Method for directly oxidizing ethylene sulfite by using oxygen

Abstract

The invention relates to the technical field of synthesis of ethylene sulfate, provides a method for directly oxidizing ethylene sulfite by using oxygen, and overcomes the defects that an ethylene sulfate synthesis method in the prior art is not environment-friendly, and a used catalyst is difficult to recover and high in price. According to the method, O2 is reduced into peroxide radicals (OOH-) through a catalyst firstly, the peroxide radicals (OOH-) are adsorbed to the surface of a carrier to form an active intermediate (Ti-OOH), and then S = O in ethylene sulfite is oxidized into O = S = O through the Ti-OOH. The method specifically comprises the following steps: 1) preparation of a catalyst and 2) synthesis of ethylene sulfate.

Description

Technical Field

[0001] The invention relates to the technical field of vinyl sulfate synthesis, and in particular to a method for directly oxidizing vinyl sulfite by utilizing oxygen. Background Art

[0002] In recent years, with the proposal of the "dual carbon" goal, the global new energy market has flourished, especially power lithium batteries have attracted widespread attention. Power lithium batteries are mainly composed of electrode materials, electrolytes, diaphragms, battery shells, etc. Among them, the electrolyte plays an important role in the thermal stability and safety performance of lithium-ion batteries. By adding a small amount of additives to the electrolyte (usually accounting for about 5wt% of the electrolyte), the solid electrolyte interface (SEI) formed between the electrode and the electrolyte can be stabilized, thereby improving the discharge performance and safety performance of lithium-ion batteries and extending their service life. Therefore, the development and application of electrolyte additives have received increasing attention from the industry in recent years. Unsaturated carbonates, sulfur-containing salts and lithium salts are the most widely used additives in SEI film-forming additives. Among them, ethyl sulfate (DTD) has good compatibility with silicon negative electrodes, can improve the low-temperature performance of batteries, increase the initial discharge capacity of batteries, and inhibit the expansion of batteries. It has broad application prospects in new electrolyte additives. In addition, DTD is also widely used in the synthesis of pharmaceutical intermediates and surfactants. Therefore, large-scale synthesis of DTD has attracted widespread attention.

[0003] At present, DTD is mainly synthesized by oxidation of ethylene sulfite (ES) in industry. Patent CN111533728A discloses a method using RuCl 3 The method of synthesizing DTD by homogeneous oxidation of ES as a catalyst is also the most common synthesis scheme in the industry. This scheme uses NaClO as an oxidant and dichloromethane as a solvent in an intermittent homogeneous reactor. Although this scheme is mature and simple in process, the homogeneous reaction makes it difficult to recover the catalyst, and RuCl 3 The price is expensive. In addition, the use of NaClO oxidant will also cause some "three wastes" containing Cl to be produced. Based on this, patents CN109422719A and CN116425715A respectively disclose the use of titanium silicon molecular sieve (TS-1) and hydrogen peroxide (H 2 O 2 ) as catalyst and oxidant, among which patent CN109422719A is carried out in an intermittent reactor, while CN116425715A solves the problem of continuous reaction and strong heat release. Patent CN116351413B discloses the use of Ru-loaded CeZrO x The catalyst catalyzes the oxidation of vinyl sulfite in the presence of oxygen, but the Ru loading in this scheme is high and the catalyst is expensive.2 O 2 The reaction system solved RuCl 3 -NaClO system, and is green and environmentally friendly. However, the anthraquinone method is currently the main method for synthesizing H 2 O 2 , will produce more "three wastes", and due to H 2 O 2 The solution itself contains a large number of water molecules, which will cause the hydrolysis of the product DTD, thereby reducing the selectivity of DTD. Therefore, it is very worthy of attention to develop a system for synthesizing DTD by oxidizing ES using oxygen directly as an oxidant and avoiding the participation of water molecules. Summary of the invention

[0004] Therefore, in view of the above problems, the present invention provides a method for directly oxidizing vinyl sulfite using oxygen to solve the defects of the prior art vinyl sulfate synthesis method that is not environmentally friendly, the catalyst used is difficult to recover and is expensive.

