CN117402135A - Method for extracting vinylene carbonate from vinylene carbonate kettle residues - Google Patents
Method for extracting vinylene carbonate from vinylene carbonate kettle residues Download PDFInfo
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- CN117402135A CN117402135A CN202311340186.0A CN202311340186A CN117402135A CN 117402135 A CN117402135 A CN 117402135A CN 202311340186 A CN202311340186 A CN 202311340186A CN 117402135 A CN117402135 A CN 117402135A
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- Prior art keywords
- vinylene carbonate
- extracting
- residue
- kettle
- cooling
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011085 pressure filtration Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BIYFBWRLDKOYMU-UHFFFAOYSA-N 1-(3,4-dichlorophenyl)-2-(ethylamino)propan-1-one Chemical compound CCNC(C)C(=O)C1=CC=C(Cl)C(Cl)=C1 BIYFBWRLDKOYMU-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for extracting vinylene carbonate from vinylene carbonate kettle residues, which adopts an organic solvent to dissolve the vinylene carbonate kettle residues, then carries out filter pressing, and carries out post-treatment after the filter pressing to obtain the vinylene carbonate. The method for extracting the vinylene carbonate from the vinylene carbonate kettle residue does not need to use water as an extractant, and directly adopts an organic solvent for dissolving and then filtering, thereby reducing the participation of water and improving the extraction yield. The operation is simple and convenient, the vinylene carbonate can be rapidly and effectively extracted without high-temperature environment treatment, the residue of the vinylene carbonate kettle is efficiently recovered, and the cost is reduced.
Description
Technical Field
The invention relates to the field of lithium battery additives, in particular to a method for extracting vinylene carbonate from vinylene carbonate kettle residues.
Background
Adding chloroethylene carbonate into an organic solvent, adding a catalyst to obtain vinylene carbonate, and extracting the vinylene carbonate in a rectification process, wherein in the extraction process, partial residual vinylene carbonate cannot be normally extracted at a certain production temperature due to the fact that materials are sticky in the later period, the residual vinylene carbonate can only be discharged as kettle residues, the kettle residues cannot be recycled, the kettle residues can only be used as dangerous wastes, and the waste is caused. The residue of vinylene carbonate contains a large amount of tar, about 20% of vinylene carbonate, and a small amount of EC, DCEC, triethylamine and the like. At present, lithium batteries are rapidly developed, more and more vinylene carbonate is needed, and further improvement and development are needed for improving the recovery rate of vinylene carbonate when vinylene carbonate is extracted from vinylene carbonate residues.
Disclosure of Invention
In order to solve the problems, a method for extracting vinylene carbonate from vinylene carbonate kettle residues is provided, and the following technical scheme is provided:
a method for extracting vinylene carbonate from vinylene carbonate kettle residues adopts an organic solvent to dissolve the vinylene carbonate kettle residues and then carries out post-treatment to obtain the vinylene carbonate.
Further, the organic solvent is at least one of chlorinated alkane such as dichloromethane and dichloroethane.
Further, the dosage ratio of the residue of the vinylene carbonate kettle to the organic solvent is 5:1-4.
Further, the filter pressing is performed by a filter press, and the porosity of the filter cloth adopted by the filter press is in the range of 0.1-50 mu m.
Further, the filtering is performed by a filter press, the porosity of the filter cloth adopted by the filter press ranges from 0.1 to 50 mu m, and the pressure of the filter press is set to be 0.02Mpa to 0.05Mpa.
Further, the post-treatment comprises reduced pressure distillation and temperature reduction.
Further, the conditions of the reduced pressure distillation are as follows: the vacuum degree is between-0.09 Mpa and 0Mpa, the temperature is raised from room temperature to 50 ℃ until no extract is produced, and the temperature raising rate is 5-10 ℃ in every two hours.
Further, the organic solvent is collected in the reduced pressure distillation process, and the collected organic solvent is used for dissolving the residue of the vinylene carbonate kettle.
Further, the reduced pressure distillation is followed by two times of cooling, the first cooling cools the product obtained after the reduced pressure distillation to 25-28 ℃, and the second cooling cools from 25-28 ℃ to 5-10 ℃.
