CN115557927A - Preparation method of vinyl sulfate - Google Patents
Preparation method of vinyl sulfate Download PDFInfo
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- CN115557927A CN115557927A CN202211124157.6A CN202211124157A CN115557927A CN 115557927 A CN115557927 A CN 115557927A CN 202211124157 A CN202211124157 A CN 202211124157A CN 115557927 A CN115557927 A CN 115557927A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
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Abstract
The invention belongs to the technical field of chemical reagent preparation, and particularly relates to a preparation method of vinyl sulfate. The preparation method comprises the following steps: (1) Mixing thionyl chloride and ethylene glycol, reacting to obtain a crude product of the ethylene sulfite, and distilling to obtain a refined product of the ethylene sulfite; (2) Mixing the refined ethylene sulfite, an oxidant solution, a solvent and a catalyst ruthenium trichloride, reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding water into the organic phase, standing, taking the organic phase, and removing the solvent to obtain the vinyl sulfate. The preparation method has mild reaction temperature (below 10 ℃), high reaction safety, and high purity of the prepared vinyl sulfate (more than 99.5 percent by mass) and yield of more than 73 percent.
Description
Technical Field
The invention belongs to the technical field of chemical reagent preparation, and particularly relates to a preparation method of vinyl sulfate.
Background
The vinyl sulfate can be used as an additive of the lithium ion battery electrolyte, and has the functions of inhibiting the reduction of the initial capacity of the battery, increasing the initial discharge capacity, reducing the battery expansion after high-temperature placement, and improving the charge and discharge performance and cycle times of the battery. With the wide application of new energy, the demand of the vinyl sulfate is increasing.
The method for producing the vinyl sulfate in the prior art is complex in process and cannot be used for industrial mass production. For example, in the prior art, when ruthenium trichloride is used as a catalyst, a carrier of the catalyst needs to be prepared first, multiple solid-liquid separations are needed, the solid-liquid separation operation is slow, equipment and pipelines are easily blocked, the production efficiency is low, and the requirement of industrial mass production of the vinyl sulfate cannot be obviously met.
Therefore, it is desired to provide a method for industrially producing vinyl sulfate in a large amount, which is simple to operate.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a preparation method of vinyl sulfate. The preparation method provided by the invention has the advantages that the production process is simple to operate, the defects that a catalyst carrier is required to be used and multiple solid-liquid separations are required in the prior art are overcome, the production efficiency is greatly improved, the purity and the yield of the prepared vinyl sulfate are considerable, and the preparation method is very suitable for industrial large-scale production of the vinyl sulfate.
The invention conception of the invention is as follows: the invention takes ethylene glycol and thionyl chloride as raw materials to prepare the ethylene sulfite, the process does not relate to the use of other solvents or catalysts, so the problems of recycling or separation and purification of the catalysts and the solvents are not considered, the impurities of the ethylene sulfite intermediate product are greatly reduced, and then the ethylene sulfite, sodium hypochlorite, dichloromethane serving as the solvent and ruthenium trichloride serving as the catalyst (ruthenium trichloride does not need to use a carrier) are used for oxidation reaction to prepare the ethylene sulfate. The reaction temperature is mild (below 10 ℃), the reaction safety is high, the purity of the prepared vinyl sulfate exceeds 99.5 percent (mass fraction), and the yield exceeds 73 percent.
The invention provides a preparation method of vinyl sulfate.
Specifically, the preparation method of the vinyl sulfate comprises the following steps:
(1) Mixing thionyl chloride and ethylene glycol, reacting to obtain a crude product of the ethylene sulfite, and distilling to obtain a refined product of the ethylene sulfite;
(2) Mixing the fine ethylene sulfite, an oxidant solution, a solvent and a catalyst ruthenium trichloride, reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding water into the organic phase, standing, taking the organic phase, and removing the solvent to obtain the ethylene sulfate.
Preferably, the thionyl chloride and ethylene glycol are mixed and the reaction is carried out in a conventional glass-lined reactor. The traditional glass lining reaction kettle is adopted, so that large-scale industrial production can be realized, economic benefits are created, the maintenance or replacement of equipment is realized, the price is low, and the investment cost is low. In the prior art, the ethylene sulfite is prepared by using microchannel equipment, but the method cannot produce the ethylene sulfite in large quantity, and the microchannel equipment is relatively expensive to manufacture.
Preferably, in the step (1), the molar ratio of the thionyl chloride to the ethylene glycol is 1.0-1.2:1; further preferably, the molar ratio of thionyl chloride to ethylene glycol is 1.0434:1.
preferably, in step (1), the temperature of the reaction is 10 ℃ or less, preferably-5 to 0 ℃.
