Ozone catalyst, method for preparing the same, and use thereof

Abstract

The application provides an ozone catalyst and a preparation method and application thereof, and the ozone catalyst comprises a carrier and a transition metal catalyst supported on the carrier; the transition metal catalyst is at least two of titanium, chromium, molybdenum, iron, manganese, cobalt, nickel, copper and zinc. The ozone catalyst has the advantages of easy availability of raw materials, low price, high catalytic activity, high selectivity for synthesizing cyclic sulfate from cyclic sulfite by ozone oxidation, few side reactions, high yield, effective reduction of production cost, meeting the needs of industrial production, no use of aqueous system in the process of synthesizing cyclic sulfate by using the ozone catalyst, no hydrolysis problem, high synthesis efficiency, no generation of salt-containing wastewater, recyclable solvent, safety and environmental protection.

Description

Technical Field

[0001] This invention belongs to the field of ozone catalyst synthesis and application technology, and in particular relates to an ozone catalyst, its preparation method and application, and also provides a process method for catalytic synthesis of cyclic sulfates. Background Technology

[0002] Cyclic sulfates, represented by vinyl sulfate (DTD), are used as additives in lithium-ion battery electrolytes. Their function is to inhibit the decline in initial battery capacity, increase initial discharge capacity, reduce battery swelling after high-temperature storage, and improve battery charge-discharge performance and cycle life. Lithium batteries are the "heart" of new energy vehicles. With the rapid development of my country's new energy vehicle industry, lithium batteries, as one of the most important components, directly affect the market competitiveness and popularity of new energy vehicles through their performance and cost. The development of new energy vehicles has directly driven the expansion of vinyl sulfate production capacity. In addition, vinyl sulfate can also be used as a hydroxyethylating agent in organic synthesis, an intermediate in the synthesis of pharmaceuticals, and as a raw material for synthesizing certain heterocyclic compounds used in gelatin curing, antihypertensive drugs, and novel dual surfactants.

[0003] Currently, the main method for synthesizing vinyl sulfate is to prepare vinyl sulfite from thionyl chloride and ethylene glycol, and then further oxidize vinyl sulfite to obtain vinyl sulfate. Existing processes differ mainly in the type of oxidant and the oxidation method. For example, some processes use titanium silicate molecular sieves to catalyze the oxidation of vinyl sulfite with hydrogen peroxide, while others use sodium tungstate as a catalyst to catalyze the oxidation of vinyl sulfite with sodium hypochlorite. These methods all suffer from problems such as generating large amounts of saline wastewater, low yield, high impurity content, difficulty in purification, or the use of precious metal catalysts, which do not meet current green and environmentally friendly requirements. Another method involves loading ruthenium onto a cerium-zirconium composite oxide and then using this catalyst to catalyze the oxidation of vinyl sulfite to produce vinyl sulfate. In this method, ruthenium is a precious metal, and cerium is a rare earth metal, resulting in expensive and difficult-to-obtain raw materials and high operating costs. Furthermore, vinyl sulfate decomposes in water, leading to low efficiency in synthesizing vinyl sulfate in aqueous systems. Summary of the Invention

[0004] In view of this, to solve the above problems, this invention proposes a supported high-efficiency ozone catalyst, its preparation method, and its application, and also proposes a process for synthesizing cyclic sulfates using this ozone catalyst. The ozone catalyst of this invention uses readily available and inexpensive raw materials, resulting in low production costs, while possessing high catalytic activity. Furthermore, it exhibits high selectivity for the ozone oxidation of cyclic sulfites to cyclic sulfates, with few side reactions, high yield, and effectively reduces production costs, meeting the needs of industrial production. The process of synthesizing cyclic sulfates using this ozone catalyst does not use an aqueous system, eliminates hydrolysis problems, achieves high synthesis efficiency, does not generate saline wastewater, and the solvent can be recycled, making it safe and environmentally friendly.

[0005] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0006] The present invention provides an ozone catalyst, comprising a support and a transition metal catalyst supported on the support; the transition metal catalyst is at least two of titanium, chromium, molybdenum, iron, manganese, cobalt, nickel, copper and zinc, and the molar ratio of each transition metal is between 0.5 and 2.