[0005] To achieve the above object, the present invention adopts the following technical scheme: a method for directly oxidizing vinyl sulfite using oxygen, comprising the following steps: (1) Catalyst preparation A certain amount of metal salt 1 solid was weighed and dissolved in acetone solution. After being uniformly dissolved, a Ti-containing composite carrier was added and stirred until uniformly. Then, it was placed in a 70°C-75°C oil bath. After the acetone was completely evaporated, the obtained solid was dried in a drying oven. The dried solid was ground into powder and dispersed in ultrapure water. The metal salt 2 aqueous solution was added thereto. After being stirred uniformly, it was transferred to an 85°C-90°C oil bath and refluxed for 9h-10h. The suspension after reflux was evaporated to dryness in an 80°C-85°C oil bath, and dried in an oven overnight. The obtained solid was ground into powder and then refluxed in 5% H 2 / N 2 Reduction is performed in the mixed gas to obtain a powder catalyst; (2) Synthesis of vinyl sulfate The powdered catalyst obtained in step 1) and the substrate ES are weighed and sealed in a high-pressure reactor filled with a solvent and tested for leaks. After the leak test is completed, a certain proportion and pressure of O is injected into the reactor. 2 and H 2 The mixed gas is maintained for a period of time. After the mixed gas is fully dissolved in the solvent, stirring is started, and the temperature is gradually raised to the target reaction temperature for a period of time. Then, stirring is stopped to obtain a liquid containing the reaction product vinyl sulfate, and the liquid is subjected to gas phase analysis to quantify the reaction product; The metal salt is selected from HAuCl 4 , H 2 PdCl 4 、Pd(NO3 ) 2 、Pd(CH 3 COO 2 , PdCl 2 、RuCl 3 , H 2 PtCl 6 ,Ni(NO 3 ) 2 、Ni(CH 3 COO 2 、Cu(NO 3 ) 2 、Co(CH 3 COO 2 Any one or any combination of two or more; The Ti-containing composite carrier is TiO 2 , TS-1, TS-2 or a mixture of two or more in any ratio.

[0006] Further: In the catalyst preparation of step (1), the metal salt 1 and the metal salt 2 are the same substance or different substances, and the total metal loading is 0.1 wt%-5.0 wt%. When they are different substances, the ratio of the metal loading is 0.1-4.0.

[0007] Further: In step (1) of catalyst preparation, the reduction temperature is 200-600°C.

[0008] Further: In the synthesis of vinyl sulfate in step (2), the O 2 and H 2 The ratio is 0.5-4.0 and the pressure is 0.5MPa-4 MPa.

[0009] Further: In the synthesis of vinyl sulfate in step (2), the solvent includes acetonitrile, methanol, ethanol, dimethyl carbonate, and dichloromethane.

[0010] Further: In the synthesis of vinyl sulfate in step (2), the target reaction temperature is 20°C-60°C.

[0011] By adopting the above technical solution, the beneficial effects of the present invention are as follows: the present invention uses metal-loaded TS-1 as a catalyst to solve the problem of industrial RuCl 3 The high cost of the catalyst and the difficulty in separating the homogeneous reaction. In addition, the present invention directly uses oxygen as the oxidant and introduces H 2 Under the action of catalyst, O 2 Activated into peroxide (OOH - ), and through OOH -Direct oxidation of ES to synthesize DTD not only solves the problem of using NaClO solution or H 2 O 2 When the solution is an oxidant, the generation of "three wastes" reduces the cost of using the oxidant and can also inhibit the hydrolysis of the product DTD in water. The successful implementation of this invention provides a new reaction path for the green and low-cost synthesis of DTD from ES. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 In Example 1 of the present invention, oxygen is passed through the intermediate (OOH - ) Schematic diagram of the synthesis of DTD prepared by oxidation of ES; Figure 2 This is the TEM image of the Pd-Au / TS-1 catalyst in Example 1 of the present invention. DETAILED DESCRIPTION

[0013] In order to illustrate the technical problems, technical solutions and beneficial effects to be solved by the present invention, the present invention is further described in detail below in conjunction with specific embodiments. Unless otherwise specified, the experimental methods adopted in the present invention are all conventional methods, and the experimental equipment and reagents used can be obtained from commercial sources. Example 1

