CN115677652A - Method for continuously preparing vinyl sulfate - Google Patents
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- CN115677652A CN115677652A CN202211419856.3A CN202211419856A CN115677652A CN 115677652 A CN115677652 A CN 115677652A CN 202211419856 A CN202211419856 A CN 202211419856A CN 115677652 A CN115677652 A CN 115677652A
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Abstract
The invention discloses a method for continuously preparing vinyl sulfate, and belongs to the technical field of preparation of lithium ion battery electrolyte additives. The method for continuously preparing the vinyl sulfate, disclosed by the invention, has the advantages that the whole preparation process is carried out in a constant-temperature continuous state, meanwhile, the waste gas generated by the reaction is continuously introduced and the excessive thionyl chloride is introduced into the alkali liquor to be completely absorbed, so that the dissipation of the waste gas is reduced, and the method is more environment-friendly; acetonitrile capable of interacting with water is used as a solvent, so that hydrogen peroxide can be better combined with raw materials, and the reaction is promoted; the used dehydration molecular sieve effectively removes trace residual moisture in the product and effectively reduces the final water content of the product; moreover, the used hierarchical pore titanium silicalite molecular sieve can be recycled and reused through suction filtration and drying after the reaction is finished, so that the generation of waste solids is reduced; the method has the advantages of simple operation, low energy consumption, continuous operation, low preparation cost and the like, and is easy to industrialize.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrolyte additives, and particularly relates to a method for continuously preparing vinyl sulfate.
Background
The vinyl sulfate is used as a film forming additive, so that the using effect of the lithium ion battery electrolyte is better, mainly due to the fact that the center of the vinyl sulfate contains a sulfur atom with strong electronegativity, the reduction of the vinyl sulfate on the graphite surface is stronger than that of corresponding carbonic ester, therefore, the vinyl sulfate can be reduced on the graphite surface to form a stable SEI film in advance of a solvent, the reductive decomposition of solvent molecules is prevented, and the graphite electrode can be subjected to effective lithium removal and insertion cycle. Therefore, the stability of the graphite negative electrode can be improved by adding the vinyl sulfate in the electrolyte in a proper proportion, and the cycle performance of the battery can be improved.
The current method for preparing the vinyl sulfate mainly comprises the following steps: 1. taking ethylene sulfite as a raw material, taking sodium hypochlorite as a catalyst, and reacting at the temperature of 5 ℃. The method has the following defects: the raw materials are expensive, the single batch conversion rate is low, a large amount of wastewater is generated in the preparation process, the reaction is incomplete, the process is complicated and incoherent, the energy consumption is high, and meanwhile, the used noble metal catalyst ruthenium trichloride is difficult to recycle; because the ruthenium used is an extremely expensive rare noble metal and is expensive, the synthesis process of the vinyl sulfate is very high in cost. 2. The method for preparing the vinyl sulfate by using the sulfur trioxide and the ethylene oxide belongs to gas phase reaction, and has the defects of high dangerousness in the reaction process, high requirement on equipment and difficult industrial production.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for continuously preparing vinyl sulfate, which is used for solving the technical problems of incoherent preparation process, low yield, high energy consumption, serious environmental pollution, high cost and the like of the conventional preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a method for continuously preparing vinyl sulfate, which comprises the following steps:
s1: adding ethylene glycol into a container, heating, and then dripping thionyl chloride for reaction; after the reaction is finished, removing unreacted thionyl chloride to obtain a mixed reaction solution; sequentially adding acetonitrile, a hierarchical pore titanium silicalite molecular sieve and hydrogen peroxide into the mixed reaction liquid for reaction to obtain reaction liquid containing the vinyl sulfate after the reaction is finished;
s2: adding an organic solvent into the reaction liquid containing the vinyl sulfate, standing, separating to obtain an organic solution, and cleaning, standing and layering the organic solution to obtain an organic phase layer and an aqueous phase layer; extracting the aqueous phase layer to obtain an extraction liquid, and combining the extraction liquid and the organic phase layer to obtain an organic solution containing vinyl sulfate; and then carrying out dehydration treatment and recrystallization treatment on the organic solution containing the vinyl sulfate to obtain the vinyl sulfate.
