CN116217539A - Method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation - Google Patents
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Abstract
The invention discloses a method for preparing vinyl sulfate by catalyzing hydrogen peroxide to oxidize, which comprises the following steps: adding an organic solvent, ethylene sulfite, an auxiliary agent and a heterogeneous carrier catalyst into a reaction kettle, dropwise adding hydrogen peroxide into the mixture under stirring to perform catalytic oxidation reaction, filtering the heterogeneous carrier catalyst after the reaction is finished, standing the filtrate for layering, washing and drying an organic layer, and concentrating and crystallizing to obtain the ethylene sulfate product. The method uses the cheap hydrogen peroxide to directly catalyze and oxidize the ethylene sulfite to prepare the ethylene sulfate, and has the advantages of mild reaction conditions, easiness in control, few reaction byproducts and high conversion rate; on the other hand, the produced waste water is less, and the production process is environment-friendly; the heterogeneous carrier catalyst can be recycled and reused, so that the consumption of noble metal is reduced, and the production cost is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of new energy material synthesis, and particularly relates to a method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation.
Background
As a film forming additive of a solid electrode interface film (SEI) in lithium ion battery electrolyte, the vinyl sulfate can effectively inhibit the reduction of the initial capacity of the lithium ion battery, increase the initial discharge capacity, improve the charge-discharge performance and cycle times of the battery, improve the high-low temperature cycle performance, reduce the thermal expansion of the battery after being placed at a high temperature, and is an electrolyte additive which is particularly suitable for high-power ternary lithium ion battery system anode materials. In the pharmaceutical industry, the vinyl sulfate can be used as a hydroxyethylation reagent for organic synthesis of pharmaceutical intermediates, antihypertensive drugs, raw materials of novel double-surfactant and the like. Its wide use and increasing market demand have led to great commercial value in studying the green and efficient synthetic routes of vinyl sulfate.
The laboratory preparation methods and industrial production processes of the vinyl sulfate reported at present mainly comprise an acylation method, a substitution method, an addition method, a dioxane synthesis method and an oxidation method. Among them, the oxidation method is the most commonly used method and the production process in industrial production is more mature.
The oxidation processes disclosed are more routes, and there are mainly the following five methods according to the oxidation source.
The first method is to obtain vinyl sulfate (CN 109485633A) under the catalysis of ruthenium trichloride aqueous solution by taking hypochlorite as an oxidant. The method is widely used in industrial production, and has the advantages of simple production process, high product yield and low overall production cost due to easy separation. However, hypochlorite is not stable enough chemically, and the content of active oxygen generated in a reaction system is low, so that a large amount of oxidant is required to be input in industrial production, so that the amount of wastewater generated after production is large, and a large amount of salt-containing wastewater becomes a main factor for restraining the development of the production process. In addition, a large amount of sodium ions and chloride ions from the oxidant are easy to exceed standard, and high requirements are put on the purification of the product. The second method is to synthesize vinyl sulfate (Flavia P., et al, JACS,2013,135,17176-186) with high efficiency using sodium periodate as an oxidizing agent, without adding or adding a small amount of a metal catalyst. The reaction condition is mild, the product yield is high, but the sodium periodate is extremely expensive, the cost is too high, industrialization is difficult to realize, and iodized impurities are easy to introduce into the product, so that the purification is difficult. The third method is to use potassium permanganate as an oxidant, and the method has the advantages of more side reactions, low yield and difficult product purification (Berridge M.S., et al, J.Org.chem.,1990,55,1211-7). In the fourth method, the potassium hydrogen persulfate composite salt is used as an oxidant to obtain the vinyl sulfate (CN 104744427A) under the catalysis of a ruthenium trichloride aqueous solution. The reaction condition is mild and easy to control, but the cost of the oxidant and the catalyst ruthenium salt is high, and a large amount of sulfate byproducts also cause serious three-waste problems.