[0014] refer to Figure 1 and Figure 2 , a method for directly oxidizing vinyl sulfite using oxygen, comprising the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.3 wt% and dissolve it in an acetone solution. After it is evenly dissolved, add 1 g of titanium silicalite (TS-1) to it. Place the resulting suspension in a 70°C oil bath. After the acetone is completely evaporated, dry the resulting solid in a drying oven. Grind the resulting solid into powder and further disperse it in ultrapure water. Add a metal Au salt aqueous solution (chloroauric acid) with a loading of 0.3 wt% to it. After stirring evenly, transfer it to an 85°C oil bath and continue to reflux for 10 h. Place the refluxed suspension at 80°C. o The water was evaporated in an oil bath and dried in an oven overnight. The obtained solid was ground into powder and then stirred at 5% H 2 / N 2 The mixture was reduced at 450 °C, and the obtained powder was recorded as 0.3Pd-0.3Au / TS-1; (2) Weigh 0.15 g of the above 0.3Pd-0.3Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES) and place the resulting suspension in a high-pressure reactor. Use nitrogen to replace the gas in the high-pressure reactor three times and then check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it.2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The volume ratio is 1. After the gas is rushed in and the pressure is held for 30 minutes to make the gas completely dissolved in the solvent, stirring is started and the temperature is raised to 35°C for 4 hours. The resulting suspension is filtered through an organic filter membrane and then subjected to gas phase analysis. The results show that the ES conversion rate reaches 46% and the DTD selectivity reaches 70%. Example 2

[0015] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.15 wt% and dissolve it in an acetone solution. After the solution is uniformly dissolved, add 1 g of titanium silicalite (TS-1) to the suspension, place the resulting suspension in a 70°C oil bath, and dry the resulting solid in a drying oven after the acetone is completely evaporated; grind the resulting solid into powder and further disperse it in ultrapure water, add a metal Au salt aqueous solution (chloroauric acid) with a loading of 0.15 wt% to the powder, and after stirring evenly, transfer it to an 85°C oil bath and continue to reflux for 10 h; evaporate the water in an 80°C oil bath and dry it in an oven overnight; grind the resulting solid into powder and reflux it in a 5% by volume H 2 / N 2 The mixture was reduced at 450 °C, and the obtained powder was recorded as 0.15Pd-0.15Au / TS-1; (2) Weigh 0.15 g of the above 0.15Pd-0.15Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES). Place the resulting suspension in a high-pressure reactor. Replace the gas in the high-pressure reactor with nitrogen three times and check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The ratio is 1; after the gas is rushed in and the pressure is held for 30 minutes to make the gas completely dissolved in the solvent, stirring is turned on and the temperature is raised to 35°C for 4 hours; the resulting suspension is filtered through an organic filter membrane and then subjected to gas phase analysis; the results show that the ES conversion rate is 34% and the DTD selectivity is 53%. Example 3

[0016] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading amount of 0.4 wt%, dissolve it in an acetone solution, add 1 g of titanium silicalite (TS-1) to the suspension after it is evenly dissolved, place the resulting suspension in a 70°C oil bath, dry the resulting solid in a drying oven after the acetone is completely evaporated, grind the resulting solid into powder and further disperse it in ultrapure water, add a metal Au salt aqueous solution (chloroauric acid) with a loading amount of 0.4 wt%, stir evenly and transfer to an 85°C oil bath and continue to reflux for 10 h, evaporate the water in an 80°C oil bath and dry it in an oven overnight; grind the resulting solid into powder and reflux it in a 5% by volume H 2 / N 2 The mixture was reduced at 450 °C, and the obtained powder was recorded as 0.4Pd-0.4Au / TS-1; (2) Weigh 0.15 g of the above 0.4Pd-0.4Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES). Place the resulting suspension in a high-pressure reactor. Replace the gas in the high-pressure reactor with nitrogen three times and check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 After the gas is injected and the pressure is held for 30 min to completely dissolve the gas in the solvent, stirring is started and the temperature is raised to 35 o C for 4 h; the resulting suspension was filtered through an organic filter membrane and then subjected to gas phase analysis; the results showed that the ES conversion rate reached 54% and the DTD selectivity reached 78%. Example 4