Further, in S1, putting ethylene glycol into a container, and continuously introducing nitrogen into the container for heating; when the thionyl chloride is dropped for reaction, alkali liquor is dropped into the container through a path of introducing nitrogen; the heating temperature of the ethylene glycol is 40-50 ℃.
Further, in S1, the molar ratio of the ethylene glycol to the thionyl chloride is 1: (1.1-1.2); the flow rate of the introduced nitrogen is 0.2L/min.
Further, in S1, the silicon-titanium ratio of the hierarchical pore titanium silicalite molecular sieve is (40-70): 1; the reaction time is 4-5h.
Further, in S1, the mass ratio of the ethylene glycol, the acetonitrile, the hierarchical pore titanium silicalite molecular sieve to the hydrogen peroxide is 1: (20-30): (2-8): (10-15).
Further, in S2, the density of the organic solvent may be higher or lower than that of water; preferably, the organic solvent is one or more of chloroform, carbon tetrachloride, dichloroethane, dichloromethane, dichloropropane and trichloropropane; the mass ratio of the ethylene glycol to the organic solvent is 1: (35-55); the standing time is 5-10min.
Further, in S2, the dehydration process includes: adding magnesium sulfate and a dehydrated molecular sieve into an organic solution containing vinyl sulfate in sequence, sealing and standing, filtering, and carrying out reduced pressure heating treatment.
Further, in S2, the dehydrated molecular sieve is a 3A molecular sieve or a 4A molecular sieve; the mass ratio of the ethylene glycol to the dehydrated molecular sieve is 1: (1-2); the time of the closed standing is 12-24h; the mass ratio of the ethylene glycol to the magnesium sulfate is 1: (0.5-1).
Further, in S2, the recrystallization step is: and (3) dehydrating the organic solution containing the vinyl sulfate, continuously adding a non-polar organic solvent to obtain a white solid, and drying the white solid to obtain the vinyl sulfate.
Further, the mass ratio of the ethylene glycol to the non-polar organic solvent is 3: (2-5).
Further, the drying is carried out in a vacuum drying mode; the temperature of the vacuum drying is 40-70 ℃, the time is 3-5h, and the vacuum degree is-0.1-0.06 MPa.
Further, in S3, the organic solution is washed by: adding deionized water into the organic solution, stirring and washing, and standing for layering to obtain a lower organic phase and an upper aqueous phase; the weight ratio of the ethylene glycol to the deionized water is 1: (5-10).
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a method for continuously preparing vinyl sulfate, the whole preparation process is carried out under a constant temperature and continuous state, meanwhile, nitrogen is continuously introduced to guide the waste gas of the reaction and part of excessive thionyl chloride to be introduced into alkali liquor to be completely absorbed, the dissipation of the waste gas is reduced, the method is more environment-friendly, and the technical problem of serious environmental pollution of the existing preparation method is solved; in addition, the adopted acetonitrile can be mutually dissolved with water and an organic solvent at the same time, so that hydrogen peroxide can be better combined with the raw materials, the reaction is promoted, the reaction time is shortened, and the molar yield of the product is improved; secondly, the used dehydration molecular sieve effectively removes trace residual moisture in the product and effectively reduces the final water content of the product; moreover, the used hierarchical pore titanium silicalite molecular sieve can be recycled and recycled through suction filtration and drying after the reaction is finished, so that the production cost is greatly saved, and the generation of waste solids is reduced; the method disclosed by the invention has the advantages of simplicity in operation, low energy consumption, mild reaction, continuity in operation, small environmental pressure, low preparation cost and the like, and is easy to industrialize. The hierarchical pore titanium silicalite molecular sieve used in the preparation process can be recycled for a plurality of times, thereby greatly reducing the production cost and reducing the generation of waste solids. The prepared vinyl sulfate has the advantages of high molar yield, high purity and low moisture content, and has wide application prospect.