The fifth method is to oxidize the ethylene sulfite by preparing peroxide by using hydrogen peroxide as an oxidant or by catalyzing active oxygen of a hydrogen peroxide decomposition product to obtain the product. Hydrogen peroxide is widely developed and applied as a safe and green oxidant, wherein the first proposal is to prepare vinyl sulfate (CN 110386916A) by oxidizing with peroxosulfuric acid as an intermediate product. The method has the advantages of low raw material cost and high product yield, but the reaction is a peroxy strong acid system, high equipment requirement, large amount of sulfate byproducts generated in production and large amount of wastewater. Recently, CN109422719A discloses a method for preparing vinyl sulfate by catalyzing hydrogen peroxide to decompose and oxidize by taking a titanium-silicon molecular sieve (TS-1) as a catalyst. The method has the advantages of mild reaction process, easy control, less byproducts and small wastewater amount, and is a green and environment-friendly method. However, the reported product yields are low, the mass yields are only
And the TS-1 molecular sieve has high price, so that the whole production cost is high. CN111909129a discloses a method for catalyzing oxydol to oxidize sulfite by self-made solid catalyst containing ruthenium metal. The method is easy to control, high in reaction conversion rate, low in energy consumption and less in wastewater, but the preparation process of the solid catalyst is complex, high in cost and difficult to popularize and apply in industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing vinyl sulfate by catalyzing hydrogen peroxide to oxidize, which comprises the steps of dripping hydrogen peroxide into a mixed system of an organic solvent, vinyl sulfate, a heterogeneous carrier catalyst and an auxiliary agent to perform catalytic oxidation reaction, pressurizing and filtering the reacted system, standing and separating liquid, washing and drying, decompressing and rotary steaming, heat-preserving and crystallizing, decompressing and filtering and vacuum drying, wherein the conversion rate is more than 99%, the highest yield can be 82%, the highest purity can be 99.6%, and the method has the characteristics of high conversion rate and high applicable performance.
In order to solve the technical problems, the invention adopts the following technical scheme: the method for preparing the vinyl sulfate by catalyzing hydrogen peroxide oxidation is characterized by comprising the following steps of: mixing an organic solvent, ethylene sulfite, a heterogeneous carrier catalyst and an auxiliary agent to obtain a mixed system A, dripping hydrogen peroxide into the mixed system A, performing catalytic oxidation reaction for 10min to 12h at the temperature of minus 10 ℃ to 80 ℃, and performing pressure filtration, standing and liquid separation, washing and drying, reduced pressure rotary evaporation, heat preservation crystallization, reduced pressure filtration and vacuum drying on the reacted system to obtain ethylene sulfate;
the ratio S of the amount of the sulfur atom in the ethylene sulfite to the amount of the hydrogen peroxide in the hydrogen peroxide is H 2 O 2 =1, (0.5 to 2.5); the mass concentration of the hydrogen peroxide is not less than 1%; the mass of the organic solvent is 1-20 times of that of the ethylene sulfite; the mass of the heterogeneous carrier catalyst is 0.05-10% of that of ethylene sulfite, and the mass fraction of metal in the heterogeneous carrier catalyst is 0.01-20%; the mass of the auxiliary agent is 0.1-10 times of that of the heterogeneous carrier catalyst.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the reaction temperature of the catalytic oxidation reaction is 0-50 ℃ and the reaction time is 30 min-8 h.
The method for preparing the vinyl sulfate by catalyzing the oxidation of the hydrogen peroxide is characterized in that the ratio S of the amount of sulfur atoms in the vinyl sulfite to the amount of hydrogen peroxide in the hydrogen peroxide is H 2 O 2 =1 (1.0-2.0), the mass concentration of the hydrogen peroxide is 15% -50%.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the mass of the organic solvent is 2-10 times of that of the vinyl sulfite.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the mass of the heterogeneous carrier catalyst is 0.1-5% of the mass of the vinyl sulfite, and the mass fraction of metal in the heterogeneous carrier catalyst is 0.05-10%.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the mass of the auxiliary agent is 0.5-5 times of the mass of the heterogeneous carrier catalyst.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the heterogeneous carrier catalyst comprises a carrier and metal loaded on the carrier, wherein the metal is one or more of Ti, V, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, W, re, os, ir, pt, au and Hg; the metal form is one or more of simple substance, oxide, chloride, hydroxide, sulfate, carbonate, nitrate, phosphate, borate, carboxylate and sulfonate; the carrier is graphite, talcum powder, active carbon and SiO 2 、Al 2 O 3 And one or more of diatomaceous earth.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the auxiliary agent is one or more of organic base, inorganic base and Lewis base.
The method for preparing the vinyl sulfate by catalyzing the oxydol oxidation is characterized in that the organic base is one or more of triethylamine, diethylamine, ethylenediamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide; the inorganic base is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium acetate, ammonia water, lithium hydroxide, sodium hydroxide, potassium hydrogen phosphate and potassium phosphate; the Lewis base is one or more of propylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane and diethyl ether.
