Process for the synthesis of oxygenates by oxidation of olefins catalyzed by a molecular sieve supported metal catalyst

Abstract

The present application relates to the technical field of chemical separation and purification, and discloses a method for synthesizing oxygen-containing compounds by catalyzing olefin oxidation with a molecular sieve supported metal catalyst, which uses olefin as raw material and reacts under the conditions of a solvent, an acid, a co-oxidant and a molecular sieve supported metal catalyst, wherein the molecular sieve supported metal catalyst comprises a zeolite molecular sieve and a zeolite molecular sieve supported metal catalyst; the method uses a zeolite molecular sieve as a carrier, the zeolite molecular sieve has a regular topological structure, has high enrichment capacity for substrate molecules, can effectively regulate the geometric / electronic properties of metal particles, accelerates the adsorption and conversion of substrate molecules on the surface of the catalyst, significantly improves the conversion rate of olefin and the yield of target products, and significantly improves the reaction efficiency; in addition, the method provided in the present application has low reaction temperature, does not produce toxic substances, is green, environmentally friendly, energy-saving and efficient.

Description

Technical Field

[0001] This invention relates to the field of chemical catalytic synthesis technology, and in particular to a method for catalyzing the oxidation of olefins to oxide-containing compounds using a molecular sieve-supported metal catalyst. Background Technology

[0002] Olefin oxidation to prepare oxygen-containing compounds is an important industrial reaction. Its oxidation products include aldehydes, ketones, 1,2-diones, and epoxides. These oxidation products have wide applications in the synthesis of fragrances, pharmaceutical intermediates, coatings, and paints. Currently, the olefin oxidation reactions that are relatively mature in industrial production and laboratories include ozone oxidation, Wacker oxidation, Lemieux-Johnson oxidation, and olefin epoxidation. These strategies often require the use of precious metal catalysts that are scarce, expensive, and highly toxic, or require equivalent or even excessive amounts of heavy metals or high-iodine compounds as oxidants. The reaction conditions are harsh, the operation is complex, the catalytic activity is low, and the selectivity is poor, which restricts the application of olefin oxidation reactions in industrial production.

[0003] With increasingly serious environmental problems, clean and green production processes have become an inevitable trend in the chemical industry. Both domestically and internationally, efforts are focused on finding suitable catalytic methods to achieve the selective oxidation of olefins. However, the selective oxidation of olefins is a very difficult process, often facing problems such as low selectivity of the target product, easy over-oxidation, and harsh reaction conditions. Therefore, developing efficient catalysts to achieve the selective oxidation of olefins to prepare oxygen-containing compounds under mild conditions is of great significance. Currently, efficient catalysts are mainly porous supported metal catalysts, such as the catalyst, preparation method, and application of cyclohexene catalytic oxidation to cyclohexanone disclosed in publication number CN110975924B, which uses the porous material SBA-1. Five catalysts were prepared by supporting Pd metal. This method can achieve a cyclohexene conversion rate of up to 89.7% and a cyclohexanone yield of up to 75.3%. Moreover, the cyclohexanone yield remains at 70% after four catalytic cycles. Another example is a method for preparing cyclohexanone disclosed in publication CN111747832A. In this method, the catalyst Fe-MIL-101 catalyzes the preparation of cyclohexene from cyclohexene, achieving a cyclohexene conversion rate of up to 95.5% and a cyclohexanone selectivity of up to 98.5%. Currently, existing technologies have high olefin conversion rates but low target product yields, indicating that the substrate molecules are not effectively converted. Therefore, it is of great significance to provide a method that significantly improves both olefin conversion and target product yield. Summary of the Invention

[0004] To overcome the above-mentioned technical problems, the present invention provides a method for catalyzing the oxidation of olefins to synthesize oxides using a molecular sieve-supported metal catalyst. This method uses zeolite molecular sieves as the support for the molecular sieve-supported metal catalyst. Zeolite molecular sieves have a regular topological structure, controllable acid-base properties, and efficient enrichment ability for substrate molecules. At the same time, using zeolite molecular sieves as a support can also effectively regulate the geometric / electronic properties of the metal catalyst particles, accelerate the adsorption and transformation of substrate molecules on the catalyst surface, significantly improve the olefin conversion rate and the yield of the target product, and significantly improve the reaction efficiency.