Further, after the first cooling, preserving heat for 4-5 hours at 25-28 ℃, filtering after the heat preservation is finished, and after the filtering is finished, carrying out the second cooling.
Further, cooling for 3-4 hours at the temperature of 5-10 ℃ after the second cooling, and carrying out solid-liquid separation after cooling to obtain the vinylene carbonate solid.
By adopting the technical scheme, the invention has the beneficial technical effects that:
1. according to the method for extracting the vinylene carbonate from the vinylene carbonate kettle residue, water is not required to be used as an extractant, and the filter pressing is performed after the vinylene carbonate kettle residue is directly dissolved by an organic solvent, so that the participation of water is reduced, and the extraction yield is improved;
2. according to the invention, the overall processes of organic solvent dissolution, filtration, reduced pressure distillation and cooling are designed in sequence, so that the vinylene carbonate is extracted from the vinylene carbonate kettle residue, and the processes are matched in sequence to extract the vinylene carbonate from the vinylene carbonate kettle residue, so that the recovery rate of the vinylene carbonate reaches more than 95%;
3. the method is simple and convenient to operate, does not need high-temperature environment treatment, can rapidly and effectively extract the vinylene carbonate, efficiently recovers the vinylene carbonate kettle residues, and reduces the cost.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following description of the technical solution of the present invention will be made in detail by combining the embodiments of the present invention, and based on the embodiments in the present application, other similar embodiments obtained by those skilled in the art without making creative efforts shall fall within the scope of protection of the present application.
A method for extracting vinylene carbonate from vinylene carbonate kettle residues adopts an organic solvent to dissolve the vinylene carbonate kettle residues, then filter-press the residues, and finally post-treat the residues after filter-press to obtain the vinylene carbonate. The method for extracting the vinylene carbonate from the vinylene carbonate kettle residue does not need to use water as an extractant, and directly adopts an organic solvent for dissolving and then filtering, thereby reducing the participation of water and improving the extraction yield. The operation is simple and convenient, the vinylene carbonate can be rapidly and effectively extracted without high-temperature environment treatment, the residue of the vinylene carbonate kettle is efficiently recovered, and the cost is reduced. The organic solvent can dissolve the residue of the vinylene carbonate kettle; the filter pressing process can filter out solid particles and a large amount of tar, and the rest materials are basically extraction solvent, vinylene carbonate, ethylene carbonate and the like.
The method is simple and convenient to operate, can be used for purifying the vinylene carbonate product rapidly and effectively, reduces the generation of hazardous waste, improves the yield of enterprises, and is more suitable for the theme of safe and environment-friendly production.
The scheme aims at improving the recovery rate and content of the vinylene carbonate extracted from the vinylene carbonate kettle residue, a new extraction process and various process parameters are explored, the sequence of the extraction process and parameter conditions can have a larger influence on the recovery rate and content of the vinylene carbonate, and when the extraction process or parameter condition setting is changed, the recovery rate of the vinylene carbonate can be reduced, and the purity of the obtained vinylene carbonate can be reduced.
After pressure filtration, the solvent is separated and recovered by means of reduced pressure distillation, the solvent can be recycled for a plurality of times, and pure vinylene carbonate, ethylene carbonate, a small amount of unfiltered tar and the like are obtained after reduced pressure distillation. The obtained high-content vinylene carbonate is put into the production section again for use, thereby achieving the effect of recycling.
Example 1
100 parts of vinylene carbonate kettle residue is dissolved in 80 parts of dichloromethane, and then a filter press is adopted for filter pressing, wherein the porosity of a filter cloth of the filter press is 5 mu m, and the pressure of the filter pressing is 0.02Mpa. Distilling the liquid after pressure filtration under reduced pressure, placing the liquid after pressure filtration into a closed reaction kettle, starting stirring, vacuumizing, slowly heating from room temperature to 50 ℃ until no extraction is performed under the vacuum degree of 0Mpa, wherein the heating rate is thatThe temperature was raised by 5℃every two hours. The temperature of the liquid obtained after the reduced pressure distillation is reduced to 28 ℃ Preserving heat for 4 hours, and filtering after the heat preservation is finished; and (3) cooling the filtered liquid for the second time, cooling the liquid material to 8 ℃ for 3 hours, and performing solid-liquid separation after cooling to obtain pure vinylene carbonate with the vinylene carbonate content of 90% and the recovery rate of 80%.