The method for preparing the vinyl sulfate by catalyzing the oxidation of the hydrogen peroxide is characterized in that the organic solvent is one or more of ketones, nitriles, esters, alkanes, halogenated hydrocarbons and aromatic hydrocarbons; the ketone organic solvent is acetone, butanone, methyl isobutyl ketone or cyclohexanone; the nitrile organic solvent is acetonitrile or propionitrile; the ester organic solvent is methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate; the alkane organic solvent is n-pentane, n-heptane, n-hexane, cyclohexane or petroleum ether; the halogenated hydrocarbon organic solvent is dichloromethane or dichloroethane; the aromatic hydrocarbon organic solvent is benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene.
Compared with the prior art, the invention has the following advantages:
1. the method for preparing the vinyl sulfate by catalyzing hydrogen peroxide oxidation comprises the steps of dripping hydrogen peroxide into a mixed system of an organic solvent, the vinyl sulfate, a heterogeneous carrier catalyst and an auxiliary agent, performing catalytic oxidation reaction, and performing pressurized filtration, standing and liquid separation, washing and drying, reduced pressure rotary evaporation, heat preservation crystallization, reduced pressure filtration and vacuum drying on the reacted system, wherein the conversion rate is more than 99%, the yield is up to 82%, the purity is up to 99.6%, and the method has the characteristics of high conversion rate and high applicable performance.
2. The method uses the cheap hydrogen peroxide to directly oxidize the ethylene sulfite to prepare the ethylene sulfate under the catalysis of the carrier catalyst, and has the advantages of mild reaction process, easy control of reaction, few byproducts, thorough reaction, high conversion rate and low energy consumption.
3. In the method, the used heterogeneous carrier catalyst has simple industrial production process, can be recycled through simple filtration and separation, has no obvious reduction of catalytic effect after application, greatly reduces the dependence on noble metals, greatly reduces the production cost and has wide market prospect.
4. The vinyl sulfate prepared by the method can be used as an additive of lithium ion battery electrolyte, can also be used as an intermediate for preparing medicines and synthesizing pesticides, and has wide application range.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention will be described in detail by examples. In the following examples, unless otherwise specified, all the raw materials used were commercial industrial grade products.
Example 1
The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation in the embodiment specifically comprises the following steps:
adding 50kg of organic solvent dimethyl carbonate into a 100L reaction kettle, stirring at 200rpm for 10min, adding 20kg of ethylene sulfite, 1kg of heterogeneous carrier catalyst Pd/C and 5kg of auxiliary agent diethylene glycol dimethyl ether, and stirring for 0.5h to obtain a mixed system A; the reaction kettle is a jacketed reaction kettle with a high-low temperature integrated machine, the mass percentage content of Pd in the heterogeneous carrier catalyst Pd/C is 5%, and the preparation method of the heterogeneous carrier catalyst Pd/C comprises the following steps: dissolving palladium salt and an auxiliary agent precursor in water, then dipping the mixture on an active carbon carrier, drying and reducing the mixture to obtain a heterogeneous carrier catalyst Pd/C; the soaking time can be more than 12h, the drying is carried out at 100 ℃ for 10h, the drying temperature can also be 80 ℃ or 150 ℃, the drying time can also be 6h or 20h, and the reduction is carried out at N 2 And H 2 Reducing in a mixed atmosphere at 200-400 ℃ for 2-6 h, and the auxiliary agentThe agent precursor is NaCl, and the auxiliary agent precursor can also be Mn (NO 3 ) 2 、Ni(NO 3 ) 2 ·6H 2 O、CuCl 2 、Mg(NO 3 ) 2 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 One or two of O, or NaCl and Mn (NO 3 ) 2 、Ni(NO 3 ) 2 ·6H 2 O、CuCl 2 、Mg(NO 3 ) 2 ·3H 2 O or Zn (NO) 3 ) 2 ·6H 2 A combination of O; the palladium salt may be PdCl 2 ；
Step two, under the condition of continuing stirring, introducing a refrigerant at 50 ℃ into the jacket of the reaction kettle with the jacket, keeping the temperature of the mixed system A at 50 ℃, after 0.5h, increasing the stirring speed to 500rpm, adding 22.1kg of hydrogen peroxide with the mass percentage concentration of 50%, and continuing stirring for 3h to obtain a post-reaction system; adding hydrogen peroxide at a constant speed, wherein the time for adding hydrogen peroxide is 1h; adding hydrogen peroxide and maintaining the system temperature at 50 ℃ in the reaction;
step three, maintaining the reaction temperature, and treating the reacted system by using a pressurizing filter to obtain a retentate and a filtrate, wherein the retentate is a recovered catalyst; the method for treating the reacted system by using the pressurized filter specifically comprises the following steps: guiding out the reacted system through an opening at the lower part of the reaction kettle, transmitting the reacted system into a filter provided with filter cloth 729, sealing the filter, introducing nitrogen gas for filtering, opening a liquid guiding opening at the lower part of the filter for guiding out filtrate, stopping introducing nitrogen gas after the filtrate is guided to be dry, taking out the filter cloth for drying, and obtaining a retentate on the filter cloth; the internal pressure of the filter after the nitrogen is introduced can be 0.2MPa.G; the drying can be carried out for 12 hours in a blast drying oven at 50 ℃;