[0007] In some preferred embodiments of the ozone catalyst of the present invention, the support is one or more of activated alumina, silica, diatomaceous earth, activated carbon, and molecular sieve.

[0008] In some preferred embodiments of the ozone catalyst of the present invention, the transition metal catalyst is loaded onto the support by a co-precipitation method.

[0009] In some preferred embodiments of the ozone catalyst of the present invention, the co-precipitation method specifically involves fully contacting transition metal ions with a support in water, and slowly adding an alkaline solution to uniformly precipitate and load the transition metal ions onto the support; wherein the concentration of transition metal ions in water is controlled at 0.5–1 mol / L, the mass ratio of the support to the transition metal compound is 1–2:1, the amount of alkaline solution used is 1.3–1.6 times that required for metal ion precipitation, and the concentration of the alkaline solution is 0.5–1 mol / L.

[0010] In some preferred embodiments of the ozone catalyst of the present invention, the support is a cylindrical or spherical particulate support with a diameter of 1.5 to 5 mm.

[0011] A second aspect of the present invention provides a method for preparing an ozone catalyst, comprising the following steps:

[0012] S1. Dissolve a transition metal salt in deionized water to obtain an aqueous solution of transition metal ions; wherein the transition metal salt is at least two of the following: titanium salt, chromium salt, molybdenum salt, iron salt, manganese salt, cobalt salt, nickel salt, copper salt, and zinc salt.

[0013] S2. Add the carrier to the aqueous solution of transition metal ions and stir to ensure that the carrier and transition metal ions are in full contact.

[0014] S3. Prepare an alkaline solution and slowly add it dropwise to an aqueous solution of transition metal ions containing a carrier;

[0015] S4. After the addition is complete, continue the reaction. After the reaction is complete, filter the solid. The filtered solid is dried and activated to obtain the ozone catalyst.

[0016] In some preferred embodiments of the ozone catalyst preparation method of the present invention, the concentration of the transition metal ion aqueous solution is 0.5-1 mol / L; the concentration of the alkaline solution is 0.5-1 mol / L.

[0017] A third aspect of the present invention provides the application of an ozone catalyst in the catalytic synthesis of cyclic sulfates.

[0018] In some preferred embodiments of the use of the ozone catalyst of the present invention, the cyclic sulfate is ethylene sulfate or pentaerythritol bicyclic sulfate.

[0019] A fourth aspect of the present invention provides a process for synthesizing cyclic sulfates using the ozone catalyst, comprising the following steps:

[0020] D1. Place the ozone catalyst, solvent, and cyclic sulfate into the reaction vessel;

[0021] D2. Ozone gas is introduced into the reaction vessel, and the reaction proceeds.

[0022] D3. After the reaction is complete, the cyclic sulfate ester is obtained through post-treatment.

[0023] The reaction formula is as follows:

[0024]

[0025] In some preferred embodiments of the process for synthesizing cyclic sulfates using ozone catalysts according to the present invention, in step D1, the solvent is one or a mixture of several of the following: ethanol, cyclohexane, dimethyl carbonate, ethyl acetate, N,N-dimethylformamide, acetonitrile, methanol, acetic acid, and acetone.

[0026] In some preferred embodiments of the process for synthesizing cyclic sulfates using ozone catalysts according to the present invention, in D1, the solvent is one or a mixture of several of cyclohexane, dimethyl carbonate, ethyl acetate, acetonitrile, and methanol.

[0027] In some preferred embodiments of the process for synthesizing cyclic sulfates using ozone catalyst of the present invention, in D1, the amount of ozone catalyst used is 5 to 20 wt% of the amount of the subcyclic sulfate; the volume ratio of solvent to subcyclic sulfate is 2 to 5:1.

[0028] In some preferred embodiments of the process for synthesizing cyclic sulfates using ozone catalysts according to the present invention, the reaction temperature in D2 is controlled between 0 and 50°C.

[0029] In some preferred embodiments of the process for synthesizing cyclic sulfates using ozone catalysts according to the present invention, in D2, the ozone gas introduction rate is 20-60 g / h, the ozone gas concentration is 50-100 mg / L, and the ozone gas introduction time is 3-10 h.