Detailed Description
To make the features and effects of the invention comprehensible to those skilled in the art, general description and definitions shall be provided below with respect to terms and words mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention provides a method for continuously preparing vinyl sulfate, which comprises the following steps:
1) Preparing vinyl sulfate: adding ethylene glycol into a three-neck flask, introducing nitrogen, starting stirring, heating to 40-50 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding thionyl chloride into the three-neck flask for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along a nitrogen path for absorption; after the dropwise addition is finished, sequentially adding acetonitrile, the hierarchical pore titanium silicalite molecular sieves with different silicon-titanium ratios and hydrogen peroxide (30% aqueous solution) into the mixed reaction liquid in the three-necked bottle, stirring and reacting, and stopping the reaction to obtain the reaction liquid containing the vinyl sulfate.
2) Purifying vinyl sulfate: and (2) adding an organic solvent into the reaction liquid containing the vinyl sulfate in the step (1), fully stirring, standing for 5-10min, separating and taking out the organic solution. Adding deionized water into the solution, fully stirring and washing, standing for layering, separating an organic phase layer, adding an organic solvent into the aqueous phase layer for extraction once, combining an extract liquid with the separated organic phase, repeating the washing for 5-8 times to obtain an organic solution containing vinyl sulfate, adding anhydrous magnesium sulfate, stirring and filtering, adding a dehydrated molecular sieve, standing for 12-24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating to remove most of the organic solvent, adding a non-polar organic solvent, cooling to room temperature, filtering to obtain a white solid, putting into a vacuum oven, and drying under reduced pressure to obtain a vinyl sulfate finished product.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 63.5g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1000mL of acetonitrile is sequentially added into the mixed reaction solution in the three-necked bottle, and 80g of the mixture has a silicon-titanium ratio of 70:1, stirring and reacting 300mL of hydrogen peroxide (30 mass percent of aqueous solution) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 1000mL of dichloroethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 5min, separating, taking out the organic solution, adding 200mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 30g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (dehydrated molecular sieve) and standing for 12 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 40g, adding 200g of an organic solvent of n-hexane, cooling to room temperature, filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 4 hours to obtain 18.08g of vinyl sulfate; the molar yield of the vinyl sulfate is 30.13 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 2
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 40 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 68.5g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1000mL of acetonitrile is sequentially added into the mixed reaction solution in the three-necked bottle, and 80g of the mixture has a silicon-titanium ratio of 55:1, stirring and reacting 300mL of hydrogen peroxide (30 mass percent of aqueous solution) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 1000mL of dichloroethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 10min, separating, taking out the organic solution, adding 200mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 25g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (dehydrated molecular sieve) and standing for 24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 60g, adding 300g of an organic solvent of n-hexane, cooling to room temperature and filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 3 hours to obtain 32.42g of vinyl sulfate; the molar yield of the vinyl sulfate is 54.03 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 3
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1000mL of acetonitrile is sequentially added into the mixed reaction solution in the three-necked bottle, and 160g of the mixed reaction solution has a silicon-titanium ratio of 55:1, stirring and reacting 300mL of hydrogen peroxide (30 mass percent of aqueous solution) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 1000mL of dichloroethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 10min, separating, taking out the organic solution, adding 200mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 25g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (dehydrated molecular sieve) and standing for 24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 90g, adding 450g of an organic solvent of n-hexane, cooling to room temperature, filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 4 hours to obtain 41.56g of vinyl sulfate; the molar yield of the vinyl sulfate is 69.27 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 4