[0005] The specific technical solution of this invention is as follows: A method for catalyzing the oxidation of olefins to synthesize oxides using a molecular sieve-supported metal catalyst involves reacting olefins as raw materials under conditions of solvent, acid, co-oxidant, and molecular sieve-supported metal catalyst; wherein the molecular sieve-supported metal catalyst uses zeolite molecular sieve as a support and metal catalyst as a loading material.

[0006] This invention provides a method for the oxidative synthesis of oxides from olefins using a molecular sieve-supported metal catalyst. The method uses olefins as raw materials and reacts them under conditions of solvent, acid, co-oxidant, and a molecular sieve-supported metal catalyst to obtain oxide-containing compounds. The molecular sieve-supported metal catalyst in this method uses zeolite molecular sieves as a support. Zeolite molecular sieves have a porous structure and a regular topology. Using zeolite molecular sieves to support metals can effectively control the geometric / electronic properties of the metal, resulting in efficient enrichment of substrate molecules. This accelerates the adsorption and conversion of substrate molecules on the catalyst surface, significantly improving the olefin conversion rate and the yield of the target product, thus significantly improving the reaction efficiency.

[0007] Preferably, the zeolite molecular sieve is selected from one of the following: silicalite-1 molecular sieve, ZSM-5 molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, Y molecular sieve, Beta molecular sieve, AlPO4-5 molecular sieve, AlPO4-11 molecular sieve, AlPO4-17 molecular sieve, and AlPO4-34 molecular sieve.

[0008] Preferably, the metal catalyst contains one or more of palladium, platinum, iron, cobalt, nickel, copper, or ruthenium.

[0009] Preferably, the loading of the metal catalyst is 0.1 to 10 wt%.

[0010] Preferably, the reaction conditions include: a reaction temperature of 30–180°C, a reaction pressure of 0.1–3.0 MPa, and a reaction time of 0.1–36 h.

[0011] Preferably, the olefin has a mass fraction of 0.01–80%, the co-oxidant has a mass fraction of 0.01–5%, the molecular sieve-supported metal catalyst has a mass percentage of 0.01–10%, and the acid has a mass fraction of 0.01–5%.

[0012] Preferably, the olefin is selected from one of cyclohexene, ethylene, propylene, butene, pentene, hexene, styrene, and styrene.

[0013] Preferably, the solvent is selected from one or more of methanol, ethanol, acetonitrile, water, ethyl acetate, dichloromethane, toluene, or cyclohexane.

[0014] Preferably, the acid is selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, acetic acid, or molecular sieve solid acids.

[0015] Preferably, the co-oxidant is selected from H3PMo. 12 O 40 One or more of BQ, FePc, HQ / FePc, CuSO4 / FePc / HQ or HQ / NPMoV.

[0016] Compared with the prior art, this application has the following technical effects: This application provides a method for the oxidative synthesis of oxides from olefins using a molecular sieve-supported metal catalyst. This method employs a zeolite molecular sieve as the support for the molecular sieve-supported metal catalyst. Zeolite molecular sieves possess a regular topological structure, controllable acid-base properties, and a highly efficient enrichment capacity for substrate molecules. Furthermore, using a zeolite molecular sieve as a support can effectively control the geometric / electronic properties of the metal catalyst particles, accelerating the adsorption and conversion of substrate molecules on the catalyst surface, significantly improving the olefin conversion rate and the yield of the target product, and significantly enhancing the reaction efficiency. In addition, the method provided in this application involves a low reaction temperature, produces no toxic substances, and is green, environmentally friendly, energy-efficient, and highly effective. Detailed Implementation

[0017] The present invention will be further described below with reference to embodiments.