step four, standing the filtrate for separating liquid to obtain an organic layer; performing GC analysis on the liquid, and calculating the conversion rate of the product by using an area normalization method;
step five, adding 20kg of water into the organic layer, stirring at 500rpm for 0.5h at room temperature to enable the organic phase to fully contact with the water phase, standing for liquid separation to obtain a washed organic layer, passing the washed organic layer through anhydrous sodium sulfate to obtain a dehydrated system, and performing reduced pressure rotary evaporation on the dehydrated system until the volume of the organic layer is 20% of the volume of the organic layer before adding water to obtain a residual liquid phase; the steam is distilled out by rotation to be used as a solvent for recycling;
step six, under the stirring condition of 200rpm, carrying out heat preservation crystallization on the residual liquid phase at the temperature of minus 10 ℃ to obtain crystals, and carrying out reduced pressure filtration and vacuum drying on the crystals to obtain white solid vinyl sulfate; the pressure of the decompression filtration is 5mmHg; the temperature of the vacuum drying is 30 ℃, the vacuum degree is 0.2mmHg, the vacuum drying time is 12 hours, the mass of the white solid is 40.8kg, and the purity is 99.2%. The experimental results are listed in table 1 below.
Example 2
This embodiment is the same as embodiment 1, except that: in the embodiment, the catalyst is 0.8kg heterogeneous carrier catalyst Ru/C, wherein the Ru mass percentage content in the Ru/C is 10%, and the auxiliary agent is 5kg NaHCO with 20% mass concentration 3 An aqueous solution.
Example 3
This example provides a method of applying, specifically comprising synthesizing vinyl sulfate using the heterogeneous supported catalyst recovered in example 1, according to the method of example 1; the catalyst used in this example was a combination of the heterogeneous supported catalyst recovered in example 1 and a new heterogeneous supported catalyst.
Example 4
This example provides a method of applying, specifically comprising synthesizing vinyl sulfate using the heterogeneous supported catalyst recovered in example 3, according to the method of example 1; the catalyst used in this example was a combination of the heterogeneous supported catalyst recovered in example 3 and a new heterogeneous supported catalyst.
Example 5
This example provides a method of applying, specifically comprising synthesizing vinyl sulfate using the heterogeneous supported catalyst recovered in example 4, according to the method of example 1; the catalyst used in this example was a combination of the heterogeneous supported catalyst recovered in example 4 and a new heterogeneous supported catalyst.
Example 6
The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation in the embodiment specifically comprises the following steps:
adding 200kg of organic solvent acetone into a 100L reaction kettle, stirring at 200rpm for 10min, adding 20kg of ethylene sulfite, 0.02kg of heterogeneous carrier catalyst Pd/C and 0.1kg of auxiliary agent triethylamine, and stirring for 0.5h to obtain a mixed system A; the reaction kettle is a jacketed reaction kettle with a high-low temperature integrated machine, and the mass percentage of Pd in the heterogeneous carrier catalyst Pd/C is 0.05%;
step two, under the condition of continuing stirring, introducing a refrigerant at 0 ℃ into the jacket of the jacketed reaction kettle, keeping the temperature of the mixed system A at 0 ℃, after 0.5h, increasing the stirring speed to 500rpm, adding 83.9kg of hydrogen peroxide with the mass percentage concentration of 15%, and continuing stirring for 0.5h to obtain a post-reaction system; adding hydrogen peroxide at a constant speed, wherein the time for adding hydrogen peroxide is 1h; adding hydrogen peroxide and maintaining the system temperature at 0 ℃ in the reaction;
step three, maintaining the reaction temperature, and treating the reacted system by using a pressurizing filter to obtain a retentate and a filtrate, wherein the retentate is a recovered catalyst;
step four, standing the filtrate for separating liquid to obtain an organic layer; performing GC analysis on the liquid, and calculating the conversion rate of the product by using an area normalization method;
step five, adding 20kg of water into the organic layer, stirring at 500rpm for 0.5h at room temperature to enable the organic phase to fully contact with the water phase, standing for liquid separation to obtain a washed organic layer, passing the washed organic layer through anhydrous sodium sulfate to obtain a dehydrated system, and performing reduced pressure rotary evaporation on the dehydrated system until the volume of the organic layer is 20% of the volume of the organic layer before adding water to obtain a residual liquid phase; the steam is distilled out by rotation to be used as a solvent for recycling;
step six, under the stirring condition of 200rpm, carrying out heat preservation crystallization on the residual liquid phase at the temperature of minus 10 ℃ to obtain crystals, and carrying out reduced pressure filtration and vacuum drying on the crystals to obtain white solid vinyl sulfate; the pressure of the decompression filtration is 1mmHg; the temperature of the vacuum drying is 30 ℃, the vacuum degree is 0.1mmHg, and the vacuum drying time is 12 hours. The experimental results are listed in table 1 below.
