CN108822073B - Preparation method and application of vinyl sulfate - Google Patents
Preparation method and application of vinyl sulfate Download PDFInfo
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- CN108822073B CN108822073B CN201810631491.8A CN201810631491A CN108822073B CN 108822073 B CN108822073 B CN 108822073B CN 201810631491 A CN201810631491 A CN 201810631491A CN 108822073 B CN108822073 B CN 108822073B
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention relates to a preparation method and application of vinyl sulfate. The catalyst is prepared by taking ethylene sulfite as a raw material, water as a reaction medium, metal and/or metal oxide as a catalyst and ozone as an oxidant through catalytic oxidation reaction. The method has the characteristics of high yield, convenient operation, simple post-treatment, no environmental pollution and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of vinyl sulfate.
Background
With the development of electronic information industry in China, the performance requirements on chemical power sources are higher and higher. The lithium ion battery is a main power source of the portable electronic device by virtue of the advantages of small volume, good safety performance, light weight, no pollution and the like. Lithium batteries release heat during charging and discharging, which causes a reduction in battery performance. In the prior art, the performance of the battery under the high temperature condition is improved by adding a vinyl sulfate additive into the electrolyte. The existing method for preparing the vinyl sulfate comprises the following steps: the ethylene sulfite is oxidized into the ethylene sulfate in an inorganic oxidation system such as potassium permanganate, periodate and hypochlorite. The problem that exists is that the aftertreatment of product is comparatively troublesome and the product purity is lower to influence the performance and the life of lithium cell. There are other methods reported in the literature for the synthesis of vinyl sulfate, the reaction formula is as follows:
using hypochlorous acid in a sodium hypochlorite solution as an oxidant, oxidizing the ethylene sulfite in an organic solvent under the catalytic action of a ruthenium compound, then carrying out layering, washing and reduced pressure distillation to finally obtain the ethylene sulfate. When synthesizing the ethylene sulfite, organic matters are used as a solvent, and the defects of low oxidation efficiency and difficult product purification exist.
Disclosure of Invention
The invention aims to provide a method for synthesizing vinyl sulfate, which is simple and efficient, has a single and pure product and is suitable for industrial production.
The technical scheme adopted by the invention is as follows: a preparation method of vinyl sulfate comprises the following steps: the catalyst is prepared by taking ethylene sulfite as a raw material, water as a reaction medium, metal and/or metal oxide as a catalyst and ozone as an oxidant through catalytic oxidation reaction.
In the preparation method of the vinyl sulfate, the catalyst is Fe, Cu, Ni, Al or Al2O3、CuO、FeO、NiO、MnO2And MnO, or a combination of two or more thereof. Preferably, the catalyst is CuO, NiO and Al2O3According to the mass ratio of 1: 0.85: 1.3. Preferably, the catalyst is Cu, NiO or MnO2According to the mass ratio of 1: 1.2: 0.8 in combination. Preferably, the catalyst is Fe, MnO and Al2O3According to the mass ratio of 1: 1.1: 0.9 in combination. Preferably, the catalyst is CuO, MnO and Al2O3According to the mass ratio of 1: 1.2: 0.9 in combination.
In the above method for preparing vinyl sulfate, the ozone is gaseous. Ozone is added by surface contact.
A preparation method of vinyl sulfate comprises the following steps: slowly stirring ethylene sulfite, distilled water and a catalyst uniformly, controlling the temperature to be 0-20 ℃, introducing ozone, reacting for 30-100min, standing for layering, taking an organic layer, and washing to obtain a target product. Preferably, the temperature is controlled to be 0-5 ℃. Preferably, the ozone is introduced in the form of mixed gas of ozone and air, and the ozone content is 20 mL/L; the flow rate of ozone was 0.05L/min.
The invention has the beneficial effects that:
1. according to the invention, water is used as a reaction medium, ozone is used as an oxidant, and the two substances are environment-friendly substances, are low in cost and are easy to obtain, so that the reaction process is not only environment-friendly, but also the post-treatment is simple.
2. In order to increase the reaction efficiency, the metal and/or metal oxide catalyst added into the reaction system is added in a powder or granular form, and the vinyl sulfate is finally generated by adopting a slow stirring mode.
3. The method has the advantages of high yield, no pollution and convenient operation, and the content of the vinyl sulfate in the product can reach about 95 percent.
4. According to the invention, the solid catalyst after ozone oxidation can be directly filtered and removed, and the reaction product is single and pure.
5. The excessive ozone in the method for synthesizing the vinyl sulfate can be decomposed by using activated carbon or hopcalite as a catalyst, and can also be decomposed by using a catalytic combustion method.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to these examples.
Example 1
108.2g (1mol) of ethylene sulfite, 200ml of distilled water and 0.2g of a powdery catalyst (CuO: NiO: Al in mass ratio)2O31: 0.85: 1.3), slowly stirring uniformly, controlling the temperature to be 5 ℃, introducing ozone for 0.05L/min (the concentration of the ozone is 20mL/L), and reacting for 45 minutes. And after the reaction is finished, standing for layering, taking an organic layer, washing the organic layer twice by using distilled water, and drying to obtain the vinyl sulfate with the yield of 94.53%. The product was analyzed by liquid chromatography, and the results showed that the content of vinyl sulfate was 94.36% and the content of vinyl sulfite was 5.52%.