Example 2
100 parts of ethylene carbonate kettle residues are dissolved in 20 parts of dichloroethane, and then a filter press is adopted for filter pressing, wherein the porosity of a filter cloth of the filter press is 1 mu m, and the pressure of the filter pressing is 0.03Mpa. And (3) carrying out reduced pressure distillation on the liquid after pressure filtration, putting the liquid after pressure filtration into a closed reaction kettle, starting stirring, vacuumizing, slowly heating from room temperature to 50 ℃ until no extraction is carried out, wherein the heating rate is 8 ℃ every two hours, and the vacuum degree is-0.07 Mpa. The temperature of the liquid obtained after reduced pressure distillation is reduced to 25 ℃, the heat preservation is carried out for 5 hours, and the filtration is carried out after the heat preservation is completed; and (3) carrying out second cooling on the filtered liquid, cooling the liquid material to 5 ℃ for 4 hours, and carrying out solid-liquid separation after cooling to obtain pure vinylene carbonate with the vinylene carbonate content of 80% and the recovery rate of 65%.
Example 3
100 parts of ethylene carbonate kettle residues are dissolved in 40 parts of dichloroethane, and then a filter press is adopted for filter pressing, wherein the porosity of a filter cloth of the filter press is 10 mu m, and the pressure of the filter pressing is 0.05Mpa. And (3) carrying out reduced pressure distillation on the liquid after pressure filtration, putting the liquid after pressure filtration into a closed reaction kettle, starting stirring, vacuumizing, slowly heating from room temperature to 50 ℃ until no extraction is carried out, wherein the heating rate is 10 ℃ every two hours, and the vacuum degree is-0.09 Mpa. The temperature of the liquid obtained after reduced pressure distillation is reduced to 27 ℃, the heat preservation is carried out for 4 hours, and the filtration is carried out after the heat preservation is completed; and (3) carrying out second cooling on the filtered liquid, cooling the liquid material to 10 ℃ for 4 hours, and carrying out solid-liquid separation after cooling to obtain pure vinylene carbonate with the vinylene carbonate content of 95% and the recovery rate of 90%.
Comparative example 1
Adding 100 parts of vinylene carbonate kettle residues into 120 parts of water, heating in a water bath at 80 ℃ for two hours, pouring into a separating funnel, collecting a lower solution, performing reduced pressure distillation on the lower solution, putting the liquid after filter pressing into a closed reaction kettle, starting stirring, vacuumizing, heating from room temperature to 75 ℃ at a vacuum degree of-0.09 Mpa, and heating up to 5 ℃ every two hours. The distilled liquid in the early stage of reduced pressure distillation is not needed after being extracted, and the extraction in the middle and later stages is VC. The VC obtained was crystallized at 8℃for 3 hours. After cooling, the solid-liquid separation is carried out, the solid is vinylene carbonate, the vinylene carbonate content is 80%, and the yield is 40%. A part of vinylene carbonate reacts with water to cause part waste, and when the vinylene carbonate is distilled and extracted under reduced pressure, a mixed solution of water and vinylene carbonate is initially produced, wherein the mixed solution water accounts for a large part, and the vinylene carbonate accounts for a small part and cannot be used.
Comparative example 2
In comparison with example 1, no press filtration was performed, and the other steps were the same as in example 1, with a vinylene carbonate content of 60% and a recovery rate of 40%.
Comparative example 3
The porosity of the filter cloth of the filter press is 70 mu m, and the pressure of the filter press is 0.01Mpa. The vinylene carbonate content was 75% and the recovery was 60%.