[0030] In some preferred embodiments of the process method for synthesizing cyclic sulfates using ozone catalyst of the present invention, in step D3, the post-treatment specifically involves: filtering out the ozone catalyst, concentrating the filtrate and crystallizing it to obtain crude cyclic sulfate, and then purifying it by recrystallization in dimethyl carbonate, ethyl acetate or dichloromethane to obtain the cyclic sulfate.

[0031] Compared with existing technologies, the ozone catalyst, its preparation method, and its application described in this invention have the following advantages:

[0032] (1) The ozone catalyst described in this invention does not use expensive precious metals, and the transition metals used are all inexpensive and readily available, effectively reducing production costs; it has high catalytic activity, which can ensure that the catalytic synthesis of cyclic sulfates is carried out under mild reaction conditions; it has high selectivity for the synthesis of cyclic sulfates by ozone oxidation of cyclic sulfites, with few side reactions and high yield; it achieves a good balance between significantly reduced production costs and good yield in the synthesis of cyclic sulfates, meeting the needs of industrial production;

[0033] (2) The process of using ozone catalyst to catalyze the synthesis of cyclic sulfate esters described in this invention does not use an aqueous system, does not have hydrolysis problems, has high synthesis efficiency, does not produce saline wastewater, the solvent can be recycled, is safe and environmentally friendly, and has low production cost. Attached Figure Description

[0034] Figure 1 The gas chromatogram of ethylene sulfate prepared in Example 5 of this invention;

[0035] Figure 2 This is a gas chromatogram of vinyl sulfate prepared in Example 9 of the present invention. Detailed Implementation

[0036] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0037] The present invention will be described in detail below with reference to the embodiments.

[0038] Example 1

[0039] Preparation of ozone catalysts:

[0040] S1. In a 500ml reactor equipped with a thermometer, a constant pressure dropping funnel and a stirrer, add 5g cobalt chloride hexahydrate, 5g manganese chloride tetrahydrate and 6g ferric chloride hexahydrate, add 200ml deionized water, and stir in a 30℃ constant temperature water bath for 30min to fully dissolve each metal salt in the deionized water.

[0041] S2. After the metal salt is fully dissolved, add 20g of activated alumina and stir for 1 hour.

[0042] S3. Weigh 8g of sodium hydroxide and dissolve it in 80ml of deionized water to prepare a solution; place the sodium hydroxide solution in a constant pressure dropping funnel and slowly add it dropwise to the aqueous solution of transition metal ions with a carrier while stirring;

[0043] S4. After the addition is complete, continue the reaction for 2 hours. After the reaction is complete, filter out the solid, dry it in a vacuum oven at 80°C for 5 hours, and activate it in a vacuum oven at 150°C for 10 hours to obtain 26.3g of the ozone catalyst No. 1 product.

[0044] Example 2

[0045] Preparation of ozone catalysts:

[0046] S1. In a 500ml reactor equipped with a thermometer, a constant pressure dropping funnel and a stirrer, add 5g of nickel chloride hexahydrate, 5g of manganese chloride tetrahydrate and 6g of ferric chloride hexahydrate, add 200ml of deionized water, and stir in a 30℃ constant temperature water bath for 30min to fully dissolve each metal salt in the deionized water.

[0047] S2. After the metal salt is fully dissolved, add 20g of diatomaceous earth and stir for 1 hour.

[0048] S3. Weigh 8g of sodium hydroxide and dissolve it in 80ml of deionized water to prepare a solution; place the sodium hydroxide solution in a constant pressure dropping funnel and slowly add it dropwise to the aqueous solution of transition metal ions with a carrier while stirring;

[0049] S4. After the addition is complete, continue the reaction for 2 hours. After the reaction is complete, filter out the solid, dry it in a vacuum oven at 80°C for 5 hours, and activate it in a vacuum oven at 150°C for 10 hours to obtain 25.5g of the ozone catalyst No. 2 product.

[0050] Example 3

[0051] Preparation of ozone catalysts:

[0052] S1. In a 500ml reactor equipped with a thermometer, a constant pressure dropping funnel and a stirrer, add 5g of nickel chloride hexahydrate, 5g of chromium chloride hexahydrate and 6g of ferric chloride hexahydrate, add 200ml of deionized water, and stir in a 30℃ constant temperature water bath for 30min to fully dissolve each metal salt in the deionized water.