Example 2
216.3g (2mol) of ethylene sulfite, 200ml of distilled water and 0.4g of a particulate catalyst (Cu: NiO: MnO in mass ratio)21: 1.2: 0.8), slowly stirring uniformly, controlling the temperature to be 5 ℃, introducing 0.05L/min of ozone (the concentration of the ozone is 20mL/L), and reacting for 45 min. After the reaction is finished, standing and layering, taking an organic layer, washing the organic layer twice by using distilled water, and drying to obtain the vinyl sulfate with the yield of 95.84%. The product was analyzed by liquid chromatography, and the results showed that the content of vinyl sulfate was 95.63% and the content of vinyl sulfite was 4.28%.
Example 3
2.161kg (2mol) of ethylene sulfite, 2L of distilled water and 4g of powdery catalyst (Fe: MnO: Al in mass ratio)2O31: 1.1: 0.9), slowly stirring uniformly, controlling the temperature to be 5 ℃, introducing ozone for 0.05L/min (the concentration of the ozone is 20mL/L), reacting for 60min, standing and layering after the reaction is finished, taking an organic layer, washing the organic layer twice by using distilled water, and drying to obtain the vinyl sulfate, wherein the yield is 95.17%. The product was analyzed by liquid chromatography, and the results showed that the content of vinyl sulfate was 95.13% and the content of vinyl sulfite was 4.68%.
Example 4
6.483kg (6mol) of ethylene sulfite, 6L of distilled water and 20g of powdered catalyst (CuO: MnO: Al in mass ratio)2O31: 1.2: 0.9), slowly stirring uniformly, controlling the temperature to be 5 ℃, introducing ozone for 0.05L/min (the concentration of the ozone is 20mL/L), reacting for 100min, standing and layering after the reaction is finished, taking an organic layer, washing the organic layer twice by using distilled water, and drying to obtain the vinyl sulfate, wherein the yield is 95.20%. The product was analyzed by liquid chromatography, and the results showed that the content of vinyl sulfate was 95.16% and the content of vinyl sulfite was 4.62%.
Example 5
108.2g (1mol) of ethylene sulfite, 200ml of distilled water and 0.2g of powdery catalyst (CuO: NiO: Al in mass ratio)2O31: 0.85: 1.3), stirring slowly and uniformly, controlling the temperature to be 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃ and 25 ℃, respectively, introducing ozone for 0.05L/min (the concentration of the ozone is 20mL/L), and reacting for 45 minutes. And after the reaction is finished, standing for layering, taking an organic layer, washing the organic layer twice by using distilled water, and drying to obtain the vinyl sulfate. The product was analyzed by liquid chromatography and the results are shown in Table 1.
TABLE 1
| 0℃ | 5℃ | 10℃ | 15℃ | 20℃ | 25℃ | |
| Vinyl sulfate yield% | 95.83 | 94.53 | 92.66 | 85.51 | 68.70 | 53.31 |
| Content of vinyl sulfate% | 95.74 | 94.36 | 92.58 | 85.36 | 68.55 | 53.02 |
| Content of ethylene sulfite | 4.19 | 5.42 | 7.20 | 14.52 | 31.16 | 46.42 |
Claims (5)
1. The preparation method of the vinyl sulfate is characterized by comprising the following steps: taking ethylene sulfite as a raw material, water as a reaction medium, metal and/or metal oxide as a catalyst, and ozone as an oxidant, slowly and uniformly stirring ethylene sulfite, water and the catalyst, controlling the temperature to be 0-5 ℃, introducing ozone, reacting for 30-100min, standing for layering, taking an organic layer, and washing to obtain a target product; the catalyst is CuO, NiO and Al2O3According to the mass ratio of 1: 0.85: 1.3.
2. The method of claim 1, wherein the catalyst is replaced with Cu, NiO, and MnO2According to the mass ratio of 1: 1.2: 0.8 in combination.
3. The method of claim 1, wherein the catalyst is replaced with Fe, MnO and Al2O3According to the mass ratio of 1: 1.1: 0.9 in combination.
4. The method of claim 1, wherein the catalyst is replaced with CuO, MnO and Al2O3According to the mass ratio of 1: 1.2: 0.9 in combination.
5. The method for preparing vinyl sulfate according to claim 1, wherein the concentration of ozone is 20mL/L, and the flow rate of ozone is 0.05L/min.
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| CN201810631491.8A CN108822073B (en) | 2018-06-19 | 2018-06-19 | Preparation method and application of vinyl sulfate |
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| CN109988145B (en) * | 2019-05-13 | 2021-05-28 | 福建博鸿新能源科技有限公司 | Preparation method of vinyl sulfate |
| CN114685424B (en) * | 2020-12-25 | 2023-09-05 | 浙江蓝天环保高科技股份有限公司 | Preparation method of vinyl dithionate |
| CN115215834B (en) * | 2022-08-29 | 2023-12-12 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
| CN115504959B (en) * | 2022-10-22 | 2023-06-27 | 山东师范大学 | Synthesis method of vinyl sulfate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288692A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone from dimethyl sulfoxide |
| CN106187989A (en) * | 2016-07-26 | 2016-12-07 | 张家港瀚康化工有限公司 | The preparation method of sulfuric acid vinyl ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288692A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone from dimethyl sulfoxide |
| CN106187989A (en) * | 2016-07-26 | 2016-12-07 | 张家港瀚康化工有限公司 | The preparation method of sulfuric acid vinyl ester |
Non-Patent Citations (1)
| Title |
|---|
| Catalytic oxidation of dimethyl sulfide with ozone: Effects of promoter and physico-chemical properties of metal oxide catalysts;Venu Gopal Devulapelli et al.;《Applied Catalysis A: General》;20080704;第348卷;第86-93页 * |
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