Preferably, in step (1), the reaction time is 10 to 15 hours, preferably 11 to 15 hours.
Preferably, in the step (1), the mixing process of the thionyl chloride and the ethylene glycol is dropping the ethylene glycol into the thionyl chloride.
Preferably, in the step (1), tail gas HCl is generated in the reaction process, and the tail gas HCl is treated by adopting a two-stage falling film absorber and a one-stage alkali absorption tower to obtain a 30% mass fraction HCl solution.
Preferably, in the step (1), after the crude product of the ethylene sulfite is prepared, before distillation, the method further comprises an acid removal process, wherein the vacuum degree in the acid removal process is-80 to-85 KPa, the temperature is 60 to 62 ℃, and the time is 1 to 2 hours.
Preferably, in the step (1), the vacuum degree in the distillation process is-80 to-85 KPa, and the temperature is 60 to 62 ℃.
Preferably, in the step (1), the distillation may be carried out in a distillation column, from the upper part of which a fine product of vinyl sulfite is partially distilled, and the lower end of which a residue is obtained.
Preferably, in step (1), the purity of the refined ethylene sulfite product is more than 95% (by mass fraction), and the yield is more than 81%, for example, 82%.
Preferably, in the step (2), the oxidant solution is a sodium hypochlorite solution or hydrogen peroxide. The sodium hypochlorite solution is relatively good, and the hydrogen peroxide is adopted, so that the yield of the final target product, namely the vinyl sulfate, is reduced. Preferably, the concentration of the sodium hypochlorite solution is not more than 15% by mass, for example 8-12%.
Preferably, in the step (2), the solvent is at least one of dichloromethane, dichloroethane, dimethyl carbonate, diethyl carbonate or ethyl methyl carbonate.
Preferably, in the step (2), the molar ratio of the ethylene sulfite refined product to the oxidant in the oxidant solution to the solvent is 1: (10.5-12): (15-20), preferably 1: 17.
preferably, in the step (2), the mass of the catalyst ruthenium trichloride is 0.1-0.8%, preferably 0.3-0.8% of the mass of the refined product of the ethylene sulfite. The dosage of each raw material is accurately controlled, and the quantity of byproducts is favorably reduced.
Preferably, in step (2), the temperature of the reaction is 10 ℃ or less, preferably 2 to 6 ℃.
Preferably, in step (2), the reaction time is 3 to 5 hours, preferably 4 to 5 hours.
In the step (2), after the reaction is finished, standing to obtain an organic phase and a water phase, wherein the organic phase is a dichloromethane solution containing vinyl sulfate, and the water phase contains a catalyst ruthenium trichloride.
Preferably, in step (2), water is added into the organic phase, the mixture is stirred for 0.1 to 0.8 hour, the mixture is kept stand to obtain an organic phase and an aqueous phase, the aqueous phase is removed, the organic phase is remained, and then the organic phase is subjected to desolventizing treatment. The purpose of adding water to the organic phase is to wash off the by-product chlorohydrin, which is soluble in water, whereas vinyl sulfate is poorly soluble in water.
Preferably, in the step (2), the temperature is 30-35 ℃, the pressure is-70 KPa to-90 KPa, and the time is 4-5 hours during the solvent removal process.
Preferably, in the step (2), after the solvent is removed, vacuum drying is carried out, wherein the temperature of the vacuum drying is 20-30 ℃, and the pressure is-80 KPa to-90 KPa.
Preferably, in step (2), reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding dichloromethane, sodium hypochlorite and alkali liquor (such as sodium hydroxide solution, and adjusting pH to 7-10) into the aqueous phase, standing for layering to obtain an organic phase and an aqueous phase, and removing the aqueous phase to retain the organic phase. The catalyst remains in the organic phase (the valence state of the ruthenium in the catalyst changes, leading to a change in the solubility with organic solvents or water) and the purpose of this operation is to recover the catalyst. The water phase is high-salt wastewater and can be treated by evaporation (can be treated by an MVR triple-effect evaporator).
Preferably, in the step (2), the solvent obtained by the solvent removal treatment can be recycled. The ethylene sulfate obtained by the solvent removal is vacuum-dried to obtain ethylene sulfate powder, and the ethylene sulfate powder is mixed with a solvent (for example, ethyl methyl carbonate) to obtain an electrolyte solution.