[0018] Example 1: (Catalyst Pd / S-1) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / S-1 (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40(Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0019] Example 2: (Catalyst Pd / ZSM-5) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / ZSM-5 (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0020] Example 3: (Catalyst Pd / 4A) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / 4A (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0021] Example 4: (Catalyst Pd / 5A) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / 5A (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0022] Example 5: (Catalyst Pd / 13X) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / 13X (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0023] Example 6: (Catalyst Pd / Y) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / Y (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0024] Example 7: (Catalyst Pd / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / Beta (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0025] Example 8: (Catalyst Pd / AlPO4-5) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / AlPO4-5 (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0026] Example 9: (Catalyst Pd / AlPO4-11) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / AlPO4-11 (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0027] Example 10: (Catalyst Pd / AlPO4-17) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / AlPO4-17 (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0028] Example 11: (Catalyst Pd / AlPO4-34) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pd / AlPO4-34 (Pd loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0029] Example 12: (Catalyst Pt / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Pt / Beta (Pt loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0030] Comparative Example 1: (Conventional catalyst Pd / Al2O3) Compared to Examples 1 to 12, Comparative Example 12 used a conventional supported catalyst, Pd / Al2O3, while the other conditions were the same as in Examples 1 to 12.

[0031] Table 1. Cyclohexane conversion and cyclohexanone yield of Examples 1 to 12 and Comparative Example 1 Example 1 Pd / S-1 5.6 5.0 Example 2 Pd / ZSM-5 3.2 3.0 Example 3 Pd / 4A 0.6 0.6 Example 4 Pd / 5A 0.5 0.5 Example 5 Pd / 13X 0.2 0.2 Example 6 Pd / Y 0.9 0.8 Example 7 Pd / Beta 6.9 6.8 Example 8 <![CDATA[Pd / AlPO4-5]]> 3.2 3.0 Example 9 <![CDATA[Pd / AlPO4-11]]> 2.9 2.9 Example 10 <![CDATA[Pd / AlPO4-17]]> 1.6 1.6 Example 11 <![CDATA[Pd / AlPO4-34]]> 3.7 3.7 Example 12 Pt / Beta 5.7 5.7 Comparative Example 1 <![CDATA[Pd / Al2O3]]> ＜1 ＜1 Table 1 shows the conversion rates of cyclohexane and the yields of cyclohexanone catalyzed by zeolite molecular sieve-supported metal catalysts. The results indicate that when the metal catalyst is Pd, S-1, ZSM-5, Beta, AlPO4-5, AlPO4-11, AlPO4-17, and AlPO4-34 molecular sieves exhibit high catalytic efficiencies, with Beta molecular sieve showing the highest efficiency. Even when the metal catalyst is Pt, Beta molecular sieve still demonstrates high catalytic efficiency. Conventional Al2O3-supported catalysts show low catalytic efficiencies, with both cyclohexene conversion and cyclohexanone yields less than 1%. Furthermore, 4A, 5A, 13X, and Y molecular sieves also show low cyclohexene conversion and cyclohexanone yields. These results suggest that zeolite molecular sieves, when used as metal catalyst supports, exhibit high catalytic efficiency for the oxidation synthesis of olefins; however, not all zeolite molecular sieves possess high catalytic efficiency.

[0032] Example 13: (Catalyst Ru / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Ru / Beta (Ru loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0033] Comparative Example 2: (Conventional catalyst Ru / Al2O3) Compared to Example 13, Comparative Example 2 used a conventional supported catalyst Ru / Al2O3, with all other conditions being the same as in Example 13.

[0034] Example 14: (Catalyst Fe / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Fe / Beta (Fe loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40(Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0035] Comparative Example 3: (Conventional catalyst Fe / Al2O3) Compared to Example 3, Comparative Example 3 used a conventional supported catalyst Fe / Al2O3, and the other conditions were the same as in Example 14.

[0036] Example 15: (Catalyst Co / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Co / Beta (Co loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0037] Comparative Example 4: (Conventional catalyst Co / Al2O3) Compared to Example 15, Comparative Example 4 used a conventional supported catalyst Co / Al2O3, with all other conditions being the same as in Example 15.

[0038] Example 16: (Catalyst Ni / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Ni / Beta (Ni loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0039] Comparative Example 5: (Conventional catalyst Ni / Al2O3) Compared to Example 16, Comparative Example 5 used a conventional supported catalyst Ni / Al2O3, with all other conditions being the same as in Example 16.