Example 7
The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation in the embodiment specifically comprises the following steps:
adding 40kg of organic solvents n-pentane and methylene dichloride into a 100L reaction kettle, wherein the mass ratio of the n-pentane to the methylene dichloride is 1:1, stirring for 10min at 200rpm, adding 20kg of ethylene sulfite, 1kg of heterogeneous carrier catalyst Pd/C and 0.5kg of auxiliary agent triethylamine and propylene glycol dimethyl ether, wherein the mass ratio of the triethylamine to the propylene glycol dimethyl ether is 1:1, and stirring for 0.5h to obtain a mixed system A; the reaction kettle is a jacketed reaction kettle with a high-low temperature integrated machine, and the mass percentage of Pd in the heterogeneous carrier catalyst Pd/C is 10%;
step two, under the condition of continuing stirring, introducing a refrigerant at 10 ℃ into the jacket of the jacketed reaction kettle, keeping the temperature of the mixed system A at 10 ℃, after 0.5h, increasing the stirring speed to 500rpm, adding 20.9kg of hydrogen peroxide with the mass percentage concentration of 30%, and continuing stirring for 8h to obtain a post-reaction system; adding hydrogen peroxide at a constant speed, wherein the time for adding hydrogen peroxide is 1h; adding hydrogen peroxide and maintaining the system temperature at 10 ℃ in the reaction;
step three, maintaining the reaction temperature, and treating the reacted system by using a pressurizing filter to obtain a retentate and a filtrate, wherein the retentate is a recovered catalyst;
step four, standing the filtrate for separating liquid to obtain an organic layer; performing GC analysis on the liquid, and calculating the conversion rate of the product by using an area normalization method;
step five, adding 20kg of water into the organic layer, stirring at 500rpm for 0.5h at room temperature to enable the organic phase to fully contact with the water phase, standing for liquid separation to obtain a washed organic layer, passing the washed organic layer through anhydrous sodium sulfate to obtain a dehydrated system, and performing reduced pressure rotary evaporation on the dehydrated system until the volume of the organic layer is 20% of the volume of the organic layer before adding water to obtain a residual liquid phase; the steam is distilled out by rotation to be used as a solvent for recycling;
step six, under the stirring condition of 200rpm, carrying out heat preservation crystallization on the residual liquid phase at the temperature of minus 10 ℃ to obtain crystals, and carrying out reduced pressure filtration and vacuum drying on the crystals to obtain white solid vinyl sulfate; the pressure of the decompression filtration is 5mmHg; the temperature of the vacuum drying is 30 ℃, the vacuum degree is 0.2mmHg, and the vacuum drying time is 12 hours. The experimental results are listed in table 1 below.