Preferably, in step (2), the purity of the vinyl sulfate is more than 99.5% by mass, and the yield is more than 73.5%, for example, 77.4%.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes ethylene glycol and thionyl chloride as raw materials to prepare the ethylene sulfite, the process does not relate to the use of other solvents or catalysts, so the problems of recycling or separation and purification of the catalysts and the solvents are not considered, the impurities of the ethylene sulfite intermediate product are greatly reduced, and then the ethylene sulfite, sodium hypochlorite, dichloromethane serving as the solvent and ruthenium trichloride serving as the catalyst (ruthenium trichloride does not need to use a carrier) are used for oxidation reaction to prepare the ethylene sulfate. The reaction temperature is mild (below 10 ℃), the reaction safety is high, the purity of the prepared vinyl sulfate exceeds 99.5 percent (mass fraction), and the yield exceeds 73 percent.
Drawings
FIG. 1 is a schematic flow chart of the process for preparing vinyl sulfate according to example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods.
Example 1: preparation of vinyl sulfate
A preparation method of vinyl sulfate comprises the following steps:
(1) Mixing thionyl chloride and ethylene glycol according to a molar ratio of 1.0434:1, and the mixing process of the thionyl chloride and the ethylene glycol is to drop the ethylene glycol into the thionyl chloride for reaction at the temperature of 0 ℃ for 14 hours, the reaction is carried out in a traditional glass lining reaction kettle to prepare a crude product of the ethylene sulfite, the acid is removed, the vacuum degree in the acid removing process is-82 KPa, the temperature is 61 ℃ for 1 hour, the distillation is carried out, the vacuum degree in the distillation process is-82 KPa, and the temperature is 61 ℃ to obtain a refined product of the ethylene sulfite;
(2) Mixing fine ethylene sulfite, an oxidant sodium hypochlorite solution (the mass fraction concentration of the sodium hypochlorite solution is 10%), a solvent dichloromethane and a catalyst ruthenium trichloride, wherein the molar ratio of the fine ethylene sulfite to the oxidant sodium hypochlorite to the solvent dichloromethane is 1.11.72: 17, the mass of the catalyst ruthenium trichloride is 0.5 percent of the mass of the refined ethylene sulfite product, the reaction is carried out at the temperature of 5 ℃ for 4 hours, an organic phase and a water phase are obtained by standing, the organic phase and the water phase are separated, water is added into the organic phase, the mixture is stirred for 0.5 hour, the mixture is kept standing, the water phase (the water phase is acidic wastewater) is removed, the organic phase is taken, the solvent is removed, and the temperature is 35 ℃, the pressure is-80 KPa and the time is 4 hours in the process of removing the solvent, so that the ethylene sulfate is prepared.
In the step (1), tail gas HCl is generated in the reaction process, and water and sodium hydroxide solution are adopted to treat the tail gas HCl to obtain HCl solution with the mass fraction of 30%.
In the step (1), the distillation may be carried out in a distillation column, a fine vinyl sulfite product being partially distilled from the upper part of the distillation column, and a residue being obtained at the lower end of the distillation column.
In the step (1), the purity of the refined ethylene sulfite product is 96.3% (by mass fraction), and the yield is 82.5%.
In the step (2), reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding dichloromethane, sodium hypochlorite and an alkali solution (such as a 0.1mol/L sodium hydroxide solution, adjusting the pH value to 8) into the aqueous phase, standing for layering to obtain the organic phase and the aqueous phase, removing the aqueous phase, and retaining the organic phase. The catalyst remains in the organic phase and the purpose of this operation is to recover the catalyst. The water phase is high-salinity wastewater and can be subjected to evaporation treatment (can be treated by an MVR triple-effect evaporator).
In the step (2), the solvent obtained by the solvent removal treatment can be recycled. The ethylene sulfate obtained by the solvent removal is vacuum-dried to obtain ethylene sulfate powder, and the ethylene sulfate powder is mixed with a solvent (for example, ethyl methyl carbonate) to obtain an electrolyte solution.
In the step (2), the purity of the vinyl sulfate ester by mass fraction was 99.7%, and the yield was 77.4%.
FIG. 1 is a schematic diagram of the process for preparing vinyl sulfate according to example 1 of the present invention.