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1000mL of acetonitrile was sequentially added to the mixed reaction solution in the three-necked flask, and 240g of a mixture of acetonitrile and silicon-titanium in a ratio of 55:1, stirring and reacting 300mL of hydrogen peroxide (30 mass percent of aqueous solution) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 1000mL of dichloroethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 10min, separating, taking out the organic solution, adding 200mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 25g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (a dehydrated molecular sieve) and standing for 24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 100g, adding 500g of an organic solvent of n-hexane, cooling to room temperature and filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 4 hours to obtain 48.48g of vinyl sulfate; the molar yield of the vinyl sulfate is 80.80 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 5
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1000mL of acetonitrile is sequentially added into the mixed reaction solution in the three-necked bottle, and 80g of silicon-titanium ratio is 40:1, stirring and reacting 300mL of hydrogen peroxide (30 mass percent of aqueous solution) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 1000mL of dichloroethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 10min, separating, taking out the organic solution, adding 200mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 25g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (a dehydrated molecular sieve) and standing for 24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 90g, adding 200g of an organic solvent of n-hexane, cooling to room temperature, filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 4 hours to obtain 43.77g of vinyl sulfate; the molar yield of the vinyl sulfate is 72.95 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 6
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1000mL of acetonitrile is sequentially added into the mixed reaction solution in the three-necked bottle, and the ratio of 160g of silicon to titanium is 40:1, stirring and reacting 300mL of hydrogen peroxide (aqueous solution with the mass fraction of 30%) for 5 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 905mL of dichloropropane into a reaction liquid containing the vinyl sulfate, fully stirring, standing for 5min, separating, taking out an organic solution, adding 200mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 25g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (dehydrated molecular sieve) and standing for 20 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 100g, adding 500g of an organic solvent of n-hexane, cooling to room temperature, filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 4 hours to obtain 48.37g of vinyl sulfate; the molar yield of the vinyl sulfate is 80.62 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 7
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 1100mL of acetonitrile was sequentially added to the mixed reaction solution in the three-necked flask, and 240g of a silicon-titanium ratio of 40:1, stirring and reacting 400mL of hydrogen peroxide (aqueous solution with the mass fraction of 30%) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 1100mL of dichloroethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 10min, separating, taking out the organic solution, adding 150mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 400mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 30g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 50g of a 3A molecular sieve (dehydrated molecular sieve) and standing for 24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 100g, adding 500g of an organic solvent of n-hexane, cooling to room temperature and filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 60 ℃ for 4 hours to obtain 49.17g of vinyl sulfate; the molar yield of the vinyl sulfate is 81.95 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 8
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, starting stirring, heating to 45 ℃, continuously introducing nitrogen, starting stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 900mL of acetonitrile was added to the mixed reaction solution in a three-necked flask in sequence, and 200g of a mixture of silicon and titanium with a silicon-titanium ratio of 40:1, stirring and reacting 280mL of hydrogen peroxide (aqueous solution with the mass fraction of 30%) for 4 hours to obtain reaction liquid containing vinyl sulfate;
s2: adding 659mL of carbon tetrachloride into a reaction liquid containing vinyl sulfate, fully stirring, standing for 10min, separating, taking out an organic solution, adding 300mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of dichloroethane into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; adding 15g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate in sequence, stirring and filtering, adding 30g of a 3A molecular sieve (dehydrated molecular sieve) and standing for 24 hours in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 100g, adding 500g of an organic solvent of n-hexane, cooling to room temperature and filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.08 MPa and the temperature of 40 ℃ for 5 hours to obtain 48.65g of vinyl sulfate; the molar yield of the vinyl sulfate is 81.08 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
Example 9
A process for the continuous production of vinyl sulfate comprising the steps of:
s1: adding 30g of ethylene glycol into a three-necked bottle, introducing nitrogen at a flow rate of 0.2L/min, stirring, heating to 50 ℃, continuously introducing nitrogen, stirring, slowly dropwise adding 66g of thionyl chloride into the three-necked bottle for reaction, and obtaining a mixed reaction solution after the reaction is finished; introducing tail gas generated in the reaction process and part of redundant thionyl chloride into alkali liquor along with a nitrogen path for absorption; after the dropwise addition, 950mL of acetonitrile was sequentially added to the mixed reaction solution in the three-necked flask, and 210g of a silicon-titanium ratio of 55:1, stirring 280mL of hydrogen peroxide (aqueous solution with the mass fraction of 30%) to react for 4 hours, and stopping the reaction to obtain reaction liquid containing vinyl sulfate;
