Example 5
To a dry 500mL reaction flask, 116.3g of chlorosulfonic acid, 3.0g of HND-5w heteropolyacid and 3.0g of HND-580 heteropolyacid were added, the mixture was purged with nitrogen, heated to 80-110℃and 184.0g of chlorosulfonyl isocyanate was added dropwise. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. When the reaction is finished and the temperature is reduced to about 40 ℃, the filtered catalyst is directly applied to the next batch, the mother liquor starts high vacuum reduced pressure distillation, 185.5g of the dichlorosulfimide fraction is collected after the fraction temperature is higher than 95 ℃, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 86.7%.
Example 6
To a dry 500mL reaction flask was added 116.5g chlorosulfonic acid, the catalyst recovered in example 5, purged with nitrogen, heated to 80-110℃and 184.2g chlorosulfonyl isocyanate was added dropwise. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. When the reaction is finished and the temperature is reduced to about 40 ℃, the filtered catalyst is directly applied to the next batch, the mother liquor starts high vacuum reduced pressure distillation, 184.2g of the dichlorosulfimide fraction is collected after the fraction temperature is more than 95 ℃, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 86.1%.
Example 7
To a dry 500mL reaction flask was added 116.2g chlorosulfonic acid, the catalyst recovered in example 6, purged with nitrogen, heated to 80-110℃and 184.3g chlorosulfonyl isocyanate was added dropwise. After the dripping is finished, slowly heating to 120-135 ℃, and continuing to perform heat preservation reaction for 15h. After the reaction is finished, the temperature is reduced to about 40 ℃, the catalyst is filtered, the mother solution starts high vacuum reduced pressure distillation, 185.2g of dichloro-sulfonyl-imide fraction is collected after the fraction temperature is more than 95 ℃, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 86.5%.
Comparative examples
To a dry 500mL reaction flask was added 116.5g chlorosulfonic acid, purged with nitrogen, heated to 100-110℃and 184.5g chlorosulfonyl isocyanate was added dropwise. After the dripping is finished, slowly heating to 130-140 ℃, and continuing to perform heat preservation reaction for 30h. After the reaction is finished and the temperature is reduced to about 40 ℃, high-vacuum reduced pressure distillation is started, after the temperature of the fraction is higher than 95 ℃, 151.1g of dichloro-sulfonyl-imide fraction is collected, the fraction is colorless and transparent, and the white solid is solidified at room temperature, and the yield is 70.6%.
The above description is only of specific embodiments of the invention and is not intended to limit the invention, but various modifications and variations can be made by those skilled in the art. Any modification, equivalent replacement, supplement, etc. made within the principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A heterogeneous catalytic synthesis method of dichloro-sulfonyl-imide is characterized in that: the synthetic route is as follows:
the method comprises the following steps: mixing raw material chlorosulfonic acid with a heterogeneous catalyst to form a heterogeneous mixed system, then heating and dropwise adding chlorosulfonyl isocyanate for reaction, filtering and separating the heterogeneous catalyst after the reaction is finished, directly applying the heterogeneous catalyst to the next batch of reaction, and collecting target fraction of dichloro-sulfonyl imide by vacuum fractionation of mother liquor.
2. The synthesis method according to claim 1, characterized in that: heterogeneous catalyst and chlorosulfonic acid mass ratio m (catalyst) /m (Chlorosulfonic acid) ＝1/(5～200)。
3. The method according to claim 2, characterized in that: heterogeneous catalyst and chlorosulfonic acid mass ratio m (catalyst) /m (Chlorosulfonic acid) ＝1/10～1/100。
4. The synthesis method according to claim 1, characterized in that: the molar ratio N of chlorosulfonic acid to chlorosulfonyl isocyanate (Chlorosulfonic acid) :N (chlorosulfonyl isocyanate) ＝1:0.9～1:1.5。
5. The method according to claim 4, characterized in that: the molar ratio N of chlorosulfonic acid to chlorosulfonyl isocyanate (Chlorosulfonic acid) :N (chlorosulfonyl isocyanate) ＝1:1.1～1:1.3。
6. The synthesis method according to claim 1, characterized in that: the reaction temperature of the reaction system is 80-140 ℃.
7. The method according to claim 6, characterized in that: the reaction temperature of the reaction system is 100-130 ℃.
8. The synthesis method according to claim 1, characterized in that: the heterogeneous catalyst is solid super acid heteropolyacid catalyst, which is insoluble in the reaction solution and adopts SiO 2 Zeolite molecular sieve or MCM-41 as a carrier.
9. The method according to claim 8, characterized in that: the heterogeneous catalyst is selected from: HND-580, HND-587, HND-583, HND-5w, HND-31, HND-64, HND-270 or HND-260.
10. The synthesis method according to claim 1, characterized in that: the heterogeneous catalyst may be one or a combination of heteropolyacid catalysts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN2023100822626 | 2023-02-08 | ||
| CN202310082262 | 2023-02-08 |
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