Example 2: preparation of vinyl sulfate
A preparation method of vinyl sulfate comprises the following steps:
(1) Mixing thionyl chloride and ethylene glycol according to a molar ratio of 1.05:1, and the mixing process of the thionyl chloride and the ethylene glycol is to drop the ethylene glycol into the thionyl chloride for reaction at the temperature of minus 2 ℃ for 14 hours, the reaction is carried out in a traditional glass lining reaction kettle to prepare a crude product of the ethylene sulfite, remove acid, the vacuum degree in the acid removing process is minus 83KPa, the temperature is 62 ℃, the time is 1 hour, the vacuum degree in the distillation process is minus 83KPa, and the temperature is 62 ℃ to obtain a refined product of the ethylene sulfite;
(2) Mixing refined ethylene sulfite, oxidant sodium hypochlorite (the mass fraction concentration of a sodium hypochlorite solution is 10.2%), solvent dichloromethane and catalyst ruthenium trichloride, wherein the molar ratio of the refined ethylene sulfite to the oxidant sodium hypochlorite to the solvent dichloromethane is 1:18, the mass of the catalyst ruthenium trichloride is 0.6 percent of the mass of the refined ethylene sulfite product, the reaction is carried out at the temperature of 4 ℃ for 5 hours, an organic phase and a water phase are obtained by standing, the organic phase and the water phase are separated, water is added into the organic phase, the mixture is stirred for 0.5 hour, the mixture is kept stand, the water phase is removed, the organic phase is taken, the solvent is removed, and the temperature is 35 ℃, the pressure is-80 KPa and the time is 4 hours in the process of removing the solvent, so that the ethylene sulfate is prepared.
In the step (1), tail gas HCl is generated in the reaction process, and the tail gas HCl is treated by adopting water and a sodium hydroxide solution to obtain an HCl solution with the mass fraction of 29.8%.
In the step (1), the distillation may be carried out in a distillation column, a fine vinyl sulfite product being partially distilled from the upper part of the distillation column, and a residue being obtained at the lower end of the distillation column.
In the step (1), the purity of the refined ethylene sulfite product is 96.4% (by mass fraction), and the yield is 82.4%.
In the step (2), reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding dichloromethane, sodium hypochlorite and an alkali solution (such as a 0.1mol/L sodium hydroxide solution, adjusting the pH to 7) into the aqueous phase, standing for layering to obtain the organic phase and the aqueous phase, removing the aqueous phase, and keeping the organic phase. The catalyst remains in the organic phase and the purpose of this operation is to recover the catalyst. The water phase is high-salinity wastewater and can be evaporated.
In the step (2), the solvent obtained by the solvent removal treatment can be recycled. The ethylene sulfate obtained by removing the solvent is vacuum-dried to obtain ethylene sulfate powder, and the ethylene sulfate powder is mixed with a solvent (for example, ethyl methyl carbonate) to obtain an electrolyte solution.
In the step (2), the purity of the vinyl sulfate ester by mass fraction was 99.6%, and the yield was 77.2%.
Example 3: preparation of vinyl sulfate
A preparation method of vinyl sulfate comprises the following steps:
(1) Mixing thionyl chloride and ethylene glycol according to a molar ratio of 1.1:1, and the mixing process of the thionyl chloride and the ethylene glycol is to drop the ethylene glycol into the thionyl chloride for reaction at the temperature of 0 ℃ for 15 hours, the reaction is carried out in a traditional glass lining reaction kettle to prepare a crude product of the ethylene sulfite, remove acid, distill, and obtain a refined product of the ethylene sulfite at the temperature of 60 ℃ and the vacuum degree of-85 KPa in the process of distillation, wherein the vacuum degree is-85 KPa in the process of acid removal and the temperature is-85 KPa in the process of distillation;
(2) Mixing fine ethylene sulfite, sodium hypochlorite serving as an oxidant (the mass fraction concentration of a sodium hypochlorite solution is 9.9%), dichloromethane serving as a solvent and ruthenium trichloride serving as a catalyst, wherein the molar ratio of the fine ethylene sulfite to the sodium hypochlorite serving as the oxidant to the dichloromethane is 1:18, the mass of the catalyst ruthenium trichloride is 0.4 percent of the mass of the refined ethylene sulfite product, the reaction is carried out at the temperature of 8 ℃ for 5 hours, an organic phase and a water phase are obtained by standing, the organic phase and the water phase are separated, water is added into the organic phase, the mixture is stirred for 0.5 hour, the mixture is kept stand, the water phase is removed, the organic phase is taken, the solvent is removed, and the temperature is 35 ℃, the pressure is-80 KPa and the time is 4 hours in the process of removing the solvent, so that the ethylene sulfate is prepared.
In the step (1), tail gas HCl is generated in the reaction process, and the tail gas HCl is treated by adopting water and a sodium hydroxide solution to obtain an HCl solution with the mass fraction of 30.1%.
In the step (1), the distillation may be carried out in a distillation column, a fine product of vinyl sulfite is partially distilled from the upper part of the distillation column, and a residue is obtained at the lower end of the distillation column.
In the step (1), the purity of the refined ethylene sulfite product is 96.4% (by mass fraction), and the yield is 82.7%.