[0053] S2. After the metal salt is fully dissolved, add 20g of activated carbon and stir for 1 hour.

[0054] S3. Weigh 8g of sodium hydroxide and dissolve it in 80ml of deionized water to prepare a solution; place the sodium hydroxide solution in a constant pressure dropping funnel and slowly add it dropwise to the aqueous solution of transition metal ions with a carrier while stirring;

[0055] S4. After the addition is complete, continue the reaction for 2 hours. After the reaction is complete, filter out the solid, dry it in a vacuum oven at 80°C for 5 hours, and activate it in a vacuum oven at 150°C for 10 hours to obtain 25.1g of the ozone catalyst No. 3 product.

[0056] Example 4

[0057] Preparation of ozone catalysts:

[0058] S1. In a 500ml reactor equipped with a thermometer, a constant pressure dropping funnel and a stirrer, add 3g titanium tetrachloride, 5g molybdenum sulfate, 5g anhydrous copper sulfate and 3g zinc chloride, add 200ml deionized water, and stir in a 30℃ constant temperature water bath for 30min to fully dissolve each metal salt in the deionized water.

[0059] S2. After the metal salt is fully dissolved, add 20g of activated carbon and stir for 1 hour.

[0060] S3. Weigh 12g of sodium hydroxide and dissolve it in 120ml of deionized water to prepare a solution; place the sodium hydroxide solution in a constant pressure dropping funnel and slowly add it dropwise to the aqueous solution of transition metal ions with a carrier while stirring;

[0061] S4. After the addition is complete, continue the reaction for 2 hours. After the reaction is complete, filter out the solid, dry it in a vacuum oven at 80°C for 5 hours, and activate it in a vacuum oven at 150°C for 10 hours to obtain 28.6g of the ozone catalyst #4 product.

[0062] Example 5

[0063] Ozone catalyst for the synthesis of vinyl sulfate:

[0064] D1. In a 500ml reactor equipped with a thermometer and a stirrer, add 108g of vinyl sulfite, 200ml of methanol, and 10g of ozone catalyst #1. Turn on the stirrer and place the reactor in a 30℃ water bath until completely dissolved.

[0065] D2. Introduce ozone gas at a rate of 30 g / h (ozone concentration of 50 mg / L) into the reaction vessel and react for 6 hours.

[0066] D3. After the reaction is complete, the solid ozone catalyst is filtered out. The filtrate is concentrated by heating and then cooled to precipitate the wet material. After drying, 115.3 g of crude vinyl sulfate is obtained. The crude product is recrystallized in dichloromethane to obtain 112.5 g of vinyl sulfate product, with a yield of 90.7% and a purity of 99.92%. The gas chromatogram is shown below. Figure 1 As shown.

[0067] Example 6

[0068] Ozone catalyst for the synthesis of vinyl sulfate:

[0069] D1. In a 500ml reactor equipped with a thermometer and a stirrer, add 108g of vinyl sulfite, 200ml of dimethyl carbonate, and 10g of ozone catalyst #2. Turn on the stirrer and place the reactor in a 20℃ water bath until completely dissolved.

[0070] D2. Introduce 20 g / h of ozone gas (ozone concentration of 50 mg / L) into the reaction vessel and react for 5 hours;

[0071] D3. After the reaction is complete, the solid ozone catalyst is filtered out. The filtrate is heated and concentrated, then cooled to precipitate wet material. After drying, 116.4 g of crude vinyl sulfate is obtained. The crude product is recrystallized in dichloromethane to obtain 113.2 g of vinyl sulfate product, with a product yield of 91.3% and a product purity of 99.91%.

[0072] Example 7

[0073] Ozone catalyst for the synthesis of vinyl sulfate:

[0074] D1. In a 500ml reactor equipped with a thermometer and a stirrer, add 108g of vinyl sulfite, 200ml of N,N-dimethylformamide, and 10g of ozone catalyst 3#. Turn on the stirrer and place the reactor in a 30℃ water bath until completely dissolved.

[0075] D2. Introduce ozone gas at a rate of 30 g / h (ozone concentration of 70 mg / L) into the reaction vessel and react for 3 hours.