Example 8
The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation in the embodiment specifically comprises the following steps:
adding 400kg of organic solvents of methyl acetate and benzene into a 100L reaction kettle, wherein the mass ratio of the methyl acetate to the benzene is 1:2, stirring for 10min at 200rpm, adding 20kg of ethylene sulfite, 0.01kg of heterogeneous carrier catalyst Pd/C and 0.1kg of auxiliary agent sodium bicarbonate and tetrahydrofuran, wherein the mass ratio of the sodium bicarbonate to the tetrahydrofuran is 2:1, and stirring for 0.5h to obtain a mixed system A; the reaction kettle is a jacketed reaction kettle with a high-low temperature integrated machine, and the mass percentage of Pd in the heterogeneous carrier catalyst Pd/C is 20%;
step two, under the condition of continuing stirring, introducing a refrigerant at the temperature of minus 10 ℃ into the jacket of the reaction kettle with the jacket, keeping the temperature of the mixed system A at the temperature of minus 10 ℃, after 0.5h, increasing the stirring speed to 500rpm, adding 315kg of hydrogen peroxide with the mass percentage concentration of 1%, and continuing stirring for 12h to obtain a system after reaction; adding hydrogen peroxide at a constant speed, wherein the time for adding hydrogen peroxide is 1h; adding hydrogen peroxide and maintaining the system temperature at-10 ℃ in the reaction;
step three, maintaining the reaction temperature, and treating the reacted system by using a pressurizing filter to obtain a retentate and a filtrate, wherein the retentate is a recovered catalyst;
step four, standing the filtrate for separating liquid to obtain an organic layer; performing GC analysis on the liquid, and calculating the conversion rate of the product by using an area normalization method;
step five, adding 20kg of water into the organic layer, stirring at 500rpm for 0.5h at room temperature to enable the organic phase to fully contact with the water phase, standing for liquid separation to obtain a washed organic layer, passing the washed organic layer through anhydrous sodium sulfate to obtain a dehydrated system, and performing reduced pressure rotary evaporation on the dehydrated system until the volume of the organic layer is 20% of the volume of the organic layer before adding water to obtain a residual liquid phase; the steam is distilled out by rotation to be used as a solvent for recycling;
step six, under the stirring condition of 200rpm, carrying out heat preservation crystallization on the residual liquid phase at the temperature of minus 10 ℃ to obtain crystals, and carrying out reduced pressure filtration and vacuum drying on the crystals to obtain white solid vinyl sulfate; the pressure of the decompression filtration is 10mmHg; the temperature of the vacuum drying is 30 ℃, the vacuum degree is 0.2mmHg, and the vacuum drying time is 12 hours. The experimental results are listed in table 1 below.
Example 9
The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation in the embodiment specifically comprises the following steps:
step one, adding 20kg of organic solvent acetonitrile into a 100L reaction kettle, stirring at 200rpm for 10min, adding 20kg of ethylene sulfite, 2kg of heterogeneous carrier catalyst Pd/C and 0.2kg of auxiliary agent sodium carbonate, and stirring for 0.5h to obtain a mixed system A; the reaction kettle is a jacketed reaction kettle with a high-low temperature integrated machine, and the mass percentage of Pd in the heterogeneous carrier catalyst Pd/C is 0.01%;
step two, under the condition of continuing stirring, introducing a refrigerant at 80 ℃ into the jacket of the jacketed reaction kettle, keeping the temperature of the mixed system A at 80 ℃, after 0.5h, increasing the stirring speed to 500rpm, adding 52.3kg of hydrogen peroxide with the mass percentage concentration of 30%, and continuing stirring for 10min to obtain a post-reaction system; adding hydrogen peroxide at a constant speed, wherein the time for adding hydrogen peroxide is 1h; adding hydrogen peroxide and maintaining the system temperature at 80 ℃ in the reaction;
step three, maintaining the reaction temperature, and treating the reacted system by using a pressurizing filter to obtain a retentate and a filtrate, wherein the retentate is a recovered catalyst;
step four, standing the filtrate for separating liquid to obtain an organic layer; performing GC analysis on the liquid, and calculating the conversion rate of the product by using an area normalization method;
step five, adding 20kg of water into the organic layer, stirring at 500rpm for 0.5h at room temperature to enable the organic phase to fully contact with the water phase, standing for liquid separation to obtain a washed organic layer, passing the washed organic layer through anhydrous sodium sulfate to obtain a dehydrated system, and performing reduced pressure rotary evaporation on the dehydrated system until the volume of the organic layer is 20% of the volume of the organic layer before adding water to obtain a residual liquid phase; the steam is distilled out by rotation to be used as a solvent for recycling;
step six, under the stirring condition of 200rpm, carrying out heat preservation crystallization on the residual liquid phase at the temperature of minus 10 ℃ to obtain crystals, and carrying out reduced pressure filtration and vacuum drying on the crystals to obtain white solid vinyl sulfate; the pressure of the decompression filtration is 1mmHg; the temperature of the vacuum drying is 30 ℃, the vacuum degree is 0.1mmHg, and the vacuum drying time is 12 hours. The experimental results are listed in table 1 below.
