CN116217538A - Method for synthesizing vinylene carbonate by low-temperature oxidation - Google Patents
Method for synthesizing vinylene carbonate by low-temperature oxidation Download PDFInfo
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- CN116217538A CN116217538A CN202211567536.2A CN202211567536A CN116217538A CN 116217538 A CN116217538 A CN 116217538A CN 202211567536 A CN202211567536 A CN 202211567536A CN 116217538 A CN116217538 A CN 116217538A
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- 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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- 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
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- 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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Abstract
The invention relates to a method for synthesizing vinylene carbonate by low-temperature oxidation, which is characterized in that vinylene carbonate is used as a raw material, ozone is used as an oxidant, a tubular reactor is used as a reaction device for reaction, and the reacted material enters a product separation unit to obtain high-purity vinylene carbonate. The invention adopts a one-step oxidation method, can obtain the vinylene carbonate with high selectivity, and solves the problems of serious pollution, poor safety, low yield, high cost and the like of the prior chlorination-dechlorination two-step process. The reaction temperature of the method for synthesizing vinylene carbonate by low-temperature oxidation is 40-80 ℃, the VC yield is 42.3-83.2%, and when the temperature is 50-60 ℃, the VC yield is more than 70%.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for synthesizing vinylene carbonate by low-temperature oxidation.
Background
Vinylene carbonate is an important polymer intermediate and a key additive in lithium battery electrolytes. In recent years, lithium ion batteries, particularly lithium ion power batteries, have been rapidly growing in demand, and the demand for vinylene carbonate has also been rapidly growing. At present, ethylene carbonate is industrially produced by taking ethylene carbonate as a raw material, performing photocatalytic chlorination to obtain chlorinated ethylene carbonate, dechlorinating the chlorinated ethylene carbonate under the action of triethylamine to synthesize the ethylene carbonate, and performing reduced pressure rectification and crystallization on a crude product to obtain a product. The main disadvantage of the process is that the reaction time is longer, the reaction yield is lower, the byproducts are more, the three wastes are obvious, impurities are wrapped in the product obtained by crystallization, and the purity is difficult to further improve. The production of vinylene carbonate has grown slowly, resulting in a rapid increase in the price of vinylene carbonate in recent years, subject to the process and the specificity of chlorine gas raw materials. Therefore, how to clean and efficiently and selectively prepare the high-purity vinylene carbonate is a key technical problem to be solved in the industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for synthesizing vinylene carbonate by low-temperature oxidation. The catalyst related by the method is cheap and easy to obtain and has high activity. The reaction time is short, and continuous production can be realized.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a method for synthesizing vinylene carbonate by low-temperature oxidation, which takes vinylene carbonate as a raw material, ozone as an oxidant, a tubular reactor as a reaction device for reaction, and the reacted material enters a product separation unit to obtain high-purity vinylene carbonate.
In some embodiments of the invention, the molar ratio of ethylene carbonate to ozone is between 1:1 to 1:5, preferably 1:1 to 1:2.
In some embodiments of the invention, packing in the tubular reactor increases the gas-liquid contact area, increasing the mass transfer rate.
In some embodiments of the invention, the pressure of the reaction is atmospheric and the temperature of the reaction is 40-100 ℃, preferably 40-60 ℃.
In some embodiments of the invention, the product separation unit comprises a gas-liquid separation tank, a primary vacuum rectification column, a secondary vacuum rectification column, and an ozone absorber tank.
Further, the separation process of the product separation unit is as follows:
after the outlet material of the tubular reactor is separated by a gas-liquid separation tank, the gas phase material is emptied after being treated by an ozone absorption tank, the liquid phase material enters a first-stage vacuum rectifying tower, the top of the first-stage vacuum rectifying tower is used for extracting water vapor and other light component byproducts, and the bottom material of the first-stage vacuum rectifying tower enters a second-stage vacuum rectifying tower for further separating vinylene carbonate and unreacted ethylene carbonate.
In some embodiments of the invention, the ozone absorber tank is a sodium thiosulfate solution during the separation process of the product separation unit.
In some embodiments of the invention, during the separation of the product separation unit, the temperature of the bottoms of the first-stage vacuum rectification column is 40-80 ℃, preferably 50-70 ℃, and the absolute pressure of the top of the column is 0-20kPa, preferably 5-10kPa.
In some embodiments of the invention, during the separation of the product separation unit, the temperature of the bottoms of the two-stage vacuum rectification column is 70-120 ℃, preferably 80-100 ℃, and the absolute pressure of the top of the column is 0-20kPa, preferably 5-10kPa.
In some embodiments of the invention, during the separation process of the product separation unit, the top of the secondary vacuum rectification column obtains vinylene carbonate, and the bottom of the column obtains unreacted ethylene carbonate.
The invention provides a method for synthesizing vinylene carbonate by low-temperature oxidation, which is a continuous synthesis method and involves the following steps: the ethylene carbonate enters the reactor through a liquid delivery pump; o (O) 3 After being generated by an ozone generator, the wastewater is conveyed to a reactor; in the reactor, ethylene carbonate is oxidized by ozone to generate vinylene carbonate; and carrying out multistage reduced pressure rectification on the product after gas-liquid separation to obtain pure vinylene carbonate.
Compared with the prior art, the method adopts a one-step oxidation method, can obtain the vinylene carbonate with high selectivity, and avoids the problems of serious pollution, poor safety, low yield, high cost and the like of the prior chlorination-dechlorination two-step process. The reaction temperature of the method for synthesizing vinylene carbonate by low-temperature oxidation is 40-80 ℃, the VC yield is 42.3-83.2%, and when the temperature is 50-60 ℃, the VC yield is more than 70%.