[0076] D3. After the reaction is complete, the solid ozone catalyst is filtered out. The filtrate is heated and concentrated, then cooled to precipitate wet material. After drying, 116.7g of crude vinyl sulfate is obtained. The crude product is recrystallized in dichloromethane to obtain 113.1g of vinyl sulfate product, with a product yield of 91.2% and a product purity of 99.92%.

[0077] Example 8

[0078] Ozone catalyst for the synthesis of vinyl sulfate:

[0079] D1. In a 500ml reactor equipped with a thermometer and a stirrer, add 108g of vinyl sulfite, 200ml of dimethyl carbonate, and 10g of ozone catalyst #4. Turn on the stirrer and place the reactor in a 20℃ water bath until completely dissolved.

[0080] D2. Introduce 20 g / h of ozone gas (ozone concentration of 50 mg / L) into the reaction vessel and react for 5 hours;

[0081] D3. After the reaction is complete, the solid ozone catalyst is filtered out. The filtrate is heated and concentrated, then cooled to precipitate wet material. After drying, 115.7g of crude vinyl sulfate is obtained. The crude product is recrystallized in dichloromethane to obtain 112.8g of vinyl sulfate product, with a product yield of 91.1% and a product purity of 99.93%.

[0082] Example 9

[0083] Ozone catalyst for the synthesis of vinyl sulfate:

[0084] Based on Example 5, but differing from Example 5, ozone catalyst #1, which had been reused five times, was used; after drying the material, 114.6 g of crude vinyl sulfate was obtained; the crude product was then recrystallized and purified in dichloromethane to obtain 113.3 g of vinyl sulfate product, with a product yield of 90.6% and a product purity of 99.95%. The gas chromatogram is shown below. Figure 2 As shown.

[0085] Example 10

[0086] Ozone catalyst for the synthesis of vinyl sulfate:

[0087] Based on Example 6, the difference from Example 6 is that ozone catalyst 2#, which has been applied 5 times, is used.

[0088] Example 11

[0089] Ozone catalyst for the synthesis of vinyl sulfate:

[0090] Based on Example 7, the difference is that ozone catalyst #3, which has been applied 5 times, is used.

[0091] Example 12

[0092] Ozone catalyst for the synthesis of vinyl sulfate:

[0093] Based on Example 8, the difference is that ozone catalyst #4, which has been applied 5 times, is used.

[0094] Example 13

[0095] Ozone catalyst for the synthesis of pentaerythritol bicyclic sulfate:

[0096] D1. In a 500ml reactor equipped with a thermometer and a stirrer, add 228g pentaerythritol dicyclic sulfite, 200ml dimethyl carbonate, and 10g ozone catalyst #3. Turn on the stirrer and place the reactor in a 30℃ water bath until completely dissolved.

[0097] D2. Introduce ozone gas at a rate of 30 g / h (ozone concentration of 50 mg / L) into the reaction vessel and react for 6 hours.

[0098] D3. After the reaction is complete, the solid ozone catalyst is filtered out. The filtrate is heated and concentrated, then cooled to precipitate wet material. After drying, 116.7g of crude pentaerythritol dicyclic sulfate is obtained. The crude product is recrystallized in dichloromethane to obtain 236.2g of pentaerythritol dicyclic sulfate product with a purity of 99.91% and a yield of 90.8%.

[0099] The yields and purities of the vinyl sulfate synthesized in Examples 5-8 are shown in Table 1.

[0100] Table 1

[0101] Example 5 1# 93.0％ 90.7％ 99.92％ Example 6 2# 93.9％ 91.3％ 99.91％ Example 7 3# 94.1％ 91.2％ 99.92％ Example 8 4# 93.4％ 91.1％ 99.93％

[0102] As shown in Table 1, the supported high-efficiency ozone catalyst prepared according to this invention catalyzes the ozone oxidation of vinyl sulfite to vinyl sulfate, achieving a crude product yield between 92.4% and 94.1%, a finished product yield between 90.7% and 91.3%, and a purified product purity of over 99.9%. In summary, this invention significantly reduces manufacturing costs while producing products with both required purity and yield, achieving a good balance between production cost, yield, and purity, making it suitable for industrial production.