Example 10
The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation in the embodiment specifically comprises the following steps:
step one, adding 20kg of organic solvent into a 100L reaction kettle, stirring at 200rpm for 10min, adding 20kg of ethylene sulfite, 0.5kg of heterogeneous carrier catalyst and 0.25kg of auxiliary agent, and stirring for 0.5h to obtain a mixed system A; the reaction kettle is a jacketed reaction kettle with a high-low temperature integrated machine, and the mass percentage of Pd in the heterogeneous carrier catalyst Pd/C is 10%; the organic solvent is butanone, and the organic solvent can be one or more of other ketones, nitriles, esters, alkanes, halogenated hydrocarbons and aromatic hydrocarbons; the ketone organic solvent can also be butanone, methyl isobutyl ketone or cyclohexanone; the nitrile organic solvent is acetonitrile or propionitrile; the ester organic solvent is methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate; the alkane organic solvent is n-pentane, n-heptane, n-hexane, cyclohexane or petroleum ether; the halogenated hydrocarbon organic solvent is dichloromethane or dichloroethane; the aromatic hydrocarbon organic solvent is benzene, toluene, dimethylbenzene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene;
the heterogeneous carrier catalyst is Pd/C, and the heterogeneous carrier catalyst can also be a carrier metal which is a transition metal element Ti, V, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, W, re, os, ir,The heterogeneous carrier catalyst of one or more of Pt, au and Hg, wherein the form of the load metal is one or more of simple substance, oxide, chloride, hydroxide, sulfate, carbonate, nitrate, phosphate, borate, carboxylate and sulfonate of the transition metal element, and the carrier of the heterogeneous carrier catalyst is graphite, talcum powder, active carbon, siO 2 、Al 2 O 3 And one or more of diatomaceous earth;
the auxiliary agent is potassium carbonate, the auxiliary agent can be one or more of other electrodeless base, organic base and Lewis base, and the organic base is one or more of triethylamine, diethylamine, ethylenediamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide; the inorganic base is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium acetate, ammonia water, lithium hydroxide, sodium hydroxide, potassium hydrogen phosphate and potassium phosphate; the Lewis base is one or more of propylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane and diethyl ether;
step two, under the condition of continuing stirring, introducing a refrigerant at 80 ℃ into the jacket of the jacketed reaction kettle, keeping the temperature of the mixed system A at 80 ℃, after 0.5h, increasing the stirring speed to 500rpm, adding 20.9kg of hydrogen peroxide with the mass percentage concentration of 30%, and continuing stirring for 10min to obtain a post-reaction system; adding hydrogen peroxide at a constant speed, wherein the time for adding hydrogen peroxide is 1h; adding hydrogen peroxide and maintaining the system temperature at 80 ℃ in the reaction;
step three, maintaining the reaction temperature, and treating the reacted system by using a pressurizing filter to obtain a retentate and a filtrate, wherein the retentate is a recovered catalyst;
step four, standing the filtrate for separating liquid to obtain an organic layer; performing GC analysis on the liquid, and calculating the conversion rate of the product by using an area normalization method;
step five, adding 20kg of water into the organic layer, stirring at 500rpm for 0.5h at room temperature to enable the organic phase to fully contact with the water phase, standing for liquid separation to obtain a washed organic layer, passing the washed organic layer through anhydrous sodium sulfate to obtain a dehydrated system, and performing reduced pressure rotary evaporation on the dehydrated system until the volume of the organic layer is 20% of the volume of the organic layer before adding water to obtain a residual liquid phase; the steam is distilled out by rotation to be used as a solvent for recycling;
step six, under the stirring condition of 200rpm, carrying out heat preservation crystallization on the residual liquid phase at the temperature of minus 10 ℃ to obtain crystals, and carrying out reduced pressure filtration and vacuum drying on the crystals to obtain white solid vinyl sulfate; the pressure of the decompression filtration is 1-10 mmHg; the temperature of the vacuum drying is 30 ℃, the vacuum degree is 0.1-0.2 mmHg, and the vacuum drying time is 12h.
In the embodiment, the conversion rate is 96.5% -99.8%, the yield is 77.0% -82.0%, and the purity is 98.5% -99.5%.
Comparative example 1
This comparative example provides a method for preparing vinyl sulfate by catalyzing the oxidation of hydrogen peroxide, which is the same as example 1, except that no catalyst is added.
Comparative example 2
This comparative example provides a method for preparing vinyl sulfate by catalyzing the oxidation of hydrogen peroxide, which is the same as example 1, except that no auxiliary agent is added.