Drawings
FIG. 1 is a schematic diagram of a process flow for synthesizing vinylene carbonate by low-temperature oxidation in an embodiment of the invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Referring to FIG. 1, a schematic diagram of a process for synthesizing vinylene carbonate by low-temperature oxidation is shown, wherein ozone is prepared from oxygen through an ozone generator. Ethylene Carbonate (EC) is first stored in an EC tank and pumped via an EC pump into an oxidation reactor (using a tubular reactor). The method for synthesizing vinylene carbonate by low-temperature oxidation is characterized in that ethylene carbonate is used as a raw material, ozone is used as an oxidant, a tubular reactor is used as a reaction device for reaction, and reacted materials enter a product separation unit which comprises a gas-liquid separation tank, a first-stage vacuum rectifying tower, a second-stage vacuum rectifying tower and an ozone absorption tank. Wherein, the separation process of the product separation unit is as follows: and (3) separating an outlet material of the tubular reactor by a gas-liquid separation tank, emptying a gas-phase material after the gas-phase material is treated by an ozone absorption tank, enabling a liquid-phase material to enter a first-stage vacuum rectifying tower, enabling a tower top material of the first-stage vacuum rectifying tower to enter a second-stage vacuum rectifying tower for further separation, and enabling a tower bottom material of the first-stage vacuum rectifying tower to enter a second-stage vacuum rectifying tower for further separation, wherein the tower top of the second-stage vacuum rectifying tower is used for obtaining vinylene carbonate (pure VC product), and enabling a tower bottom to obtain unreacted ethylene carbonate.
Table 1 shows the O under the different conditions in examples 1-10 3 Reaction conditions and yield of synthesizing vinylene carbonate by catalytic oxidation of ethylene carbonate. Examples 1 to 10 in Table 1 were conducted in a tubular reactor, and the products after the reaction were subjected to gas-liquid separation and vacuum distillation to remove water, byproducts and unreacted EC in the products, and the components after the vacuum distillation were analyzed by gas chromatography, whereby the VC yield was calculated.
In examples 1 to 10 below, sodium thiosulfate solution was contained in the ozone absorption tank. The temperature of the tower bottom of the first-stage vacuum rectifying tower is 60 ℃, and the absolute pressure of the tower top is 8kPa. The temperature of the tower bottom of the second-stage vacuum rectifying tower is 90 ℃, and the absolute pressure of the tower top is 8kPa.
TABLE 1O under different conditions 3 Catalytic oxidation of ethylene carbonateYield of vinylene carbonate synthesis
Examples 1 to 5
The volume flow rate of the ethylene carbonate is 0.1mL/min, O 3 The mass flow is 5g/h, the reaction temperature is 40-80 ℃, the products after the reaction are subjected to gas-liquid separation, then the products are subjected to reduced pressure rectification to obtain pure vinylene carbonate, the pure vinylene carbonate is subjected to gas chromatography and quantified, the VC yield is 42.3-83.2% when the reaction is carried out at 40-80 ℃, and the VC yield is more than 70% when the reaction temperature is 50-60 ℃.
Examples 6 to 10
The volume flow rate of the ethylene carbonate is 0.1mL/min, O 3 The mass flow is 10g/h, the reaction temperature is 40-80 ℃, the products after the reaction are subjected to gas-liquid separation, then the products are subjected to reduced pressure rectification to obtain pure vinylene carbonate, the pure vinylene carbonate is subjected to gas chromatography and quantified, the VC yield is 60.6-84.8% when the reaction is carried out at 40-80 ℃, and the VC yield is more than 75% when the reaction temperature is 50-60 ℃.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A method for synthesizing vinylene carbonate by low-temperature oxidation is characterized in that vinylene carbonate is used as a raw material, ozone is used as an oxidant, a tubular reactor is used as a reaction device for reaction, and the reacted material enters a product separation unit to obtain high-purity vinylene carbonate.
2. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 1, wherein the molar ratio of ethylene carbonate to ozone is 1:1 to 1:5.
3. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 2, wherein the molar ratio of ethylene carbonate to ozone is 1:1 to 1:2.
4. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 1, wherein the packing material in the tubular reactor increases the gas-liquid contact area and improves the mass transfer rate.
5. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 1, wherein the pressure of the reaction is normal pressure and the temperature of the reaction is 40-100 ℃.
6. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 5, wherein the pressure of the reaction is normal pressure and the temperature of the reaction is 40-60 ℃.
7. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 1, wherein the product separation unit comprises a gas-liquid separation tank, a primary vacuum rectification column, a secondary vacuum rectification column and an ozone absorption tank;
the separation process of the product separation unit comprises the following steps:
after the outlet material of the tubular reactor is separated by a gas-liquid separation tank, the gas phase material is emptied after being treated by an ozone absorption tank, the liquid phase material enters a first-stage vacuum rectifying tower, the top of the first-stage vacuum rectifying tower is used for extracting water vapor and other light component byproducts, and the bottom material of the first-stage vacuum rectifying tower enters a second-stage vacuum rectifying tower for further separating vinylene carbonate and unreacted ethylene carbonate.
8. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 7, wherein the ozone absorption tank is filled with sodium thiosulfate solution.
9. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 7, wherein the temperature of the tower bottom of the first-stage vacuum rectification tower is 40-80 ℃, preferably 50-70 ℃, and the absolute pressure of the tower top is 0-20kPa, preferably 5-10kPa.
10. The method for synthesizing vinylene carbonate by low-temperature oxidation according to claim 7, wherein the temperature of the bottom of the secondary vacuum rectification column is 70-120 ℃, preferably 80-100 ℃, and the absolute pressure of the top of the column is 0-20kPa, preferably 5-10kPa.
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