[0040] Example 17: (Catalyst Cu / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g Cu / Beta (Cu loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0041] Comparative Example 6: (Conventional catalyst Cu / Al2O3) Compared to Example 17, Comparative Example 6 used a conventional supported catalyst Cu / Al2O3, with all other conditions being the same as in Example 17.

[0042] Example 18: (Catalyst PdCu / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdCu / Beta (PdCu loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0043] Comparative Example 7: (Conventional catalyst PdCu / Al2O3) Compared to Example 18, Comparative Example 18 used a conventional supported catalyst, PdCu / Al2O3, with all other conditions being the same as in Example 18.

[0044] Example 19: (Catalyst PdFe / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdFe / Beta (PdFe loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mixed thoroughly; 1 MPa oxygen was introduced, and the reaction was carried out at 100 °C for 24 hours. The cyclohexene conversion rate was 10.6%, and the cyclohexanone yield was 10.6%.

[0045] Comparative Example 8: (Conventional catalyst PdFe / Al2O3) Compared to Example 19, Comparative Example 8 used a conventional supported catalyst, PdFe / Al2O3, with all other conditions being the same as in Example 19.

[0046] Example 20: (Catalyst PdNi / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0047] Comparative Example 9: (Conventional catalyst PdNi / Al2O3) Compared to Example 20, Comparative Example 9 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 20.

[0048] Example 21: (Catalyst PdCo / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdCo / Beta (PdCo loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0049] Comparative Example 10: (Conventional catalyst PdCo / Al2O3) Compared to Example 21, Comparative Example 21 used a conventional supported catalyst, PdCo / Al2O3, with all other conditions being the same as in Example 21.

[0050] Example 22: (Catalyst PdPt / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdPt / Beta (PdPt loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0051] Comparative Example 11: (Conventional catalyst PdPt / Al2O3) Compared to Example 22, Comparative Example 22 used a conventional supported catalyst, PdPt / Al2O3, with all other conditions being the same as in Example 22.

[0052] Example 23: (Catalyst PdRu / Beta) A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdRu / Beta (PdRu loading 1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0053] Comparative Example 12: (Conventional catalyst PdRu / Al2O3) Compared to Example 23, Comparative Example 12 used a conventional supported catalyst, PdRu / Al2O3, with all other conditions being the same as in Example 23.

[0054] Table 2. Cyclohexane conversion and cyclohexanone yield in Examples 13 to 23 and Comparative Examples 2 to 12 Example 13 Ru / Beta 2.3 2.3 Example 14 Fe / Beta 0.3 0.3 Example 15 Co / Beta 0.6 0.6 Example 16 Ni / Beta 0.4 0.4 Example 17 Cu / Beta 0.5 0.5 Example 18 PdCu / Beta 36.9 35.9 Example 19 PdFe / Beta 10.6 10.6 Example 20 PdNi / Beta 56.8 55.3 Example 21 PdCo / Beta 21.6 21.3 Example 22 PdPt / Beta 41.2 41.1 Example 23 PdRu / Beta 42.9 42.0 Comparative Example 2 <![CDATA[Ru / Al2O3]]> ＜1 ＜1 Comparative Example 3 <![CDATA[Fe / Al2O3]]> ＜1 ＜1 Comparative Example 4 <![CDATA[Co / Al2O3]]> ＜1 ＜1 Comparative Example 5 <![CDATA[Ni / Al2O3]]> ＜1 ＜1 Comparative Example 6 <![CDATA[Cu / Al2O3]]> ＜1 ＜1 Comparative Example 7 <![CDATA[PdCu / Al2O3]]> ＜1 ＜1 Comparative Example 8 <![CDATA[PdFe / Al2O3]]> ＜1 ＜1 Comparative Example 9 <![CDATA[PdNi / Al2O3]]> ＜1 ＜1 Comparative Example 10 <![CDATA[PdCo / Al2O3]]> ＜1 ＜1 Comparative Example 11 <![CDATA[PdPt / Al2O3]]> ＜1 ＜1 Comparative Example 12 <![CDATA[PdRu / Al2O3]]> ＜1 ＜1 As shown in Table 2, the conversion rate of cyclohexane and the yield of cyclohexanone catalyzed by molecular sieve-supported metal catalysts with different metal catalyst compositions are presented. The results show that the catalytic efficiency is extremely low when the metal catalyst is a single Fe, Co, Ni, or Cu catalyst. However, the conversion rate of cyclohexane and the yield of cyclohexanone are significantly improved when Pb is incorporated into the catalyst, with the conversion rate of cyclohexane reaching 56.8% and the yield of cyclohexanone reaching 55.3%. In addition, the conversion rate of cyclohexane and the yield of cyclohexanone of conventional supported metal catalysts are both less than 1%, indicating extremely low catalytic efficiency. From the above results, it can be seen that the molecular sieve-supported metal catalyst of the present invention has significantly improved catalytic efficiency compared with conventional supported metal catalysts.