s2: adding 1245mL of dichloromethane into the reaction liquid containing the vinyl sulfate, fully stirring, standing for 10min, separating, taking out the organic solution, adding 225mL of deionized water into the organic solution, fully stirring, cleaning, standing and layering to obtain an organic phase layer and an aqueous phase layer; adding 200mL of chloroform into the aqueous phase layer for extraction once, combining the extract with the separated organic phase layer, and repeating the water washing for 4 times to obtain an organic solution containing vinyl sulfate; sequentially adding 20g of anhydrous magnesium sulfate into an organic solution containing vinyl sulfate, stirring and filtering, adding 60g of 4A molecular sieve (dehydrated molecular sieve) and standing for 20h in a closed manner, filtering and separating the dehydrated molecular sieve, then heating the solution under reduced pressure, evaporating the organic solvent until the mass of the residual liquid is 100g, adding 500g of organic solvent of n-hexane, cooling to room temperature and filtering to obtain a white solid, putting the white solid into a vacuum oven, drying under reduced pressure at the vacuum degree of-0.06 MPa and the temperature of 70 ℃ for 5h to obtain 46.02g of vinyl sulfate; the molar yield of the vinyl sulfate is 76.70 percent (calculated by ethylene glycol), the chromatographic content is more than or equal to 99.5 percent, and the water content is less than or equal to 30ppm.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for continuously preparing vinyl sulfate is characterized by comprising the following steps:
s1: adding ethylene glycol into a container, heating, and then dripping thionyl chloride for reaction; after the reaction is finished, removing unreacted thionyl chloride to obtain a mixed reaction solution; sequentially adding acetonitrile, a hierarchical pore titanium silicalite molecular sieve and hydrogen peroxide into the mixed reaction liquid for reaction to obtain reaction liquid containing the vinyl sulfate after the reaction is finished;
s2: adding an organic solvent into a reaction liquid containing the vinyl sulfate, standing, separating to obtain an organic solution, and cleaning, standing and layering the organic solution to obtain an organic phase layer and an aqueous phase layer; extracting the aqueous phase layer to obtain an extraction liquid, and combining the extraction liquid and the organic phase layer to obtain an organic solution containing vinyl sulfate; and then carrying out dehydration treatment and recrystallization treatment on the organic solution containing the vinyl sulfate to obtain the vinyl sulfate.
2. The method for continuously preparing the vinyl sulfate according to claim 1, wherein in S1, the ethylene glycol is put into a container, and the container is continuously filled with nitrogen for heating; when the thionyl chloride is dropped for reaction, the generated tail gas and the unreacted thionyl chloride are introduced into alkali liquor along the path of introducing nitrogen; the heating temperature of the ethylene glycol is 40-50 ℃.
3. The method for continuously preparing the vinyl sulfate according to claim 1, wherein the molar ratio of the ethylene glycol to the thionyl chloride in S1 is 1: (1.1-1.2); the flow rate of the introduced nitrogen is 0.2L/min.
4. The method for continuously preparing the vinyl sulfate according to claim 1, wherein in S1, the silicon-titanium ratio of the hierarchical pore titanium silicalite molecular sieve is (40-70): 1; the reaction time is 4-5h.
5. The method for continuously preparing the vinyl sulfate according to claim 1, wherein in S1, the mass ratio of the ethylene glycol, the acetonitrile, the hierarchical pore titanium silicalite molecular sieve to the hydrogen peroxide is 1: (20-30): (2-8): (10-15).
6. The method for continuously preparing the vinyl sulfate according to claim 1, wherein in S2, the organic solvent is one or more of chloroform, carbon tetrachloride, dichloroethane, dichloromethane, dichloropropane and trichloropropane; the mass ratio of the ethylene glycol to the organic solvent is 1: (35-55); the standing time is 5-10min.
7. The method for continuously preparing vinyl sulfate according to claim 1, wherein in S2, the step of dehydration treatment is as follows: adding magnesium sulfate and a dehydrated molecular sieve into an organic solution containing vinyl sulfate in sequence, sealing and standing, filtering, and carrying out reduced pressure heating treatment.
8. The method for continuously preparing the vinyl sulfate according to claim 7, wherein in S2, the dehydrated molecular sieve is a 3A molecular sieve or a 4A molecular sieve; the mass ratio of the ethylene glycol to the dehydrated molecular sieve is 1: (1-2); the time of the closed standing is 12-24h; the mass ratio of the ethylene glycol to the magnesium sulfate is 1: (0.5-1).
9. The method for continuously preparing vinyl sulfate according to claim 8, wherein in S2, the step of recrystallization comprises: and (3) dehydrating the organic solution containing the vinyl sulfate, continuously adding a non-polar organic solvent to obtain a white solid, and drying the white solid to obtain the vinyl sulfate.
10. The method for continuously preparing the vinyl sulfate according to claim 9, wherein the mass ratio of the ethylene glycol to the non-polar organic solvent is 3: (2-5).
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