[0017] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.3 wt% and dissolve it in an acetone solution. After the solution is uniformly dissolved, add 1 g of titanium silicalite (TS-1) to the suspension. Place the resulting suspension in a 70°C oil bath. After the acetone is completely evaporated, dry the resulting solid in a drying oven. Grind the resulting solid into powder and further disperse it in ultrapure water. Add a metal Co salt aqueous solution (cobalt acetate) with a loading of 0.3 wt%. After stirring evenly, transfer it to an 85°C oil bath and continue to reflux for 10 h. Evaporate the water of the refluxed suspension in an 80°C oil bath and dry it in an oven overnight. Grind the resulting solid into powder and reflux it in a 5% by volume H 2 / N 2 450 in mixed gas oC was reduced, and the obtained powder was recorded as 0.3Pd-0.3Co / TS-1; (2) Weigh 0.15 g of the above 0.3Pd-0.3Co / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES). Place the resulting suspension in a high-pressure reactor. Replace the gas in the high-pressure reactor with nitrogen three times and check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The ratio of 1 to 2 is 1; after the gas is injected and the pressure is held for 30 minutes to make the gas completely dissolved in the solvent, stirring is started and the temperature is raised to 35°C for 4 hours; the resulting suspension is filtered through an organic filter membrane and then subjected to gas phase analysis. The results show that the ES conversion rate is 17% and the DTD selectivity is 41%. Example 5

[0018] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.3 wt%, dissolve it in an acetone solution, add 1 g of titanium silicalite (TS-1) to it after it is evenly dissolved, place the resulting suspension in a 70°C oil bath, and dry the resulting solid in a drying oven after the acetone is completely evaporated; grind the resulting solid into powder and further disperse it in ultrapure water, add a metal Pt salt aqueous solution (chloroplatinic acid) with a loading of 0.3 wt%, stir evenly, transfer it to an 85°C oil bath and continue to reflux for 10 h; evaporate the water in an 80°C oil bath and dry it in an oven overnight. Grind the resulting solid into powder and place it in a 5% by volume H 2 / N 2 The reduction was carried out at 450 °C in the mixed gas, and the obtained powder was recorded as 0.3Pd-0.3Pt / TS-1; (2) Weigh 0.15 g of the above 0.3Pd-0.3Pt / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES) and place the resulting suspension in a high-pressure reactor. Use nitrogen to replace the gas in the high-pressure reactor three times and then check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2The ratio is 1; after the gas is rushed in and the pressure is held for 30 minutes to make the gas completely dissolved in the solvent, stirring is turned on and the temperature is raised to 35°C for 4 hours; the resulting suspension is filtered through an organic filter membrane and then subjected to gas phase analysis. The results show that the ES conversion rate is 84% ​​and the DTD selectivity is 76%. Example 6

[0019] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.4 wt%, dissolve it in an acetone solution, add 1 g of titanium silicalite (TS-1) to it after it is evenly dissolved, place the resulting suspension in a 70°C oil bath, and dry the resulting solid in a drying oven after the acetone is completely evaporated; grind the resulting solid into powder and further disperse it in ultrapure water, add a metal Au salt aqueous solution (chloroauric acid) with a loading of 0.2 wt%, stir evenly, transfer it to an 85°C oil bath and continue to reflux for 10 h; evaporate the water in an 80°C oil bath and dry it in an oven overnight. Grind the resulting solid into powder and reflux it in 5% H 2 / N 2 450 in mixed gas o C was reduced, and the obtained powder was recorded as 0.4Pd-0.2Au / TS-1; (2) Weigh 0.15 g of the above 0.4Pd-0.2Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES). Place the resulting suspension in a high-pressure reactor. Replace the gas in the high-pressure reactor with nitrogen three times and check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The ratio of 1 to 2 is 1; after the gas is rushed in and the pressure is held for 30 minutes to make the gas completely dissolved in the solvent, stirring is turned on and the temperature is raised to 35 ℃ for 4 hours; the resulting suspension is filtered through an organic filter membrane and then subjected to gas phase analysis; the results show that the ES conversion rate is 76% and the DTD selectivity is 86%. Example 7