As can be seen from examples 1-3 and comparative examples 1-3, the method for extracting vinylene carbonate from vinylene carbonate kettle residues does not use water as an extractant, and directly adopts an organic solvent for dissolution and then filter pressing, so that the participation of water is reduced, the recovery rate can be further improved, and meanwhile, heating treatment is needed when water is added for extraction, and the operation is relatively troublesome. In addition, compared with a separating funnel, the solid particles and a large amount of tar can be filtered cleanly by adjusting and controlling the porosity of the filter cloth of the filter press and the pressure of the filter press. Specifically, a part of vinylene carbonate in comparative example 1 reacts with water to cause a part of waste, and when the mixture is distilled under reduced pressure, a mixed liquid of water and vinylene carbonate is produced initially, the mixed liquid water occupies a large part, and the vinylene carbonate occupies a small part, so that the catalyst cannot be used. Comparative example 2 was not subjected to press filtration, a part of vinylene carbonate was mixed in tar, and the extracted vinylene carbonate was also low in tar content, resulting in low purity and low yield. Comparative example 3 used a filter element, but the porosity was large, resulting in a small amount of tar in vinylene carbonate, resulting in a decrease in purity.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A method for extracting vinylene carbonate from vinylene carbonate kettle residues is characterized in that an organic solvent is adopted to dissolve the vinylene carbonate kettle residues, then filter pressing is carried out, and post treatment is carried out after the filter pressing to obtain the vinylene carbonate.
2. The method for extracting vinylene carbonate from vinylene carbonate residue as in claim 1, characterized in that the organic solvent is at least one of dichloromethane and dichloroethane.
3. The method for extracting vinylene carbonate from vinylene carbonate residue according to claim 1, wherein the ratio of the vinylene carbonate residue to the organic solvent is 5:1-4.
4. The method for extracting vinylene carbonate from vinylene carbonate residue according to claim 1, wherein the filter pressing is performed by a filter press, the porosity of the filter cloth of the filter press is 0.1-50 μm, and the pressure of the filter press is set to be 0.02Mpa-0.05Mpa.
5. The method for extracting vinylene carbonate from vinylene carbonate residue according to claim 1, wherein the post-treatment comprises reduced pressure distillation and temperature reduction.
6. The method for extracting vinylene carbonate from vinylene carbonate still residue according to claim 5, wherein the condition of reduced pressure distillation is: the vacuum degree is between-0.09 Mpa and 0Mpa, the temperature is raised from room temperature to 50 ℃ until no extract is produced, and the temperature raising rate is 5-10 ℃ after every two hours.
7. The method for extracting vinylene carbonate from vinylene carbonate residue as in claim 6, characterized in that the organic solvent is collected during vacuum distillation, and the collected organic solvent is used for dissolving vinylene carbonate residue.
8. The method for extracting vinylene carbonate from vinylene carbonate residue as in claim 5, characterized in that the reduced pressure distillation is followed by two cooling steps, the first cooling step is to cool the product obtained after the reduced pressure distillation to 25-28 ℃ and the second cooling step is to cool from 25-28 ℃ to 5-10 ℃.
9. The method for extracting vinylene carbonate from vinylene carbonate residue according to claim 8, wherein the temperature is kept at 25-28 ℃ for 4-5h after the first cooling, the filtration is performed after the temperature is kept, and the second cooling is performed after the filtration is finished.
10. The method for extracting vinylene carbonate from vinylene carbonate kettle residue according to claim 9, wherein the vinylene carbonate is cooled at 5-10 ℃ for 3-4h after the second cooling, and the vinylene carbonate solid is obtained by solid-liquid separation after the cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311340186.0A CN117402135A (en) | 2023-10-17 | 2023-10-17 | Method for extracting vinylene carbonate from vinylene carbonate kettle residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311340186.0A CN117402135A (en) | 2023-10-17 | 2023-10-17 | Method for extracting vinylene carbonate from vinylene carbonate kettle residues |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117402135A true CN117402135A (en) | 2024-01-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311340186.0A Pending CN117402135A (en) | 2023-10-17 | 2023-10-17 | Method for extracting vinylene carbonate from vinylene carbonate kettle residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117402135A (en) |
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2023
- 2023-10-17 CN CN202311340186.0A patent/CN117402135A/en active Pending
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