[0103] Examples 9-12 used ozone catalysts that had been reused five times. The data for synthesizing vinyl sulfate are compared with those of the ozone catalysts used for the first time in Examples 5-8, as shown in Table 2.

[0104] Table 2

[0105]

[0106] As shown in Table 2, the ozone catalyst still has high catalytic activity after being reused 5 times, which can meet the production needs.

[0107] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for the catalytic synthesis of cyclic sulfate esters with an ozone catalyst, characterized in that, Includes the following steps: D1. Place the ozone catalyst, solvent, and cyclic sulfate into the reaction vessel; D2. Ozone gas is introduced into the reaction vessel, and the reaction proceeds. D3. After the reaction is complete, the cyclic sulfate ester is obtained through post-processing. In D1, the ozone catalyst includes a support and a transition metal catalyst supported on the support; the transition metal catalyst is at least two of titanium, chromium, molybdenum, iron, manganese, cobalt, nickel, copper, and zinc; the solvent is one or a mixture of several of cyclohexane, dimethyl carbonate, ethyl acetate, acetonitrile, and methanol; the support is one or a combination of activated alumina, silica, diatomaceous earth, activated carbon, and molecular sieves; the transition metal catalyst is loaded onto the support by a co-precipitation method; specifically, the co-precipitation method involves fully contacting the transition metal ions with the support in water, slowly adding an alkaline solution, so that the transition metal ions are uniformly precipitated and loaded onto the support; wherein the concentration of the transition metal ions in the water is controlled at 0.5–1 mol / L, the mass ratio of the support to the transition metal compound is 1–2:1, the amount of alkaline solution used is 1.3–1.6 times that required for metal ion precipitation, and the concentration of the alkaline solution is 0.5–1 mol / L. mol / L; the amount of ozone catalyst used is 5-20 wt% of the amount of the cyclic sulfate; the volume ratio of solvent to cyclic sulfate is 2-5:1; In D2, the reaction temperature is controlled at 20–50°C; the ozone gas injection rate is 20–60 g / h; the ozone gas concentration is 50–100 mg / L; and the ozone gas injection time is 3–10 h. The cyclic sulfate ester is vinyl sulfate or pentaerythritol bicyclic sulfate ester; The cyclic sulfate is vinyl sulfite or pentaerythritol dicyclic sulfite.

2. The process for the catalytic synthesis of cyclic sulfate esters with ozone catalyst according to claim 1, characterized by the fact that: The carrier is a cylindrical or spherical granular carrier with a diameter of 1.5 to 5 mm.

3. The process for the catalytic synthesis of cyclic sulfate esters with ozone catalyst according to claim 1, characterized in that, The method for preparing the ozone catalyst includes the following steps: S1. Dissolve a transition metal salt in deionized water to obtain an aqueous solution of transition metal ions; wherein the transition metal salt is at least two of the following: titanium salt, chromium salt, molybdenum salt, iron salt, manganese salt, cobalt salt, nickel salt, copper salt, and zinc salt. S2. Add the carrier to the aqueous solution of transition metal ions and stir to ensure that the carrier and transition metal ions are in full contact. S3. Prepare an alkaline solution and slowly add it dropwise to an aqueous solution of transition metal ions containing a carrier; S4. After the addition is complete, continue the reaction. After the reaction is complete, filter the solid. The filtered solid is dried and activated to obtain the ozone catalyst.

4. The process for the catalytic synthesis of cyclic sulfate esters with ozone catalyst according to claim 1, characterized by the fact that: In D3, the post-processing specifically involves: filtering out the ozone catalyst, concentrating the filtrate and crystallizing it to obtain a crude cyclic sulfate ester, and then recrystallizing and purifying it to obtain the cyclic sulfate ester.

5. Use of an ozone catalyst in a process for the catalytic synthesis of cyclic sulfate esters according to claim 1, characterized in that: Applications in the catalytic synthesis of cyclic sulfates.

6. Use of an ozone catalyst according to claim 5 in a process for the catalytic synthesis of cyclic sulfate esters by means of ozone, characterized in that: The cyclic sulfate is vinyl sulfate or pentaerythritol bicyclic sulfate.

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