[0020] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.45 wt%, dissolve it in an acetone solution, add 1 g of titanium silicalite (TS-1) to it after it is evenly dissolved, place the resulting suspension in a 70°C oil bath, and dry the resulting solid in a drying oven after the acetone is completely evaporated; grind the resulting solid into powder and further disperse it in ultrapure water, add a metal Au salt aqueous solution (chloroauric acid) with a loading of 0.15 wt%, stir evenly, transfer it to an 85°C oil bath and continue to reflux for 10 h; evaporate the water in an 80°C oil bath and dry it in an oven overnight. Grind the resulting solid into powder and place it in a 5% by volume H 2 / N 2 The reduction was carried out at 450 °C in the mixed gas, and the obtained powder was recorded as 0.45Pd-0.15Au / TS-1; (2) Weigh 0.15 g of the above 0.45Pd-0.15Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of substrate ethylene sulfite (ES). Place the resulting suspension in a high-pressure reactor. Replace the gas in the high-pressure reactor with nitrogen three times and check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 After the gas is injected and the pressure is held for 30 min to completely dissolve the gas in the solvent, stirring is started and the temperature is raised to 35 o C for 4 h; the obtained suspension was filtered through an organic filter membrane and then subjected to gas phase analysis; the results showed that the ES conversion rate reached 92% and the DTD selectivity reached 90%; while when the temperature was 45 o C for 4 h, the ES conversion rate can be increased to 95%, and the DTD selectivity can also be increased to 96%. Example 8

[0021] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Weigh a metal Pd salt (palladium acetate) with a loading of 0.6 wt% and dissolve it in an acetone solution. After the solution is uniformly dissolved, add 1 g of titanium silicalite (TS-1) to the solution. Place the resulting suspension in a 70°C oil bath. After the acetone is completely evaporated, dry the resulting solid in a drying oven. Grind the resulting solid into powder and immerse it in a 5% by volume H 2 / N 2 The reduction was carried out at 450 °C in the mixed gas, and the obtained powder was recorded as 0.6Pd / TS-1; (2) Weigh 0.15 g of the above 0.6Pd / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent. Add 0.1 g of the substrate ethylene sulfite (ES). Place the resulting suspension in a high-pressure reactor. Replace the gas in the high-pressure reactor with nitrogen three times and check for leaks. After confirming that the reactor is completely sealed, flush it with 3.5 MPa of O 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The ratio of 1 to 2 was 1. After the gas was injected and the pressure was held for 30 min to make the gas completely dissolved in the solvent, stirring was started and the temperature was raised to 35°C for 4 h. The resulting suspension was filtered through an organic filter membrane and then subjected to gas phase analysis. The results showed that the ES conversion rate reached 71% and the DTD selectivity reached 76%. Example 9

[0022] A method for directly oxidizing vinyl sulfite using oxygen comprises the following steps: (1) Disperse 1 g of titanium silicalite (TS-1) in ultrapure water, add a 0.6 wt% aqueous solution of metal Au salt (chloroauric acid), stir evenly and transfer to an 85 °C oil bath for reflux for 10 h; evaporate the water in an 80 °C oil bath and dry in an oven overnight; grind the obtained solid into powder and precipitate it in a 5% by volume H 2 / N 2 The reduction was carried out at 450 °C in the mixed gas, and the obtained powder was recorded as 0.6Au / TS-1; (2) Weigh 0.15 g of the above 0.6Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent, add 0.1 g of substrate ethylene sulfite (ES), and place the resulting suspension in a high-pressure reactor. Use nitrogen to replace the gas in the high-pressure reactor three times and then check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The ratio is 1. After the gas is flushed in and the pressure is held for 30 min to make the gas completely dissolved in the solvent, stirring is started and the temperature is raised to 35°C for 4 h; the resulting suspension is filtered through an organic filter membrane and then subjected to gas phase analysis; the results show that the ES conversion rate is 6.5% and no DTD product is detected.

[0023] Comparative Example 1 (no metal loading) Weigh 0.15 g of TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent, add 0.1 g of substrate ethylene sulfite (ES), and place the resulting suspension in a high-pressure reactor. Use nitrogen to replace the gas in the high-pressure reactor three times and then check for leaks. After confirming that the reactor is completely sealed, inject 3.5 MPa of O into it. 2 , H 2 and N 2 Mixed gas, of which O 2 and H 2 The ratio was 1; after the gas was rushed in and the pressure was held for 30 min to make the gas completely dissolved in the solvent, stirring was started and the temperature was raised to 35°C for 4 h; the obtained suspension was filtered through an organic filter membrane and then subjected to gas phase analysis; the results showed that ES had almost no conversion.