[0055] Example 24: A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 0.1wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0056] Example 25 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0057] Example 26 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 10wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent.12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0058] Example 27 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.02g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.1%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0059] Example 28 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 1.8g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 10%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0060] Example 29 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), 0.183g FePc (mass concentration in the mixture: 1.1%), and 0.1g sulfuric acid (mass concentration in the mixture: 0.6%) to 10g water and 5g acetonitrile solvent, mix thoroughly; introduce 1MPa oxygen and react at 100℃ for 24 hours.

[0061] Example 30 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), 0.183g HQ / FePc (mass concentration in the mixture: 1.1%), and 0.1g sulfuric acid (mass concentration in the mixture: 0.6%) to 10g water and 5g acetonitrile solvent, mix thoroughly; introduce 1MPa oxygen and react at 100℃ for 24 hours.

[0062] Example 31 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), 0.183g CuSO4 / FePc / HQ (mass concentration in the mixture: 1.1%), and 0.1g sulfuric acid (mass concentration in the mixture: 0.6%) to 10g water and 5g acetonitrile solvent, mix thoroughly; introduce 1MPa oxygen and react at 100℃ for 24 hours.

[0063] Example 32 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), 0.183g HQ / NPMoV (mass concentration in the mixture: 1.1%), and 0.1g sulfuric acid (mass concentration in the mixture: 0.6%) to 10g water and 5g acetonitrile solvent, mix thoroughly; introduce 1MPa oxygen and react at 100℃ for 24 hours.

[0064] Example 33 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.02g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40(Mass concentration in the mixture: 0.01%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0065] Example 34 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.8g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 5%), 0.1g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1MPa oxygen and react at 100℃ for 24 hours.

[0066] Example 35 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g nitric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0067] Example 36 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 Add 0.1 g hydrochloric acid (mass concentration in the mixture: 1.1%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0068] Example 37 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g acetic acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0069] Example 38 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g acetic acid (mass concentration in the mixture: 0.6%), mix well; introduce 1 MPa oxygen, react at 100°C for 24 hours.

[0070] Example 39 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g molecular sieve solid acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen, react at 100℃ for 24 hours.

[0071] Example 40 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.016 g sulfuric acid (mass concentration in the mixture: 0.01%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0072] Example 41 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.9 g sulfuric acid (mass concentration in the mixture: 5.0%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0073] Example 42 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 3 MPa oxygen and react at 100°C for 24 hours.

[0074] Example 43 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40(Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 0.1 MPa oxygen, react at 100°C for 24 hours.

[0075] Example 44 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 180°C for 24 hours.

[0076] Example 45 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 30°C for 24 hours.

[0077] Example 46 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen, react at 100°C for 0.1 hours.

[0078] Example 47 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 36 hours.