In the step (2), reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding dichloromethane, sodium hypochlorite and an alkali solution (such as a 0.1mol/L sodium hydroxide solution, adjusting the pH to 9) into the aqueous phase, standing for layering to obtain the organic phase and the aqueous phase, removing the aqueous phase, and keeping the organic phase. The catalyst remains in the organic phase and the purpose of this operation is to recover the catalyst. The water phase is high-salinity wastewater and can be evaporated.
In the step (2), the solvent obtained by the solvent removal treatment can be recycled. The ethylene sulfate obtained by removing the solvent is vacuum-dried to obtain ethylene sulfate powder, and the ethylene sulfate powder is mixed with a solvent (for example, ethyl methyl carbonate) to obtain an electrolyte solution.
In the step (2), the purity of the vinyl sulfate ester by mass fraction was 99.8%, and the yield was 77.7%.
Claims (10)
1. The preparation method of the vinyl sulfate is characterized by comprising the following steps:
(1) Mixing thionyl chloride and ethylene glycol, reacting to obtain a crude product of the ethylene sulfite, and distilling to obtain a refined product of the ethylene sulfite;
(2) Mixing the fine ethylene sulfite, an oxidant solution, a solvent and a catalyst ruthenium trichloride, reacting, standing to obtain an organic phase and an aqueous phase, separating the organic phase and the aqueous phase, adding water into the organic phase, standing, taking the organic phase, and removing the solvent to obtain the ethylene sulfate.
2. The method of claim 1, wherein the thionyl chloride and ethylene glycol are mixed and the reaction is carried out in a conventional glass-lined reactor.
3. The method according to claim 1, wherein in the step (1), the molar ratio of the thionyl chloride to the ethylene glycol is 1.0 to 1.2:1; in the step (1), the reaction temperature is below 10 ℃.
4. The method according to claim 1, wherein the step (1) comprises a step of removing acid after the crude product of the ethylene sulfite is obtained and before the distillation, wherein the vacuum degree in the step of removing acid is-80 to-85 KPa, the temperature is 60 to 62 ℃, and the time is 1 to 2 hours.
5. The method according to claim 1, wherein in the step (1), the purity of the refined product of ethylene sulfite is more than 95% and the yield is more than 81% by mass.
6. The preparation method according to claim 1, wherein in the step (2), the oxidant solution is a sodium hypochlorite solution or hydrogen peroxide; in the step (2), the solvent is at least one of dichloromethane, dichloroethane, dimethyl carbonate, diethyl carbonate or ethyl methyl carbonate.
7. The method according to claim 1, wherein in the step (2), the molar ratio of the ethylene sulfite refined product to the oxidant in the oxidant solution to the solvent is 1: (10.5-12): (15-20).
8. The preparation method according to claim 1, wherein in the step (2), the mass of the catalyst ruthenium trichloride is 0.1-0.8% of the mass of the refined product of the ethylene sulfite.
9. The method according to claim 1, wherein in the step (2), the reaction temperature is 10 ℃ or less; in the step (2), the reaction time is 3-5 hours.
10. The method according to claim 1, wherein in the step (2), the temperature is 30-35 ℃, the pressure is-70 to-90 KPa, and the time is 4-5 hours during the desolvation process.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| CN109776361A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of sulfuric acid vinyl ester |
| CN111533728A (en) * | 2020-07-08 | 2020-08-14 | 东营市海科新源化工有限责任公司 | Preparation method of vinyl sulfate |
| CN111825652A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for preparing vinyl sulfate |
| CN111925352A (en) * | 2020-07-09 | 2020-11-13 | 常州孚新睿科新材料有限公司 | Method for synthesizing vinyl sulfate |
| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
| WO2022092833A1 (en) * | 2020-10-30 | 2022-05-05 | 솔브레인 주식회사 | Method for in-situ preparation of organic sulfur compound |
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2022
- 2022-09-13 CN CN202211124157.6A patent/CN115557927A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| CN109776361A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of sulfuric acid vinyl ester |
| CN111825652A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for preparing vinyl sulfate |
| CN111533728A (en) * | 2020-07-08 | 2020-08-14 | 东营市海科新源化工有限责任公司 | Preparation method of vinyl sulfate |
| CN111925352A (en) * | 2020-07-09 | 2020-11-13 | 常州孚新睿科新材料有限公司 | Method for synthesizing vinyl sulfate |
| WO2022092833A1 (en) * | 2020-10-30 | 2022-05-05 | 솔브레인 주식회사 | Method for in-situ preparation of organic sulfur compound |
| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
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