TABLE 1 reaction results of catalytic oxydol oxidation to vinyl sulfate
As shown in Table 1, the method for preparing the vinyl sulfate has the advantages of high conversion rate of over 99 percent, high yield up to 82 percent, high purity up to 99.6 percent, high applicable performance, mild reaction condition, easy control, less reaction byproducts and high conversion rate, and the heterogeneous carrier catalyst has the advantages of simple recovery process and high recovery rate, can be used repeatedly by circulation, reduces the consumption of noble metals, and further reduces the production cost.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent variation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The method for preparing the vinyl sulfate by catalyzing hydrogen peroxide oxidation is characterized by comprising the following steps of: mixing an organic solvent, ethylene sulfite, a heterogeneous carrier catalyst and an auxiliary agent to obtain a mixed system A, dripping hydrogen peroxide into the mixed system A, performing catalytic oxidation reaction for 10min to 12h at the temperature of minus 10 ℃ to 80 ℃, and performing pressure filtration, standing and liquid separation, washing and drying, reduced pressure rotary evaporation, heat preservation crystallization, reduced pressure filtration and vacuum drying on the reacted system to obtain ethylene sulfate;
the ratio S of the amount of the sulfur atom in the ethylene sulfite to the amount of the hydrogen peroxide in the hydrogen peroxide is H 2 O 2 =1, (0.5 to 2.5); the mass concentration of the hydrogen peroxide is not less than 1%; the mass of the organic solvent is 1-20 times of that of the ethylene sulfite; the mass of the heterogeneous carrier catalyst is 0.05-10% of that of ethylene sulfite, and the mass fraction of metal in the heterogeneous carrier catalyst is 0.01-20%; the mass of the auxiliary agent is 0.1-10 times of that of the heterogeneous carrier catalyst.
2. The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation according to claim 1, wherein the reaction temperature of the catalytic oxidation reaction is 0-50 ℃ and the reaction time is 30 min-8 h.
3. The method for preparing vinyl sulfate by catalyzing oxydol oxidation according to claim 1, wherein the ratio S of the amount of sulfur atoms in the vinyl sulfite to the amount of hydrogen peroxide in the oxydol is H 2 O 2 =1 (1.0-2.0), the mass concentration of the hydrogen peroxide is 15% -50%.
4. The method for preparing vinyl sulfate by catalyzing oxydol oxidation according to claim 1, wherein the mass of the organic solvent is 2-10 times of the mass of the vinyl sulfite.
5. The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation according to claim 1, wherein the mass of the heterogeneous carrier catalyst is 0.1-5% of the mass of vinyl sulfite, and the mass fraction of metal in the heterogeneous carrier catalyst is 0.05-10%.
6. The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation according to claim 1, wherein the mass of the auxiliary agent is 0.5-5 times of the mass of the heterogeneous carrier catalyst.
7. The method for preparing vinyl sulfate by catalyzing oxydol oxidation according to claim 1, wherein the heterogeneous carrier catalyst comprises a carrier and a metal loaded on the carrier, wherein the metal is one or more of Ti, V, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, W, re, os, ir, pt, au and Hg; the metal is in the form of simple substance, oxide, chloride, hydroxide, sulfate, carbonate, nitrate, phosphate, borate,One or more of carboxylate and sulfonate; the carrier is graphite, talcum powder, active carbon and SiO 2 、Al 2 O 3 And one or more of diatomaceous earth.
8. The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation according to claim 1, wherein the auxiliary agent is one or more of organic base, inorganic base and Lewis base.
9. The method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation according to claim 8, wherein the organic base is one or more of triethylamine, diethylamine, ethylenediamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide; the inorganic base is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium acetate, ammonia water, lithium hydroxide, sodium hydroxide, potassium hydrogen phosphate and potassium phosphate; the Lewis base is one or more of propylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane and diethyl ether.
10. The method for preparing vinyl sulfate by catalyzing oxydol oxidation according to claim 1, wherein the organic solvent is one or more of ketones, nitriles, esters, alkanes, halogenated hydrocarbons and aromatic hydrocarbons; the ketone organic solvent is acetone, butanone, methyl isobutyl ketone or cyclohexanone; the nitrile organic solvent is acetonitrile or propionitrile; the ester organic solvent is methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate; the alkane organic solvent is n-pentane, n-heptane, n-hexane, cyclohexane or petroleum ether; the halogenated hydrocarbon organic solvent is dichloromethane or dichloroethane; the aromatic hydrocarbon organic solvent is benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene.
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| CN117019021B (en) * | 2023-10-08 | 2023-12-05 | 山东海科新源材料科技股份有限公司 | Device and method for continuous reaction of synthesizing vinyl sulfate |
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