[0079] Example 48 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g methanol solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0080] Example 49 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g ethanol solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0081] Example 50 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g acetonitrile solvent.12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0082] Example 51 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g of aqueous solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0083] Example 52 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g ethyl acetate solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0084] Example 53 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g dichloromethane solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0085] Example 54 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g toluene solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0086] Example 55 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g cyclohexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 15g cyclohexane solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0087] Example 56 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.01g cyclohexene (mass concentration in the mixture: 0.01%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0088] Example 57 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 65.0g cyclohexene (mass concentration in the mixture: 80%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent.12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0089] Table 3. Cyclohexene conversion, cyclohexanone yield, and cyclohexanone production in Examples 24 to 57 Example 24 Loading amount 0.1wt% 28.1 28.0 Example 25 5wt% loading 69.8 69.5 Example 26 10wt% loading 46.3 46.2 Example 27 Add 0.02g catalyst 18.2 18.1 Example 28 Add 1.8g catalyst 89.6 86.3 Example 29 0.183g co-catalyst FePc 35.6 35.3 Example 30 0.183g cocatalyst HQ / FePc 45.8 45.6 Example 31 <![CDATA[0.183 g co-catalyst CuSO4 / FePc / HQ]]> 63.2 63.2 Example 32 0.183g cocatalyst HQ / NPMoV 58.1 58.0 Example 33 <![CDATA[0.02 g cocatalyst H3PMo 12 O 40 > 35.4 35.0 Example 34 <![CDATA[0.8g cocatalyst H3PMo 12 O 40 > 62.1 62.0 Example 35 0.1g nitric acid 58.9 58.2 Example 36 0.1g hydrochloric acid 44.8 44.6 Example 37 0.1g acetic acid 46.7 46.6 Example 38 0.1g acetic acid 49.5 49.9 Example 39 0.1g molecular sieve solid acid 63.8 63.0 Example 40 0.016g sulfuric acid 10.8 10.6 Example 41 0.9g sulfuric acid 94.6 94.5 Example 42 Fill with 3MPa oxygen 95.8 95.0 Example 43 Fill with 0.1 MPa oxygen 2.6 2.3 Example 44 Reaction temperature 180℃ 98.8 98.3 Example 45 Reaction temperature 30℃ 1.3 0.9 Example 46 Reaction time: 0.1 hours 6.5 6.2 Example 47 Reaction time 36 hours 96.1 96.2 Example 48 15g methanol solvent 36.8 36.4 Example 49 15g ethanol solvent 40 39.8 Example 50 15g acetonitrile solvent 50.3 50.0 Example 51 15g water solvent 62.5 62.0 Example 52 15g ethyl acetate solvent 10.6 10.3 Example 53 15g dichloromethane solvent 12.8 12.5 Example 54 15g toluene solvent 36.5 36.2 Example 55 15g cyclohexane solvent 33.5 33.0 Example 56 0.01g cyclohexene 98.3 98.2 Example 57 65.0g cyclohexene 8.3 8.2 As shown in Table 3, the conversion rate of cyclohexene and the yield of cyclohexanone under different loading, catalyst usage, solvent, acid, co-oxidant and reaction conditions are used to determine the optimal conditions for the synthesis of oxide-containing olefins by molecular sieve supported metal catalysts.

[0090] Example 58 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g ethylene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0091] Comparative Example 13 Compared to Example 58, Comparative Example 13 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 58.

[0092] Example 59 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g propylene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0093] Comparative Example 14 Compared to Example 59, Comparative Example 14 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 59.

[0094] Example 60 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g butene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0095] Comparative Example 15 Compared to Example 60, Comparative Example 15 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 60.

[0096] Example 61 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g pentene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0097] Comparative Example 16 Compared to Example 61, Comparative Example 16 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 61.

[0098] Example 62 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g hexene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent.12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0099] Comparative Example 17 Compared to Example 62, Comparative Example 17 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 62.

[0100] Example 63 A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g styrene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0101] Comparative Example 18 Compared to Example 63, Comparative Example 18 used a conventional supported catalyst, PdNi / Al2O3, with all other conditions being the same as in Example 63.

[0102] Example 64: A method for synthesizing oxide-containing olefins by catalysis using a molecular sieve-supported metal catalyst includes the following steps: Add 0.1g PdNi / Beta (PdNi loading 5wt%, catalyst mass fraction in the mixture: 0.6%), 0.4g styrene (mass concentration in the mixture: 2.4%), and 0.183g H3PMo to 10g water and 5g acetonitrile solvent. 12 O 40 (Mass concentration in the mixture: 1.1%), 0.1 g sulfuric acid (mass concentration in the mixture: 0.6%), mix thoroughly; introduce 1 MPa oxygen and react at 100°C for 24 hours.