[0024] Comparative Example 2 (without adding H 2 ) Weigh 0.15 g of the above 0.45Pd-0.45Au / TS-1 catalyst and disperse it in 25 mL of acetonitrile solvent, add 0.1 g of substrate ethylene sulfite (ES), and place the resulting suspension in a high-pressure reactor. Use nitrogen to replace the gas in the high-pressure reactor three times and check for leaks. After confirming that the reactor is completely sealed, flush 3.5 MPa of air into it. After the gas is flushed in and the pressure is held for 30 minutes to facilitate the complete dissolution of the gas in the solvent, start stirring and raise the temperature to 35 o C was reacted for 4 h; the resulting suspension was filtered through an organic filter membrane and then subjected to gas phase analysis; the results showed that ES had almost no conversion.

[0025] Wherein, the metal salt of the present invention is selected from HAuCl 4 , H 2 PdCl 4 、Pd(NO 3 ) 2 、Pd(CH 3 COO 2 , PdCl 2 、RuCl 3 , H 2 PtCl 6 ,Ni(NO 3 ) 2 、Ni(CH 3 COO 2 、Cu(NO 3 ) 2 、Co(CH 3 COO 2 Any one or any combination of two or more of the above, wherein the Ti-containing composite carrier is TiO 2Any one of TS-1, TS-2 or a mixture of two or more in any ratio, any selection within the above range can achieve the purpose of the present invention.

[0026] The above examples and comparative examples show that, in the present invention, metal can effectively promote O 2 Converted into peroxide OOH - Active intermediate, and used for direct oxidation of ES to prepare DTD.

[0027] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for directly oxidizing vinyl sulfite using oxygen, characterized in that: The following steps are involved: (1) Catalyst preparation Weigh a certain amount of metal salt 1 solid and dissolve it in acetone solution. After it is evenly dissolved, add the Ti-containing composite carrier and continue to stir until it is evenly dissolved. Then, place it in a 70°C-75°C oil bath. After the acetone is completely evaporated, dry the obtained solid in a drying oven. Grind the dried solid into powder and disperse it in ultrapure water. Add the metal salt 2 aqueous solution thereto, stir evenly and transfer it to an 85°C-90°C oil bath and continue to reflux for 9h-10h. Evaporate the water of the refluxed suspension in an 80°C-85°C oil bath and dry it in an oven overnight. Grind the obtained solid into powder and reduce it in a 5% by volume H2 / N2 mixed gas to obtain a powder catalyst. (2) Synthesis of vinyl sulfate Weigh the powdered catalyst obtained in step (1) and the substrate ES, seal them together in a high-pressure reactor filled with a solvent and check for leaks. After the leak check is completed, a mixture of O2 and H2 in a certain proportion and pressure is injected into the reactor and maintained for a period of time. After the mixture is fully dissolved in the solvent, stirring is started, and the temperature is gradually raised to the target reaction temperature for a period of time. After that, stirring is stopped to obtain a liquid containing the reaction product vinyl sulfate, and the liquid is subjected to gas phase analysis to quantify the reaction product; The metal salt 1 and the metal salt 2 are selected from any one or any combination of two or more of HAuCl4, H2PdCl4, Pd(NO3)2, Pd(CH3COO)2, PdCl2, RuCl3, H2PtCl6, Ni(NO3)2, Ni(CH3COO)2, Cu(NO3)2, and Co(CH3COO)2; The Ti-containing composite carrier is any one of TiO2, TS-1, and TS-2, or a mixture of two or more of them in any ratio.

2. A method for directly oxidizing vinyl sulfite using oxygen according to claim 1, characterized in that In the catalyst preparation of step (1), the metal salt 1 and the metal salt 2 are the same substance or different substances, and the total metal loading is 0.1 wt%-5.0 wt%. When they are different substances, the ratio of the metal loading is 0.1-4.

0.

3. A method for directly oxidizing vinyl sulfite using oxygen according to claim 1, characterized in that : In the step (1) of catalyst preparation, the reduction temperature is 200-600°C.

4. A method for directly oxidizing vinyl sulfite using oxygen according to claim 1, characterized in that : In step (2) the synthesis of vinyl sulfate, the ratio of O2 to H2 is 0.5-4.0, and the pressure is 0.5 MPa-4 MPa.

5. A method for directly oxidizing vinyl sulfite using oxygen according to claim 1, characterized in that In step (2) of synthesizing vinyl sulfate, the solvent includes acetonitrile, methanol, ethanol, dimethyl carbonate, and dichloromethane.

6. A method for directly oxidizing vinyl sulfite using oxygen according to claim 1, characterized in that In the step (2) of synthesizing vinyl sulfate, the target reaction temperature is 20°C-60°C.

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