[0103] Comparative Example 19: Compared to Example 64, Comparative Example 19 used a conventional supported catalyst, PdNi / Al2O3, with the other conditions being the same as in Example 30.

[0104] Table 4. Olefin conversion and product yield of Examples 58 to 64 and Comparative Examples 13 to 19 Example 58 0.1g PdNi / Beta Ethylene / 85.3 Acetaldehyde / 85.2 Example 59 0.1g PdNi / Beta Propylene / 82.6 Propionaldehyde / 82.0 Example 60 0.1g PdNi / Beta Butene / 74.9 Butyraldehyde / 74.0 Example 61 0.1g PdNi / Beta Pentene / 32.6 Pentanal / 31.0 Example 62 0.1g PdNi / Beta Hexene / 26.3 Hexanal / 26.1 Example 63 0.1g PdNi / Beta Styrene / 56.9 Benzaldehyde / 56.1 Example 64 0.1g PdNi / Beta styrene / 36.8 Phenylacetaldehyde / 36.3 Comparative Example 13 <![CDATA[0.1g PdNi / Al2O3]]> Ethylene / <1 Acetaldehyde / <1 Comparative Example 14 <![CDATA[0.1g PdNi / Al2O3]]> Propylene / <1 Propionaldehyde / <1 Comparative Example 15 <![CDATA[0.1g PdNi / Al2O3]]> Butene / <1 Butyraldehyde / <1 Comparative Example 16 <![CDATA[0.1g PdNi / Al2O3]]> Pentene / <1 Pentanal / <1 Comparative Example 17 <![CDATA[0.1g PdNi / Al2O3]]> Hexene / <1 Hexanal / <1 Comparative Example 18 <![CDATA[0.1g PdNi / Al2O3]]> Styrene / <1 Benzaldehyde / <1 Comparative Example 19 <![CDATA[0.1g PdNi / Al2O3]]> Benzenepropylene / <1 Phenylacetaldehyde / <1 As shown in Table 4, Examples 58 to 64 and Comparative Examples 13 to 19 show the olefin conversion and product yield of ethylene, propylene, butene, pentene, hexene, styrene and phenylpropylene catalyzed by molecular sieve supported catalysts. The results show that the molecular sieve supported metal catalysts provided by the present invention have significantly higher catalytic efficiency than conventional supported catalysts when catalyzing the oxidation of ethylene, propylene, butene, pentene, hexene, styrene and phenylpropylene.

[0105] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for catalyzing the oxidation of olefins to oxide-containing compounds using a molecular sieve-supported metal catalyst, characterized in that, Includes the following steps: Add molecular sieve supported metal catalyst, olefin, and H3PMo to water and acetonitrile 12 O 40 The mixture is thoroughly mixed with sulfuric acid and then purged with oxygen to carry out the reaction. The molecular sieve supported metal catalyst is PdNi / Beta molecular sieve.

2. The method according to claim 1, characterized in that, The loading of PdNi in molecular sieve-supported metal catalysts is 0.1–10 wt%.

3. The method according to claim 1, characterized in that, The reaction conditions include: reaction temperature 30~180 ℃, reaction pressure 0.1~3.0 MPa, and reaction time 0.1~36 h.

4. The method according to claim 1, characterized in that, The olefin is one of cyclohexene, ethylene, propylene, butene, pentene, hexene, styrene, and styrene.

5. The method according to claim 1, characterized in that, The mass fraction of olefins ranges from 0.01% to 80%.

6. The method according to claim 1, characterized in that, H3PMo 12 O 40 The mass fraction is 0.01~5%.

7. The method according to claim 1, characterized in that, The mass percentage of the metal catalyst supported on the molecular sieve is 0.01% to 10%.

8. The method according to claim 1, characterized in that, The mass fraction of sulfuric acid is 0.01-5%.